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Title:
COATED FINE PARTICLE AND THEIR MANUFACTURING METHOD, AND CONDUCTIVE FINE PARTICLE
Document Type and Number:
WIPO Patent Application WO/2006/101263
Kind Code:
A1
Abstract:
The present invention provides a coated fine particle that is flexible and excellent in elasticity and has good adhesion to metals, a manufacturing method thereof, and conductive fine particle having the polymer coated fine particle as a core fine particle. The coated fine particle comprises a core fine particle containing an organic material or an organic and inorganic composite material and a polymer coated layer on a surface of the core fine particle formed by ring-opening reaction and/or polycondensation reaction on the surface of the core fine particle.

Inventors:
YAMASHITA TSUYOSHI (JP)
KUSHINO MITSUO (JP)
KUROSAWA MAMIKO (JP)
Application Number:
PCT/JP2006/306597
Publication Date:
September 28, 2006
Filing Date:
March 23, 2006
Export Citation:
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Assignee:
NIPPON CATALYTIC CHEM IND (JP)
YAMASHITA TSUYOSHI (JP)
KUSHINO MITSUO (JP)
KUROSAWA MAMIKO (JP)
International Classes:
C08G12/06; C08J3/12; C08J7/04
Foreign References:
JP2004075996A2004-03-11
JPS6391130A1988-04-21
JPS6190731A1986-05-08
Attorney, Agent or Firm:
Ueki, Kyuichi (1-16 Dojima 2-chome, Kita-ku, Osaka-sh, Osaka 03, JP)
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Claims:
CLAIMS
1. A coated fine particle comprising, a core fine particle containing an organic material or an organic and inorganic composite material, and a polymer coated layer on a surface of the core fine particle formed by ringopening reaction and/or polycondensation reaction on the surface of the core fine particle.
2. The coated fine particle according to claim 1, wherein an average particle diameter is 1.0 to 100 μm and a coefficient of variation of the particle diameter (Cv value) is 10% or less.
3. The coated fine particle according to claim 1 or 2, wherein said polymer coated layer contains a polymer having at least one kind of organic group selected from the group consisting of an amino group, an imino group, a carboxyl group, a hydroxyl group, an epoxy group, a sulfonic acid group, an aldehyde group and a phosphate group.
4. A method of manufacturing a coated fine particle having a polymer coated layer on a surface of the core particle containing an organic material or an organic and inorganic composite material, wherein said polymer coated layer is formed by a ringopening reaction and/or polycondensation reaction in a waterbased medium in which said core particle is dispersed, and in the presence of a surfactant.
5. The method of manufacturing coated fine particle according to claim 4, wherein said surfactant has a structure shown by the following general formula, R1 (CH2CH2O) nXmR2 wherein, R1 indicates an aliphatic or aromatic hydrophobic group of 5 to 25 in carbon number, R2 indicates a polymer chain having a polyamine structure or a polycarboxylic acid structure of 300 to 10,000 in weight average molecular weight, n indicates an integer of 3 to 85, X indicates a group that is derived from a group being possible to react with at least one kind of group selected from the group consists of an amino group, an imino group and a carboxyl group and is formed after said reaction, and m indicates 1 or 0.
6. The method of manufacturing coated fine particle according to claim 4 or 5, wherein said polymer coated layer has a structure that is obtained by the polycondensation reaction of at least one kind selected from the group consists' of urea, thiourea, melamine, benzoguanamine, acetoguanamine and cyclohexylguanamine with formaldehyde.
7. A conductive fine particle comprising a coated fine particle according to any of claims 1 to 3, and a conductor layer on a surface of the coated fine particle.
Description:
DESCRIPTION

COATED FINE PARTICLE AND THEIR MANUFACTURING METHOD, AND CONDUCTIVE FINE PARTICLE

TECHNICAL FIELD

The present invention relates to a coated fine particle that have good adhesion to metals and the manufacturing method, and to a conductive fine particle using the coated fine particle.

