DESCRIPTION

METHOD FOR PRODUCING MATERIAL MADE OF POLYALKYLENE OXIDE RESIN

TECHNICAL FIELD The present invention relates to a method for producing a material made of a polyalkylene oxide resin.

BACKGROUND ART

Polyalkylene oxide resins are useful as polymeric materials from which various products are produced, such as polyurethane resins for use as adhesives, paints, sealants, elastomers, and floor agents; hard, soft, or semihard polyurethane resins; surfactants; sanitary products; a deinking agent; lubricating oil; operating fluids; and the like. Recently, because of the versatility of the polyalkylene oxide resin, other various new uses of the polyalkylene oxide resin have been conceived (e. g. , see Non-patent Literature 1 ) .

Conventionally, a method for producing the polyalkylene oxide resin, particularly a method for purifying and collecting the resin after a polymerization reaction, has been generally known. An example of the methods is a method including the steps of: precipitating the resin by adding, into a large amount of poor solvent, a polymerization reaction liquid after

solution polymerization; filtering out or centrifugally separating the resin; and subjecting the resin to drying and pulverization. Another example of the methods is a method including the step of: subjecting, to filtration or centrifugal separation, a polymerization reaction liquid after precipitation polymerization, so as to obtain the resin; and subjecting the resin to drying and pulverization. Still another example of the methods is a method including the steps of: volatilizing off a solvent from the resin after a polymerization reaction; adding a stabilizer to the resin from which the solvent has been volatilized off; mixing and kneading the resin to which the stabilizer has been added; processing the resin into a sheet; and pelletizing the sheet-like resin by using a cutting machine. The resin thus pulverized or pelletized is supplied to an extruder as required. To the resin, a predetermined additive is added. Then, the mixture is mixed and kneaded. Then, the resin is continuously extruded from a die so as to be shaped into a longitudinally shaped product having a predetermined cross sectional shape.

Moreover, the resin thus pulverized or pelletized can be dissolved in a predetermined solvent thereby to be a coating material. The coating material thus prepared is applied to an application obj ect (to which the coating material is to be applied) by an applicator. In this case, the solvent is not

particularly limited as long as it is a solvent capable of dissolving the polyalkylene oxide resin. The solvent may be used solely, or a mixture of two or more solvents may be used. Or a solvent mixture in which one or more solvents capable of dissolving the polyalkylene oxide resin is mixed with one or more solvents incapable of dissolving the polyalkylene oxide resin are mixed. The resin is dissolved in a solvent selected from among these solvents and solvent mixtures, and then is transported in the form of a solution. Then, the resin is processed to a coating material.

The polyalkylene oxide resin has an ether bond in a main chain thereof. As such, the polyalkylene oxide resin has such a property that it has a chemical structure very heat susceptible. This raises such a problem in that: in cases where the resin thus pulverized or pelletized is transported, for example, by a ship, the resin is fused because the temperature in the ship including a storage in which the resin is stored becomes high, and it becomes very difficult to handle the resin after the transportation. Such a problem is solved as follows . Specifically, the pulverized or pelletized resin is dissolved in a solvent just for transporting the resin in a solution state, or if the resin is used as a coating material as described above, because resin is dissolved in the solvent in the end. However, in the former case, it may be necessary that pulverization or pelletization

be carried out again after the transportation. Further, a considerable amount of solvent is required so that the solution state is stably maintained at a certain level. The use of the solvent would violate transportation regulations on handling of dangerous drugs and articles. Further, putting the resin in the solution state leads to longer process, increased costs, and the like.

In either case, actually loading and unloading of the resin on and from transportation means are carried out by handling the resin in a package. This raises such a problem in that transportation of a large total amount of resin requires a very large labor and time for the loading and unloading.

[Non-patent Literature 1 ] Herman F. Mark, Norbert M. Bikales, Charles G. Overberger, Georg Menges ed. , " Encyclopedia of

Polymer Science and Engineering" , vol. 6, Wiley Interscience,

1986, p. 225-322.

DISCLOSURE OF INVENTION An object of the present invention is to provide a method for producing a material made of a polyalkylene oxide resin.

The method requires a shorter time in which the polyalkylene oxide resin is exposed to heat, and prevents deterioration of the polyalkylene oxide resin. In order to attain the object, a method acceding to the

present invention for producing a material made of a polyalkylene oxide resin, includes: (a) heating an upper surface of the polyalkylene oxide resin contained in a container, so as to melt the polyalkylene oxide resin, and removing the melted polyalkylene oxide resin from the container.

The method is preferably arranged such that: in the step (a) , the upper surface of the polyalkylene oxide resin is heated to a temperature not less than the melting point of the polyalkylene oxide resin, but not more than 300 ⁰ C, so as to melt the polyalkylene oxide resin.

The method is preferably arranged such that: the melting point of the polyalkylene oxide resin is not less than 0 ⁰ C but not more than 60 ⁰ C . The method is preferably arranged such that the polyalkylene oxide resin has an elongational viscosity of not less than 100 Pa-s but not more than 1 ,000, 000 Pa-s when measured at a temperature of not less than 100 ⁰ C but not more than 1 10 ⁰ C and with shear rate of not less than 100 ( 1 / s) but not more than 500 ( 1 / s) .

The method is preferably arranged to further include: (b) polymerizing, in a solvent, a monomer mixture whose main content is an alkylene oxide, so as to obtain the polyalkylene oxide resin; and (c) volatilizing off the solvent from the polyalkylene oxide resin obtained in the step (b) , wherein in

the step (a) , the polyalkylene oxide resin from which the solvent has been volatilized off is removed.

The method is preferably arranged such that: in the step

(a) , a solvent concentration in the polyalkylene oxide resin is not less than 0.01 % by mass and not more than 30% by mass, and water content of the polyalkylene oxide resin is not more than 200ppm.

The method is preferably arranged such that: the monomer mixture in the step (b) is made of ethylene oxide and butylene oxide, or of ethylene oxide, butylene oxide and allylglycidylether, and the monomer mixture has such a mixture ratio that ethylene oxide is in a range of 90 to 99 mol%, butylene oxide is in a range of 1 to 10 mol%, and allylglycidylether is in a range of 0 to 2 mol%. The method is preferably arranged such that: the polyalkylene oxide resin obtained in the step (b) has a mass average molecular weight of not less than 50,000 but not more than 150,000.

The method is preferably arranged such that: in the step (a) , the upper layer of the polyalkylene oxide resin is heated by using a melter so as to melt the polyalkylene oxide resin, and the melted polyalkylene oxide resin is removed from the container.

The method is preferably arranged such that: (d) introducing the polyalkylene oxide resin in the container, the

container being an open head drum, the step (d) including: (e) adding, into an open head drum, the melted polyalkylene oxide resin in a liquid state.

The method is preferably arranged such that: in the step (e) , the polyalkylene oxide resin adjusted to a temperature of not less than (mp + 10) ( ⁰ C) but not more than 300 ⁰ C is added into the open head drum in an atmosphere of an introducing gas that is inert, where mp ( ⁰ C) is a melting point of the polyalkylene oxide resin. The method is preferably arranged such that: the introducing gas used in step (e) has a dew point of -30 ⁰ C or less .

The method is preferably arranged such that: the introducing gas used in step (e) has an oxygen concentration of less than 21 % by volume.

The method is preferably arranged such that: the step (d) further includes, after the step (e) : (f) cooling the polyalkylene oxide resin in the open head drum in an atmosphere of a cooling gas that is inert. The method is preferably arranged such that: in the step

(f) , an opening of the open head drum is closed with a lid that has an inlet and an outlet, and that surface of the polyalkylene oxide resin which is in contact with a space in the open head drum is cooled down to a temperature equal to or less than mp ( ⁰ C) while introducing the cooling gas via the

inlet into the space and discharging the cooling gas via the output from the space .

The method is preferably arranged such that: in the step

(f) , the cooling gas has a dew point of -30 ⁰ C or less . The method is preferably arranged such that: in the step

(f) , the cooing gas has an oxygen concentration of less than

21 % by volume .

The method is preferably arranged such that: from the step (e) to the step (f) , the polyalkylene oxide resin has, in its surface, water content of l OOOppm or less.

The method is preferably arranged to further include: (g) sealing a gas into the space in the open head drum in which the polyalkylene oxide resin is contained, the gas having a dew point of -30 ⁰ C or less, and the space having been produced in the step (d) , so that the gas sealed in the space has a pressure not less than a standard atmospheric pressure but not more than tolerable pressure of the open head drum; and after the step (g) but before the step (a) , (h) transferring or storing the open head drum while the dew point of the gas sealed in the space in the step (g) is kept at or below -30 ⁰ C .

The method is preferably arranged such that: in the step

(h) , the polyalkylene oxide resin has a solvent concentration of 30% or less by mass, and water content of l OOOppm or less. The method is preferably arranged to include: (i)

_ g .

dissolving, into a solvent, the polyalkylene oxide resin removed in the step (a) .

The method is preferably arranged such that: the step (i) includes: (j) dissolving the polyalkylene oxide resin in the solvent in a dissolving tank, while supplying, into the dissolving tank, the polyalkylene oxide resin whose temperature adjusted to be equal to or higher than (mp+ 10)°C, the dissolving tank having a system temperature of (mp)°C or higher, where mp ⁰ C is the melting point of the polyalkylene oxide resin.

The method is preferably arranged such that: the step (i) includes: (k) stirring the solution in the dissolving tank with power requirement of impeller (PV) of 0. 1 (kW/ m ³ ) or greater.

The method is preferably arranged such that: in the step (j) , the polyalkylene oxide resin whose temperature adjusted to be not less than (mp+ 10)°C but not more than 300 ⁰ C is supplied into the dissolving tank, and the dissolving tank has a system temperature of not less than (mp)°C but not more than 300 ⁰ C . The method is preferably arranged to further include (1) shaping the polyalkylene oxide resin removed in the step (a) .

The method is preferably arranged to further include (m) transferring the melted polyalkylene oxide resin to a mixing device by liquid-transferring means, the melted polyalkylene oxide resin being removed in the step (a) , the

liquid-transferring means including: a melting tank for storing the melted polyalkylene oxide resin therein; a pump for transferring the melted polyalkylene oxide resin from the melting tank to the mixing device; and a liquid-transferring line through which the melted polyalkylene oxide resin flows from the melting tank to the mixing device, the pump pumping out the melted polyalkylene oxide resin with F of 6% or less, where F is fluctuation tolerance in a pumping-out amount of the melted polyalkylene oxide resin per unit of time, and expressed by Equation (I) :

F = 3 ^χ σ / A x 100 ^{• • •} (I) ,

where A is an average in the pumping-out amount, and σ is a standard deviation of the pumping-out amount.

The method is preferably arranged such that: the melting tank of the liquid-transferring means is capable of allowing an internal pressure thereof to be increased by introduction of an inert gas therein, and comprises a first temperature adjusting means for adjusting a temperature of the melted polyalkylene oxide resin contained in the melting tank, the pump is capable of changing the pumping-out amount of the melted polyalkylene oxide resin per unit of time according to a revolution speed of a shaft, and comprises a second temperature adjusting means for adjusting the

temperature of the melted polyalkylene oxide resin inside the pump, the liquid-transferring line of the liquid-transferring means comprises a third temperature adjusting means for adjusting the temperature of the melted polyalkylene oxide resin inside liquid-transferring line, and F is controlled by the internal pressure of the melting tank, the revolution speed of the shaft of the pump, the temperature of the melted polyalkylene oxide resin in the melting tank, which temperature is. adjusted by the first temperature adjusting means, the temperature of the melted polyalkylene oxide resin inside the pump, which temperature is adjusted by the second temperature adjusting means, and the temperature of the melted polyalkylene oxide resin inside the liquid-transferring line, which temperature is adjusted by the third temperature adjusting means.

The method is preferably arranged such that: in the step (m) , the melted polyalkylene oxide resin in the melting tank has water content of l OOOppm or less, and oxygen concentration in the space inside the melting tank is less than 21 % by volume.

According to the present invention, it is possible to remove the polyalkylene oxide resin from the container (e. g. , open head drum) just as much as required. This reduces the time in which the polyalkylene oxide resin is exposed to heat, thereby preventing the deterioration of the resin material.

Further, because the polyalkylene oxide resin is transported in a bulk state, not in a powder or pellet form, to a site at which the next step is to be carried out. This prevents the resin from being thermally melted and fused together. Because the resin can be transported without being solving in a solvent, good workability and safety, as well as low cost, of the polyalkylene oxide resin can be achieved.

For a fuller understanding of the nature and advantages of the invention, reference should be made to the ensuing detailed description taken in conjunction with the accompanying drawings.

BRIEF DESCRIPTION OF DRAWINGS

FIG. 1 is a perspective view schematically illustrating an open head drum for use in a method according to the present invention for introducing the polyalkylene oxide resin.

FIG. 2 is a partially cutway front view illustrating the open head drum of FIG. 1 being used in an introducing apparatus for use in the introducing step. FIG. 3 is a partially cutway right-side view illustrating the introducing apparatus of FIG. 2.

FIG. 4 is a partially cutway side view illustrating the open head drum of FIG. 1 being used in the cooling step.

FIG. 5 is a partially cutway view illustrating removal of the polyalkylene oxide resin from the open head drum.

FIG. 6 is a view schematically illustrating an apparatus for the removing step and the dissolving step.

FIG. 7 is a partially cutway perspective view illustrating the removal of the polyalkylene oxide resin from the open head drum by using a melter.

FIG. 8 is a perspective view illustrating an example of the polyalkylene oxide resin used in Examples .

FIG. 9 is a view schematically illustrating a structure of an apparatus used in Example.

REFERENCE NUMERALS 2 : Open Head Drum 108 : Open Head Drum (Open Drum) 402 : Open Head Drum 12 : Inlet 14 : Outlet 22 : Pump

322 : Pump (Rotary Pump) 56: Opening Section 88 : Opening Section 412 : Opening Section 414 : Opening Section 84 : Space Section 100: Space Section 107: Polyalkylene Oxide Resin

3 16: Liquid Transferring Means 318 : Mixing Apparatus 320 : Melting Tank 324 : Liquid Transferring Line 326: Liquid Transferring Line

BEST MODE FOR CARRYING OUT THE INVENTION

In the following, a polyalkylene oxide resin producing method according to the present invention will be described. However, the scope of the present invention is not limited to these explanations. Apart from those exemplified below, the present invention includes modifications within the gist of the present invention.

In the present invention, the term "weight" is used as a synonym of the term "mass" , and the term "% by weight" is used as a synonym of the term "% by mass" . The phrase "main component" is used as meaning a component that accounts for 50 % by mass or more. Further, the term " (meth)acryloyl" means the term acryloyl or methacryloyl, and the range of "X to Y" is not less than X but not more than Y. <Polymerizing Step (step (b)) >

A method according to the present invention for polymerizing a polyalkylene oxide resin may be any polymerizing method as long as it is a method by which a polyalkylene oxide resin is obtained. Preferably, a

polyalkylene oxide resin according to the present invention is obtained by a polymerizing step of polymerizing, with the use of a solvent, a monomer mixture composed mainly of alkylene oxide. The polyalkylene oxide resin according to the present invention (an alkylene oxide polymer, an alkylene oxide copolymer, or an alkylene oxide terpolymer) is not particularly limited as long as it is a resin which has a molecular structure composed mainly of a constituent derived from an alkylene oxide monomer and which has an ether bond in a main chain thereof.

Examples of the polyalkylene oxide resin according to the present invention include a polymer whose essential raw material (raw material monomer) is one or more types of oxirane compounds that may have a substituent. The polymer is obtained, for example, by carrying out such polymerization that: while a monomeric mixture whose essential raw material is one or more types of oxirane compounds that may have a substituent is being stirred in a solvent (polymerization solvent) , the monomeric mixture is polymerized by using a polymerization catalyst. Examples of the polymerization solvent include solvents made of one or more types of compounds selected from the group consisting of aliphatic hydrocarbons, aromatic hydrocarbons, ketones, ketone derivatives, esters, ethers, nitrile compounds, and organic

Jialides .

Examples of the oxirane compound that may have a substituent include a compound represented by the following structural formula ( 1 ) :

R 1 R ³

(where R ¹ , R ² , R ³ , and R ⁴ are independently Ra (Ra is a hydrogen atom, an alkyl group of a carbon number of 1 to 20, a cycloalkyl group of a carbon number of 1 to 20, an aryl group of a carbon number of 1 to 20, an aralkyl group of a carbon number of 1 to 20, a (meth) acryloyl group of a carbon number of 1 to 20, an alkenyl group of a carbon number of 1 to 20, or an alkaryl group of a carbon number of 1 to 20. Any two substituents selected from the group consisting of R ¹ , R ² , R ³ , and R ⁴ . may form a ring together with the epoxy carbon atom to which they are bonded ) or a -CU2-O-Re-Ra group (Re has a structure of ~(CH2-CH2-O)p- (p is an integer of 0 to 10))) . Here , the word "the epoxy carbon atom" refers to a carbon atom constituting an oxirane ring. Further, R ¹ , R ² , R ³ , and R ⁴

may be identical to or different from one another.

The polyalkylene oxide resin according to the present invention is preferably obtained by polymerizing a comonomer group containing (i) ethylene oxide and (ii) a substituted

5 oxirane compound represented by the following structural formula (2) :

R ⁵

CH. CH C2)

10

O

(where R5 is Ra (Ra is any one of an alkyl group, an cycloalkyl group, an aryl group, an aralkyl group, a

, c . (meth) acryloyl group, and an alkenyl group each of which has a carbon number of 1 to 16 independently) or a -CIHb-O-Re-Ra group (Re has a structure of - (CH2-CH2-O)p- (p is an integer of 0 to 10))) . It is preferable that this polymerization be ring-opening polymerization of oxirane group of each material _Q monomer. R5 is the structural formula (2) is a substituent of the substituted oxirane compound.

The substituted oxirane compound used as the raw material monomer may contain one or more types of substituted oxirane compounds represented by the structural 5 formula ( 1 ) or (2) . Examples of the oxirane compound

represented by the structural formula ( 1 ) or (2) include ethylene oxide, propylene oxide, butylene oxide, 1 ,2-epoxypentane, 1 ,2-epoxyhexane, 1 ,2-epoxyoctane, cyclohexene oxide, styrene oxide, methyl glycidyl ether, ethyl glycidyl ether, ethylene glycol methyl glycidyl ether, and the like . Furthermore, in cases where the substituent R5 is a crosslinking substituent, i.e. , in cases where the substituent R5 has an aryl group, an alkenyl group, an acryloyl group, a methaacrylol group, or the like, examples of the oxirane compound represented by the structural formula (2) also include epoxybutene, 3,4-epoxy- l -penetene, l ,2-epoxy-5,9-cyclododecadiene, 3,4-epoxy- l -vinyl cyclohexene, l ,2-epoxy-5-cyclooctene, glycidyl acrylate, glycidyl methacrylate, glycidyl sorbate, glycidyl-4-hexanoate, vinyl glycidyl ether, allyl glycidyl ether, 4-vinyl cyclohexyl glycidyl ether, α-terpenyl glycidyl ether, cyclohexenyl methyl glycidyl ether, 4-vinyl benzyl glycidyl ether, 4-allyl benzyl glycidyl ether, and the like. As described above, they may be used solely. As an alternative, a combination of two or more of them may be used.

The raw material monomer of the polyalkylene oxide resin according to the present invention can contain a monomer other than the ethylene oxide and the substituted oxirane compound. The polyalkylene oxide resin according to the present invention is preferably a combination of specific

monomers especially because the polymer to be obtained has a melting point that can be easily adjusted so as to fall within a desired range mentioned later. Specifically, the polyalkylene oxide resin according to the present invention is more preferably either (i) a copolymer made up of ethylene oxide and butylene oxide, or (ii) a monomer mixture made up of ethylene oxide, butylene oxide, and allylglycidylether.

A monomer concentration in a reaction system (an amount of monomer to be used in the reaction system) is not particularly limited, but is preferably set so that in a reaction mixture after the polymerization, the amount of an alkylene oxide polymer obtained by polymerization falls within a range of 10 % by mass to 80 % by mass, more preferably 20 % by mass to 70 % by mass, still more preferably 30 % by mass to 60 % by mass. The amount of the alkylene oxide polymer less than 10 % by mass would possibly result in that productivity is low and that the polymer thus obtained lacks of practicality. The amount of the alkylene oxide polymer exceeding 80 % by mass would possibly result in that the viscosity of the polymer is increased to such an extent that it becomes difficult to stir the polymerization reaction solution, and it becomes difficult to remove polymerization heat generated by the polymerization reaction. Therefore, it may become impossible to easily obtain the polymer with high productivity and high repeatability.

A mixture ratio between ethylene oxide and the other monomers (especially the substituted oxirane compound) each of which is contained in the monomer mixture is not particularly limited, and may be appropriately set so that the viscosity of the reaction mixture after the polymerization is not unnecessarily increased or reduced to such an extent that the polymer loses practicality. Further, in cases where a substituted oxirane compound having a crosslinking substituent is used, the substituted oxirane compound can be used in an arbitrary proportion to the total amount of the substituted oxirane compound used.

In cases where the monomer mixture is the combination of specific monomers, the copolymer to be obtained has a melting point that can be easily adjusted. For the purpose of putting the melting point in a desired range mentioned later, the copolymer preferably has such a mixture ratio that ethylene oxide is in a range of 90 mol% to 99 mol%, butylene oxide is in a range of 1 mol% to 10 mol%, and allylglycidylether is in a range of 0 mol% to 2 mol%. Particularly, in cases where the monomer mixture is made up of ethylene oxide and butylene oxide, the monomeric mixture preferably has such a mixture ratio that ethylene oxide is in a range of 92 mol% to 96 mol% and butylene oxide is in a range of 4 mol% to 8 mol% . Further, in cases where the monomer mixture is made up of ethylene oxide, butylene oxide, and

allylglycidylether, the monomer mixture preferably has such a mixture ratio that ethylene oxide is in a range of 92 mol% to 97.8 mol%, butylene oxide is in a range of 2 mol% to 6 mol%, and allylglycidylether is in a range of 0.2 mol% to 2 mol%. Preferable examples of the polymerizing method used in the polymerizing step include a solution polymerization method, a precipitation polymerization method, a bulk polymerization method, and the like. The solution polymerization method is more preferable than the other methods because the solution polymerization method excels in productivity. A solution polymerization method by which polymerization is carried out while a monomer component is being supplied to a solvent that has been fed in a reactor vessel in advance is particularly preferable because the method does not only excels in productivity, but also makes it easy to remove reaction heat and excels in safety.

The solvent (the solvent used for the solution polymerization) is not particularly limited, but is preferably a solvent having no active hydrogen. Active hydrogen reacts with a polymerization initiator and a growing end of the polymer . The use of the solvent having no active hydrogen is preferable, for example, for the following reasons ( 1 ) and (2) : ( 1 ) the solvent causes few side reactions, and the molecular weight and melting point of the polymer are easily controlled; and (2) the solvent is easily managed because water content

in the solvent can be reduced to a predetermined amount. Preferable examples of the solvent used for the polymerization include an organic solvent, and examples of the organic solvent include: aromatic hydrocarbon solvents such as benzene, toluene, xylene, and ethylbenzene; aliphatic hydrocarbon solvents such as heptane, octane, n-hexane, n-pentane, and 2 ,2,4-trimethylpentane; alicyclic hydrocarbon solvents such as cyclohexane, cyclopentane, and methylcyclohexane; ether solvents such as diethyl ether, dibutyl ether, and methyl butyl ether; ethylene glycol dialkyl ether solvents such as dimethoxyethane; cyclic ether solvents such as THF (tetrahydrofuran) and dioxane; ketone solvents such as acetone and methyl ethyl ketone; ester solvents such as ethyl acetate and butyl acetate; nitrile solvents such as acetonitrile; organic halogen solvents such as methylene chloride, chloroform, and carbon tetrachloride; and ketone derivative solvents such as acetal and ketal each of which is obtained from ketone and alcohol. Among them, toluene, xylene, tetrahydrofuran, acetone, and acetonitrile are particularly preferable because they have no active hydrogen that inhibits polymerization. As the solvent used for the polymerization, the organic solvent containing no water at all is more preferable.

The step of polymerizing the monomer mixture (polymerizing step) preferably includes at least two stages.