Background Art

Polymer particles are widely used in displays such as crystal displays, spacers for cell gaps (or panel gaps) such as touch panels, conductive adhesives for mounting microelements, and conductive gap fillers such as anisotropic conductive adhesives. In these applications, it is required to have nearly uniform particle shapes and to be flexible and excellent in elasticity. From such point of view, organic materials and organic and inorganic composite materials in which organic components and inorganic components are used together have been used as materials for the polymer particles.

For example, in Japanese Examined Patent Publication No. H7-1.7723, organic resin particles

consisting of amino resins (for example, urea resin, melamine resin, and guanamine -t ype resin) are disclosed. Because these amino resin fine particles have a number of functional groups on the surface of the fine particle, they have good adhesive to metals to be easy to form metal coated layer. Consequently, they are widely used as base material particles.

On the other hand, in Japanese Patent Laid-Open Publication No. 2003-183337, organic and inorganic composite fine particles containing organic polymer skeletal structure and polysiloxane skeletal structure are disclosed. According to the technique, it is described that fine particles having the desired properties can be obtained by controlling the kinds and amounts of constituent materials of the fine particles.

DISCLOSURE OF THE INVENTION

However, because the above-mentioned amino resin fine particles have minute crosslinked structure, the particles are too hard to be compres s ively deformed, for example, when being used between electrodes as conductive fine particles, they could not broaden the contact area with the surfaces of the electrodes and the contact resistance was

difficult to be reduced. Moreover, there was such a problem that when the compressive deformation volume is enlarged to broaden the contact area, the particles break down at which time the strain of particles becomes large and are, as a result, inferior for connecting reliability. On the other hand, there was such a problem that because the above-mentioned organic and inorganic composite fine particles have flexibility but are inferior to the above-mentioned amino resin fine particles for adhesion to metals, metal coated layers prepared on the surfaces of the organic and inorganic composite fine particles can not follow the deformation of the fine particles and peel off. Further, in Japanese Patent Laid-Open publication No. 2001-126532, the technique of improving plate adhesion to silicone fine particles has been disclosed to solve these problems. However, problems such as melting and aggregation of silicone resin in etching process that are carried out before plating process had not been settled completely and there was further room for improvement.

The present invention has been made in consideration of the above-mentioned circumstances, and the aims are to provide a coated fine particle that is excellent in. flexibility and have good

adhesion to metals and the manufacturing method, and to provide a conductive fine particle having the coated fine particle as the core fine particle.

The coated fine particle of the present invention that could settle the above-mentioned problems have the essential points that the coated fine particle comprises a core fine particle containing an organic material or an organic and inorganic composite material, and a polymer coated layer on a surface of the core fine particle, wherein the polymer coated layer is formed by ring-opening reaction and/or polycondens at ion reaction on the surface of the core fine particle.

The present inventors have advanced the study of obtaining such fine particle that are excellent in flexibility and elasticity and have good adhesion to metals, and have repeated the process of trial and error based on their idea that getting the above-mentioned properties from different materials, respectively, and integrating them may lead to the effect of satisfying the settlement of the problems. Of course, the above-mentioned properties cannot be sufficiently revealed by merely integrating such materials. The essential point of the present invention is that the composition is made so as to

get the flexibility and elasticity of the fine particle from the core fine particle constituting the center parts of the fine particle and to get the adhesion to metals from polymer coated layer coating the core particle and further this polymer coated layer is formed by ring-opening and/or polycondensation reaction. That is, because uniform polymer coated layer exist on the core fine particle, it became possible to obtain the coated fine particle that have, of course, flexibility and elasticity and are excellent in adhesion to metals.

A method of manufacturing a coated fine particle of the present invention is manufacturing a coated fine particle having a polymer coated layer on a surface of the core particle containing an organic material or an organic and inorganic composite material, wherein said polymer coated layer is formed by a ring-opening reaction and/or polycondensation reaction in a water-based medium in which said core particle is dispersed, and in the presence of a surfactant .

BRIEF DESCRIPTION OF DRAWINGS

Fig. 1 is a schematic cro s s -sect ional diagram of a coated fine particle of the present invention.

Fig. 2 is a schematic cros s - s ect ional diagram of a conductive fine particle of the present invention .

Fig. 3 is an electron microscopic (SEM: scanning electron microscope) picture showing a core fine particle before the formation of a polymer coated layer (Synthesis example (3) ) .

Fig. 4 is an electron microscopic (SEM) picture showing a core fine particle after the formation of a polymer coated layer (Manufacturing example 1) . (Explanation of Numerals)

1: Core fine particle

2: Polymer coated layer

3: Conductive layer

BEST MODE FOR CARRYING OUT THE INVENTION

The coated fine particle of the present invention is characterized in that it has polymer coated layer formed by ring-opening reaction and/or polycondensation reaction on the surface of the core fine particle comprising an organic material or an organic and inorganic composite material.

As described above, the points of the present invention are that not only physical properties to be reguired for the core fine particle (for example,

flexibility and elasticity) are provided, but polymer coated layer, which is excellent in adhesion to metals, are uniformly formed on the surfaces of the core fine particle. Accordingly, first, the above-mentioned polymer coated layer will be described.

The polymer coated layer included in the present invention give good adhesion to metals to the coated fine particle of the present invention and are formed on the surface of the core fine particle through the ring-opening reaction and/or polycondensation reaction of a compound, which is a raw material of the above-mentioned polymer coated layer, in a water-based medium in which the above-mentioned core particles are dispersed, and in the presence of a surfactant (for example a compound shown by the general formula (1) as described later) .

As a raw material of the above-mentioned polymer coated layer, compounds (A) and compounds (B) (will be described later) can be cited. The above-mentioned compounds (A) are preferable to be those containing a m.ixture of at least one kind selected from th.e group consisting of urea, thio urea, melamine, benz oguanamine , acetoguanamine , and cyclohexylguanamine .(hereinafter referred to as the

"amino compounds") and of formaldehyde, or an initial condensation compound obtained by reacting at least one kind selected from these amino compounds with formaldehyde. Further, it is preferable to use an initial condensation compound as a compound (A) in terms of high affinity for water and the rapid formation of a polymer coated layer.

Here, a compound obtained from the reaction of the above-mentioned amino compounds with formaldehyde is what is called an amino resin (urea type resins, melamine type resins, and guanamine type resins) , and an initial condensation compound is a compound that is a precursor of an amino resin. That is, a polymer coated layer that essentially contains an amino resin structure is formed by the use of the above-mentioned compound (A) .

Moreover, the above-mentioned initial condensation compound is, in case of using (i) at least one kind of urea and thio urea (hereinafter referred to as the "urea type compounds") and formaldehyde, an initial condensation compound that can be a constituent in a urea resin, in case of using (ii) melamine and formaldehyde, an melamine resin, and in case of using (iii) at least one kind selected from the group consisting of benzoguanamine ,

acetoguanamine, and cyclohexylguanamine (hereinafter, compounds of guanamine series) and formaldehyde, an initial condensation compound that can be a constituent in guanamine resins. Moreover, in case of using (iv) a compound obtained by reacting two kinds or more of compounds among urea type compounds, melamine and guanamine type compounds with formaldehyde, the above-mentioned initial condensation compound is a compound that can be a constituent in a resin in which two kinds or more among urea type resins, melamine resin and guanamine type resins are mixed. Any one kind of these initial condensation compounds may be used, or two or more kinds may be used together as the above-mentioned initial condensation compound.

As suitable amino compounds when the above-mentioned initial condensation compound is synthesized, urea type compounds, melamine, co-condensates of a urea type compounds and melamine, and co-condensates of melamine and a guanamine type compounds are preferable, urea type compounds, melamine, and co-condensation compounds of a urea type compounds and melamine are more preferable, and melamine, and co-condensates of a urea type compounds and melamine are further preferable.

Moreover, other amino compounds other than the above-mentioned amino compounds may be used together. As such other amino compounds, for example, capryguanamine , amerine, ameride, ethyleneurea , propyleneurea , and acethyleneurea can be cited. In cases where other amino compounds are used, the above-mentioned amino compound and other amino compound shall be collectively treated as an amino compound that may be a raw material for the above-mentioned condensation compound (or may be contained in a polymer coated layer) .