Specifically, the polymerizing step preferably includes: at least one stage of supplying and polymerizing only ethylene oxide; and at least one stage of supplying and polymerizing ethylene oxide and another monomer (a monomer other than ethylene oxide) . This makes it possible to prepare a polyalkylene oxide resin having a desired composition ratio and a desired molecular weight as originally designed, and further having a desired melting point. Specifically, the alkylene oxide copolymer to be obtained has a molecular structure part (structural portion) of which only a structural unit(s) derived from ethylene oxide constitute, so that the higher one of two melting points of the copolymer is controlled. Conditions are appropriately set so that the copolymer as a whole has the desired monomer composition ratio and the desired molecular weight. The higher one of the two melting points corresponds to a melting point of polyethylene oxide that corresponds to the size of the structural portion. Therefore, the higher one of the two melting points of the copolymer can be adjusted by the extent of the polymerization of only ethylene oxide in the polymerization reaction.

The polymerization reaction liquid may contain another component in addition to the alkylene oxide resin component and the solvent component. Examples of such another component include a reaction initiator, an antioxidant, and a

solubilizer each of which is commonly used in a polymerization reaction. Preferable examples of the reaction initiator include: (i) alkali catalysts such as sodium hydroxide, potassium hydroxide, potassium alcoholate, sodium alcoholate, potassium carbonate, and sodium carbonate; (ii) metals such as metallic potassium and metallic sodium; (iii) Al-Mg complex oxide catalysts that may or may not be surface-modified such as aluminum-hydroxide-and-magnesium calcinated product (e.g., see Japanese Unexamined Patent Publication No. 268919/1996), a metal-ion-added magnesium oxide (e.g., see Japanese Unexamined Patent Publications No. 15038/1994 and No. 227540/1995), or calcinated hydrotalsite (e.g., see Japanese Unexamined Patent Publication No. 718441/1990), a surface modified Al-Mg complex oxide (e.g., see Japanese Unexamined Patent Publication No. 334782/1994); (iv) an acid catalyst such as barium oxide, barium hydroxide (e.g., see Japanese Unexamined Patent Publication No. 75187/1979), a layered compound (e.g., see Japanese Unexamined Patent Publication No. 505986/1994), strontium oxide, strontium hydroxide (e.g., see Japanese Unexamined Patent Publication No. 32055/1988), a calcium compound (e.g., see Japanese Unexamined Patent Publication 134336/1990), a cesium compound (e.g., see Japanese Unexamined Patent Publication No.70308/1995), a composite

metal cyanide complex (e.g. , see Japanese Unexamined Patent Publication No . 339361 / 1993) ; Lewis acids; and Friedel-Crafts catalysts. Among them, metallic alcoholates are particularly preferable. The type of metal preferable for the purpose of inhibiting a side reaction is potassium. The alkyl group of alcoholate preferable for the purpose of high reactivity is tert-butoxide having a tert-butyl group. The polymerization reaction liquid may contain one or more types of reaction initiators, and is not particularly limited. The manner in which the reaction initiator is introduced or added in the polymerizing step is not particularly limited. For example, the total amount of the reaction initiator to be used may be fed together with the solvent before the supply of the monomer mixture is started, so that the reaction initiator is added together with the solvent. As an alternative, the reaction initiator may be added in one step or stepwise (continuously or intermittently) after the monomer mixture has started to be supplied.

In the polymerizing step, a reactor is not particularly limited provide that it has a function of stirring its contents (e.g. , the fed solvent, the supplied monomer mixture) . The reactor is preferably a stirring tank which is provided with a stirring impeller and which can arbitrarily stir its contents under a predetermined condition. Examples of the stirring impeller include an anchor impeller, a helical ribbon impeller,

a double helical ribbon impeller, a helical screw impeller provided with a draft tube, a Superblend impeller, a Maxblend impeller, a Fullzone impeller, a Supermix imperller, a Sanmeler Impeller, a twisted lattice impeller, a turbine impeller, a paddle impeller, a Pfaudler impeller, a Burmargin impeller, a propeller impeller, and the like.

The reactor is preferably provided with equipment capable of (i) heating, to a temperature not more than a desired reaction temperature, the contents that has been fed into the reactor and (ii) maintaining the temperature of the contents. Specifically, preferable examples of the equipment include, but are not limited to , a jacket, a coil, an external recirculating heat exchanger, and the like. In addition to the equipment, various pieces of equipment can be arbitrarily provided for the purpose of effectively carrying out the polymerization reaction. Examples of such equipment include: a baffle; respective detecting ends of a thermometer, a pressure gauge, and the like; a supplying apparatus for uniformly dispersing raw material into a liquid or a gas phase; an apparatus for cleaning the interior of a reactor and the interior of a reaction layer; and the like.

In the polymerizing step, it is preferable to use a reactor whose inner atmosphere has been sufficiently replaced with an inert gas after the interior of the reactor has been cleaned with the solvent and then thermally dried and before the

monomer mixture is polymerized. As an alternative, it is preferable to use a reactor whose interior has been put in a vacuum state. It is preferable that the solvent and the like be fed into the reactor after the cleaning and before the polymerization of the monomer mixture . Then, the inner atmosphere of the reactor is preferably replaced again by an inert gas. As an alternative, the interior of the reactor is preferably put in a reduced pressure state or in a vacuum state. Normally, the polymerization reaction is carried out by stirring the monomer mixture together with the solvent and the like . The stirring is preferably carried out before the supply of the monomer mixture to the solvent, for example, by rotating the stirring impeller provided in the reactor. The stirring can be started at any timing. For example, the stirring may be started (i) during the supply of the monomer mixture, (ii) at the start of the supply, or (iii) at the start of the polymerization. The stirring is preferably continued until the polymerization is completed. The polymerization reaction is preferably carried out at a temperature of less than 120°C, more preferably not more than 1 10°C, still more preferably not more than 100°C . When the reaction temperature exceeds 120°C, chain transfer reactions occur more frequently. This may easily cause reduction in molecular weight. In this case, the molecular

weight may be reduced to such an extent as to become unable to be controlled by adjusting the amount of the reaction initiator that is to be added.

In the polymerizing step, it is preferable that the reaction mixture contained in the reactor be aged as required after the supply of the monomer mixture is finished. Conditions (temperature, time, and the like) for the aging is not particularly limited. At the time of normalizing the pressure of the reactor after the maturation, the solvent and/ or an unreacted raw material monomer may exist in the gas phase. Therefore, gas in the gas phase is completely burned, as required, by using a waste gas burning apparatus.

The mass average molecular weight (Mw) and molecular weight distribution (Mw/ Mn) of the alkylene oxide copolymer that has been polymerized in the polymerizing step can be set in consideration of uses and the like to the extent that the copolymer does not significantly lack of practicality, e.g. , that the viscosity of the copolymer does not become unnecessarily low. The mass average molecular weight (Mw) and molecular weight distribution (Mw/ Mn) of the alkylene oxide copolymer can be set by appropriately setting the aforementioned polymerization conditions and the like. Note that Mn refers to the number average molecular weight of the alkylene oxide copolymer. The mass average molecular weight (Mw) of the

copolymer to be obtained preferably falls within a range of 10,000 to 500,000. The lower limit of the mass average molecular weight (Mw) is preferably 30 ,000, more preferably 40,000, still more preferably 50, 000. The upper limit of the mass average molecular weight (Mw) is preferably 300,000, more preferably 200,000, still more preferably 150 , 000. When Mw is less than 10,000, the melting point of the copolymer may become so low as to become unable to be put in a desired range. When Mw exceeds 500, 000, the viscosity of the polymerization reaction liquid becomes so high that it would become difficult to stir the reaction solution in the polymerizing step. The molecular weight distribution (Mw/ Mn) of the copolymer to be obtained preferably falls within a range of 1.0 to 5.0. The upper limit of the molecular weight distribution (Mw/ Mn) is preferably 3.0. A molecular weight distribution (Mw/ Mn) exceeding 5.0 would cause tucking when the resin is shaped into a product. This may cause poor handling. A mass average molecular weight (Mw) less than 50,000 has such a risk that, when the copolymer is used as a material for a battery, an amount of active hydrogen is increased at a polymer end, so that the polymer becomes more reactive with ions contained in the battery. This may- deteriorate the performance of the battery. When the mass average molecular weight (Mw) exceeds 150,000, formability during coating and extrusion deteriorates.

In the polymerizing step, the polymerization is adjusted in order that the higher melting point mp (°C) of the copolymer to be obtained, i. e. , of the polyalkylene oxide resin may be at a desired value . For example, the polymerization is adjusted by controlling the extent to which the aforementioned stage of polymerizing only ethylene oxide is carried out. The melting point mp ("C) preferably falls within a range of 0°C to 60 ⁰ C. The lower and upper limits of the melting point are preferably 35°C and 55°C, respectively. A melting point mp (°C) exceeding 60°C reduces conductivity of a battery material obtained from the copolymer. When the melting point mp ("C) is less than 0 ^° C , a film obtained from the polymer has a low intensity at an operating temperature.

It is preferable that the copolymer to be obtained, i. e . , the polyalkylene oxide resin have an elongational viscosity of not less than 100 Pa- s but not more than 1 , 000 ,000 Pa- s when measured at a temperature of not less than 100 ⁰ C but not more than 1 10 ⁰ C and with a shear rate of not less than 100 ( 1 / s) but not more than 500 ( 1 / s) . The lower limit of the elongational viscosity is more preferably 500 Pa- s, and is still more preferably 1 , 000 Pa- s. The upper limit of the elongational viscosity is more preferably 500,000 Pa- s, and is still more preferably 100,000 Pa- s. When the elongational viscosity is not more than 1 ,000 ,000 Pa- s, the viscosity of the polyalkylene oxide resin being supplied in the dissolving step

(step (i)) tends to be low, and the dissolution rate is likely to be high. Further, for example, in a case where the polymer having an elongational viscosity of less than 100 Pa- s is processed into a film, the melted resin may be cut by even slight tension when being fabricated into the film. Further, for example, in a case where the polymer having an elongational viscosity of more than 1 , 000,000 Pa- s is processed into a film, high torque is produced when the polymer is extruded so as to be formed into the film, so that the extrusion of the polymer may become impossible .

It is preferable that the solvent in the pplyalkylene oxide resin obtained in the polymerizing step be volatilized off in a step of volatilizing off the solvent (volatilizing-off step (step (c))) . The solvent in polyalkylene oxide resin may not be completely volatilized off so that no solvent component is contained in the polyalkylene oxide resin at all after the volatilizing-off step. Normally, the solvent component in the resin is reduced to a desired solvent concentration by volatilizing off the solvent therefrom as described below. The volatilizing-off may be carried out by adapting a method, an apparatus, and various conditions which are normally adapted. Details will be described below. Normally, the volatilizing-off method is preferably a two-stage process including a preliminary volatilizing-off stage and a main volatilizing-off stage. However, the volatilizing-off method is

not particularly limited, and may be a one-stage process. The reason why the volatilizing-off is preferably carried out in two stages is that the efficiency of the volatilizing-off can be improved (e.g. , cost reduction, shortening of the processing time, and improved quality of the resin) . Specifically, a slow volatilizing-off process follows a volatilizing-off process in which the solvent contained in a large amount in the polymerization reaction solution that is to be volatilized off is rapidly reduced to such an amount that the volatilizing-off process can be efficiently carried out. For the following reasons ( 1 ) and (2) and other reasons, it is theoretically preferable that the volatilizing-off be carried out in two stages. The reason ( 1 ) is that the equipment size can be made smaller by carrying out the two-stage volatilizing-off process including the former stage of carrying out the volatilizing-off at normal pressures and the latter stage of carrying out the volatilizing-off in vacuum (under reduced pressure) than by carrying out the one-stage volatilizing-off process. The reason (2) is that: because the viscosity may be suddenly increased in a certain concentration range during the volatilizing-off, the driving system can be made smaller than in the case of the one-stage process. However, depending on the type of polymerization reaction liquid that is to be subjected to the volatilizing-off process, even the one-stage process may bring about the same effects as the two-stage process does.

Therefore, the volatilizing-off method is selected as appropriate.

Preferable examples of the volatilizing-off apparatus include, but are not particularly limited to, a mixer evaporator, a falling-film evaporator, a thin-film evaporator, a surface-renewal-type polymerizer, a kneader, a roll mixer, an intensive mixer (so called a Banbury mixer) , an extruder, and the like . The volatilizing-off is preferably carried out by using at least one of these apparatuses. Further, it is possible to appropriately set use conditions in accordance with the apparatus used. The mixer evaporator excels in that it can deal with a wide range of viscosities and a wide range of residual solvent concentrations. Preferable examples of the mixer evaporator include : a stirring tank provided with a helical impeller; a stirring tank provided with a double helical ribbon impeller; a vertical concentric biaxial stirring tank (e.g. , product name: SUPERBLEND, manufactured by Sumitomo Heavy Industries. Ltd.) provided with a Superblend impeller (inner impeller: Maxblend impeller, outer impeller: spiral deformed baffle) ; a VCR inverted-cone-ribbon-type reactor (manufactured by Mitsubishi Heavy Industries, Ltd.) ; and the like. These are preferably used for a batch-type process. Further, because of its characteristic, the mixer evaporator requires a large amount of time for discharging after the process. Therefore, the mixer evaporator is more

suitable for a process of accurately processing a small amount of resin than for a process of processing a large amount of resin and the like.

Preferable examples of the falling-film evaporator include : a tubular-exchanger-type evaporator (e.g. , product name: Sulzer Mixer, manufactured by Sumitomo Heavy Industries . Ltd. ; product name: Static Mixer, manufactured by Noritake Co . , Ltd.) ; a plate-heat-exchanger-type evaporator (e.g. , product name: Hiviscous Evaporator, manufactured by Mitsui Engineering & Shipbuilding Co . , Ltd. ) ; and the like. Preferable examples of the thin-film evaporator include: a horizontal thin-film evaporator (e.g. , product name: EVA reactor, manufactured by Kansai Chemical Engineering Co . , Ltd.) ; a fixed-impeller-type vertical thin-film evaporator (e.g. , product name: EXEVA, manufactured by Shinko Pantec Co . , Ltd.) ; a movable-impeller-type vertical thin-film evaporator (e.g. , product name: WIPRENE, manufactured by Shinko Pantec Co. , Ltd.) ; a tank-type (mirror-type) thin-film evaporator (e. g. , product name: Recovery, manufactured by Kansai Chemical Engineering Co . , Ltd.) ; and the like. The surface-renewal-type polymerizer (horizontal thin-film polymerizer) excels in that it exhibits high volatilizing-off performance by renewing a gas-liquid interface. Preferable examples of the surface-renewal-type polymerizer include: a single screw surface-renewal-type polymerizer, and a twin

screw siirface-renewal-type polymerizer (e. g. , product name: BIVOLAK, manufactured by Sumitomo Heavy Industries. Ltd. ; product name: Hitachi spectacle-shaped impeller polymerization machine, manufactured by Hitachi, Ltd. ; product name: Hitachi lattice-impeller polymerization machine, manufactured by Hitachi, Ltd. ; product name : SC processor, manufactured by Kurimoto, Ltd.) ; and the like.

The extruder is suitable for mixing highly viscous melted materials and the like, and has a volatilizing-off capability in addition to a heating function, a melting function, and a mixing and kneading function. Preferable examples of the extruder include: a single-screw extruder, a twin-screw extruder (e .g. , product name: SUPERTEXaII, manufactured by Japan Steel Works, Ltd. ; product name: BT-30-S2 , manufactured by Plastic Technology Laboratory) ; SCR self-cleaning-type reactor (manufactured by Mitsubishi Heavy Industries, Ltd.) ; and the like.

As described above, preferable examples of the volatilizing-off method include the method in which the main volatilizing-off step is carried out after the preliminary volatilizing-off step. Among the various volatilizing-off apparatuses described above, examples of a volatilizing-off apparatus that can be preferably used for the preliminary volatilizing-off step include, but are not particularly limited to, (i) the stirring tank provided with the double helical ribbon

impeller, (ii) the vertical concentric biaxial stirring tank provided with the Superblend impeller, (iii) the plate-heat-exchanger-type falling-film evaporator, (iv) the fixed-impeller-type vertical thin-film evaporator, and (v) the like . Further, examples of a volatilizing-off apparatus that can be used for the main volatilizing-off step include, but are not particularly limited to, (a) the fixed-impeller-type vertical thin-film evaporator, (b) the twin screw surface-renewal-type polymerizer, (c) the kneader, (d) the twin-screw extruder, and (e) the like.

The polymerization reaction liquid may be volatilized off by using any one of the above-enumerated various volatilizing-off apparatuses connected directly to the preceding apparatus, i.e. , the apparatus used for the polymerizing step in which the solvent is used. As an alternative, the polymerization reaction liquid may be volatilized off by using the use of the volatilizing-off apparatus to which the polymerization reaction liquid is transferred from the preceding apparatus. Examples of the latter case include: an arrangement in which the preceding apparatus is connected to the volatilizing-off apparatus via a liquid-transferring line; an arrangement in which an intermediate tank (cushion tank) including a jacket and a stirring machine is provided between the preceding apparatus and the volatilizing-off apparatus; and the like.

The volatilizing-off step is preferably arranged such that the solvent remaining in the polyalkylene oxide resin from which the solvent has been volatilized off has a concentration of not more than 30% by mass, more preferably not more than 20% by mass, still more preferably not more than 10% by mass. Further, in cases where the concentration of the residual solvent exceeds 30% by mass, the residual solvent may adversely affect the formability of the polyalkylene oxide resin. Further, in cases where the concentration of the residual solvent exceeds 30% by mass, the transportation of the polyalkylene oxide resin becomes dangerous due to the solvent volatilized off during the transportation.

The water content in the polyalkylene oxide resin from which the solvent has been volatilized off comes from, e.g. , the solvent, the monomer, and the like used for the polymerization. The water content is preferably not more than 1000 ppm, more preferably not more than 200 ppm, still more preferably not more than 100 ppm, particularly preferably not more than 10 ppm. A water content exceeding 1000 ppm causes the resin to be conductive . Therefore, in cases where the obtained polyalkylene oxide resin is used, for example, as a protective film of a color filter, the protective film may utterly deteriorate in function. Further, the moisture reacts with metal ions and the like, thereby forming hydroxides and the like. Therefore, in cases where the polyalkylene oxide

resin is used, for example, as an electrolyte layer of a battery whose electrode is made of metal, there is a possibility that an insulating layer is formed on the interface between the metal and the electrolyte layer. This continuously increases a voltage required to obtain the same current, and thus deteriorates the battery in cycling characteristics.

The water content is adjusted, for example, by (i) reducing the amount of water that is introduced by the material, the handled gas, the cleansing solvent, and the like during the polymerization, (ii) reducing the amount of water on a surface of the polymerizing apparatus (including a pipe, a valve, and the like) , and/ or (iii) preventing, as much as possible, moisture contamination in each step carried out after the polymerization. When the solvent is volatilized off from the polymerization reaction liquid under heated conditions by using the aforementioned volatilizing-off apparatus, the temperature is preferably in a range of 40°C to 300 ⁰ C. Its lower limit is more preferably 60 ⁰ C, and still more preferably 90 ⁰ C . Its upper limit is more preferably 250°C , still more preferably 200°C. After the volatilizing-off step carried out in this temperature range, the polyalkylene oxide resin having the aforementioned desirable residual solvent concentration and water content can be obtained. A temperature of lower than 4O ⁰ C leads to a risk of increasing the amount of the

residual solvent. A temperature higher than 300°C leads to a risk of thermally deteriorating the polyether. As the term used herein, the "temperature" refers to a temperature of the polyalkylen oxide resin contained in the volatilizing-off apparatus.

Similarly, the solvent is preferably volatilized off under a pressure in a range of 13 Pa to 100,000 Pa. The lower limit is more preferably 133 Pa, and still more favorably 1 ,333 Pa. The upper limit is more preferably 70,000 Pa, and still more favorably 40,000 Pa. By satisfying this pressure range, the polyalkylene oxide resin having the solvent concentration as described above can be obtained after the volatilizing-off. A pressure of lower than 13 Pa leads to a risk that the solvent is flashed and foaming is caused. A pressure of higher than 100, 000 Pa would requires the temperature to be increased to such an extent that the polyether is decomposed. As the term used herein, the "pressure" refers to an internal pressure of the tank provided in the volatilizing-off apparatus. <Introducing Step (step (d)) > The polyalkylene oxide resin has a hygroscopic property.

In other words, the polyalkylene oxide resin is capable of absorbing moisture . The absorbed moisture can cause the polyalkylene oxide resin to deteriorate in its quality. When the polyalkylene oxide resin is put in a bulk state, the polyalkylene oxide resin has a small surface area, so that the

area of the polyalkylene oxide resin exposed to the atmosphere is minimized. With this, the amount of water to be absorbed by the polyalkylene oxide resin is suppressed. However, it is more preferable that the water content be further reduced.

As described above, the polyalkylene oxide resin has a characteristic of being very easily affected by heat because of its chemical structure. For this reason, when the polyalkylene oxide resin is introduced into a container such as a drum, and then is heated and melted for the purpose of obtaining the polyalkylene oxide resin in a bulk state, the polyalkylene oxide resin may undergo quality deterioration such as decomposition, crosslinking, or the like . It is preferable that the melted polyalkylene oxide resin be inhibited from being deteriorated in quality.

When the polyalkylene oxide resin in a melted state is introduced into a container such as a drum, and then is cooled with the container sealed, the internal pressure of the container is reduced to such an extent that the container is undesirably deformed.

As will be described below, the introducing step according to the present invention makes it possible to (i) suppress the water content of the polyalkylene oxide resin and (ii) inhibit the polyalkylene oxide resin from undergoing quality deterioration such as decomposition, crosslinking, or

the like.

(a) Adding Step (step (e))

After the volatilizing-off step, the polyalkylene oxide resin is added into an open head drum (also referred to as "open drum") . The adding step is a step of adding the polyalkylene oxide resin into the open head drum. The introducing step , according to the present invention, of introducing the polyalkylene oxide resin includes the adding step . It is preferable that a highly airtight open head drum be used for the introducing step. The use of the highly airtight open head drum makes it easier to keep the internal pressure of the open head drum higher than the standard atmospheric pressure. For the purpose of increasing the air tightness, a gasket is preferably provided between (i) an opening of a body of the open head drum and (ii) a lid of the open head drum. Further, in cases where the lid is provided with openings such as an inlet and an outlet, each of the openings is preferably closed by a screw-type plug with packing. The open head drum is preferably provided with a well-known band (ring) . The band is a circular member provided so as to coil around (a) an outer circumference of the lid and (ii) an edge portion surrounding the opening of the body. By coiling the band around, a greater air tightness is attained between the lid and the body. Examples of the well-known band include a

bolting-type band, an inner-level-type band, an outer-lever-type band, and the like.

FIG. 1 is a perspective view schematically illustrating a structure of an open head drum 2 for use in the introducing method according to the present invention for introducing a polyalkylene oxide resin. The open head drum 2 includes a main body 4, a bottom board (bottom plate) 6, and a lid 8. The main body 4 has a cylindrical shape. The main body 4 has a lower opening that is closed with the bottom board 6. The main body 4 and the bottom board 6 are seamed with a well-known seaming structure and sealed with a sealing agent applied on an inner side of the seaming structure. In FIG. 1 , the main body 4 has an upper opening that is closed with the lid 8. Between an edge portion of the opening of the main body 4 and the lid 8, a gasket (not illustrated) is provided. Moreover, the main body 4 and the lid 8 are seamed with a band 10, which is a band 10 of a bolting type, which is tighten up by using a bolt. In the introducing method, an open head drum 2 having, for example, a capacity in a range of 20 liter to 200 liter is used suitably. Hereinafter, "liter" is abbreviated as "L" for easy explanation.

The lid 8 has an inlet 12 and an outlet 14. Even though it is not illustrated here, the inlet 12 and outlet 14 have internal threads on their internal circumferences. The inlet 12 is configured such that an inlet valve will be connected

thereto in a cooling step (step (f)) described later. The outlet 14 is configured such that a outlet valve will be connected thereto in the cooling step described later. FIG. 1 illustrates that the inlet 12 and outlet 14 are closed with a plug 16, which has a bolt-like shape and provided with packing.