Formaldehyde to be reacted with the above-mentioned amino compounds is especially not limited as long as any compound that yields formaldehyde within the reaction system. Moreover, in the reaction from which the above-mentioned initial condensation compounds are obtained, since water is generally used as a solvent, in addition to aqueous formaldehyde solution (formalin), trioxane or paraformaldehyde may be added into water so as to be able to generate formaldehyde in water.

As concrete modes of reaction for obtaining the above-mentioned initial condensation compounds, the following methods can be preferably cited: a method

that an amino compound is added in aqueous formaldehyde solution (formalin) and reacted, a method that the above-mentioned amino compound is added in the aqueous solution in which trioxane or paraformaldehyde has been added and reacted, and others. Among these methods, the former method is preferable because no bath for preparing aqueous formaldehyde solution is needed and formalin is available easily. Moreover, the above-mentioned reaction is acceptable to be a mode in which an amino compound and formaldehyde react in the mixed state, for example, the mode may be a mode in which aqueous formaldehyde solution is added into an amino compound other than a mode in which an amino compound is added into aqueous formaldehyde solution. The above-mentioned reaction is preferably carried out under stirring with a well known stirring device.

In the reaction for obtaining the above-mentioned initial condensation compound, mole ratio of an amino compound and formaldehyde [an amino compound (mole) / formaldehyde (mole)] is preferable to be 1 / 0.5 to 1 / 10, more preferable to be 1 / 1 to 1 / 8, and further preferable to be 1 / 1 to 1 / 6. When the blending ratio of an amino compound and formaldehyde (mole ratio) is out of the

above-mentioned range, either of the compounds remains in large amounts as it is unreacted in the reaction system.

Moreover, in case of using water as a solvent, the amount an amino compound and formaldehyde added to water, that is, the concentration of the amino compound and formaldehyde at the time of feeding is desirable to be higher unless no obstacle is observed in the reaction. The above-mentioned initial condensation compound is preferable to be 100% or more in water mixing degree (an index of the degree of polycondens at ion rate) and more preferable to be 200% or more, and preferable to be 5000% or less and more preferable to be 3000% or less. When the water mixing degree is over the above-mentioned range, it means that the initial condensation compound has high hydrophilic property, and in such a case, the formation of a polymer coated layer is apt to need a long time. On the other hand, the water mixing degree is less than the above-mentioned range, the reaction control at the time of the formation of polymer coated layer becomes difficult and it may become difficult to obtain the properties of a polymer coated layer ( flexib-ilit y , mechanical strength,

plating property and the like) . Moreover, the water mixing degree indicates the degree of the polymerization rate of the initial condensation compound obtained by the reaction of an amino compound with formaldehyde, and is a value obtained by multiplying the ratio of the mass of water needed to generate white turbidity in case of addition of water in the initial condensation compound (5 g, 15°C) and the mass of the initial condensation compound (that is, [water (g) / initial condensation compound (g)]) by 100.

Water mixing degree= [water (g) / initial condensation compound (g) ] *100

Although the degree of the polycondens at ion rate of the above-mentioned initial condensation compound can be controlled methods other than that of water mixing degree, for example, GPC (Gel Permeation Chromatography) , LC (Liquid Chromatography) and the like, the method of water mixing degree is preferably adopted because it can be easily carried out and its repeatability is also good.

The reaction of the initial condensation compound is preferably carried out within the range of 65 to 75°C. It is because in such temperature range, the state of progress of the reaction can be grasped

with time and instantly and the desired end of the reaction (the aimed point) can be exactly ascertained by the above-mentioned water mixing degree, and further the reaction can be easily stopped by cooling the reaction liquid and the like at the time. The reaction time is not especially limited, and may be decided properly while confirming the progress situation of the reaction.

Moreover, as a raw material of the above-mentioned polymer coated layer, in place of the above-mentioned compound (A) , or in addition to the above-mentioned compound (A) , an epoxy compound (a compound having an epoxy group) can be used as compound (B) . Accordingly, the polymer coated layer containing an epoxy resin formed by ring-opening and polycondensati on of an epoxy compound is also included in the present invention. Through containing an epoxy resin, the coated fine particle that is more flexible and have higher mechanical strength can be obtained.

As epoxy compounds that are raw materials of the above-mentioned epoxy resins, compounds having two or more epoxy groups in one molecule and showing water solubility are preferable. Such epoxy compounds include, for example-, sorbitol polyglycidyl ester,

( poly ) glycerol polyglycidyl ester, pent ae rythrit ol polyglycidyl ester, glycidyl t ri s ( 2 -hydroxyethyl ) i socyanurate , t rimethylolpropane polyglycidyl ester, neopent ylglycol diglycidyl ester, ethylene glycol diglycidyl ester, polyethylene glycol diglycidyl ester, propylene glycol diglycidyl ester, polypropylene glycol diglycidyl ester, and diglycidyl adipate. These compounds may be used independently, and may be used in combination of two or more kinds .

The dissolution ratio of the above-mentioned epoxy compound in water is preferable to be 50 % by mass or more, more preferable to be 60 % by mass or more, further preferable to be 70 % by mass or more, and especially preferable to be 100 % by mass. When the dissolution ratio is within the range, such excellent effects can be obtained as the formation of epoxy resin layer (polymer coated layer) progresses uniformly and rapidly and the thickness of the epoxy resin layer can be easily controlled. Further, the dissolution ratio of an epoxy resin in water that is prescribed in the present invention means values obtained by the following measurement method. After 25.0 g of a sample compound (an epoxy compound) is weighed -accurately into a 300 ml beaker

and 225 g of water is added, the mixture is stirred with a magnetic stirrer for one hour to dissolve the sample compound. Then, the solution is left at rest for one hour. After that, not dissolved sample compound (oily matter) that was sedimented at the bottom of the beaker is extracted and put into a measuring cylinder of 10 ml (or 5 ml) , and the measuring cylinder is further left at rest for 30 minutes. Then, the fluid volume of the sample compound (oily matter) is read down to the first decimal place. The obtained value is substituted in the following formula to calculate the dissolution ratio (%) of the sample compound (an epoxy compound) in water . The dissolution ratio in water (%) = 100 - (A / 21) x 100

(wherein A indicates the fluid volume of the sample compound that was read (ml) .)

The weight average molecular weight of the above-mentioned epoxy compound is preferable to be 300 or more and 10,000 or less, and more preferable to be 300 or more and .5,000 or less. When the weight average molecular weight is within the above-mentioned range, such excellent effects can be obtained as the thickness of the epoxy resin layer

(the polymer coated layer) can be easily controlled. On the other hand, the weight average molecular weight is less than the above-mentioned range, it is difficult to obtain the improvement of flexibility by the formation of epoxy resin layer and the formation of uniform epoxy resin layer may be difficult. When the weight average molecular weight is over the above-mentioned range, the viscosity of the reaction fluid rises rapidly at the time of the formation of polymer coated layer and stirring may be difficult. At this time, the reaction fluid is stirred by force, coated fine particle may be damaged or broken .

When the above-mentioned epoxy resin layer is formed, in addition to an epoxy compound, a crosslinking agent may be added. Strength of the epoxy resin layer, consequently strength of the coated fine particle can be further increased by using a crosslinking agent, and as a result, isolation of coated fine particles and their damage and broken in the cleaning process can be effectively controlled. The timing of the addition of the above-mentioned crosslinking agent is not especially limited, it may be added together with an epoxy compound and may be added before or afte.r the addition of an epoxy

compound, it is preferably added after the addition of an epoxy compound.