Even though it is not illustrated here, the open head drum 2 is coated internally with a coating film. This coating film is thermally fixed to the open head drum 2. The coating film prevents the open head drum 2 from being deteriorated. The coating film may be, for example, epoxyphenol-based, epoxy-based, and phenol-based. In consideration of heat tolerance, durability, and reactivity of the coating film with the polyalkylene oxide resin, it is preferable that the coating film be epoxyphenol-based. FIG. 2 is a partially cutway front view illustrating that a adding apparatus 18 is dealing with the open head drum 2 illustrated in FIG. 1 . The adding apparatus 18 is for use in An adding step (step e) included in the introducing method according to the present invention for introducing the polyalkylene oxide resin. The lateral directions in FIG. 2 correspond to the right and left of the adding apparatus 18. The left side of the drawing is the right side of the adding apparatus 18. The vertical directions with respect to the surface of the drawing correspond to the front side and back side of the adding apparatus 18. The front side of the drawing

is the front side of the adding apparatus 18. FIG. 3 is a partially cutway right-side view of the adding apparatus 18 of FIG. 2. In FIG. 3, the lateral directions corresponds to the front side and back side of the adding apparatus 18. The right side of the drawing is the front side of the adding apparatus 18. The vertical directions with respect to the surface of the drawing correspond to the right and left of the adding apparatus 18. The front side of the drawing is the left side of the adding apparatus 18. In FIGs. 2 and 3 , the adding apparatus 18 and the open head drum 2 are illustrated. The adding apparatus 18 includes a supplying section 20 , a airtight section 22, a transporting section 24, and an operation section 26. In the introducing method according to the present embodiment, the adding step uses the adding apparatus 18 so as to introduce, into the open head drum 2, the polyalkylene oxide resin that have been thermally melted. In FIGs. 2 and 3 , the symbol "P" indicates polyalkylene oxide resin.

The supplying section 20 introduces the polyalkylene oxide resin into the open head drum 2. The supplying section 20 includes a nozzle 28, and an elevating apparatus 30. The nozzle 28 includes an introducing pipe 32 and a connecting section 34 that is located above the introducing pipe 32. The elevating apparatus 30 includes a hydraulic apparatus 36 and a supporting bar 38. The elevating apparatus 30 is configured

such that the supporting bar 38 moves up and down by use of the hydraulic apparatus 36. On an upper surface of the connecting section 34 , the supporting bar 38 is attached. Thereby, the supplying section 20 is configured such that the nozzle 28 is capable to move up and down by the effect of the elevating apparatus 30.

By the effect of the airtight section 22 , the space in which the polyalkylene oxide resin contained in the open head drum 2 is separated from the surrounding thereof. The airtight section 22 includes a first airtight room 40 , a second airtight room 42 , an introducing line 44, a discharging line 46, and a transferring device 48. The first airtight room 40 covers the space in an upper portion of the open head drum 2. The second airtight room 42 is located on the left of the first airtight room 40. There is no partition between the first airtight room 40 and the second airtight room 42. The space separated by the first airtight room 40 and the space separated by the second airtight room are in communication with each other. The first airtight room 40 includes an inserting slot 50 into which a nozzle 28 of the supplying section 20 is inserted, and a cover 52 provided at a lower side of the first airtight room 40. The cover 52 is located outside of the open head drum 2. Even though it is not illustrated here, the cover 52 is foldable in an accordion-like manner upward. By this, a lower

end of the cover 52 is movable up and down. In the introducing method according to the present embodiment, a ring member 54 is provided between the cover 52 and the open head drum 2. The ring member 54 is attached on an outer surface of the open head drum 2. An outer surface of the ring member 54 is so configured as to be in contact with an inter surface of the cover 52. The introducing apparatus 18 is so configured that the airtight section 22 includes the ring member 54. This gives higher airtightness to the space which the polyalkylene oxide resin contained in the open head drum 2 is in contact with.

The second airtight room 42 receives the lid 8 of the open head drum 2 during the introduction of the polyalkylene oxide resin into the open head drum 2. The second airtight room 42 has an opening section 56 on an upper surface thereof. Via the opening section 56, the lid 8 is introduced into the second airtight room 42. After the lid 8 is contained in the second airtight room 42 , the opening section 56 is closed with a lid 58. The transferring' apparatus 48 is located on the left side of the second airtight room 42. The transferring apparatus 48 includes a hydraulic apparatus 60 and a transfer bar 62. The transfer bar 62 is movable right and left by the effect of the hydraulic apparatus 60. On a tip of the transfer bar 62 , a grapping jig 64 is provided. The grapping jig 64 is so

configured to be capable of grapping the lid 8. The grapping jig 64 has a chuck system that is pneumatically operated. As illustrated in FIG.3, the inlet 12 of the lid 8 is attached with an inlet valve 68 via a connecting member 66. The inlet valve 68 is used for the cooling step described later. The outlet 14 of the lid 8 is attached with an outlet valve 70 via a connecting member 66. The outlet valve 70 is used for the cooling step described later. When the polyalkylene oxide resin is introduced into the open head drum 2, the grapping jig 64 grapes the connecting members 66 so as to hold the lid 8.

The introducing line 44 is a pipe. The introducing line 44 is attached to the upper surface of the airtight section 22 in a well-known method. Via the introducing line 44, a gas is flown into the airtight section 22. The introducing line 44 is provided with an inlet valve 72. By opening and closing the inlet valve 72, an amount of the gas to be introduced and the like are adjusted. In the present invention, the gas to be introduced into the airtight section 22 via the introducing line 44 is referred to as an introducing gas.

The discharging line 46 is a pipe. The discharging line 46 is attached to the upper surface of the airtight section 22 in a well-known method, together with the introducing line 44. The introducing gas flown into the airtight section 22 is discharged out of the airtight section 22 via the discharging

line 46 while circulating inside the airtight section 22. The discharging line 46 is provided with a outlet valve 74. By- opening and closing the outlet valve 74 , an amount of the introducing gas to be discharged and the like are adjusted. The transferring section 24 includes a fix seat 76 for carrying the open head drum 2 and an elevating seat 78 for moving the open head drum 2 up and down. The fix seat 76 and the elevating seat 78 are provided with a plurality of bars 80 serving as transferring means. The bars 80, extended in a forward and backward direction, are aligned in a rightward and leftward direction with their upper faces being at the same level substantially in a height direction. The bars 80 are configured to rotate in the rightward and leftward direction. The open head drum 2 is placed on the bars 80. The bars 80 are rotated when a force is applied to the open head drum 2 in a rightward and leftward direction. The open heard drum 2 can be easily transported by the rotation. Below the elevating seat 78 , a hydraulic apparatus 82 is provided, which moves the elevating seat 78 up and down. Even though it is not illustrated here, the elevating seat 78 is so configured that it can be used to weigh the open head drum 2.

The operating section 26 includes control means for moving the introducing apparatus 18. The control means controls the operations of the transferring section 24, supplying section 20 and airtight section 22.

In the introducing step, an empty open head drum 2 is placed on the elevating seat 78 via the fix seat 76. Next, the ring member 54 is attached to the upper portion of the open head drum 2. After that, the elevating seat 78 is moved upward by the hydraulic apparatus 82 , so that the upper portion of the open head drum 2 is covered with the cover 52. If a lower edge of the cover 52 is still above a lower surface of the ring member 54, the elevating seat 78 is adjusted in its height position by the hydraulic apparatus 82 so that the lower edge comes below the lower surface. Next, the lid 8 of the open head drum 2 is introduced into the second airtight room 42 via the opening section 56 of the second airtight room 42. At this stage, the inlet valve 68 and the output valve 70 of the lid 8 are closed. Then, the opening section 56 is closed with the lid 58, thereby forming the space surrounded by the airtight section 22 and the open head drum 2. This space is separated from its surroundings. In this specification, this space is referred to as a first space section 84.

The nozzle 28 of the supplying section 20 is introduced into the first space section 84 via the inserting slot 50 of the first airtight room 40. The nozzle 28 is so introduced that an end of an introducing pipe 32 of the nozzle 28 is positioned in the vicinity of the bottom board 6 of the open head drum 2. Next, the inlet valve 72 is opened to flow the introducing gas into the first space section 84, so as to fill the first space

section 84 with the introducing gas. During the introduction of the introducing gas, the outlet valve 74 is also opened, so that gas present in the first space section 84 is replaced with the introducing gas. In this way, the first space section 84 is filled with the introducing gas.

The melted polyalkylene oxide resin having been treated with the volatilizing-off step described above is introduced into the open head drum 2 via the nozzle 28 of the supplying section 20. Because the first space section 84 is filled with the introducing gas, the introduction of the polyalkylene oxide resin is carried out in an atmosphere of the introducing gas. FIG. 2 illustrates the situation when the introduction of the polyalkylene oxide resin is carried out. As an amount of the polyalkylene oxide resin in the open head drum 2 is increased, the surface 86 of the polyalkylene oxide resin raises. In the introducing method, the position of the lower end of the nozzle 28 is moved up by the effect of the hydraulic apparatus 36 of the supplying section 20 as the surface 86 raises. When the polyalkylene oxide resin in the open head drum 2 reaches a predetermined weight, the introduction of the polyalkylene oxide resin from the supplying section 20 is stopped. For example, when the open head drum 2 of 200L capacity is used, the introduction of the polyalkylene oxide resin is stopped when the polyalkylene oxide resin in the open head drum 2 is weighed in a range of 180kg to 190kg. In the

introducing step, the introduction of the polyalkylene oxide resin into the open head drum 2 is carried out while the introducing gas is circulated inside the first space section 84 by keeping the inlet valve 72 and outlet valve 74 open. As described above, the ring member 54 is in contact with the inner surface of the cover 52. This gives high airtightness in the space which the polyalkylene oxide resin introduced in the open head drum 2 is in contact with. Therefore, the polyalkylene oxide resin may be introduced into the open head drum 2 in an atmosphere in which the circulation of the introducing gas is stopped by closing the inlet valve 72 and the outlet valve 74 after filling the first space section 84 with the introducing gas.

After the introduction of the polyalkylene oxide resin into the open head drum 2 is completed, the nozzle 28 is moved up by the effect of the hydraulic apparatus 36. Next, the lid 8 is transferred from the second airtight room 42 where the lid 8 has been contained, to a position right above the opening section 88 of the open head drum 2. When the lid 8 reaches the position right above the opening section 88, the grapping jig 64 releases the lid 8 so as to close the opening section 88 with the lid 8. Next the inlet valve 72 is closed to stop the inflow of the introducing gas. FIG. 3 illustrates this stage. Next, by the transferring section 24, the open head drum 2 containing the polyalkylene oxide resin 2 is replaced

with another open head drum 2 in which the polyalkylene oxide resin has not been introduced yet. By this, the adding step is completed.

In the adding step according to the present embodiment, the polyalkylene oxide resin has a temperature of not less than (mp + 10 ( ⁰ C) but not more than 300 ⁰ C when the polyalkylene oxide resin is introduced, where mp is the melting point of the polyalkylene oxide resin. This arrangement in which the polyalkylene oxide resin has a temperature of not less than (mp + 10 ( ⁰ C) shortens time required for introducing the polyalkylene oxide resin into the open head drum 2. The shortening of the adding time causes a reduction in production cost. Because of this, the temperature is more preferably not less than (mp + 30) ("C) , and is particularly preferably not less than (mp + 50) ("C) . The temperature not more than 300°C inhibits the polyalkylene oxide resin from being decomposed. Because of this, the temperature is more preferably not more than (mp + 150) ( ^° C) , and is particularly preferably not more than (mp + 130) ("C) . In the adding step according to the present embodiment, the introducing gas has a dew point of -30°C or less. The dew point at -30°C or less reduces water absorption in the polyalkylene oxide resin that has been added into the open head drum 2. Because of this, the dew point is more preferably -35°C or less, and is particularly preferably -40°C

or less .

In the adding step according to the present embodiment, the introducing gas has an oxygen concentration of less than 2 1 % by volume. By setting the oxygen concentration at less than 21 % by volume, the polyalkylene oxide resin that has been added into the open head drum 2 by the introducing method can be inhibited from undergoing quality deterioration such as decomposition, crosslinking, or the like. In the introducing method according to the present embodiment, the quality of the polyalkylene oxide resin can be stable. Because of this, the oxygen concentration is preferably not more than 10% by volume, and is particularly preferably not more than 1 % by volume .

In the adding step, the polyalkylene. oxide resin is added into the open head drum 2 in an atmosphere of the introducing gas that is inert. The polyalkylene oxide resin that has been added into the open head drum 2 by the introducing method can be inhibited from undergoing quality deterioration such as decomposition, crosslinking, or the like. According to the introducing method, the quality of the polyalkylene oxide resin can be stable. Examples of the introducing gas that is inert include nitrogen, helium, and argon. In terms of versatility, the introducing gas is preferably nitrogen. In the adding step according to the present embodiment,

when the introducing gas is introduced into the first space section 84, the oxygen concentration and dew point in the space section 84 are measured. When each of the oxygen concentration and dew point in the space section 84 reaches such a value that the quality of the polyalkylene oxide resin is not affected, the polyalkylene oxide resin starts to be added. The flow rate of the introduction of the introducing gas into the space section 84 is appropriately determined in consideration of the capacity of the open head drum and the mass of the polyalkylene oxide resin to be added into the open head drum. For example, in cases where a polyalkylene oxide resin whose mass is in a range of 180 kg to 190 kg is added into an open head drum 2 whose capacity is 200L, the flow rate is adjusted so as to fall within a range of 3 L/ min to 30 L/ min. Note that the oxygen concentration of the space section is measured by using an oxygen content meter (product name : "model G0A-6H" manufactured by Gastec Corporation) . The dew point of the space section is measured by using a dew point meter (product name : "DIGIPONT-H" manufactured by Nagano Electric Industrial Co. , Ltd.) . For the purpose of retaining the quality of the polyalkylene oxide resin, the oxygen concentration of the space section 84 into which the polyalkylene oxide resin starts to be added is preferably less than 2 1 % by volume, more preferably not more than 10% by volume, particularly preferably not more than

1 % by volume. The dew point of the space section 84 is preferably -30 ⁰ C or less, more preferably not more than -35 ⁰ C, particularly preferably not more than -40°C. Note that the time until the polyalkylene oxide resin starts to be added is referred to as "conditioning time" .

In the adding step according to the present embodiment, the period of time between the start and end of the adding of the polyalkylene oxide resin into the open head drum 2 is referred to as " adding time" . The polyalkylene oxide resin that is in a melted state after the volatilizing-off step is stored in an intermediate tank and the like, and then -is transferred to the supplying section by using a gear pump. The adding time is appropriately determined in consideration of (i) the liquid-transferring capacity of the gear pump, (ii) the temperature of the polyalkylene oxide resin, (iii) the quality of the polyalkylene oxide resin that has been finished with the adding step, and (iv) the like. Note that when the adding time is lengthened, the polyalkylene oxide resin is maintained in a melted state for a longer time. The time during which the polyalkylene oxide resin is maintained in a melted state affects the quality of the polyalkylene oxide resin. The adding time also affects production cost. In view of the quality of the polyalkylene oxide resin and productivity, the adding time is preferably short. In the adding step, the first space section 84 is filled with the introducing gas whose oxygen concentration

and dew point are controlled. For this reason, in the introducing method according to the present invention, the adding time has little influence on the quality of the polyalkylene oxide resin and the like. In the adding step according to the present embodiment, the first space section 84 is filled with the introducing gas . The internal pressure of the first space section 84 is adjusted by using the inlet valve 72 and the outlet valve 74 for respectively introducing and discharging the introducing gas. The internal pressure is not less than the standard atmospheric pressure but not more than the tolerable pressure of the adding apparatus 18. The standard atmospheric pressure refers to 1 atm, i.e. , 101.33 kPa when measured based on the absolute pressure. When the internal pressure is caused to be not less than the standard atmospheric pressure, air is effectively inhibited from entering into the first space section 84 from the surrounding environment.

In the adding step according to the present embodiment, the polyalkylene oxide resin to be added preferably has water content of not more than 1 ,000 ppm, more preferably not more than 200 ppm, particularly preferably not more than 50 ppm. By reducing the water content of the polyalkylene oxide resin to be added, it becomes easy to reduce the water content in the transferring or storing step described later.

The polyalkylene oxide resin to be added preferably has a solvent concentration of not more than 30% by mass, more preferably not more than 5% by mass, particularly preferably not more than 1 % by mass. By reducing the solvent concentration of the polyalkylene oxide resin to be added, the transferring or storing step described later becomes less dangerous and less costly.

Note that the water content of the polyalkylene oxide resin can be measured in the same manner as described above.

(b) Cooling Step

After the adding step, the polyalkylene oxide resin is cooled. The cooling step is a step of cooling the polyalkylene oxide resin. The method according to the present invention for introducing the polyalkylene oxide resin may include the cooling step.

Fig. 4 is a partially cutway front view illustrating that the open head drum of Fig. 1 is being subj ected to the cooling step according to the present invention. In Fig. 4, the lid 8 and main body 4 of the open head drum 2 are seamed with the band 10. In other words, the opening of the open head drum 2 is closed by the lid 8 including the inlet 12 and the outlet 14. The open head drum 2 contains the polyalkylene oxide resin (indicated by P in Fig. 4) that has been added in the aforementioned adding step. The polyalkylene oxide resin

is in a melted state. As described above, in the adding step, the inlet valve 68 and the outlet valve 70 are attached to the inlet 12 and the outlet 14, respectively. As shown in Fig. 4, the lid 8 is provided with a pressure gauge 90 for measuring the internal pressure of the open head drum 2. In the introducing method according to the present embodiment, the lid 8 that closed the opening section 88 in the adding step is configured to be able to be used continuously in the cooling step . By a well-known method, the inlet valve 68 is connected to an introducing line 92 for introducing gas. The introducing line 92 is a pipe. By a well-known method, the outlet valve 70 is connected to a discharging line 94 for discharging gas. The discharging line 94 is a pipe. The lid 8 is provided with an auxiliary opening 96 which is provided near the outlet 14. The auxiliary opening 96 is for use in measuring temperature by allowing a thermometer 98 to be inserted into the open head drum 2 therethrough. The thermometer 98 has a tip having contact with the surface 86 of the polyalkylene oxide resin. In the open head drum 2, a space is formed between the lid 8 and the surface 86 of the polyalkylene oxide resin. In this Specification, the space is referred to as "second space section 100" . The surface 86 of the polyalkylene oxide resin has contact with the second space section 100. In the cooling step, the polyalkylene oxide resin is

cooled while a gas is being introduced into the second space section 100. In this specification, the gas used in the cooling step is referred to as " cooling gas" . The cooling gas is supplied through the introducing line 92. The cooling gas is introduced into the second space section 100 through the inlet 12 by opening the inlet valve 68. The cooling gas is discharged from the second space section 100 through the outlet 14 by opening the outlet valve 70. In the cooling step according to the present embodiment, the surface 86 of the polyalkylene oxide resin is cooled while the cooling gas is being added into the second space section 100 through the inlet 12 and discharged from the second space section 2 through the outlet 14. When the polyalkylene oxide resin is cooled and becomes solidified, the inlet valve 68 is closed, so that the supply of the cooling gas is stopped. In this way, the cooling step is completed.

In the introducing method according to the present embodiment, the cooling step is carried out subsequent to the adding step. The polyalkylene oxide resin being cooled has a temperature not less than its melting point. In the cooling step according to the present embodiment, the cooling gas continues to be added into the second space section 100 through the inlet 12. The cooling gas continues to be discharged from the outlet 14 while circulating in the second space section 100. For this reason, even when the

polyalkylene oxide resin is cooled and contracts in volume, the internal pressure of the open head drum 2 can be adjusted to be kept substantially constant. In the cooling step, the open head drum 2 is not deformed. In the cooling step according to the present embodiment, the internal pressure of the open head drum 2 is adjusted by using the inlet valve 68 and the outlet valve 70. The internal pressure of the open head drum 2 is not less than the standard atmospheric pressure but not more than the tolerable pressure of the open head drum 2. The standard atmospheric pressure refers to 1 atm, i. e. , 101 .33 kPa when measured based on the absolute pressure. When the internal pressure in the open head drum 2 is caused to be not less than the standard atmospheric pressure, air is effectively inhibited from entering into the second space section 100 from the surrounding environment. The cooling gas is introduced into the second space section 100 at a flow rate appropriately adjusted so as to fall within a range of 3 L/ min to 30 L/ min . In the cooling step according to the present embodiment, the polyalkylene oxide resin is cooled so that the surface 86 of the polyalkylene oxide resin has a temperature of not more than mp ( ¹ C) , where mp ("C) is a melting point of the polyalkylene oxide resin. The surface 86 is an upper surface of the polyalkylene oxide resin contained in the open head

drum 2 , and is a surface having contact with the second space section 100. By cooling the polyalkylene oxide resin so that the surface 86 of the polyalkylene oxide resin has a temperature of not more than mp (°C) , the solidification of the surface 86 of the polyalkylene oxide resin is accelerated. When the temperature of the surface 86 of the polyalkylene oxide resin is reduced, molecules constituting the surface 86 of the polyalkylene oxide resin become less active, thereby reducing free volume that encourages passage of gas. This inhibits air and moisture from permeating from the surface 86 of the polyalkylene oxide resin into the bulk of the polyalkylene oxide resin. The quality of the polyalkylene oxide resin is stably retained. When the temperature of the surface 86 is sufficiently reduced, the temperature of the entire bulk of the polyalkylene oxide resin is sufficiently reduced. In the sealing step (step (g)) carried out after the cooling step, the temperature of a gas (after-mentioned sealing gas) that has been sealed into the second space section 100 is not increased due to heat remaining in the polyalkylene oxide resin. Also in the sealing step, the internal pressure of the open head drum 2 is not changed, so that the open head drum 2 is not deformed. The internal pressure does not become lower than the atmospheric pressure, so that no air enters from outside into the open head drum 2. Further, since no air enters the open head drum 2 , no moisture enters the

open head drum 2 , either. The water content of the polyalkylene oxide resin is not increased. With this, the quality of the polyalkylene oxide resin is stably retained.

In the cooling step, for the purpose of retaining the quality of the polyalkylene oxide resin, the polyalkylene oxide resin having been cooled preferably has a temperature of not more than 100 ⁰ C, more preferably not more than 80°C, particularly preferably not more than 60°C.

In the cooling step, the cooling gas preferably has a dew point of -30°C or less . By setting the dew point of the cooling gas at -30 ⁰ C or less, the amount of moisture to be absorbed by the polyalkylene oxide resin being cooled in the introducing method according to the present embodiment can be held down. Because of this, the dew point of the cooling gas is more preferably not more than -35°C, and is particularly preferably not more than -40°C.

In the cooling step, the cooling gas has an oxygen concentration of less than 21% by volume. By setting the oxygen concentration at less than 2 1 % by volume, the polyalkylene oxide resin being cooled by the introducing method can be inhibited from undergoing quality deterioration such as decomposition, crosslinking, or the like. In the introducing method, the quality of the polyalkylene oxide resin can be stably retained. Because of this, the oxygen concentration is preferably not more than 10% by

volume, and is particularly preferably not more than 1 % by volume.

In the cooling step, the polyalkylene oxide resin is cooled while the introducing gas that is inert is being distributed. The polyalkylene oxide resin being cooled in the introducing method according to the present embodiment can be inhibited from undergoing quality deterioration such as decomposition, crosslinking, or the like. In the introducing method, the quality of the polyalkylene oxide resin can be stably retained. Examples of the introducing gas that is inert include nitrogen, helium, and argon. In terms of versatility, the introducing gas is preferably nitrogen.

In the cooling step, the period of time between the end of the adding step and the start of the cooling step is referred to as "cooling preparation period" . During the cooling preparation period, the following operations are carried out. First, the lid 8 is seamed with the band 10. Next, it is confirmed whether the inlet valve 68 and the outlet valve 70 each of which is installed in the lid 8 are opened or closed. After it has been confirmed that the inlet valve 68 and the outlet valve 70 are closed, the open head drum 2 is removed from the airtight section 22. Therefore, the cooling preparation period should be long enough for completing the operations. During the cooling preparation period, the polyalkylene oxide resin is maintained in a melted state . For

the purpose of retaining the quality of the polyalkylene oxide resin, the cooling preparation period is preferably short. For the purpose of shortening the cooling preparation time, the operations are efficiently carried out. In the cooling step, the period of time between the start and end of the cooling of the polyalkylene oxide resin is referred to as " cooling time" . When the cooling time is lengthened, the polyalkylene oxide resin is maintained in a melted state for a longer time. As described above, the time during which the polyalkylene oxide resin is maintained in a melted state affects the quality of the polyalkylene oxide resin. The cooling time also affects production cost. In view of the quality of the polyalkylene oxide resin and productivity, the cooling time is preferably short. The cooling time is preferably not more than 150 hours, more preferably not more than 100 hour, particularly preferably not more than 75 hours.