The above-mentioned crosslinking agents are not especially limited but include, for example, sodium diethyldithiocarbamate (including hydrates), diethylammonium diethyldithiocarbamate (including hydrates) , dithiooxalic acid, and dithio carbonic acid These compounds may be used independently, and two or more kinds of them may be used together. Moreover, although the amount of the above-mentioned crosslinking agent added is not limited, it is preferable to be 1 to 100 mass parts to 100 mass parts of an epoxy compound and more preferable to be 5 to 80 mass parts. When the amount of the above-mentioned crosslinking agent added is less than the above-mentioned range, controlling the thickness of the epoxy resin layer and the like may be difficult. And when being over the above-mentioned range, reactions with epoxy groups in the epoxy compound become excess and, as a result, epoxy resin layer with highly flexible and having good adhesion to metals may not be formed.

When the above-mentioned polymer coated layer is formed, surfactants to be made coexist within the reaction system include compounds shown by the

following formula (1) and emulsifying agents to be exemplified in the description of the core fine particles to be described later, for example, anionic surfactants, cationic surfactants, nonionic surfactants, amphoteric surfactants, and high-molecular surfactants.

R 1 -(CH2-CH 2 -O-)n-Xm-R 2 (1)

The above-mentioned surfactants are used to form polymer coated layer uniformly on the surfaces of the core fine particles while keeping the dispersion state of the core fine particles in the reaction system, and surfactants shown by the above-mentioned formula (1) becomes constituents of the polymer coated layer. That is, the polymer coated layer included in the present invention is formed by utilizing intermolecular force such as hydrophobic interaction acting between the core fine particles and a surfactant, and between a surfactant and the above-mentioned compound (A) and/or compound (B) . When a polymer coated layer is formed under the nonexistence of the surfactant as described above, the opening reaction and polycondensat ion reaction of the above-mentioned compound (A) and/or compound (B) progress not only on the surfaces of core fine particles but everywhere and, as a result, polymer

components having no core fine particle and derived from compound (A) and compound (B) are produced in addition to the coated fine particles included in the present invention. Consequently, it is preferable to use a surfactant, when the polymer coated layer is formed. Further, from a viewpoint of forming uniform polymer coated layer on the surface of the core fine particle, among the above-mentioned surfactants, surfactants shown by the above-mentioned formula (1) are preferably used.

In the above-mentioned formula (1) , R 1 indicates hydrophobic groups including aliphatic or organic hydrocarbon groups, for example, aliphatic hydrocarbon groups such as a pentyl group, a hexyl group, a heptyl group, an octyl group, a decyl group, an octadecyl group, a stearyl group, and a behenyl group, and aromatic hydrocarbon groups such as a phenyl group, a benzyl group, a tolyl group, a xylyl group, a biphenyl group, and a naphthyl group can be cited. The carbon number of the hydrophobic groups is preferable to be 5 or more and 25 or less (more preferably 18 or less) . When the carbon number is too small, the dispersion of core fine particles is apt to be insufficient because of hydrophil icity derived from ethylene oxide chains. On the other hand, when

the carbon number is too large, hydrophobicity is too high and the surfactant becomes difficult to be dissolved in water (a reaction solvent) . In the above-mentioned formula (1) : [- ( CH 2 -CH 2 -O- ) n ] is a polymer chain having a polyether structure (polyethylene oxide structure), and the number n of the above-mentioned polyether structures is preferable to be 3 or more, more preferable to be 5 or more, preferable to be 85 or less, more preferable to be 60 or less, and further preferable to be 50 or less. When polyether structures are too few (though depending on the balance with the above-mentioned hydrophobic group), the above-mentioned compound might be difficult to be dissolved in water-based mediums. On the other hand, when being too much, the solubility in water-based mediums is too high and consequently, the compound is apt to be difficult to be taken in polymer coated layer. In addition, if n is within the above-mentioned range, when polymer coated layer are formed, part of the surfactant reacts with the above-mentioned compound (A) and compound (B) to be taken in the polymer coated layer, which can give moderate flexibility to the coated fine particle and consequently, contributes to improve mechanical strength of the coated fine particle.