In the cooling step, the open head drum is preferably cooled for the purpose of accelerating the cooling of the polyalkylene oxide resin. Specifically, in the cooling step, the open head drum is preferably left in a room (e.g. , a warehouse) provided with air-conditioning equipment for adjusting room temperature and the like. This allows the open head drum to be cooled in an environment having a low ambient temperature. For the purpose of preventing heat from being accumulated, the open head drum is preferably exposed

to wind generated by a fan. This allows the open head drum to be efficiently cooled. For the purpose of cooling a lower side of the open head drum first, the open head drum may be placed on a pallet or the like that provides an open space below the open head drum. The open head drum left in the room is preferably located at a distance from another open head drum adj acent thereto. For the purpose of increasing cooling efficiency, the open head drum may be provided with a heat-radiating plate installed on a surface thereof. In the cooling step, the polyalkylene oxide resin to be cooled has water content of not more than 1 , 000 ppm, more preferably not more than 200 ppm, particularly preferably not more than 50 ppm. By holding down the water content of the polyalkylene oxide resin to be cooled, it becomes easy to hold down the water content in the transferring or storing step described later. The polyalkylene oxide resin to be cooled preferably has a solvent concentration of not more than 30% by mass, more preferably not more than 5% by mass, still more preferably not more than 1 % by mass. By holding down the solvent concentration of the polyalkylene oxide resin being cooled, the transferring or storing step described later becomes less dangerous and less costly.

In the introducing method, the surface 86 of the polyalkylene oxide resin has water content of not more than 1 ,000 ppm between the adding step and the cooling step. By

holding down the water content of the polyalkylene oxide resin, it becomes easy to hold down the water content in the transferring or storing step described later. Because of this, the water content of the surface 86 of the polyalkylene oxide resin is more preferably not more than 200 ppm, and is particularly preferably not more than 50 ppm. (c) Sealing Step (Step (g))

After the cooling step, the polyalkylene oxide resin is sealed into the open head drum 2. The sealing step is a step of sealing the polyalkylene oxide resin into the open head drum 2. In the sealing step, a gas is introduced into the second space section 100 of the open head drum 2 containing the polyalkylene oxide resin. The gas used in the sealing step is referred to as " sealing gas" . In the sealing step, the open head drum 2 that has been filled with the polyalkylene oxide resin is carried into a dry room under such conditions that the inlet valve 68 and the outlet valve 70 are closed. In the dry room, the inlet valve 68 and the outlet valve 70 are adjusted so that the sealing gas is introduced into the second space section 100 of the open head drum 2. When the introduction of the sealing gas is finished, the inlet valve 68 and the outlet valve 70 are closed and the introducing line 92 and the discharging line 94 are detached. The lid 8 and main body 4 of the open head drum 2 are seamed with the band 10, so that the lid 8 is securely closed. In this way, the open head

drum 2 is sealed under increased pressure. After the sealing step, the open head drum that has been filled with the polyalkylene oxide resin is transported or stored under increased pressure. In the sealing step, the sealing gas is preferably sealed under a pressure of not less than the standard atmospheric pressure but not more than the tolerable pressure of the open head drum 2. The standard atmospheric pressure refers to 1 atm, i. e. , 101 .33 kPa when measured based on the absolute pressure . When the internal pressure is caused to be not less than the standard atmospheric pressure, air is effectively- inhibited from entering into the second space section 100 during the transportation or storage. Because of this, in the sealing step, the sealing gas is preferably sealed in so that the internal pressure inside the open head drum 2 is not less than the standard atmospheric pressure but not more than the tolerable pressure of the open head drum 2. For the purpose of sealing gas at an internal pressure exceeding the standard atmospheric pressure, a well-known valve, a well-known check valve, and the like can be used.

In the sealing step, the sealing gas has a dew point of -30 ⁰ C or less. By setting the dew point of the sealing gas at -30°C or less, the amount of moisture to be absorbed by the polyalkylene oxide resin that has been added into the open head drum 2 in the introducing method can be held down. For

this perspective, the dew point of the sealing gas is more preferably not more than -35°C, and is particularly preferably not more than -40°C.

In the sealing step, the sealing gas is preferably an inert gas. The polyalkylene oxide resin that has been added into the open head drum 2 in the introducing method can be inhibited from undergoing quality deterioration such as decomposition, crosslinking, or the like. In the introducing method, the quality of the polyalkylene oxide resin can be stable. Examples of the sealing gas include nitrogen, helium, and argon. In terms of versatility, the sealing gas is preferably nitrogen.

In the sealing step, the lid 8 may be replaced with a lid which does not have an inlet 12 , an outlet 14 , and the like. In this case, the lid 8 is removed in the dry room, and is replaced with the lid which does not have an inlet 12 , an outlet 14, and the like. Therefore, dry air contained in the dry room is sealed into the second space section 100 of the open head drum 2. The internal pressure of the open head drum becomes equal to the standard atmospheric pressure. The dry air has an oxygen concentration of 21% by volume. Since the polyalkylene oxide resin contained in the open head drum has been cooled to not more than the melting point, the polyalkylene oxide resin is not deteriorated in quality by the oxygen contained in the dry air. Since the lid 8 can be

replaced with the lid which does not have an inlet 12 , an outlet 14, and the like, the lid 8 can be reused in the aforementioned adding and cooling steps. After the sealing step, the open head drum that has been filled with the polyalkylene oxide can be transported or stored under such conditions that the open head drum is sealed with the lid which does not have an inlet 12, an outlet 14, and the like .

The open head drum 2 used in the introducing method according to the present embodiment is highly airtight. Therefore, the open head drum 2 can be transported or stored while the dew point of the gas that has been sealed into the second space section 100 is being maintained at -30 ⁰ C or less. More preferably, the open head drum 2 is transported or stored while the dew point of the gas that has been sealed into the second space section 100 is being maintained at not more than -60°C. Immediately after the aforementioned sealing step, the gas that exits in the space section 100 of the open head drum 2 has the same dew point as does the introducing gas. As time passes, moisture is transported between (i) the polyalkylene oxide resin contained in the open head drum 2 and (ii) the gas that exists in the space section 100, so that the transportation of the moisture finally reaches equilibrium. In this equilibrium state, the dew point of the gas that exists in the space section 100 is -3O ⁰ C or less. In a step following the polymerizing step, for the purpose

of preventing quality deterioration such as (i) decomposition caused by oxidization and (ii) crosslinking, a small amount of an antioxidant may be added to the polyalkylene oxide resin after the polymerizing step. The antioxidant is oxidized before the polyalkylene oxide resin is oxidized, so that the polyalkylene oxide resin is prevented from being oxidized. As described above, in the introducing method, the adding step is carried out in an atmosphere of the introducing gas that is inert. The cooling step is also carried out in an atmosphere of the cooling gas that is inert. For this reason, in the introducing method, oxidation of the antioxidant is also reduced. With this, the quality of the polyalkylene oxide resin becomes stable. Moreover, the amount of an antioxidant to be added can be reduced. This makes it possible to reduce the cost of producing the polyalkylene oxide resin.

Examples of the antioxidant to be added to the polyalkylene oxide resin include a phenolic antioxidant, an amine antioxidant, and a phosphoric antioxidant. Examples of the phenolic antioxidant include 2,6-ditertbutyl-p-cresol, 2 , 6 - d i p h e n y l - 4 - o c t a d e c y l o xy p h e n o l , stearyl(3, 5 -ditertbutyl-4-hydroxyphenyl) propionate, distearyl(3,5-ditertbutyl-4-hydroxybenzyl)phosphonate, tridecyl-3,5-ditertbutyl-4-hydroxybenzylthioacetate, thiodiethylenebis[ (3, 5 -ditertbutyl-4-hydroxyphenyl) propionate ] , 4 , 4 ' - th i o b i s ( 6 - te r tbu tyl - m - c r e s o l ) ,

2-octylthio-4,6-di(3,5-ditertbutyl-4-hydroxyphenoxy)-s- triazine, 2,2'-methylenebis(4-methyl-6-tertbutylphenol), bis[3,3-bis(4-hydroxy-3-tertbutylphenyl)butylic acid] glycol ester, 4,4'-butylidenbis(2,6-ditertbutylρhenol), 4,4'-butylidenbis(6-ditertbutyl-3-methylρhenol), 2 , 2' -ethylidenbis (4 , 6-ditertbutylρhenol) , 1 , l,3-tris(2-methyl~4-hydroxy-5-tertbutylphenyl)butane, bis[2-tertbutyl-4-methyl-6-(2- hydroxy -3-tertbuty 1-5- methylbenzyl)phenyl]tereρhthalate, 1 ,3,5-tris(2,6dimethyl-3~ hydroxy-4-tertbutylbenzyl)isocianulate, 1 ,3,5-tris(3,5- ditertbutyl-4-hydroxybenzyl)isocianulate, l,3,5-tris[(3,5-ditert butyl-4-hydroxybenzyl)-2,4,6-trimethyl benzene, l,3,5-tris[(3,5-ditertbutyl-4-hydroxyphenyl)propionyloxyethy l] isocianulate, tetrakis[methylene-3-(3' ,5'-ditertbutyl-4'- hydroxyphenyl)propionate]methane, 2-tertbutyl-4-methyl- 6-(2-acroyloxy-3-tertbutyl-5-methylbenzyl)phenol, 3, 9 -bis [2 - (3-tertbutyl-4-hydroxy-5-methylhydrocinnamoiloxy)- 1,1- dimethylethyl]-2,4,8, 10-tetraoxaspiro[5.5]undecane and triethyleneglycolbis[β-(3-tertbutyl-4-hydroxy-5-methylpheny l) propionate]. Examples of the amine antioxidant include diphenylamines, dinaphthylamines, diphenylphenylenediamines and phenothiazines. Examples of the phosphoric antioxidant include triphenylphophite. These antioxidants may be used solely. As an alternative, a combination of two or more of them may be used.

<Transferring Step or Storing Step>

After the sealing step, transferring step or storing step of polyalkylene oxide resin is carried out. In the transferring or storing step, a solvent concentration of polyalkylene oxide resin preferably is preferably 30% or less by mass. Further, it is preferable in the transferring and storing step that water content of the polyalkylene oxide resin is l OOOppm or less.

Further, in the transferring and storing step, the water content of the polyalkylene oxide resin is more preferably 600ppm or less, further preferably 400ppm or less, and especially preferably 200ppm or less.

In the adding step included in the introducing method of the present invention, the water content of the polyalkylene oxide resin introduced in the open head drum 2 is kept low while the deterioration of the polyalkylene oxide resin is prevented. According to the cooling step included in the introducing method, the cooling of the polyalkylene oxide can be carried out without deforming the open head drum 2. The water content of the cooled polyalkylene oxide resin is kept low while preventing the deterioration of the polyalkylene oxide. The use of the open head drum 2 with a high airtightness and the sealing step for sealing the introducing gas having a low dew point keeps the water content of the polyalkylene oxide resin low in the transferring or storing step.

< Removing Steρ>

In the producing method according to the present invention, the polyalkylene oxide resin after volatilizing off the solvent therefrom is introduced into an open head drum of 200L and cooled down to room temperature sufficiently. The polyalkylene oxide resin completely solidified in the open head drum is melted by a melter and then the thus liquefied polyalkylene oxide resin is then transferred to the dissolving tank. Then, the polyalkylene oxide resin is subjected to a shaping step or preparing step. Examples of the melter to be used include bulk melter BM series (Product Name : BM200, made by Nordson K. K.) , drum melter FS series (Product Name: FS, Fast Corporation) , drum melter (made by Matsushita-Kogyo) , melter PU series (made by Suntool Ltd.) , and the like . These melters mentioned here have, in combination, a pump, an elevator, and a platen having a heater.

FIG. 5 is a partially cutway view illustrating the removal of the polyalkylene oxide resin from the open drum using the melter. The melter includes a platen 101 having a cylindrical shape. The platen 101 includes a pump 102 and a heater (not illustrated) . To a center portion of the patent 101 , a platen connecting section 103 is connected. In an edge portion of a front side of the pump 102, a liquid discharging section 104 having a reversed L-shape . To an end of the liquid discharging

section 104 , a liquid transferring tube 105 is connected.

Examples of the platen 101 include an axial platen having, on its back side, axes arranged radically, a smooth platen having, on its back side, a smooth surface, a fin platen having, on its back side, fins arranged in radius directions, and the like platen.

Examples of the pump 102 include a gerotor pump, a piston pump, a super gear pump, and the like . The gerotor pump and piston pump are preferable because they apply less shearing and shearing heat on the material to deal with and also they are suitable for discharging highly viscous material.

The open drum 108 contains a polyalkylene oxide resin

107 that is in a solid form. The platen 101 is moved by the effect of a hydraulic section of the melter (not illustrated) , so that the platen 101 abuts against the polyalkylene oxide resin 107 and thus the polyalkylene oxide resin 107 is heated by the heater provided to the platen 101 while being pressed by the platen 101. The heating melts the polyalkylene oxide resin 107 in its upper surface, thereby forming a melted layer 106. The heating temperature is not less than a melting temperature (melting point) of the polyalkylene oxide resin 107 or not more than 300 ⁰ C . A heating temperature less than the melting temperature of the polyalkylene oxide resin 107 does not allow the polyalkylene oxide resin 107 to be discharged from the liquid discharging section 104. A heating

temperature more than 300 ⁰ C breaks down or deteriorate the polyalkylene oxide resin 107. The polyalkylene oxide resin of the melted layer 106 thus formed goes into the pump 102 and transferred to the dissolving tank via the liquid discharging section 104 and then the liquid transferring tube 105.

According to the above-mentioned step according to the present invention, it is possible to remove the polyalkylene oxide resin 107 in a required amount by removing the polyalkylene oxide resin 107 from its surface. This shortens a time period in which the resin is exposed to heat. This reduces deterioration of the resin. Moreover, because the resin in a bulk state, not in a powdery state or pellet state, is transported to a site where a next step is carried out, the polyalkylene oxide resin 107 will not be thermally melted and stuck together during transportation. Further, the resin can be transported without solving the resin in a solvent. This gives better workability and safety, and further cost reduction.

Moreover, for better workability in removing the polyalkylene oxide resin 107, the open drum 108 containing the polyalkylene oxide resin 107 may be kept, before the removing, in a room or a water bath in which a temperature is risen so as to rise the temperature of the polyalkylene oxide resin 107, or the removing may be performed while the open drum 108 containing the polyalkylene oxide resin 107 is

heated from its side directly or indirectly by a heater, a jacket, or the like. The heating is not particularly limited to a certain method, and may be performed by one method or by two or more methods applied in combination. In order to reduce humidity absorption and decomposition of the polyalkylene oxide resin 107 during the removing, the open drum 108 containing the polyalkylene oxide resin 107 may be covered with a certain airtight covering article in advance, and the atmosphere surrounding the open drum 108, which is the standard atmosphere, is sufficiently replaced with a dried air and/ or dried nitrogen atmosphere, before performing the removing. <Dissolving Step> In case the polyalkylene oxide resin is to be used as a coating material, the polyalkylene oxide resin is removed in the removing step is dissolved in a solvent in a dissolving step (Step (i)) .

FIG. 6 is a view schematically illustrating a structure of an apparatus for performing the dissolving step, which follows the removing step. An intermediate tank container 210 containing the polyalkylene oxide resin removed by the bulk melter is heated by a heating member 2 12. The heating member 212 is, for example, a metal tube in which oil or the like is flown. The thermally melted polyalkylene oxide resin is transferred to the dissolving tank 2 16 via the liquid

transferring tube 214. Supplying rate of the polyalkylene oxide resin is adjusted by the gear pump 2 18. The apparatus is provided with valves 220 at various parts in order to control the transfer of the liquid or internal pressure. The removing step is not limited to the embodiment of

FIG. 5. However, the removing step described referring to FIG. 5 is preferable especially in case the polyalkylene oxide resin is removed from an open drum.

The liquid transferring tube 214 reaches the dissolving tank 2 16. The polyalkylene oxide resin is supplied into the dissolving tank 216 via the liquid transferring tube 214. The dissolving tank 2 16 contains a solvent 222. The polyalkylene oxide resin is supplied into the solvent 222.

The temperature of the polyalkylene oxide resin to be supplied into the dissolving tank 216 is set to be (mp + 10)°C or higher. This temperature of the polyalkylene oxide resin is the temperature of the polyalkylene oxide resin when the polyalkylene oxide resin is added into the solvent 222. On the other hand, a system temperature of the dissolving tank 2 16 is set at mp ( ⁰ C) or higher. The system temperature is a temperature of a solution 224 inside the dissolving tank 216 during the dissolving step . The polyalkylene oxide resin of a temperature of (mp + 10) ⁰ C or higher can have a better dissolving rate with respect to the solvent. The system temperature of mp ( ⁰ C) or higher can give a better dissolving

rate of the polyalkylene oxide resin with respect to the solvent. A temperature of the solvent 222 inside the dissolving tank 216 is set so that the temperature of the solvent 222 inside the dissolving tank 2 16 is the same temperature as the system temperature just before start of the dissolving step.

It is preferable that the temperature of the polyalkylene oxide resin to be supplied in the dissolving tank 216 be not less than (mp + 10) ⁰ C but not more than 300 ⁰ C. By setting this temperature to be 300 ⁰ C or less, the decomposition of the polyalkylene oxide resin is reduced. For better dissolving rate, it is preferable that the temperature of the polyalkylene oxide resin to be supplied in the dissolving tank 216 be (mp + 58) ⁰ C or higher. Moreover, it is preferable that the system temperature of the dissolving tank 216 be (mp) ⁰ C or higher. The system temperature of not less than (mp) ⁰ C can further improve the dissolving rate of the polyalkylene oxide resin. For better dissolving rate, it is more preferable that the system temperature be (mp + 9) ⁰ C or higher. Moreover, it is preferable that the system temperature be 300 ⁰ C or less . The system temperature of 300 ⁰ C or less reduces decomposition of the polyalkylene oxide resin.

For better dissolving rate, it is preferable that the solution 224 in the dissolving tank 2 16 be stirred. The stirring may be carried out concurrently with or after the supplying of the polyalkylene oxide resin. In the embodiment

illustrated in FIG. 6, the dissolving tank 2 16 includes a stirring impeller 226 inside thereof, which rotates by the effect of a motor 228. There is no particular limitation as to kinds of the stirring impeller 226, and examples of the stirring impeller 226 include an anchor impeller, a helical ribbon impeller, a double helical ribbon impeller, a helical screw impeller provided with a draft tube, a Superblend impeller, a Maxblend impeller, a Fullzone impeller, a Supermix imperller, a Sanmeler impeller, a twisted lattice impeller, a turbine impeller, a paddle impeller, a Pfaudler impeller, a Burmargin impeller, a propeller impeller, and the like .

The dissolving tank 216 includes a baffle 230 inside thereof in addition to the stirring impeller 226. The baffle 230 disturbs a stirred fluid (i. e. , the solution 224) , thereby increase stirring efficiency.

In the dissolving step, it is preferable that the solution in the dissolving tank be stirred with power requirement of impeller (PV) of 0. 1 (kW/ m ³ ) or greater. The power requirement of impeller (PV) of 0. 1 (kW/m ³ ) or greater gives better dissolving rate of the polyalkylene oxide resin.

The power requirement of impeller (PV) is power required for stirring a fluid per unit of amount of the fluid. More specifically, the power requirement of impeller (PV) is power required for stirring a content in a reactor per unit of amount

of the content, the power being calculated from an amount of the content contained in the reactor, a viscosity of the content, a shape of the reactor, a shape of a stirring impeller, a revolution speed of the stirring impeller, and the like . Moreover, because values of the power requirement of impeller (PV) depend on concentration of the resin when the revolution speed of the stirring device is the same, the values of the power requirement of impeller (PV) discussed here are based on resin concentration of 0% by mass. The power requirement of impeller (PV) is found from an equation usually used in chemical engineering. For example, how to find the power requirement of impeller (PV) is described in Kagaku Kogaku Binran (Reference Book of Chemical Engineering) (revised third edition: edited by Kagaku Kougaku Kai, published by Maruzen Co . Ltd.) , pages 1078 to 1082.

In the dissolving step, the dissolving tank 216 is heated by heating means, which is not particularly limited. In the embodiment described in FIG. 6, the dissolving tank 2 16 is heated by a liquid bath 232. Examples of the liquid bath 232 include a hot water bath, oil bath. The heating maintains the system temperature within the temperature ranges mentioned above.

In the embodiment illustrated in FIG. 6, the solvent 222 is refluxed in the dissolving step. The solvent 222 is refluxed

by a condenser (cooling device or condenser) 234. The liquid bath 232 is set to a temperature higher than a boiling point of the solvent. The refluxing keeps the system temperature in the vicinity of the boiling point of the solvent 222. In the dissolving step, the polyalkylene oxide resin may be introduced from any position. However, it is preferable that the polyalkylene oxide resin is introduced (supplied) by adding down an internal wall of the dissolving tank, in order to prevent the stirring impeller from being entangled with the introduced polyalkylene oxide resin and to attain better dissolving rate.

The polyalkylene oxide resin may be introduced at once or bit by bit (i.e. , continuous and/ or in an intermitted manner) . Moreover, another or other components may be dissolved or added into the polymer solution. The another or other components may be introduced before, after, or concurrently with the introduction of the polyalkylene oxide resin.

The producing method of the present embodiment gives a higher dissolving rate of polyalkylene oxide resin. Thus, the polyalkylene oxide resin in a bulk state can be dissolved efficiently.

One example of usage of the solution thus prepared by the dissolving step is given below. For example, in case the solution is used as a coating material, the solution thus

obtained is applied by an application apparatus, such as a flow coater, roll coater, knife coater, gravure roll, hot melt applicator, or the like. The flow coater is configured to apply the coating material by passing an application object through a stream of the coating material flowed down in a constant amount from a slit (die) having a constant width. The roll coater is configured to transfer the coating material from a pan onto an application object by using a roll that rotates to pick up the coating material from the pan. The knife coater is so configured that the coating material applied on an application object by a roll, immersion, or the like is adjusted to have a constant thickness by shaving the coating material to the constant thickness by using a doctor knife, air knife, or the like . The gravure role uses an engraved plate to transfer the coating material onto the application object. The hot melt applicator ejects the melted coating material to the application object. The thin film of the solution of the polyalkylene oxide resin thus applied is passed through a heating region in which temperature is equal to or higher than a boiling point of the solvent. This removes the solvent from the solution thereby solidifying the solution. In this way, a thin film of polyalkylene oxide resin, in approximately l Oμm to several hundred μm, can be obtained on a substrate. According to this step of the present invention, the polyalkylene oxide resin removed in the removing step can be

applied on the application target as a coating material with good workability.

<Shaping Step>

In case where the polyalkylene oxide resin is shaped, the polyalkylene oxide resin transferred into the dissolving tank via the liquid transferring tube 105 by the removing step is heated to a temperature that is not less than the melting point of the polyalkylene oxide resin but not more than a decomposition temperature of the polyalkylene oxide resin. This melts the polyalkylene oxide resin to be flowable . Then, the melted and flowable polyalkylene oxide resin is transferred to an extruder at a constant rate by the transferring step described later.

The polyalkylene oxide resin is homogenously mixed and kneaded with an additive(s) and/ or additional material(s) supplied from a side filter, and then continuously extruded out via a die by using or not using a gear pump. Thereby, a longitudinally-shaped produced having a predetermined cross sectional shape is obtained. This extrusion shaping allows to produce pipe-like shaped products, bar-like shaped products, profile extrusion products, film-like shaped products, sheet-like shaped products, and the like. Examples of the extruder includes non-screw extruder, a single screw extruder, twin screw extruder, and the like. The shaping step according to the present embodiment does not require the extruder to

have a zone for meting the resin. Thus, the extruder can have a smaller L/ D (length/ diameter) . The zone that is no longer necessary to be used for melting can be utilized for homogenous mixing with the another or other additives and/ or the like . This allows more efficient extrusion. Moreover, the supply of the melted resin into the extruder does not cause pulsating flow, which occurs in case where the polyalkylene oxide resin is supplied in a pellet state. Thus, this allows stable extrusion and gives good workability to the shaping of the polyalkylene oxide resin removed in the removing step .

<Liquid Transferring Step>

As described above, there is a case where the polyalkylene oxide resin mixed with a predetermined additive is fabricated into a longitudinal shaped product having a predetermined cross sectional shape. The shaping of such a polyalkylene oxide resin is carried out by using a mixing apparatus such as the single screw extruder or twin screw extruder. The supply of the resin into the mixing apparatus is carried out by a supplying system including a hopper, feeder, or the like. As described above, the polyalkylene oxide resin has a chemical structure that is very heat susceptible. Especially, a polyalkylene oxide resin having a melting point in a range of 0 ⁰ C to 60 ⁰ C becomes sticky at temperatures in the vicinity of human body temperature. If such a supplying

system was used to supply to the mixing apparatus the polyalkylene oxide resin in powder state or pellet state, the polyalkylene oxide resin sticks on an inner wall of the hopper, so that the amount of the resin to be supplied to the supplying system can not be kept constant. In this case, the unstable supply amount of the resin leads to poor quality of the product by unstabilizing the composition of the additive in the product. The polyalkylene oxide resin melted by abrasion with the screw would be stuck in between a screw and housing of the feeder, thereby causing clogging. In this case, the supply of the resin is stop, thereby ceasing the production of the product.