In the above-mentioned formula (1), X indicates a group being derived from groups that can react (bonding reaction) with at least one kind selected from the group consisting of an amino group, an imino group, and a carboxyl group and being formed after the reaction (bonding reaction) . Further, in the formula (1), m indicates 0 or 1. Here, the above-mentioned amino group, imino group, and carboxyl group mean an amino group and an imino group that can exist in a polymer having a polyamine structure, R 2 , which will be described later, or a carboxyl group that can exist in a polymer having a polycarboxyl ic acid structure.

Groups shown by the above-mentioned X is, for example, a group which is produced by the reaction of a functional group derived from R 2 with a group shown by X 2 in the following general formula (3) , specifically, the following groups can be exemplified: [ -CH 2 -CH 2 -S- ] derived from a group shown by the following structural formula (b), [-NH-CO-] derived from an isocyanate group, [ -CO-NH-CH2-CH2- ] derived from an oxazoline group, [-CH(OH)-] derived from an aldehyde group, [-CO-] derived from a carboxyl group, [-NH-] derived from an amino group, and [=N-] derived from an imin-o group.

In the formula (1), R 2 indicates a polymer group having a polyamine structure or a polycarboxyIic acid structure of 300 to 100,000 (more preferable 300 to 50, 000) in weight average molecular weight. When the weight average molecular weight is too small, the polymer is difficult to be precipitated as an insoluble matter, a long time may be reguired to form the polymer coated layer, and further the strength of the polymer coated layer may become insufficient. While the weight average molecular weight is too large, the viscosity of the whole reaction system rises rapidly and stirring may be difficult.

Polymer groups having the above-mentioned polyamine group are not limited, but include polymer groups having polyamine structure containing a primary amino group and/or a secondary amino group, for example, polymer groups having at least one kind of structure selected from the group consisting of polyethyleneimine , polyamine, polyetheramine , polyvinylamine , modified polyvinylamine , polyalkylamine , polyamide, polyamine epi chlorohydrin , polydial kylamino alkylvinyl ether, polydialkylamino al kyl (meth ) aerylate , polyallylamine , polyethyleneimine graft polyamideamine , and protonated polyamideamine .

Polymer groups having the above-mentioned polycarboxylic acid structure are not limited, but include polymer groups having the structure of water soluble polycarboxylic acid obtained by the polymerization of a monomer component containing 30 mole% or more of unsaturated carboxylic acid including acrylic acid, methacrylic acid, α-hydroxy acrylic acid, crotonic acid, phthalic acid, maleic acid, fumaric acid, itaconic acid, citraconic acid, aconitic acid, and vinyl acetate.

The preparation methods of surfactants shown by the above-mentioned general formula (1) are not especially limited, for example, it is preferable to adopt such a method that a compound shown by the following general formula (2) or (3) is added dropwise in an agueous solution of polyamine or polycarboxylic acid and reacted under stirring.

R i -(CH 2 -CH 2 -O-)n-i-X 1 (2) wherein, X 1 indicates a group shown by the following structural formula (a) :

C H CH 2

\ / (a)

O

R i -(CH 2 -CH2-O-)n-X 2 (3)

wherein, X 2 indicates any one kind selected from the group consisting of groups shown by the following structural formula (b) ,

- C H - C H

(b)

an isocyanate group, an oxazoline group, an aldehyde group, a carboxyl group, an amino group, and an imino group. That is, X 2 indicates a group that can react (bonding reaction) with at least one kind of group selected from the group consisting of an amino group, an imino group, and a carboxyl group.) In cases where a compound shown by the above-mentioned general formula (2) was used for preparing a surfactant shown by the above-mentioned formula (1) , the group shown by X does not exist in the above-mentioned general formula (1) (that is, m = 0) . On the other hand, in cases where a compound shown by the above-mentioned general formula (3) was used for preparing a surfactant shown by the above-mentioned formula (1) , the group shown by X exists in the above-mentioned general formula (1) (that is, m = 1) .