The liquid transferring step of the present invention can attain stable supply of the polyalkylene oxide resin to the mixing apparatus, as described below.

FIG. 7 is a view schematically illustrating liquid transferring means 316 for use in the liquid transferring step according to the present invention. The liquid transferring means 3 16 supplies the polyalkylene oxide resin to a mixing apparatus 318. The liquid transferring means 316 includes a melting tank 320, a pump 322 , a first liquid transferring line 324 that connects the melting tank 320 and pump 322, and a second liquid transferring line 326 that connects the pump 322 and the mixing apparatus 318. As illustrated in FIG. 7, the mixing apparatus 318 includes an additive supplying

means 328 for adding an additive into the polyalkylene oxide resin.

The melting tank 320 contains the melted polyalkylene oxide resin therein. The melting tank 320 includes a main body 330, a first inlet 332 , a first outlet 334, a second inlet 336, a second outlet 338, ^" and a heating member 340 that serves as a first temperature adjusting means . The main body 330 is a so-called tank. An interior of the main body 330 is sealed off from its surrounding. The polyalkylene oxide resin is introduced into the interior of the main body 330. To the first inlet 332 , a first inlet valve 342 is provided, to which a first introducing line 344 is connected. The first introducing line 344 is connected to the liquid discharging section 104 of the melter. The melted polyalkylene oxide resin flows through the first introducing line 344 and introduced into the main body 330 via the first inlet 332. The first outlet 334 is provided at a bottom of the main body 330. To the first outlet 334, the first outlet valve 346 is provided. The polyalkylene oxide resin is discharged out of the main body 330 via the first outlet 334 by opening the first outlet valve 346.

The melting tank 320 is configured to allow the gas to flow into the interior of the main body 330. In other words, the melting tank 320 is so configured that internal pressure thereof is increased by being filled with the gas. In the interior of the main body 330, the gas fills the space formed

between the surface of the polyalkylene oxide resin and internal surfaces of the main body 330. To the second inlet 336, the second inlet valve 348 is provided. The second inlet valve 348 is connected with a second introducing line 350. The gas flows through the second introducing line 350. By opening the second inlet valve 348, the gas is allowed to flow into the main body 330 via the second inlet 336. The second outlet 338 is provided with a pressure gauge 352 and a second outlet valve 354. By opening the second outlet valve 354, the gas inside the main body 330 is discharged via the second outlet 338. The pressure gauge 352 shows the internal pressure in the melting tank 320 , which is attained when the main body 330 is filled with gas. The heating member 340 includes a metal tube. Through the metal tube, a heating medium, such as oil or the like, whose temperature is adjusted, is passed through. The heating member 340 adjusts the temperature of the polyalkylene oxide resin inside the main body 330 , thereby keeping the polyalkylene oxide resin melted. The pump 322 transfers the polyalkylene oxide resin from the melting tank 320, where the polyalkylene oxide resin is contained, to the mixing apparatus 318. The pump 322 is a rotary pump 322. Although it is not illustrated, the pump 322 includes a casing and a rotary (gears) that includes a pair of gears. The pump 322 transfers the polyalkylene oxide resin by

pushing the polyalkylene oxide resin out of a space between the rotary (gears) and the main body (casing) . The pump 322 can transfer the polyalkylene oxide resin without causing pulsation. The pump 322 is configured such that an amount of the polyalkylene oxide resin to be pumped out per unit of time can be changed according to the revolution speed of shaft of the rotary. Such a pump 322 is referred to as a gear pump . The pump 322 may be a screw pump whose rotary is a screw. Configuration and specification of the pump 322 is determined appropriately in consideration of the specification of the mixing apparatus.

The pump 322 includes a first band heater 356, which serves as second temperature adjusting means. The first band heater 356 adjusts the temperature of the polyalkylene oxide resin inside the pump 322. The second temperature adjusting means may be a plate-type heater. The band heater 356 coils around the pump 322. Although it is not illustrated here, the first band heater 356 cooperates with a thermostat. Thereby, the pump 322 can be kept constant at a predetermined temperature. As an alternative, the pump 322 may be placed in a temperature-adjusted environment such as in a thermostat, instead of coiling the first band heater 356 around the pump 322. The second temperature adjusting means provided to the pump 322 may be a jacket type. The first liquid transferring line 324 is a pipe. The first

liquid transferring line 324 is connected with a first outlet valve 346. By opening the first outlet valve 346, the polyalkylene oxide resin is flown from the melting tank 320 to the pump 322 through the first liquid transferring line 324. The first liquid transferring line 324 is provided with a second band heater 358 for adjusting the temperature of the polyalkylene oxide resin flowing through the first liquid transferring line 324. Although it is not illustrated here, the second band heater 358 cooperates with a thermostat in order to keep the temperature of the first liquid transferring line 324 constant. The first liquid transferring line 324 may be provided with a metal tube, which coils around the first liquid transferring line 324 and through which a heating medium such as oil or the like flows. The first liquid transferring line 324 may be a jacketed tube configured such that a heating medium flows in its outer tube. In this case, the temperature of the liquid transferring line can be adjusted by adjusting the temperature of the heating medium. The internal pressure of the melting tank 320 is increased to be not less than the standard atmospheric pressure in advance. This speeds up the flow of the polyalkylene oxide resin from the melting tank 320 to the pump 322 when the first outlet valve 346 is opened. It is important for the liquid transferring means that the flow of the polyalkylene oxide resin is sped up by the effect of the internal pressure in the melting tank 320. Once the

polyalkylene oxide resin goes into the pump 322 , the polyalkylene oxide resin is sequentially transferred to the pump 322 from the melting tank 320 by the ability of the pump 322 to pump out the polyalkylene oxide resin. The second liquid transferring line 326 is a pipe . The polyalkylene oxide resin flows from the pump 322 to the mixing apparatus 318 through the second liquid transferring line 326. The second liquid transferring line 326 has an end 360 attached to an inlet 362 of the mixing apparatus 318. The polyalkylene oxide resin discharged from the end 360 is introduced into the mixing apparatus 318. The second liquid transferring line 326 is provided with a third band heater 364 for adjusting the temperature of the polyalkylene oxide resin flowing in the second liquid transferring line 326. Although it is not illustrated here, the third band heater 364 cooperates with a thermostat in order to keep the temperature of the second liquid transferring line 326 constant. The second liquid transferring line 326 may be provided with a metal tube, which coils around the second liquid transferring line 326, and through which a heating medium such as oil or the like flows. The second liquid transferring line 326 may be a jacketed tube configured such that a heating medium flows through its outer tube. In this case, the temperature of the liquid transferring line 326 can be adjusted by adjusting the temperature of the heating medium. In this Specification, the

third band heater 364 and the second band heater 358 serve as third temperature adjusting means for adjusting the temperature of the polyalkylene oxide resin inside the liquid transferring line that includes the first liquid transferring line 324 and the second liquid transferring line 326.

The mixing apparatus 3 18 is an apparatus for use in mixing an additive(s) in the polyalkylene oxide resin. The mixing apparatus 318 is not particularly limited. Preferable examples of the mixing apparatus 318 include mixer evaporators, falling-film evaporators, thin-film evaporators, surface-renewal-type polymerizers, kneaders, roll mixers, intensive mixers (so called Banbury mixers) , extruders, and the like. It is preferable to use at least any one of these apparatuses. Moreover, the condition of the using these apparatuses may be set as appropriate, considering which apparatus is used. Preferable examples of the falling-film evaporator include: a tubular-exchanger-type evaporator (e. g. , product name : Sulzer Mixer, manufactured by Sumitomo Heavy Industries. Ltd. ; product name: Static Mixer, manufactured by Noritake Co. , Ltd.) ; a plate-heat-exchanger-type evaporator (e .g. , product name: Hiviscous Evaporator, manufactured by Mitsui Engineering 8B Shipbuilding Co. , Ltd.); and the like. The surface-renewal-type polymerizer (horizontal thin-film polymerizer) excels in that it exhibits high volatilizing-off

performance by renewing a gas-liquid interface . Preferable examples of the surface-renewal-type polymerizer include: a single screw surface-renewal-type polymerizer, and a twin screw surface-renewal-type polymerizer (e . g. , product name: BIVOLAK, manufactured by Sumitomo Heavy Industries. Ltd. ; product name: Hitachi spectacle-shaped impeller polymerization machine, manufactured by Hitachi, Ltd. ; product name : Hitachi lattice-impeller polymerization machine, manufactured by Hitachi, Ltd. ; product name : SC processor, manufactured by Kurimoto, Ltd.) ; and the like.

The extruder is suitable for mixing highly viscous melted material and the like, and has a volatilizing ability in addition to a heating, melting, mixing, and kneading ability. Preferably examples of the extruder include single screw extruder, twin screw extruder (e .g. , product name: SUPERTEXaII, manufactured by Japan Steel Works, Ltd. ; product name : BT-30-S2, manufactured by Plastic Technology Laboratory) ; SCR self-cleaning-type reactor (manufactured by Mitsubishi Heavy Industries, Ltd.) . The kneader, the roll mixer, and the intensive mixer (so called Banbury mixer) are suitable for mixing highly viscous melted material and the like, and has a volatilizing off ability in addition, like the extruder. These apparatuses can operate batchwise and continuously. The mixing apparatus 3 18 is preferably, but not limited to, a twin screw surface-renewal-type polymerizer, kneader, or twin

screw extruder.

In the liquid-transferring step according to the present embodiment, the temperature of the melting tank 320 is adjusted by the heating member 340. By doing this, the temperature of the polyalkylene oxide resin inside the melting tank 320 is adjusted. By opening the second inlet valve 348 and the second outlet valve 354 , a headspace of the main body 330 of the melting tank 320 is replaced with the gas . How much the second inlet valve 348 and the second outlet valve 354 are opened or closed is adjusted to adjust the internal pressure of the melting tank 320. When it is confirmed that the temperature and internal pressure in the melting tank 320 are maintained at predetermined values respectively, the first discharging valve 346 is opened and the pump 322 is operated, thereby to start the supply of the melted polyalkylene oxide resin to the mixing apparatus 318. When a predetermined quantity of the product is obtained, the pump 322 is stopped thereby to complete the liquid transferring step. In the liquid transferring step according to the present embodiment, it is preferable that the internal pressure (hereinafter, pressure P) of the melting tank 320 be not less than standard atmosphere but not more than tolerable pressure of the melting tank 320. Moreover, the standard atmosphere is 1 atm, that is 101 .33 kPa when measured

based on absolute pressure . The pressure P equal to or greater than the standard atmosphere can effectively prevent the inflow of the air into the melting tank 320.

In the liquid transferring step, it is preferable that the temperature (hereinafter, temperature T l ) of the melting tank 320 is not less than (mp + 10) ⁰ C, but not more than 300 ⁰ C, where mp ( ⁰ C) is the melting point of the polyalkylene oxide resin. The temperature T l equal to or greater than (mp + 10) °C makes it possible to keep the polyalkylene oxide resin melted in the melting tank 320. The higher the temperature T l , the lower the viscosity of the polyalkylene oxide resin. This increases the mass of the polyalkylene oxide resin pumped out from the pump 322 per unit of time. The low viscosity of the polyalkylene oxide resin leads to a lower production cost. Because of this, it is more preferable that the temperature T l be not less than (mp + 30) ( ⁰ C) , and it is especially preferable that the temperature T l be not less than (mp + 50) ( ⁰ C) . The temperature T l equal to or less than 300 ⁰ C does not encourage quality deterioration, such as decomposition, crosslinking, or the like, of the polyalkylene oxide resin. Because of this, it is more preferable that the temperature T l be not more than (mp + 150) ⁰ C, and it is especially preferable that the temperature T l be not more than (mp + 130) ⁰ C . Although it is not illustrated here, the temperature Tl is measured in the vicinity of that internal

surface of the main body 330 of the melting tank 320 which is in contact with the polyalkylene oxide resin.

In the liquid transferring step, it is preferable that the temperature (hereinafter, temperature T2) of the first liquid transferring line 324 be not less than (mp + 10) ⁰ C but not more than 300 ⁰ C, where mp ( ⁰ C) is the melting point of the polyalkylene oxide resin. The temperature T2 equal to or greater than (mp + 10) ⁰ C makes it possible to keep the polyalkylene oxide resin melted in the first liquid transferring line 324. The higher the temperature T2 , the lower the viscosity of the polyalkylene oxide resin. This increases mass of the polyalkylene oxide resin pumped out by the pump 322 per unit of time. The low viscosity of the polyalkylene oxide resin leads to a lower production cost. Because of this, it is more preferable that the temperature T2 be not less than (mp + 30) ( ⁰ C) , and it is especially preferable that the temperature T2 be not less than (mp + 50) ( ⁰ C) . The temperature T2 equal to or less than 300 ⁰ C does not encourage quality deterioration, such as decomposition, crosslinking, or the like, of the polyalkylene oxide resin. Because of this, it is more preferable that the temperature T2 be not more than (mp + 150) ⁰ C, and it is especially preferable that the temperature T2 be not more than (mp + 130) ⁰ C. Although it is not illustrated here, the temperature T2 is measured in the vicinity of that internal surface of the first liquid transferring line 324 which is in

contact with the polyalkylene oxide resin.

In the liquid transferring step, it is preferable that the temperature (hereinafter, temperature T3) of the pump 322 be not less than (mp + 10) ⁰ C but not more than 300 ⁰ C, where mp ( ⁰ C) is the melting point of the polyalkylene oxide resin. The temperature T3 equal to or greater than (mp + 10) ⁰ C makes it possible to keep the polyalkylene oxide resin melted in the pump 322. The higher the temperature T3, the lower the viscosity of the polyalkylene oxide resin. This increases the mass of the polyalkylene oxide resin pumped out by the pump 322 per unit of time. The lower viscosity of the polyalkylene oxide resin leads to a lower production cost. Because of this, it is more preferable that the temperature T3 be not less than (mp + 30) ( ⁰ C) , and it is especially preferable that the temperature T3 be not less than (mp + 50) ( ⁰ C) . The temperature T3 equal to or less than 300 ⁰ C does not encourage quality deterioration, such as decomposition, crosslinking, or the like, of the polyalkylene oxide resin. Because of this, it is more preferable that the temperature T3 be not more than (mp + 150) ⁰ C, and it is especially preferable that the temperature T3 be not more than (mp + 130) ⁰ C. Although it is not illustrated here, the temperature T3 is measured in the vicinity of that internal surface of the pump 322 which is in contact with the polyalkylene oxide resin. In the liquid transferring step, it is preferable that the

temperature (hereinafter, temperature T4) of the second liquid transferring line 326 be not less than (mp + 10) °C but not more than 300 ⁰ C , where mp ( ⁰ C) is the melting point of the polyalkylene oxide resin. The temperature T4 equal to or greater than (mp + 10) ⁰ C makes it possible to keep the polyalkylene oxide resin melted in the second liquid transferring line 326. The higher the temperature T4, the lower the viscosity of the polyalkylene oxide resin. This increases mass of the polyalkylene oxide resin pumped out by the pump 322 per unit of time. The lower viscosity of the polyalkylene oxide resin leads to a lower production cost. Because of this, it is more preferable that the temperature T4 be not less than (mp + 30) ( ⁰ C) , and it is especially preferable that the temperature T4 be not less than (mp + 50) ( ⁰ C) . The temperature T4 equal to or less than 300 ⁰ C does not encourage quality deterioration, such as decomposition, crosslinking, or the like, of the polyalkylene oxide resin. Because of this, it is more preferable that the temperature T4 be not more than (mp + 150) ⁰ C, and it is especially preferable that the temperature T4 be not more than (mp + 130) ⁰ C . Although it is not illustrated here, the temperature T4 is measured in the vicinity of that internal surface of the second liquid transferring line 326 which is in contact with the polyalkylene oxide resin. In the liquid transferring step, the pressure P, and

temperatures T l , T2 , T3, and T4 are kept substantially- constant from the start to completion of the liquid transferring step. This attains stable viscosity profile of the polyalkylene oxide resin inside the transferring means 316. Therefore, it is possible to effectively adjust the pumped-out mass of the polyalkylene oxide resin by adjusting revolution speed (i.e. , number of revolution speed, revolution speed R) of the shaft of the pump 322. This maintains appropriate balance between the mass of the polyalkylene oxide resin supplied to the pump 322 from the melting tank per unit of time, and the mass of the polyalkylene oxide resin supplied from the pump 322 to the mixing apparatus 318 per unit of time . By using the liquid transferring means 3 16 having such an arrangement, it is possible to attain stable supply of the melted polyalkylene oxide resin to the mixing apparatus 3 18. Because of this, the fabrication to shape the polyalkylene oxide resin into longitudinal products having a predetermined cross sectional shape can be carried out with excellent size stability. Especially, the polyalkylene oxide resin to which a predetermined additive is added can be fabricated to products in which the additive is dispersed with even composition.

In the liquid transferring step, fluctuation tolerance F in a pumping-out amount of the melted polyalkylene oxide resin (amount of the polyalkylene oxide resin pumped out from the pump 322) per unit of time is expressed by the following

equation (I):

F= 3 * σ / A ^χ 100 ^••• (I),

where A is an average in the pumping-out amount, and σ is a standard deviation of the pumping-out amount. Using an n number of pumping-out amount data, Al, A2, ^••• , An, the average A is obtained by the following equation (II):

where ^" A ⁺ A + 4 + •••••• ⁺ A ^■

The standard deviation σ is expressed by the following equation (III):

where 4 ^{2 +} λ ²⁺ 4 ^{2+ +} λ ^'

In order to attain higher reliability for the fluctuation tolerance, a greater n (number of data) is preferable. It is more preferable that n is 5 or more. It is especially preferable that n is 10 or more. In this Specification, n is 10 as later described.

In the liquid transferring step, the fluctuation tolerance F is 6% or less. The fluctuation tolerance of 6% or less attains stable supply of the polyalkylene oxide resin to the mixing apparatus 318. Because of this, the fabrication of the polyalkylene oxide resin to longitudinal products having a predetermined cross section can be carried out with an excellent size stability. Especially, the fabrication of the polyalkylene oxide resin in which a predetermined additive is added can produce products in which the additive is evenly dispersed. The use of the liquid transferring means 3 16 attains high quality of the products. Because of this, fluctuation tolerance of 5% or less is more preferable and fluctuation tolerance of 4% or less is further preferable.

The average A and standard deviation σ of the pumping-out amount can be obtained as follows. The pumping-out amount of the polyalkylene oxide resin pumped out from the second liquid transferring line 326 in 30 seconds is measured ten times. Based on the measurements of the pumping-out amount, the pumping-out amount of the polyalkylene oxide resin pumped out from the pump 322 per

unit of time is found. From the ten measurements, the average A and standard deviation σ of the pumping-out amount are calculated out.

In the liquid-transferring step, the fluctuation tolerance F can be controlled by the pressure P, revolution speed R, and temperatures T l , T2 , T3 , and T4. More specifically, the pressure P, revolution speed R, and temperatures Tl , T2 , T3 , and T4 are adjusted so that their fluctuations is kept small from the start to completion of the liquid transferring step. In the liquid transferring step, it is preferable that the temperature of the polyalkylene oxide resin be not less than (mp + 10) ⁰ C but not more than 300 ⁰ C . The temperature of the polyalkylene oxide resin is the temperature therefore when the polyalkylene oxide resin is introduced into the mixing apparatus 318 from the second liquid transferring line 326. The temperature of the polyalkylene oxide resin being not less than (mp + 10) °C effectively reduces work load of the mixing apparatus in the shaping step performed after the liquid-transferring step. Because of this, this temperature of the polyalkylene oxide resin is preferably not less than (mp + 30) °C, and especially preferably not less than (mp + 50) ⁰ C. This temperature of the polyalkylene oxide resin equal to or less than 300°C does not encourage quality deterioration, such as decomposition, crosslinking, or the like, of the polyalkylene oxide resin. Because of this, it is more preferable

that this temperature of the polyalkylene oxide resin be not more than (mp + 150) ⁰ C, and it is especially preferable that this temperature of the polyalkylene oxide resin be not more than (mp + 130) ⁰ C. In the liquid transferring step, the liquid transferring means 316 preferably has such a temperature profile of the temperatures T l , T2 , T3, and T4 that the temperatures T l and T2 be the same. The temperatures T l and T2 are preferably set as low as possible, but within a temperature range that allows the transfer of the melted polyalkylene oxide resin without causing quality deterioration such as decomposition, etc. Because of this, the temperatures T l and T2 are preferably not less than 70 ⁰ C, and more preferably not less than 90 ⁰ C, while the temperatures Tl and T2 are further preferably not more than 130 ⁰ C, and especially preferably not more than 1 10 ⁰ C. The temperatures T3 and T4 are preferably the same. The temperatures T3 and T4 are preferably set to be the same as the mixing temperature of the mixing apparatus 318, and as high as possible, but within a temperature range that allows the transfer of the melted polyalkylene oxide resin without causing quality deterioration such as decomposition, etc. Because of this, the temperatures T3 and T4 are preferably not less than 1 10 ⁰ C, and more preferably not less than 130 ⁰ C, while the temperatures T3 and T4 are further preferably not more than 170 ⁰ C, and

especially preferably not more than 150 ⁰ C. In the liquid transferring step, it is preferable that the temperatures T3 and T4 be higher than the temperatures T l and T2. Because of this, the difference between the temperatures T l and T2 , and the temperatures T3 and T4 is set according the mixing conditions of the mixing apparatus 318.

In the liquid transferring step, water content of the polyalkylene oxide resin is preferably not more than l ,000ppm, more preferably not more than 200ppm, and especially preferably not more than 50 ppm. By keeping the water content of the polyalkylene oxide resin to be introduced, water content of the product shaped by the mixing apparatus can be kept low with ease.

In the liquid transferring step, it is preferable that oxygen concentration of the gas is less than 2 1 % by volume.

The oxygen concentration less than 21 % by volume can prevent the quality deterioration, such as decomposition, crosslinking, or the like, of the polyalkylene oxide resin that is cooled down in the open head drum. The quality of the polyalkylene oxide resin can become stable . Because of this, the oxygen concentration is more preferably not more than

10% by volume, and especially preferably not more than 1 % by volume.

In the liquid transferring step, it is preferable that a dew point of the gas be - 30 ⁰ C or less. It is more preferable that

the dew point of the gas be - 50 ⁰ C or less. It is further more preferable that the dew point of the gas be - 60 ⁰ C or less. The low dew point of the gas reduces an amount of water to be absorbed into the polyalkylene oxide resin. Examples of the gas (inert gas) for use in the liquid transferring step include nitrogen, helium, and argon. For versatility, nitrogen is preferable as the gas. The use of the gas prevents the quality deterioration, such as decomposition, crosslinking, or the like, of the polyalkylene oxide resin in the melting tank 320. In the liquid transferring step, the quality of the polyalkylene oxide resin can be maintained stable.

In the present embodiment, properties are measured as follows .

[Measurement of Melting Point (mp) of Polyalkylene Oxide Resin]

Using a differential thermal analyzer, the melting point of the polyalkylene oxide resin is measured by the following temperature pattern. A reaction mixture (including the polyalkylene oxide resin) obtained after polymerization is dried for 2 hours at 80 ⁰ C by using a reduced-pressure dryer, so as to volatilize off volatiles from the reaction mixture. After that, the reaction mixture is left in a flow of dry nitrogen for

10 hours for humidity conditioning. Thereby, the polyalkylene oxide resin as a sample is obtained. The temperature pattern is as follows. In the analyzer ("Thermal Analyzer: DSC220)

made by Seiko Instruments Inc.) , the polyalkylene oxide resin is rapidly heated to 80 ⁰ C so as to be melted once . Then, the polyalkylene oxide resin is cooled down from 80 ⁰ C to - 100 ⁰ C at a -5°C/ min. During this cooling an exothermic peak occurs due to crystallization. From the exothermic peak, crystallization temperature is worked out. The crystallized polyalkylene oxide resin is then heated to 80 ⁰ C from - 100 ⁰ C at a rate of 5°C / min. The temperature at which the crystals are completely melted in the heating is the melting point (mp) of the polyalkylene oxide resin

[Measurement of Amount of Antioxidant in Polyalkylene Oxide Resin]

The amount of the antioxidant in the polyalkylene oxide resin is measured by using a high performance liquid chromatography (analyzing apparatus: D-7000 HPLC system (Hitachi high technologies) column: ODS-3 (provided by GL Sciences Inc .) ; column temperature: 40 ⁰ C; flow rate: 1 .0 mL/ minute; injection amount: 5 μL; UV detector: 2 10 nm; carrier: mixture solution of a mixture of acetonitrile/ water/ 0. 1 % by mass phosphoric acid solution = 1972g/ 405g/ 45g. The sample for the analysis was prepared by dissolving, an antioxidant-containing polyalkylene oxide resin into a dissolving solution by 1 % by mass, and filtering the dissolving solution via a filter. As described above, a method according to the present

invention for producing a material made of a polyalkylene oxide resin, comprises the step of: (a) heating an upper surface of the polyalkylene oxide resin contained in a container, so as to melt the polyalkylene oxide resin, and removing the melted polyalkylene oxide resin from the container.

The method according to the present invention preferably further comprises: (1) shaping the polyalkylene oxide resin removed in the step (a) . The method according to the present invention preferably further comprises: dissolving the polyalkylene oxide resin removed in the step (a) .

The method according to the present invention is preferably arranged such that: in the step (a) , the upper surface of the polyalkylene oxide resin is heated to a temperature not less than the melting point of the polyalkylene oxide resin, but not more than 300 ⁰ C, so as to melt the polyalkylene oxide resin.

The method according to the present invention is preferably arranged such that the melting point of the polyalkylene oxide resin is not less than 0 ⁰ C but not more than 60 ⁰ C.

The method according to the present invention is preferably arranged such that the polyalkylene oxide resin has an elongational viscosity of not less than 100 Pa-s but not

more than 1 , 000, 000 Pa-s when measured at a temperature of not less than 100 ⁰ C but not more than 1 10 ⁰ C and with shear rate of not less than 100 ( 1 / s) but not more than 500 ( 1 / s) .

The method according to the present invention preferably further comprises : (b) polymerizing, in a solvent, a monomer mixture whose main content is an alkylene oxide, so as to obtain the polyalkylene oxide resin; and (c) volatilizing off the solvent from the polyalkylene oxide resin obtained in the step (b) , wherein in the step (a) , the polyalkylene oxide resin from which the solvent has been volatilized off is removed.

The method according to the present invention is preferably arranged such that in the step (a) , a solvent concentration in the polyalkylene oxide resin is not less than 0.01 % by mass and not more than 30% by mass, and water content of the polyalkylene oxide resin is not more than 200ppm.

The method according to the present invention is preferably arranged such that the monomer mixture in the step (b) is made of ethylene oxide and butylene oxide, or of ethylene oxide, butylene oxide and allylglycidylether, and the monomer mixture has such a mixture ratio that ethylene oxide is in a range of 90 to 99 mol%, butylene oxide is in a range of 1 to 10 mol%, and allylglycidylether is in a range of 0 to 2 mol%.

The method according to the present invention is preferably arranged such that in the step (a) , the upper layer of the polyalkylene oxide resin is heated by using a melter so as to melt the polyalkylene oxide resin, and the melted polyalkylene oxide resin is removed from the container.

In other words, the method according to the present invention is a method (introducing method) for introducing a polyalkylene oxide resin, the method comprising adding into an open head drum in an atmosphere of an introducing gas that is inert, the polyalkylene oxide resin being adjusted to a temperature of not less than (mp + 10) ( ⁰ C) but not more than 300 ⁰ C, where mp ( ⁰ C) is a melting point of the polyalkylene oxide resin.

The introducing method according to the present invention is preferably arranged such that the introducing gas used in step of introducing has a dew point of -30 ⁰ C or less.

The introducing method according to the present invention preferably further comprises adding the melted polyalkylene oxide resin into the open head drum via the opening thereof, and cooling the polyalkylene oxide resin, in an atmosphere of a cooling gas that is inert, in the open head drum whose opening is closed with a lid that has an inlet and an outlet, so as to cool, to a temperature equal to or less than mp ( ⁰ C) , that surface of the melted polyalkylene oxide resin which is in contact with a space in the open head drum is

cooled, while introducing the cooling gas via the inlet into the space and discharging the cooling gas via the output from the space, where mp is the melting point of the polyalkylene oxide resin. The introducing method according to the present invention is preferably arranged such that in the step (f) , the cooling gas has a dew point of -30 ⁰ C or less.

A preferable arrangement of the introducing method according to the present invention preferably is to comprise: introducing a polyalkylene oxide resin in an open head drum in an introducing gas that is inert; and cooling the polyalkylene oxide resin in the open head drum in an atmosphere of a cooling gas that is inert, wherein the introducing gas has a dew point of -30 ⁰ C or less, and an oxygen concentration of less than 21 % by volume, and the cooling gas has a dew point of -30 ⁰ C or less, and an oxygen concentration of less than 21% by volume.

The introducing method according to the present invention is preferably arranged such that from the step of introducing to the step of cooling, the polyalkylene oxide resin has, in its surface, water content of l OOOppm or less.

The introducing method according to the present invention is preferably arranged such that the melting point of the polyalkylene oxide resin is not less than 0 ⁰ C but not more than 60 ⁰ C.

The introducing method according to the present invention is preferably arranged such that the polyalkylene oxide resin has an elongational viscosity of not less than 100 Pa- s but not more than 1 ,000,000 Pa-s when measured at a temperature of not less than 100 ⁰ C but not more than 1 10 ⁰ C and with shear rate of not less than 100 ( 1 / s) but not more than 500 ( 1 / s) .

The introducing method according to the present invention is preferably arranged such that the polyalkylene oxide resin has been prepared by: polymerizing, in a solvent, a monomer mixture whose main content is an alkylene oxide, so as to obtain the polyalkylene oxide resin; and volatilizing off the solvent from the polyalkylene oxide resin.

The introducing method according to the present invention is preferably arranged such that the monomer mixture in the step of polymerizing is made of ethylene oxide and butylene oxide, or of ethylene oxide, butylene oxide and allylglycidylether, and the monomer mixture has such a mixture ratio that ethylene oxide is in a range of 90 to 99 mol%, butylene oxide is in a range of 1 to 10 mol%, and allylglycidylether is in a range of 0 to 2 mol%.

The introducing method according to the present invention is preferably arranged such that the polyalkylene oxide resin obtained in the step of polymerizing has a mass average molecular weight of not less than 50 , 000 but not

- I l l -

more than 150,000.

According to the step of adding comprised in the introducing method of the present invention, the water content in the polyalkylene oxide resin in the open head drum can be kept low while preventing the quality deterioration of the polyalkylene oxide resin. According to the step of cooling comprised in the introducing method, it is possible to cool the polyalkylene oxide resin without causing deformation of the open head drum. The water content in the cooled polyalkylene oxide resin can be kept low while preventing the quality deterioration of the polyalkylene oxide resin.

In other words, the method according to the present invention for producing the material made of the polyalkylene oxide resin is a method for producing a solution of the polyalkylene oxide resin, the method comprising: (j) dissolving the polyalkylene oxide resin in the solvent in a dissolving tank, while supplying, into the dissolving tank, the polyalkylene oxide resin whose temperature adjusted to be equal to or higher than (mp+ 10)°C, the dissolving tank having a system temperature of (mp) °C or higher, where mp ⁰ C is the melting point of the polyalkylene oxide resin.

The method according to the present invention is preferably arranged to comprise: (k) stirring the solution in the dissolving tank with power requirement of impeller (PV) of 0. 1 (kW/ m ³ ) or greater.

The method according to the present invention is preferably arranged such that in the step of dissolving, the polyalkylene oxide resin is dissolved while being supplied into the dissolving tank, the polyalkylene oxide resin has, when being supplied, a temperature adjusted to be not less than (mp+ 10)°C but not more than 300°C, and the dissolving tank has a system temperature of not less than (mp)°C but not more than 300 ⁰ C .

The method according to the present invention is preferably arranged such that the melting point of the polyalkylene oxide resin is not less than 0 ⁰ C but not more than 60 ⁰ C.

The method according to the present invention is preferably arranged such that the polyalkylene oxide resin has an elongational viscosity of not less than 100 Pa-s but not more than 1 ,000,000 Pa-s when measured at a temperature of not less than 100 ⁰ C but not more than 1 10 ⁰ C and with shear rate of not less than 100 ( 1 / s) but not more than 500 ( 1 / s) .

Moreover, a preferable arrangement of the method according to the present invention is to comprise: polymerizing, in a solvent, a monomer mixture whose main content is an alkylene oxide, so as to obtain the polyalkylene oxide resin; volatilizing off the solvent from the polyalkylene oxide resin; introducing, into a container, the polyalkylene oxide resin from which the solvent is volatilized off; and

removing the polyalkylene oxide resin from the container, wherein the removed polyalkylene oxide resin is dissolved in a solvent in the step of dissolving.

The method according to the present invention is preferably arranged such that in the step of removing, a solvent concentration in the polyalkylene oxide resin is not more than 30% by mass, and water content of the polyalkylene oxide resin is not more than 200ppm.

The method according to the present invention is preferably arranged such that the monomer mixture in the step (b) is made of ethylene oxide and butylene oxide, or of ethylene oxide, butylene oxide and allylglycidylether, and the monomer mixture has such a mixture ratio that ethylene oxide is in a range of 90 to 99 mol%, butylene oxide is in a range of 1 to 10 mol%, and allylglycidylether is in a range of 0 to 2 mol%.

The method according to the present invention is preferably arranged such that the polyalkylene oxide resin obtained in the step (b) has a mass average molecular weight of not less than 50,000 but not more than 150,000.

According to the method for the present invention, it is possible to effectively dissolve the polyalkylene oxide resin.

In other words, the method according to the present invention for producing the polyalkylene oxide resin is a method (handling method) for dealing with the polyalkylene

oxide resin. The dealing method according to the present invention comprises: adding, into an open head drum, the melted polyalkylene oxide resin; sealing a gas into the space in the open head drum in which the polyalkylene oxide resin is contained, the gas having a dew point of -30 ⁰ C or less, so that the gas sealed in the space has a pressure not less than a standard atmospheric pressure but not more than tolerable pressure of the open head drum; and transferring or storing the open head drum while the dew point of the gas sealed in the space is kept at or below -30°C .

The handling method according to the present invention is preferably arranged such that the melting point of the polyalkylene oxide resin is not less than 0 ⁰ C but not more than 60°C . The handling method according to the present invention is preferably arranged such that the polyalkylene oxide resin has an elongational viscosity of not less than 100 Pa-s but not more than 1 ,000, 000 Pa-s when measured at a temperature of not less than 100 ⁰ C but not more than 1 10 ⁰ C and with shear rate of not less than 100 ( 1 / s) but not more than 500 ( 1 / s) .

The handling method according to the present invention is preferably arranged such that in the step of transferring and storing, the polyalkylene oxide resin has a solvent concentration of 30% or less by mass, and water content of

l OOOppm or less.

The handling method according to the present invention is preferably arranged to comprise : producing the polyalkylene oxide resin, the step of producing comprising: polymerizing, in a solvent, a monomer mixture whose main content is an alkylene oxide, so as to obtain the polyalkylene oxide resin; and volatilizing off the solvent from the polyalkylene oxide resin.

The handling method according to the present invention is preferably arranged such that the monomer mixture in the step (b) is made of ethylene oxide and butylene oxide, or of ethylene oxide, butylene oxide and allylglycidylether, and the monomer mixture has such a mixture ratio that ethylene oxide is in a range of 90 to 99 mol%, butylene oxide is in a range of 1 to 10 mol%, and allylglycidylether is in a range of 0 to 2 mol%.

The method according to the present invention is preferably arranged such that the polyalkylene oxide resin obtained in the step of polymerizing has a mass average molecular weight of not less than 50,000 but not more than 150, 000.

According to the handling method of the present invention, it is possible to transfer or store the polyalkylene oxide resin while preventing the water content increase. In other words, the producing method according to the

present invention is a method (supplying method) for supplying the polyalkylene oxide resin. The supplying method comprises transferring the melted polyalkylene oxide resin to a mixing device by liquid-transferring means, the liquid-transferring means comprising: a melting tank for storing the melted polyalkylene oxide resin therein; a pump for transferring the melted polyalkylene oxide resin from the melting tank to the mixing device; and a liquid-transferring line through which the melted polyalkylene oxide resin flows, the pump pumping out the melted polyalkylene oxide resin with F of 6% or less, where F is fluctuation tolerance in a pumping-out amount of the melted polyalkylene oxide resin per unit of time, and expressed by Equation (I) :

F = 3 x σ / A * 100 ^{• • •} (I) ,

where A is an average in the pumping-out amount, and σ is a standard deviation of the pumping-out amount.

The supplying method according to the present invention is preferably arranged such that the melting tank of the liquid-transferring means is capable of allowing an internal pressure thereof to be increased by introduction of an inert gas therein, and comprises a first temperature adjusting means for adjusting a temperature of the melted polyalkylene oxide resin contained in the melting tank, the pump is

capable of changing the pumping-out amount of the melted polyalkylene oxide resin per unit of time according to a revolution speed of a shaft, and comprises a second temperature adjusting means for adjusting the temperature of the melted polyalkylene oxide resin inside the pump, the liquid-transferring line of the liquid-transferring means comprises a third temperature adjusting means for adjusting the temperature of the melted polyalkylene oxide resin inside liquid-transferring line, and F is controlled by the internal pressure of the melting tank, the revolution speed of the shaft of the pump, the temperature of the melted polyalkylene oxide resin in the melting tank, which temperature is adjusted by the first temperature adjusting means, the temperature of the melted polyalkylene oxide resin inside the pump, which temperature is adjusted by the second temperature adjusting means, and the temperature of the melted polyalkylene oxide resin inside the liquid-transferring line, which temperature is adjusted by the third temperature adjusting means.

The supplying method according to the present invention is preferably arranged such that in the step of transferring, the melted polyalkylene oxide resin in the melting tank has water content of l OOOppm or less, and oxygen concentration in the space inside the melting tank is less than 2 1 % by volume. The supplying method according to the present invention

is preferably arranged such that the melting point of the polyalkylene oxide resin is not less than 0 ⁰ C but not more than 60 ⁰ C.

The supplying method according to the present invention is preferably arranged such that the polyalkylene oxide resin has an elongational viscosity of not less than 100 Pa-s but not more than 1 ,000,000 Pa-s when measured at a temperature of not less than 100 ⁰ C but not more than 1 10 ⁰ C and with shear rate of not less than 100 ( 1 / s) but not more than 500 ( 1 / s) .

The supplying method according to the present invention is preferably arranged such that the polyalkylene oxide resin is a polyalkylene oxide resin obtained by the step of: polymerizing, in a solvent, a monomer . mixture whose main content is an alkylene oxide, so as to obtain the polyalkylene oxide resin; and volatilizing off the solvent from the polyalkylene oxide resin.

The supplying method according to the present invention is preferably arranged such that, in the step of polymerizing, the monomer mixture in the step (b) is made of ethylene oxide and butylene oxide, or of ethylene oxide, butylene oxide and allylglycidylether, and the monomer mixture has such a mixture ratio that ethylene oxide is in a range of 90 to 99 mol%, butylene oxide is in a range of 1 to 10 mol%, and allylglycidylether is in a range of 0 to 2 mol%.

The supplying method according to the present invention is preferably arranged such that the polyalkylene oxide resin obtained in the step of polymerizing has a mass average molecular weight of not less than 50, 000 but not more than 150, 000.

According to the supplying method according to the present invention, the pumping-out amount of the polyalkylene oxide resin pumped out from the pump per unit of time is substantially constant. This attains stable supply of the melted polyalkylene oxide resin to the mixing apparatus. In case the polyalkylene oxide resin is to be fabricated into a longitudinal product having a predetermined cross sectional shape, this allows fabrication of products excellent in size stability. Especially, in case where the polyalkylene oxide resin is to be shaped after a predetermined additive is added into the polyalkylene oxide resin, it is possible to produce products in which the additive is evenly dispersed with constant composition. This supplying method makes it possible to produce products with high quality. The invention being thus described, it will be obvious that the same way may be varied in many ways. Such variations are not to be regarded as a departure from the spirit and scope of the invention, and all such modifications as would be obvious to one skilled in the art are intended to be included within the scope of the following claims.

[Examples]

The following more specifically explains the present invention with reference to Examples; however, the present invention is not limited to these. For convenience, in the below description, a wording "hour" is merely abbreviated as

"h", and a wording "liter" is merely described as "L" .

(A) Examples concerning Removing Step (Step (a)) [Example IA]

A maxblend impeller (provided by Sumitomo Heavy Industries Ltd.) and a I L reactor having an opening for use in adding an additive were washed with a solvent (toluene) , and then the reactor with the maxblend impeller was thermally dried and air inside thereof was replaced with nitrogen. Into the reactor, (i) 286.5 mass part of toluene having been subj ected to a dehydration treatment using a molecular sieve, and (ii) 0.55 mass part of t-butoxypotassium (20 % by mass tetrahydrofuran solution) were added in this order. Thereafter, the headspace in the reactor was replaced with nitrogen.

Pressure was applied with the use of nitrogen until pressure in the reactor became 0.3 Mpa. Then, the reactor was heated by using an oil bath with stirring by rotating the maxblend impeller at 130 rpm.

After confirming that the temperature in the reactor reached 90°C, 286.5 mass part of a monomer mixture made up of ethylene oxide and butylenes oxide (ethylene oxide /

butylenes oxide = 94 mol% / 6 mol%) was supplied to the reactor. The supply of the monomer mixture was carried out under monitored and controlled temperature and pressure in the reactor, which tended to increase due to heat of polymerization. By this, reaction took place with temperatures of 100 ⁰ C ± 5°C . Thereafter, the reactor was kept to have a temperature of 90 ⁰ C or greater for 5 hours for the purpose of aging. By this, a polymerization reaction solution (2) was obtained. This polymerization reaction solution (2) contained a polyalkylene oxide resin ( 1) by 50 % by mass and toluene by 50 % by mass.

The polymerization reaction solution (2) thus obtained as a result of the solution polymerization was supplied to a thin film evaporator (product name: EXEVA, provided by Shinko Pantec Co. , Ltd.) at a j acket temperature of 180 ⁰ C under reduced pressure of 50 Torr (6666 Pa) . The polymerization reaction solution (2) was concentrated by volatilizing off volatile therefrom. Then, directly into a 200L open drum (product name: Steel Open Drum (M-class) , provided by Zenyu Metal Industry Co . Ltd) , the polymerization reaction solution (2) was introduced at a temperature of 145 ⁰ C and at a draining speed of 15 kg/ hr via a gear pump provided in a drain opening of the thin film evaporator. In this way, the polyalkylene oxide resin ( 1 ) was obtained. The polyalkylene oxide resin ( 1 ) had a mass-average molecular

weight Mw of 122 ,000, and had a dispersivity of 1 .45, which were found in accordance with methods described below, respectively. Further, the polyalkylene oxide resin ( 1) had toluene content of 0. 16 % by mass, and water content of 60 ppm, which were found in accordance with method described below, respectively. Further, the polyalkylene oxide resin ( 1) had an elongational viscosity of 6,420 Pa- S, which was measured under conditions described below.

The polyalkylene oxide resin ( 1 ) was sufficiently cooled so as to have a room temperature, with the result that the polyalkylene oxide resin ( 1 ) was completely solidified. Into the 200L open drum containing such polyalkylene oxide resin ( 1 ) , a platen of a bulk melter (product name: Bulk Melter BM series BM200 , provided by Nordson K. K.) was so put as to make contact with the polyalkylene oxide resin ( 1 ) . The platen was a fin platen, and was provided with a gerotor/ gear pump. With the platen pressed against the polyalkylene oxide resin ( 1 ) , a heater provided in the platen heated a surface of the polyalkylene oxide resin ( 1 ) to a temperature of 140 ⁰ C . After 5 / min had passed since the platen was put into the 200L open drum, the pump was started by turning a pump speed scale to Level 5 (Level 10 at maximum) . With this, the melted polyalkylene oxide resin ( 1) was discharged at a discharge speed of 1 1 kg/ hr from a discharging section provided in an upper portion of the platen. The polyalkylene oxide resin ( 1)

thus discharged had a temperature of 13 1 °C, a weight-average molecular weight of 122, 000, and a dispersivity of 1.45. The weight-average molecular weight and the dispersivity were found in accordance with the methods described below. [Measuring Amount of Solvent Remaining in Resin

Obtained through Volatilizing-off]

A part of the polyalkylene oxide resin obtained through the volatilizing-off were put in an aluminum cup whose mass had been measured in advance, and were measured. Thereafter, the polyalkylene oxide resin thus measured was put in a reduced pressure dryer heated in advance to a temperature of 1 10 ⁰ C. A purge valve was closed and a vacuum line valve was opened thereby to reduce a pressure inside the dryer to -0. 1 Mpa. The polyalkylene oxide resin was put in the dryer under the reduced pressure for 30 min to drive off the solvent therefrom. Thereafter, the vacuum line valve was closed and the purge valve was opened such that the pressure inside the dryer becomes a normal pressure . Then, the aluminum cup containing the resin was taken out from the dryer, and was allowed to cool for 10 / min in a flow of nitrogen. Thereafter, the mass of the polyalkylene oxide resin was measured. The mass of the polyalkylene oxide resin obtained before the drying was compared with the mass of the polyalkylene oxide resin obtained after the drying, so as to find how much the mass of the polyalkylene oxide resin was

decreased. From the decrease in the mass of the polyalkylene oxide resin, an amount of the solvent remaining in the polyalkylene oxide resin was worked out.

[Measuring Water Content in Resin Obtained through Volatilizing-off]

The polyalkylene oxide resin thus obtained was sample under a drying atmosphere while the polyalkylene oxide resin obtained through the volatilizing-off had a temperature close to a volatilizing-off temperature and was flowable. Then, the polyalkylene oxide resin thus sampled was naturally cooled. The polyalkylene oxide resin thus cooled, toluene serving as a solvent, a glass container, and syringes were put in a glove box and were dried for 2 hours therein. The toluene had been treated in advance with a molecular sieve - (provided by UNION SHOWA K. K; product name: Molecular Sieve 3A l .6 or Molecular Sieve 4A l .6) thereby to reduce its water content as much as possible.

After the drying, 2g of the polyalkylene oxide resin, and

18g of the toluene were put in the glass container, and the polyalkylene oxide resin was sufficiently dissolved into the toluene with the use of a magnetic stirrer, thereby preparing a resin solution. The resin solution thus obtained was fully collected by the syringe. At the same time, 18g of the toluene was collected by the other syringe. After the collection, the syringes were taken out from the glove box to outside. Then,

the water content of the resin solution and the water content of the toluene were measured with the use of AQUACOUNTERQ-7, which is a water content measuring apparatus provided by HIRANUMA. From the water contents (ppm) found by the measurement, the water content by mass (mg) in the resin solution and the water content by mass (mg) in toluene were found, respectively. From a difference between the masses thus found, the mass (mg) of water content in the polyalkylene oxide resin was found. By dividing the difference, i.e. , the mass (mg) of the water by the mass (2g) of the polyalkylene oxide resin firstly dissolved in 18g of the toluene, the water content (ppm) of the polyalkylene oxide resin was found.

[Measuring Mass-Average Molecular Weight Mw and Molecular Weight Distribution (Mw / Mn) of Polyalkylene Oxide Resin]

An analytical curve of a standard molecular weight sample of the polyalkylene oxide was obtained by using a high performance liquid chromatography (column: ODS-3 (provided by GL Sciences Inc.) ; column temperature: 40 ⁰ C; flow rate: 1 .0 mL/ minute; injection amount: 5 μL; UV detector: 2 10 nm; carrier: mixture solution of (i) acetonitrile and (ii) 0. 1 % by mass phosphoric acid solution (volume ratio : acetonitrile / 0. 1 % by mass phosphoric acid solution = 85 / 15)) . The polymerization reaction solution (including the polymer)

obtained after the reaction was dissolved into a predetermined solvent, and was measured for the sake of finding Mw and Mw / Mn.

[Measuring Elongational Viscosity] The polymerization reaction solution (2) was dried by a reduced pressure dryer at a temperature of 100 ⁰ C for 8 hours such that volatile content in the polymerization reaction solution (2) was volatilized off. Residual material was cut in the form of a pellet, and was left in a glove box under a nitrogen atmosphere for 24 hours, with the result that the concentration of volatile matter content left in the residual material was 200 ppm or less . Such residual material was used as a sample polymer. The elongational viscosity (Pa- s) of the sample polymer was measured under the following conditions :

Measuring apparatus: commercial product "Twin Capillary Rheometer RH7-2" provided by the ROSAND

Measurement temperature: 100 ⁰ C to 1 10 ⁰ C

Die: A long die having a diameter 2 mm (length of 32 mm) and a short die (length 0.25 mm)

Die angle: 180°

Measurement atmosphere: dry air atmosphere

Retention time: 10 / min

Attention: in introducing the polymer into each of the dies, the polymer should be introduced quickly (within 5

/ min) , and a bubble removing operation should be carried out (bubbles in a barrel should be sufficiently removed with the use of a piston or a pusher rod after introducing the polymer thereinto) . [Measuring Discharge Amount]

Polyalkylene oxide resin ( 1 ) discharged from the discharging section of the platen was sampled for 36 seconds and the mass thereof were measured. From the mass thus measured, a mass corresponding to the mass of polyalkylene oxide resin ( 1) discharged for 1 hour was found. See Table 1 for results of respective discharge amounts found in respective Examples.

[Quality of Discharged Products]

In accordance with the method described above, the mass-average molecular weight (Mw) and the number-average molecular weight (Mn) of each of the discharged products were found. The quality of a discharged product was judged to be "good" if a change in Mw thereof was kept within 1 % before and after the discharging and a change in Mn thereof was kept within 4% before and after the discharging. Meanwhile, the quality of a discharged product was judged to be "bad" if here the Mw varied if a change in Mw thereof exceeded 1 % before and after the discharging and a change in Mn thereof exceeded 4% before and after the discharging. See Table 1 for results of respective qualities of discharged products of

respective Examples.

[Examples 2A through 12A]

As is the case with Example IA, polyalkylene oxide resins ( 1 ) , from which volatiles were volatilized off, were obtained. Next, a removing step was carried out in the same manner as that in Example IA, except that a heating temperature of the platen and a pump speed were respectively set at levels (levels relative to the pump speed scale whose maximum Level was 10) shown in Table 1 . As a result, discharged products of Examples 2A through 12A were obtained.

Table 1 ;

to

Abbreviation: Ex. stands for Example.

From Table 1 , it was understood that: according to

Examples of the present invention, the removal of the polyalkylene oxide resin ( 1 ) never causes changes of the mass-average molecular weight and the number-average molecular weight, i. e. , never causes deterioration of the polyalkylene oxide resin. Also, it was found that the discharge amount increases as the heating temperature of the platen increases at the same pump speed. The polyalkylene oxide resin obtained in this way is used for a polyalkylene oxide resin material.

(B) Examples concerning Transferring Step or Storing Step (Step (h)) .

[Preparation for Polyalkylene Oxide Resin A]

Polymerization step and volatilizing off step were carried out in accordance with the same operations as those of

Example IA, with the use of a monomer mixture including (i) ethyleneoxide by 99 mol% and (ii) butyleneoxide by 1 mol% .

As a result, a polyalkylene oxide resin A was obtained. The resin A had a solvent concentration of 1 % by mass. The polyalkylene oxide resin A had a mass-average molecular weight (Mw) of 50 ,000, which was found in accordance with the above method.

[Preparation for Polyalkylene Oxide Resin B] Polymerization step and volatilizing off step were carried out in the same manner as those for obtaining the

polyalkylene oxide resin A, except that a monomer mixture including (i) ethyleneoxide by 96 mol%, (ii) butyleneoxide by 2 mol%, and (iii) arylglycidyl ether by 2 mol% was used. As a result, polyalkylene oxide resin B was obtained. The resin B had a solvent concentration of 0.4 % by mass. The polyalkylene oxide resin B had a mass-average molecular weight (Mw) of 80,000, which was found in accordance with the above method.

[Preparation for Polyalkylene Oxide Resin C] Polymerization step and volatilizing off step were carried out in the same manner as those for obtaining the polyalkylene oxide resin A, except that a monomer mixture including (i) ethyleneoxide by 95 mol%, (ii) butyleneoxide by 4 mol%, and (iii) arylglycidyl ether by 1 mol% was used. As a result, a polyalkylene oxide resin C was obtained. The resin C had a solvent concentration of 0.5 % by mass. The polyalkylene oxide resin C had a mass-average molecular weight (Mw) of 100,000, which was found in accordance with the above method. [Preparation for Polyalkylene Oxide Resin D]

Polymerization step and volatilizing off step were carried out in the same manner as those for obtaining the polyalkylene oxide resin A, except that a monomer mixture including (i) ethyleneoxide by 92 mol%, (ii) butyleneoxide by 6 mol%, and (iii) arylglycidyl ether by 2 mol% was used. As a

result, a polyalkylene oxide resin D was obtained. The resin D had a solvent concentration of 0.4 % by mass. The polyalkylene oxide resin D had a mass-average molecular weight (Mw) of 1 10,000, which was found in accordance with the above method.

[Preparation for Polyalkylene Oxide Resin E]

Polymerization step and volatilizing off step were carried out in the same manner as those for obtaining the polyalkylene oxide resin A, except that a monomer mixture including (i) ethyleneoxide by 94 mol% and (ii) butyleneoxide by 6 mol% was used. As a result, a polyalkylene oxide resin E was obtained. The resin E had a solvent concentration of

0.4 % by mass. The polyalkylene oxide resin E had a mass-average molecular weight (Mw) of 120,000, which was found in accordance with the above method.

[Preparation for Polyalkylene Oxide Resin F]

Polymerization step and volatilizing off step were carried out in the same manner as those for obtaining the polyalkylene oxide resin A, except that a monomer mixture including (i) ethyleneoxide by 90 mol% and (ii) butyleneoxide by 10 mol% was used. As a result, a polyalkylene oxide resin

F was obtained. The resin F had a solvent concentration of

1 % by mass. The polyalkylene oxide resin F had a mass-average molecular weight (Mw) of 150, 000 , which was found in accordance with the above method.

[Example I B]

Method described in Examples IB through 12B and Comparative Examples I B and 2B (hereinafter, also simply- referred to as "Examples I B through 12B and Comparative Examples I B and 2B") were carried out with the use of an open head drum shown in Fig. 8 or the like.

Fig. 8 is a perspective view schematically illustrating an open head drum 402 used in all the Examples and all the Comparative Examples of "(B) Examples concerning Transferring Step or Storing Step (Step (h))" . The open head drum 402 had a main body 404, a bottom board 406, and a lid 408. The main body 404 had a cylindrical shape, and had a lower opening, which was sealed with the bottom board 406. The main body 404 and the bottom board 406 were seamed with a well-known seaming structure and sealed with a sealing agent applied on an inner side of the seaming structure . The main body 404 had an upper opening, which was sealed with the lid 408. Provided between an edge portion of the opening section of the main body 404 and the lid 408 was a gasket (not shown) . The main body 404 and the lid 408 were bound by a band 410, which was a bolting-type band.

The lid 408 has a first opening section 412 and a second opening section 414. Although not shown in Fig. 8, the first opening section 412 and the second opening section 414 had internal threads on their internal circumferences, respectively.

The first opening section 412 and the second opening section 414 had a structure to which the plugs would be connected thereto, respectively. Each of the plugs was in the form of a bolt. In the present example, pipes were connected thereto instead of such plugs. Fig. 9 is a side view schematically illustrating the open head drum 402 to which the pipes were connected. Specifically, a first pipe 416 was connected to the first opening section 412 , and a second pipe 418 was connected to the second opening section 414. The pipes 416 and 418 include screwing sections, and were hermetically connected to the opening sections 412 and 414, respectively. For simplicity, each of the first pipe 4 16, the second pipe 418 , and the like is drawn with one line in Fig. 9.

The first pipe 416 was provided with a pressure gauge 420 and a valve 422. The pressure gauge 420 was provided between the valve 422 and the open head drum 402. On the other hand, the second pipe 418 is provided with a valve 424. With the use of such an open head drum 420, each of experiments according to Examples was carried out. Firstly, the polyalkylene oxide resin A was prepared as described above . 180 kg of the polyalkylene oxide resin A were so heated to a temperature of 120 ⁰ C as to be melted. Then, the polyalkylene oxide resin A thus melted were added into the open head drum. For the adding, the lid 408 was not installed in the open head drum. The open head drum had a

capacity of 200 L. The adding was carried out under a nitrogen atmosphere having a dew point of -60 ⁰ C . The adding was carried out carefully such that no air and no water came into the open head drum. The polyalkylene oxide resin A thus added had a water content of 45 ppm.

After finishing the adding of the polyalkylene oxide resin A, the lid 408 having the aforementioned first pipe 416 and the aforementioned second pipe 418 was installed in the open head drum 402, thereby sealing the upper opening of the open head drum 402. Next, the band 410 was set and a bolt thereof was screwed. Next, a cooling step was carried out. Specifically, with the valves 422 and 424 opened, nitrogen, which had a dew point of -60 ⁰ C, was supplied from the second pipe 418 to a space of the open head drum 402 at a supply speed of 10 L / min. Nitrogen kept being supplied at a supply speed of 10 L/ min until the upper surface of the polyalkylene oxide resin A had a surface temperature of 50 ⁰ C or less. Specifically speaking, it took approximately 3 days for the upper surface of the polyalkylene oxide resin A to have a surface temperature of 50 ⁰ C or less.

Next, the valves 422 and 424 were closed. Then, a gas to be supplied to the second pipe 418 was changed from nitrogen to air. The air had a dew point of -30 ⁰ C, and was supplied from the second pipe 418 to the space of the open head drum 402. This air was the aforementioned introducing gas. The air

supply was carried out for 1 hour at a supply speed of 10 L/ minute. Next, pressure of air to be supplied was adjusted such that pressure in the space was 0.2 (kg/ cm ² G) . Then, the valves 422 and 424 were closed. Next, soapsuds were put on respective connecting portions with the first opening section 412 , the second opening section 414, and the like for the sake of confirming that no gas was leaked from the space of the open head drum 402. In cases where it was confirmed that the gas was leaked, the bolt was further screwed until the gas was not leaked. Next, by operating the valves 422 and 424, the internal pressure (i.e . , pressure in the space) of the open head drum 402 was so adjusted as to be 0. 15 (kg/ cm ² G) . The pressure of 0. 15 (kg/ cm ² G) was the pressure in the space upon starting the experiment. The surface of the resin added into the open head drum

402 was exposed to the space, so that water substantially equally moves between the surface of the resin and the space upon the start of the experiment. In accordance with (i) the dew point of the introducing gas and (ii) the water content (45 ppm) that the resin had upon the introduction into the open head drum 402 , it is considered that the surface of the resin had a water content of 120 ppm upon the start of the experiment. The value, 120 ppm agreed well with actual measurements. The value is described in Table 2 below as the water content that the surface of the resin had upon the start

of the experiment.

Four such open head drums 402 were prepared, and were preserved under an atmosphere in which temperature was 20 °C and in which relative humidity was 35 RH%. The four open head drums 402 were separately measured at different timings in (i) the pressure in the space and (ii) the water content of the surface of the resin therein. The different timings were (a) upon the start of the experiment, (b) 1 month later, (c) 3 months later, and (d) 6 month later. The measuring was carried out with respect to the surface of a resin sampled from the resin after opening the lid 408. The sampling was carried out quickly. See Table 2 for a result of the measurement.

Note that: [kg/ cm ² G] indicates gauge pressure, and the gauge pressure is a value obtained by subtracting atmospheric pressure (kg/ cm ² ) from absolute pressure (kg/ cm2) .

[Example 2B]

The experiment was carried out in the same manner as that of Example I B, except that the pressure in the space was 0 (kg/ Cm ² G) upon starting the experiment. See Table 2 for a measurement result.

[Example 3B]

The experiment was carried out in the same manner as that of Example I B, except that the polyalkylene oxide resin B

was used instead of the polyalkylene oxide resin A. See Table 2 for a measurement result.

[Example 4B]

The experiment was carried out in the same manner as that of Example 2B, except that the polyalkylene oxide resin B was used instead of the polyalkylene oxide resin A. See Table 2 for a measurement result.

[Example 5B]

The experiment was carried out in the same manner as that of Example I B, except that the polyalkylene oxide resin C was used instead of the polyalkylene oxide resin A, and that air having a dew point of -60 ⁰ C was used as the introducing gas. See Table 2 for a measurement result.

[Example 6B] The experiment was carried out in the same manner as that of Example 2B , except that the polyalkylene oxide resin C was used instead of the polyalkylene oxide resin A, and that air having a dew point of -60°C was used as the introducing gas. See Table 2 for a measurement result. [Example 7B]

The experiment was carried out in the same manner as that of Example I B, except that the polyalkylene oxide resin

D was used instead of the polyalkylene oxide resin A, and that air having a dew point of -60 ⁰ C was used as the introducing gas. See Table 2 for a measurement result.

[Example 8B]

The experiment was carried out in the same manner as that of Example 2B, except that the polyalkylene oxide resin

D was used instead of the polyalkylene oxide resin A, and that air having a dew point of -60 ⁰ C was used as the introduced gas. See Table 2 for a measurement result.

[Example 9B]

The experiment was carried out in the same manner as that of Example I B, except that the polyalkylene oxide resin E was used instead of the polyalkylene oxide resin A, and that air having a dew point of -60 ⁰ C was used as the introducing gas. See Table 2 for a measurement result.

[Example 10B]

The experiment was carried out in the same manner as that of Example 2B, except that the polyalkylene oxide resin E was used instead of the polyalkylene oxide resin A, and that air having a dew point of -60 ⁰ C was used as the introducing gas. See Table 2 for a measurement result.

[Example 1 1B] The experiment was carried out in the same manner as that of Example I B, except that the polyalkylene oxide resin F was used instead of the polyalkylene oxide resin A, and that air having a dew point of -60 ⁰ C was used as the introducing gas. See Table 2 for a measurement result. [Example 12B]

The experiment was carried out in the same manner as that of Example 2B, except that the polyalkylene oxide resin F was used instead of the polyalkylene oxide resin A, and that air having a dew point of -60°C was used as the introducing gas. See Table 2 for a measurement result.

[Comparative Example I B]

The experiment was carried out in the same manner as that of Example I B, except that the polyalkylene oxide resin B was used instead of the polyalkylene oxide resin A, and that air having a dew point of - 1 1 °C was used as the introducing gas. See Table 3 for a measurement result.

[Comparative Example 2B]

The polyalkylene oxide resin F was prepared as described above . 180 kg of the polyalkylene oxide resin F was so heated to a temperature of 120 ⁰ C as to be melted. Then, the polyalkylene oxide resin A thus melted were added into the open head drum. For the adding, the lid 408 was not installed in the open head drum. The open head drum had a capacity of 200 L. The adding was carried out under a nitrogen atmosphere having a dew point of -60 ⁰ C . The adding was carried out carefully such that no air and no water came into the open head drum. The polyalkylene oxide resin F thus added had a water content of 45 ppm.

After finishing the adding of the polyalkylene oxide resin F, the lid 408 having the aforementioned first pipe 416 and

the aforementioned second pipe 418 was installed in the open head drum 402, thereby sealing the upper opening of the open head drum 402. Next, the band 410 was set and a bolt thereof was screwed. Next, a cooling step was carried out. Specifically, with the valves 422 and 424 opened, nitrogen, which had a dew point of -60 ⁰ C, was supplied from the second pipe 418 to the space of the open head drum 402 at a supply speed of 10 L / min. Nitrogen kept being supplied at a supply speed of 10 L/min until the upper surface of the polyalkylene oxide resin F had a surface temperature of 50 ⁰ C or less. Specifically speaking, it took approximately 3 days for the upper surface of the polyalkylene oxide resin A to have a surface temperature of 50 ⁰ C or less.

Next, the lid 408 was detached. Four such open head drums 402 were prepared, and were preserved under an atmosphere in which temperature was 20 ⁰ C and in which relative humidity was 35 RH%. In other words, the open head drums 402 were preserved with the respective lids 408 detached. The four open head drums 402 were separately measured at different timings in (i) the pressure in the space and (ii) the water content of the surface of the resin therein. The different timings were (a) upon the start of the experiment, (b) 1 month later, (c) 3 months later, and (d) 6 month later. The measuring was carried out with respect to the surface of resin sampled from the resin. The sampling was

carried out quickly. See Table 3 for a result of the measurement.

ND ND 1—» cπ Cπ O cπ O

Table 2 : Specification and evaluation results of Examples

CO

Abbreviation: Type stands for Resin type. IGD P strands for Introducing Gas Dew Point. P stands for pressure. WC stands for Water Content. (S) stands for start of Experiment. M stands for month(s) later. Ex. stands for Example .

to to Cπ

O Oi

Table 3

Abbreviation: Type stands for Resin type. I GDP strands for Introducing Gas Dew Point. P stands for pressure. WC stands for Water Content. (S) stands for start of Experiment. M stands for month(s) later. Ex. stands for Example.

According to Tables 2 and 3, it was confirmed that the polyalkylene oxide resin of each of Examples can be preserved and transported while keeping a very small water content therein, as compared with those of Comparative Examples. From such results, it was proved that the present invention is advantageous.

(C) Examples concerning Introducing Step (Step (d)) [Preparation for Polyalkylene Oxide Resin G] Polymerization step and volatilizing off step were carried out in the same manner as those of Example IA, except that a monomer mixture including (i) ethyleneoxide by 94 mol% and (ii) butyleneoxide by 6 mol% was used. As a result, a polyalkylene oxide resin G was obtained. The resin G had a solvent concentration of 0.45 % by mass. The polyalkylene oxide resin G had a mass-average molecular weight (Mw) of 123, 000, which was found in accordance with the aforementioned method. The polyalkylene oxide resin G had a molecular weight distribution (Mw / Mn) of 1 .40. The polyalkylene oxide resin G had a melting point mp of 47.2 ⁰ C , which was measured in accordance with the aforementioned method. The polyalkylene oxide resin G had a water content of 90 ppm, which was measured in accordance with the aforementioned method. Note that a slight amount of an antioxidant (product name "Yoshinox BB" , provided by Yoshitomi Fine Chemicals, Ltd.) was added to the polyalkylene

oxide resin G. Specifically, the polyalkylene oxide resin G contained the antioxidant at 4,830 ppm.

[Preparation for Polyalkylene Oxide Resin H]

Polymerization step and volatilizing off step were carried out in the same manner as those for obtaining the polyalkylene oxide resin G, except that a monomer mixture including (i) ethyleneoxide by 95 mol%, (ii) butyleneoxide by 4 mol%, and (iii) arylglycidyl ether by 1 mol% was used. As a result, a polyalkylene oxide resin H was obtained. The resin H had a solvent concentration of 0. 18 % by mass. The polyalkylene oxide resin H had a mass-average molecular weight (Mw) of 105,000, which was found in accordance with the aforementioned method. The polyalkylene oxide resin H had a molecular weight distribution (Mw / Mn) of 1 .65. The polyalkylene oxide resin H had a melting point mp of 47.5 ⁰ C, which was measured in accordance with the aforementioned method. The polyalkylene oxide resin H had a water content of 85 ppm, which was measured in accordance with the aforementioned method. Note that a slight amount of an antioxidant (product name "Yoshinox BB", provided by Yoshitomi Fine Chemicals, Ltd.) was added to the polyalkylene oxide resin H. Specifically, the polyalkylene oxide resin H contained the antioxidant at 5, 1 10 ppm.

(C- I ) Examples concerning Adding Step (Step (e)) [Example 1 C]

The open head drum (hereinafter, abbreviated as "drum") shown in Fig. 1 was prepared and was installed in the adding apparatus shown in Fig. 2. Note that the introducing pipe provided in the adding apparatus was connected to an auxiliary tank (not shown) in which a polyalkylene oxide resin having been subj ected to the polymerization step. The auxiliary tank was provided with a heating apparatus, so that the polyalkylene oxide resin contained in the auxiliary tank could be heated so as to be melted. Provided between the introducing pipe and the auxiliary tank was a gear pump, by which melted polyalkylene oxide resin could be supplied to the adding apparatus . Next, the polyalkylene oxide resin G (hereinafter, referred to as "polymer G") was prepared as described above. The polymer G was added into the auxiliary tank, and was heated to 180 ⁰ C, with the result that the polymer G was melted. The temperature on this occasion was a temperature that the polymer had upon being added into the drum. Next, the inlet valve was opened such that an introducing gas was introduced into the airtight section of the adding apparatus. The introducing gas was nitrogen. No oxygen was contained in the introducing gas. Thus, the introducing gas has an oxygen concentration of 0 % by volume. The introducing gas had a dew point of -30 ⁰ C . Then, the outlet valve was opened for the sake of adjusting the introduction speed of the gas to be 10 L/ minute. After

confirming the oxygen concentration and the dew point in the first space, the gear pump was activated, with the result that the polymer G started to be added into the drum. When finishing adding 180.2 kg of the polymer G, the gear pump was stopped. In the experiment of Example 1 C, the gear pump was adjusted such that a period (adding period) of adding the polymer G was 2.6 hours, i.e . , such that it took 2.6 hours to finish adding 180.2 kg of the polymer G. Therefore, in this case, the polymer G was added at a adding speed of 70 kg/ h. Thereafter, the drum was detached from the adding apparatus, and a sample for evaluation was taken from the surface of the polymer G, which surface was exposed to the space. The water content, the mass-average molecular weight, the molecular weight distribution, and the oxygen inhibitor amount of the sample were measured in accordance with the aforementioned methods, respectively. Further, the sample was put into acetonitrile for the sake of evaluating whether or not the sample could be dissolved in acetonitrile. A result of this is shown in Table 4 below. [Examples 2C and 3C]

Each of experiments of Examples 2C and 3C was carried out in the same manner as that of Example 1 C, except that a adding period (adding rate) was set as shown in Table 4 below. Specifically, in Example 2C, the adding period was set at 5.7 hours, so that the polymer G was added at a adding speed of

35 kg/ h. In the meanwhile, in Example 3C, the adding period was set at 1 1 . 1 hours, so that the polymer G was added at a adding speed of 18 kg/ h. Evaluation results are shown in Table 4 below. [Example 4C]

An experiment of Example 4C was carried out in the same manner as that of Example 1 C, except that a adding period (adding rate) was set as shown in Table 4 below. Specifically, in Example 4C, the adding period was set at 3. 1 hours, so that the polymer G was added at a adding speed of 65 kg/ h. An evaluation result is shown in Table 4 below.

[Example 5C]

An experiment of Example 5C was carried out in the same manner as that of Example 1 C, except that the polyalkylene oxide resin H (hereinafter, referred to as

"polymer H") was used and that a adding period (adding rate) was set as shown in Table 4 below. Specifically, in Example

5C, the adding period was set at 2.6 hours, so that the polymer G was added at a adding speed of 70 kg/ h. An evaluation result is shown in Table 4 below.

[Comparative Example 1 C]

An experiment of Comparative Example 1 C was carried out in the same manner as that of Example 1 C, except that dry air was introduced as the introducing gas. The introducing gas has a dew point of -30 ⁰ C, and has an oxygen

concentration of 2 1 % by volume. An evaluation result is shown in Table 4 below.

[Reference Example 1 C]

An experiment of Reference Example 1 C was carried out in the same manner as that of Example 1 C, except that the resin had a temperature shown in Table 4 below. An evaluation result is shown in Table 4 below.

[Comparative Example 2C]

An experiment of Comparative Example 2C was carried out in the same manner as that of Example 1 C , except that the polymer H was used and that a gas shown in Table 4 was used as the introducing gas. An evaluation result is shown in

Table 4 below.

K- ⁾ Oi

O Ol

Table 4: Specifications and evaluation results of Examples and Comparative Examples ;

4

Ui

Abbreviation in Table 4 :

Ex. Stands for Example;

Com. Ex. stands for Comparative Example;

Ref. Ex. stands for Reference Example; mp stands for melting point;

IG stands for Introducing Gas;

IGDP stands for Introducing Gas's Dew Point;

IGOC stands for Introducing Gas's Oxygen Content;

Mw stands for Weight Average Molecular Weight; Mw/ Mn stands for Molecular Weight Distribution;

DA stands for Distribution for Acetontrile;

AA stands for Antioxidant Amount;

WC stands for Water Content;

AS stands for Adding Speed; AP stands for Adding Period;

N stands for Nitrogen;

D stands for Dry air;

A indicates "Dissolved in Acetonitrile" ; and

B indicates "Not completely Dissolved in Acetonitrile" .

As shown in Table 4, each of the polyalkylene oxide resins of Examples was unchanged due to the adding respectively carried out under the aforementioned conditions, in terms of the mass average molecular weight (Mw) , the molecular weight distribution (Mw / Mn) , and the

dissolubility for acetonitrile . Changes such as decomposition and crosslinking were not found in the polyalkylene oxide resins respectively added under the conditions of Examples. Such evaluation results proved that the present invention is advantageous. Further, the antioxidant amount tends to decrease as the adding speed becomes slower (the adding period becomes longer) . This indicates that the antioxidant was so oxidized as to restrain each of the polyalkylene oxide resins from being changed. It was confirmed that the antioxidant amount was greater in Examples than in Comparative Example 1 C . For this reason, it is considered that the introducing method according to the present invention allows restraint of reduction of the antioxidant amount. Compare (i) Example 2C in which the adding speed was 35 kg/ h and the adding period was 5.7 hours, with (ii) Example 3C in which the adding speed was 18 kg/ h and the adding period was 1 1. 1 hours. The comparison showed that the antioxidant amount of the Example 3C is approximately 3 / 5 of that of Example 2C . Therefore, it is preferable that the adding speed be 20 kg/ h or faster. It is more preferable that the adding speed be 35 kg/ h or faster. Further, it is preferable that the adding period be 6 hours or shorter. It is more preferable that the adding period be 5 hours or shorter. Note that: in Reference Example 1 , the polymer G was not sufficiently dissolved, so that the experiment could not be

carried out. In Comparative Example 2C, the polymer H through the adding step was not dissolved in the solvent, so that the mass-average molecular weight, the molecular weight distribution, and the antioxidant amount thereof could not be measured.

(C-2) Examples concerning Cooling Step (Step(f)) [Example 6C]

An adding step was carried out under the same conditions as those of Example 1 C . Then, an introducing line and a discharging line were connected to the drum, with the result that the drum was in such a state as shown in Fig. 4. The introducing line was a line from which a cooling gas was introduced. The discharging line was a line from which the cooling gas was discharged. Then, the inlet valve was opened such that the cooling gas flew from the introducing line to the space. In this way, cooling was started. A temperature that the surface, exposed to the space, of the polyalkylene oxide resin had upon the start of the cooling step is a surface temperature (upon the start of the step) that the polyalkylene oxide resin had upon the start of the cooling step. In Example 6C, the polyalkylene oxide resin had a surface temperature (upon the start of the step) of 180 ⁰ C . Then, the outlet valve was opened such that the cooling gas circulated in the space, and it was adjusted that the cooling gas was introduced at a speed of 10 L/ minute. The cooling gas was nitrogen, and

contained no oxygen. Therefore, the cooling gas contained oxygen by 0 % by volume. The cooling gas had a dew point of -30 ⁰ C. As soon as the surface temperature of the resin reached 47°C, the inlet valve was closed, thus stopping the introduction of the cooling gas. In Example 6C, the moment at which the surface temperature reached 47°C was a moment at which the cooling step was completed. In Example 6C, it took 59 hours for the surface temperature (upon the completion of the step) of the resin to reach 47°C . Thereafter, a sample for evaluation was taken from the surface, exposed to the space, of the polyalkylene oxide resin. The water content, the mass-average molecular weight, the molecular weight distribution, and the antioxidant amount of the sample were measured in accordance with the aforementioned methods, respectively. Further, the sample was put into acetonitrile for the sake of evaluating whether or not the sample could be dissolved in acetonitrile. A result of this is shown in Table 5 below.

[Reference Example 2C] An experiment of Reference Example 2C was carried out in the same manner as that of Example 6C, except that the resin was set to have a surface temperature (upon the completion of the step) of 85°C. An evaluation result is shown in Table 5 below. [Reference Example 3C]

An experiment of Reference Example 3C was carried out in the same manner as that of Example 6C, except that the cooling gas was not circulated. The drum was hermetically sealed by seaming the lid of the drum and the main body thereof with a band. Upon the start of the experiment, the drum was so adjusted as to have an internal pressure of 15 kPa. After adjusting the internal pressure as such, the inlet valve and the outlet valve were closed. An evaluation result is shown in Table 5 below. [Reference Example 4C]

An experiment of Reference Example 4C was carried out in the same manner as that of Example 6C ₇ except that the cooling gas was dry air. An evaluation result is shown in Table 5 below. [Example 7C]

An experiment of Example 7C was carried out in the same manner as that of Example 6C, except that An adding step was carried out under the same conditions as those of the adding step of Example 2C. An evaluation result is shown in Table 5 below.

[Example 8C]

An experiment of Example 8C was carried out in the same manner as that of Example 6C, except that An adding step was carried out under the same conditions as those of the adding step of Example 3C. An evaluation result is shown

in Table 5 below.

[Comparative Example 3C]

An experiment of Comparative Example 3C was carried out in the same manner as that of Example 6C, except that: (i) the polyalkylene oxide resin H (polymer H) was used, and (ii) An adding step was carried out under the same conditions as those of the adding step of Example 5C, and (iii) the cooling gas was dry air. An evaluation result is shown in Table 5 below.

to to Ol en O Oi

Table 5 : Specifications and evaluation results of Examples of Comparative Examples ; (Constituted on the next page) 4

Oi

00

to to Oi Oi O Oi

Table 5 (continued from the previous page) ;

Ol

Abbreviation in Table 5 :

Ex. Stands for Example;

Com. Ex. stands for Comparative Example;

Ref. Ex. stands for Reference Example; mp stands for melting point;

T stands for temperature;

IG stands for Introducing Gas;

IGDP stands for Introducing Gas's Dew Point;

IGOC stands for Introducing Gas's Oxygen Content; AS stands for Adding Speed;

AP stands for Adding Period;

RS T (S) stands for Resin Surface Temperature at start of cooling step;

CG stands for Cooling Gas; CGDP stands for Cooling Gas's Dew Point;

CGOC stands for Cooling Gas's Oxygen Content;

CCG stands for Circulation of Cooling Gas;

CP stands for Cooling Period;

RS T (E) stands for Resin Surface Temperature at end of cooling step;

DD stands for Drum Deformation;

WC stands for Water Content;

Mw stands for Weight Average Molecular Weight;

Mw/ Mn stands for Molecular Weight Distribution; DA stands for Distribution for Acetontrile;

AA stands for Antioxidant Amount; N stands for Nitrogen; D stands for Dry air;

A indicates "Dissolved in Acetonitrile"; and B indicates "Not completely Dissolved in Acetonitrile" .

As shown in Table 5, in terms of the mass average molecular weight (Mw) , the molecular weight distribution (Mw / Mn) , and the dissolubility for acetonitrile, each of the polyalkylene oxide resins of Examples subjected to the cooling respectively carried out under the aforementioned conditions were kept unchanged compared with before being added. Changes such as decomposition and crosslinking were not found in the polyalkylene oxide resins respectively cooled under the conditions of Examples. Such evaluation results proved that the present invention is advantageous. Further, the antioxidant amount tends to decrease as the adding speed becomes slower (the adding period becomes longer) . This indicates that the antioxidant was so oxidized as to restrain each of the polyalkylene oxide resins from being changed. It was confirmed that the antioxidant amount was greater in Examples than in Comparative Example 4C . For this reason, it is considered that the introducing method according to the present invention allows restraint of reduction of the antioxidant amount.

(C-3) Examples concerning Introducing Gas and Cooling Gas

[Example 9C]

An experiment concerning an adding step was carried out in the same manner as those of the foregoing "(C- I )

Examples concerning Adding Step (Step (e))", and an experiment concerning a cooling step was carried out in the same manner as those of the foregoing "(C-2) Examples concerning Cooling Step (Step(f))" . In the present example, the polyalkylene oxide resin G prepared as above was used. The introducing gas was nitrogen, and contained no oxygen.

Therefore, the introducing gas contained oxygen by 0 % by volume. The introducing gas had a dew point of -30 ⁰ C. The cooling gas was nitrogen, and contained no oxygen. Therefore, the cooling gas contained oxygen by 0 % by volume. The cooling gas had a dew point of -30 ⁰ C . After the adding step, a sample for evaluation was taken from the surface, exposed to the space, of the polyalkylene oxide resin. Also, after the cooling step, a sample for the evaluation was taken therefrom. The water content, the mass-average molecular weight, the molecular weight distribution, and the antioxidant amount of each of the samples were measured in accordance with the aforementioned methods, respectively. Further, each of the samples was put into acetonitrile for the sake of evaluating whether or not the sample can be dissolved in acetonitrile. A

result of this is shown in Table 6 below. Note that Example 9C corresponds to the foregoing Example 6C . [Example 10C]

An experiment of Example 1 OC was carried out in the same manner as that of Example 9C, except that the introducing gas and the cooling gas respectively had dew points shown in Table 6. An evaluation result is shown in

Table 6.

[Example H C] An experiment of Example H C was carried out in the same manner as that of Example 9C, except that each of the introducing gas and the cooling gas was a mixture gas of oxygen and nitrogen. The mixture gas contained oxygen by 1 % by volume. The mixture gas had a dew point of -30°C . An evaluation result is shown in Table 6. [Reference Example 5C]

An experiment of Reference Example 5C was carried out in the same manner as that of Example 9C, except that the introducing gas had a dew point shown in Table 6. An evaluation result is shown in Table 6. [Reference Example 6C]

An experiment of Reference Example 6C was carried out in the same manner as that of Example 9C, except that the cooling gas had a dew point shown in Table 6. An evaluation result is shown in Table 6..

[Comparative Example 4C]

An experiment of Comparative Example 4C was carried out in the same manner as that of Example 9C, except that the introducing gas was dry air having a dew point of -30 ⁰ C. An evaluation result is shown in Table 6.

[Reference Example 7C]

An experiment of Reference Example 7C was carried out in the same manner as that of Example 9C, except that the cooling gas was dry air having a dew point of -30 ⁰ C. An evaluation result is shown in Table 6.

[Comparative Example 5C]

An experiment of Comparative Example 5C was carried out in the same manner as that of Example 9C, except that: the polyalkylene oxide resin H (polymer H) was used, and the introducing gas was dry air having a dew point of -30 ⁰ C . An evaluation result is shown in Table 6 below.

[Reference Example 8C]

An experiment of Reference Example 8C was carried out in the same manner as that of Example 9C, except that: polymer H was used, and the cooling gas was dry air having a dew point of -30 ⁰ C. An evaluation result is shown in Table 6 below.

ND Ol O Ol

;

Table 6 : Specifications and evaluation results of Examples and Comparative Examples (Continued on the Next page. )

to Oi

O ϋi

Table 6: Continued from the previous page .

Abbreviation in Table 6 :

Ex. Stands for Example;

Com. Ex. stands for Comparative Example;

Ref. Ex. stands for Reference Example; DP stands for Dew Point;

OC stands for Oxygen Content;

WC stands for Water Content;

Mw stands for Weight Average Molecular Weight;

Mw/ Mn stands for Molecular Weight Distribution; DA stands for Distribution for Acetontrile;

AA stands for Antioxidant Amount;

N stands for Nitrogen;

D stands for Dry air;

M stands for Mixture gas of oxygen by 1 % by vol. and nitrogen;

A indicates "Dissolved in Acetonitrile" ; and

B indicates "Not completely Dissolved in Acetonitrile" .

As shown in Table 6, each of the polyalkylene oxide resins used in the experiments of Examples had a water content of 1 , 000 ppm or less between the adding step and the cooling step. Each of the polyalkylene oxide resins of

Examples was unchanged when compared with before the adding respectively carried out under the aforementioned conditions, in terms of the mass average molecular weight

(Mw) , the molecular weight distribution (Mw / Mn) , and the dissolubility for acetonitrile. Changes such as decomposition and crosslinking were not found in the polyalkylene oxide resins of Examples. Such evaluation results proved that the present invention is advantageous . Further, the antioxidant amount tends to decrease between the adding step and the cooling step. This indicates that the antioxidant was so oxidized as to restrain each of the polyalkylene oxide resins from being changed. See (i) each of the antioxidant amounts of Examples 9C and 1 1 C, and Reference Example 7C, which were measured in the adding step; and (ii) each of the antioxidant amounts of Examples 9C and 1 1 C, and Comparative Example 4C, which were measured in the cooling step. In accordance with these antioxidant amounts, it is considered that the introducing method according to the present invention allows restraint of reduction of the antioxidant amount. Note that: each of the polyalkylene oxide resins of Comparative Examples 4C and 5C were changed in quality upon the completion of the adding step, so that no experiment concerning the cooling step was carried out. (D) Examples concerning Dissolving Step [Example I D]

A dissolving step was carried out with the use of the apparatus shown in Fig. 6, and a dissolving speed was checked. An intermediate tank 2 10, with a capacity of 1 OL,

containing 5 kg of a polyalkylene oxide resin was prepared. The polyalkylene oxide resin was a polymer, which contained ethylene oxide and butylene oxide at a molar ratio of 94 mol% and 6 mol%, and which had a mass-average molecular weight (Mw) of 122 ,000. The polymer had a melting point mp ( ⁰ C) of 47°C , and had an elongational viscosity of 6,400Pa' s. Explanation for the elongational viscosity is made above. In the dissolving tank 216, 4 kg of a solvent 222 was stored. To such a dissolving tank 2 16, the polyalkylene oxide resin was supplied. The solvent 222 was acetone. The supply (introduction) of the polyalkylene oxide resin was carried out while constantly keeping the solvent (acetone) refluxing. The liquid bath 232 was set to have a temperature of 63°C to 64°C . Although it is different from Fig. 6, the liquid bath 232 had a liquid level as high as that of the acetone . Pressure in the dissolving tank 2 16 was normal. The system temperature was maintained at 56.5 ⁰ C, which coincides with the boiling point of the acetone . Upon the supplying, the polyalkylene oxide resin had a temperature of 140 ⁰ C. The polymer (polyalkylene oxide resin) had a melting point mp ( ⁰ C) of 47°C, so that the system temperature was higher than the melting point mp ( ⁰ C) by 9.5°C. The temperature that the polyalkylene oxide resin had upon the supplying was higher than the melting point mp ( ⁰ C) by 93°C. The supply of the polyalkylene oxide resin was carried out while stirring, the solvent 222 (solution 224) at

power requirement of impeller (PV) of 0.2 (kW/ m ³ ) . The stirring impeller 226 was a max blending impeller, and two baffles 230 were provided. The stirring impeller 226 stirred at a revolution of 200 rpm. While stirring the solution, the polyalkylene oxide resin was continuously supplied for 4 hours and 18 min at a supply speed of 4.85 g/ min. As a result, approximately 1250 g of the polyalkylene oxide resin was supplied in total. The polyalkylene oxide resin was supplied by adding down the internal wall of the dissolving tank 2 16. Thereafter, no polyalkylene oxide resin was supplied, but the solution was further stirred for 42 min, with the result that the resin was completely dissolved in the solution. Because 1250 g of the resin was dissolved in 4000 g of the solvent as such, the final solution concentration was 24 (wt%) . Hereinafter, the stirring after the supply of the resin was also referred to as "aging" . Conditions after the supply of the resin were the same as those during the supply of the resin. Table 7 below shows specification and a result of Example I D . [Example 2D]

A producing method of Example 2D was the same as that of Example I D , except that the aging period, the dissolving period, the temperature that the resin had upon the supplying, the power requirement of impeller (PV) ₅ and the revolution of the stirring impeller were set as shown in Table 7. Also in

Example 2D, the resin was completely dissolved. Table 7 below shows specification and a result of Example 2D .

[Comparative Example I D]

A dissolving step of Comparative Example I D was carried out in the same manner as that of Example I D, except that: (i) no refluxing of the acetone was carried out, and (ii) the aging period, the dissolving period, the temperature that the resin had upon the supplying, the system temperature, and the temperature of the liquid bath were such as shown in Table 7. The introduced polyalkylene oxide resin was entangled with the stirring impeller, thereby slowing the dissolving speed extremely. Even after carrying out the dissolving for 480 min, the resin was not dissolved. Thus, the experiment was unsuccessful. Table 7 below shows specification and a result of Comparative Example I D .

[Comparative Example 2D]

The polyalkylene oxide resin was shaped in the form of a pellet and was set to have a temperature of 55°C, and 1250 g of such a polyalkylene oxide resin was introduced at a time. Then, a dissolving step of Comparative Example 2D was carried out in the same manner as that of Example I D, except that the supplying period, the aging period, the dissolving period, and the temperature that the resin had upon the supplying, the power requirement of impeller (PV) , and the revolution of the stirring, impeller were such as shown in

Table 7. As a result, even after carrying out the dissolving for 480 min, the resin was not dissolved. Thus, the experiment was unsuccessful. Table 7 below shows specification and a result of Comparative Example 2D .

to to cπ cπ O Ol

Table 7: Specification and evaluation results of Examples and Comparative Examples (Continued on the next page.)

Co

-

to Oi

O Cn

Table 7: Continued from the previous page. -

SI

According to Table 7, it was confirmed that the polyalkylene oxide resins of Examples are more dissoluble than those of Comparative Examples. Such a result proved that the present invention is advantageous. (E) Example concerning Liquid Transferring Step

[Preparation of polyalkylene oxide resin]

A polyalkylene oxide resin was prepared by performing the polymerization step and the volatilizing off step, in the same manner as in Example IA, except that the mixing ratio of the monomer mixture was such that ethylene oxide was

94mol% and butylene oxide was 6mol%. The resin had a solvent concentration of 0.45% by mass. A mass average molecular weight (Mw) of the polyalkylene oxide resin, measured in the method described above, was 123 ,000. A molecular weight distribution (Mw/ Mn) of the polyalkylene oxide resin was 1.40. The melting point of the polyalkylene oxide resin was measured in the method described above, and found to be 47.2°C. The water content of the polyalkylene oxide resin was measured in the method described above, and found to be 90ppm.

[Example I E]

A liquid means whose basic structure is illustrated in

FIG. 7 was operated under operation conditions as shown in

Table 8. A polyalkylene oxide resin contained in a solid state in the open head drum was removed from the open head drum

by using a melter, and introduced into a melting tank via a first inlet. The melting tank was heated with a heating member such that a temperature (temperature T l) of the melting tank was 100 ⁰ C (target value) . The temperature T l was monitored from the start to the end of the liquid transferring step. Before the introduction of the polyalkylene oxide resin into the melting tank, nitrogen (inert gas) was circulated in the melting tank by opening the second inlet valve and second outlet valve . The gas had an oxygen concentration of 0 % by volume. The gas had a dew point of

-30 ⁰ C . After the introduction of the polyalkylene oxide resin into the melting tank, how much the second inlet valve and the second outlet valve were opened or closed was adjusted to adjust the internal pressure of the melting tank to 20.6MPa (target value) . The pressure P was monitored from the start to the end of the liquid transferring step. Next, the pump was started to operate upon opening of the first outlet. The polyalkylene oxide resin was supplied to a twin screw extruder serving as a mixing apparatus . The pump operated with shaft revolution speed (revolution R) of 4.9 rpm (target value) . The revolution R was monitored from the start to end of the liquid transferring step. A temperature (temperature T2) of the first liquid transferring line was adjusted to 100 ⁰ C (target value) by a first band heater. A temperature (temperature T3) of the pump was adjusted to 150 ⁰ C (target

value) by a second band heater. A temperature (temperature T4) of a second liquid transferring line was adjusted to 150% (target value) by a third band heater. The temperatures T2 , T3 , and T4 were also monitored from the start to end of the liquid transferring step. The pump used in Example I E was a gear pump (provided by Leistritz Corporation) [Type A] . In Table 8 , this pump is denoted as "type A" . After the adjustment of the pressure P, temperature Tl , revolution R, temperature T2 , temperature T3 , and temperature T4 was completed, the pumping out amount of the polyalkylene oxide resin pumped out of that end of the second liquid transferring line which was to be connected with the extruder (i.e. , mass of the polyalkylene oxide resin pumped out from the pump per unit of time) was measured in the method described above . In Example I E, the pumping-out amount had an average A of

25.58g/ 30 sec and a fluctuation of 5.63% . After the pumping-out amount was confirmed, the polyalkylene oxide resin was supplied to the twin screw extruder from the liquid transferring means. By the twin screw extruder, the polyalkylene oxide resin was mixed with an additive and fabricated into a sheet (thickness = 0.02mm, width = 160mm) . The fabrication of the sheet was carried out with shaping speed of 15.3 m/min. The additive was silica as a filler (supplied from Nippon Aerogil Co . Ltd. ; product name "R972") . The silica of 1.96 parts by mass was mixed with the

polyalkylene oxide resin of 100 parts by mass. Product thus fabricated was sampled ten times in 10 min intervals after the start of the sheet fabrication by using the twin screw extruder and the liquid transferring means. The product samples thus obtained were measured in thickness, width, and filler content (silica content) . For the thickness and width, maximums and minimums thereof were found. For the filler content, an average among 10 data. Thereby, quality stability of the product was checked (evaluation 1 ) . The filler content was measured by the following method. Firstly, a piece of approximately 5g to 15g was collected from the product sample, and weighed accurately. The piece was used as analysis samples. The analysis sample was put in a holder for powder analysis . Under helium atmosphere, a quantitative analysis for silica was conducted on the analysis sample using a fluorescent X ray analyzer (PW-2404, made by Philips Electronics N. V.) . On assumption that the silica in the filler constituted silica dioxide, the filler content in the sample was worked out from the result of the quantitative analysis for silica. Using the samples whose pumping-out amounts were measured, the mass average molecular weight (Mw) , molecular weight distribution (Mw/ Mn) and water content were measured in the methods described above (evaluation 2) . The results of the measurements are shown in Table 8. [Comparative Example I E and Examples 2E and 3E]

The experiments were conducted in the same manner as in Example I E, except that the pressure P, revolution R, temperature T3, temperature T4 were varied and the pumping was carried out with the fluctuations shown in Table 8. The results of the experiments are shown in Table 8. In

Comparative Experiment I E, the fluctuation was 9.70% . In Example 2E, the fluctuation was 5.91%. In Example 3E, the fluctuation was 2.83%. In Comparative Example I E, sheet fabrication speed was 15.3 m/ min. In Example 2E, sheet fabrication speed was 49.4 m/ min. In Example 3E, sheet fabrication speed was 43.3 m/ min.

[Examples 4E, 5E and 6E]

The experiments were conducted in the same manner as in Example 1 E, except that different a pump was used, the pressure P, revolution R, temperature T3, temperature T4 were varied and the pumping was carried out with the fluctuations shown in Tables 8 and 9. The pump used here was a gear pump ("GPU- 156, CDS- 18-3" (Technovel Corporation)) [type B] . In Tables 8 and 9 , the pump was denoted as type B . Results of experiments here are shown in

Tables 8 and 9. In Experiment 4E, the fluctuation was 5.51 %. In Example 5E, the fluctuation was 5.84% . In Example 6E, the fluctuation was 5.67%.

[Comparative Example 2E] In replacement of the liquid transferring means, a

supplying system including a hoper and feeder was used to supply a polyalkylene oxide resin in a pellet state to the twin screw extruder. The feeder was a weight-based single screw feeder (K2GL (K-Tron) . ; screw type = screw 9AC) , provided with a digital mass detector. The feeder was configured to detect a supply amount by using the mass detector, and control revolution of its screw in accordance with the mass thus detected. The feeder was set to a supply amount of 9.0kg/ h. [Comparative Example 3E]

An experiment was conducted in the same manner as in Comparative Example 2E, except that a polyalkylene oxide resin in power form was supplied to the twin screw extruder.

to Oi

Cn O Oi

Table 8: Specification and evaluation results of Examples and Comparative Examples ; (continued on the next page) 4

oo

to to Oi ϋi o Oi

Table 8: continued from the previous page.

00 IO

1) Unit used in each of Examples I E, 2E , and 3E is g/ 30sec. Unit used in each of Examples 4E

to to Oi cπ O Cn

Table 9 : Specification and evaluation results of Examples and Comparative Examples (continued on the next page)

00 CO

-

to Oi

Oi O en

Table 9: continued from the previous page.

oo

1) 1) Unit used in Comparative Example IE is g/ 30sec. Unit used in Examples 6E is g/min. and 5E is g/min.

Abbreviation in Tables 8 & 9 : Ex. Stands for Example;

Com. Ex. stands for Comparative Example; Mw stands for Weight Average Molecular Weight; and Mw/ Mn stands for Molecular Weight Distribution.

As shown in Tables 8 and 9 , the products fabricated by- using the twin screw extruder in the manners described in Examples had qualities maintained at a certain level, and the filler added in the products were dispersed evenly with constant composition. From these results, it was proved that the present invention is advantageous. In Comparative Example 2E, clogging occurred in the supplying system in one hour after the start of the supply because the polyalkylene oxide resin in the pellet state clogged between the screw of the feeder and the housing thereof and melted therebetween due to the abrasion with the screw. This stopped the supply of the polyalkylene oxide resin, thereby ceasing the experiment. In Comparative Example 3E, the polyalkylene oxide resin in the powder form stuck on the inner wall of the hopper in 3 hours from the start of the supply. This caused large fluctuation in the pumping-out amount. Therefore, the experiment was ceased.

INDUSTRIAL APPLICABILITY

As described above, a producing method according to the present invention is suitable as a method for producing a material made of a polyalkylene oxide resin.