Although reaction temperatures at the time of

preparing the above-mentioned surfactant are not especially limited, in case of using polyamine, the reaction temperature is preferable to be 10 to 90°C and more preferable to be 15 to 80 0 C, and in case of using polycarboxyl i c acid, the reaction temperature is preferable to be 20 to 100°C and more preferable to be 20 to 90°C. Although the reaction time is not limited, it is preferable to be 0.5 to 5 hours and more preferable to be 1 to 5 hours. In the present invention, other compounds may be used together with a surfactant shown by the above-mentioned formula (1) or the after-mentioned emulsifying agents in the range where the effect of the present invention is not disturbe. Further, it is desirable that the above-mentioned other compounds are also water soluble as a matter of convenience that the forming reaction of polymer coated layer is carried out in water-based medium. Usable other compounds in the present invention include polyvinyl pyrrolidone, polyvinyl alcohols, all kinds of surfactants other than those shown by the above-mentioned formula (1) and the after-mentioned emulsifying agents, natural polymer dispersants such as gelatin and gum arabic, and synthetic polymer dispersants such as s tyrene-maleic acid copolymer and

i t s s a l t s .

Next, the core fine particle included in the present invention will be described. Core fine particle that is base material of the coated fine particle included in the present invention have a great influence on flexibility, elasticity, and mechanical properties of the coated fine particle. Material of core fine particle is not especially limited, and any of organic materials, organic and inorganic composite materials, or inorganic materials can be adopted. Organic materials include linear polymers such as polystyrene, polymethyl methacrylate , polyethylene, polypropylene, polyethylene terephthalate , polybutylene terephthalate , polysulfone, polycarbonate, and polyamide; network polymers obtained by the homopolymerization or polymerization with other polymeri zable monomers of divinylben zene , hexatriene, divinyl ether, divinyl sulfone, diallyl carbinol, alkylene diacrylate, oligo- or polyalkylene glycol diacrylate, oligo- or polyalkylene glycol dimethacrylate , alkylene triacrylate, alkylene tetracrylate , alkylene trimethacrylate , alkylene tetramethacrylate , alkylene bisacrylamide , alkylene bi smethacrylamide , and both terminal acryl-modi fied

polybutadiene oligomer; amino resins obtained by the polycondensati on reaction of amino compounds (for example, benzoguanamine , melamine, urea or the like) and formaldehyde, and divinylbenzene crosslinked resin particles obtained by homopolymeri z ing divinylbenzene or by copolymeri zing it with other vinyl monomers. Organic and inorganic composite materials include organic matter and inorganic composite particles that can be obtained by the reaction of polysiloxane that the raw material is a silicon compound having a hydrolyzable silyl group and a polymeri z able monomer having a polymeri zable group (for example, a vinyl group, a (meth ) acryloyl group and the like) and the like. Inorganic materials include, for example, glass, silica, and alumina. Further, from the viewpoint of being possible to relatively freely design properties of core fine particle, those consisting of organic materials or organic and inorganic composite materials are preferable.

As the above-mentioned organic and inorganic composite fine particle, polymer fine particle in which a polysiloxane skeleton and an organic polymer skeleton formed three-dimensional network structure are especially preferable. One example of the

production method of such polymer fine particle is shown in the following.

The above-mentioned organic and inorganic composite fine particle is polymer fine particle that contain a polysiloxane skeleton as a mineral part and an organic polymer skeleton as an organic matter part and have an organo s il icon atom in which at least one carbon atom in the organic polymer skeleton forms a direct chemical bond with a silicon atom in the polysiloxane skeleton (a chemical bonding type) within the molecule.

The above-mentioned polysiloxane is preferable to have an unsaturated group that can be bonded with an organic polymer skeleton, for example, preferable to have a vinyl group. This polysiloxane having a vinyl group is a compound having a polysiloxane skeleton structure that is produced by hydrolyzing and condensing a raw material of compounds containing a silicon compound having a vinyl group. For example, that is a compound produced by hydrolyzing and condensing a hydrolyzable silicon compound in solvent containing water. Further, the timing of introducing a vinyl group is not especially limited, for example, any of the following modes can be adopted: a mode of using a silicon compound having

a vinyl group as a hydrolysable silicon compound, and a mode in which after seed particles ( polys iloxane having no vinyl group) are produced by hydrolyzing and condensing a hydrolyzable silicon compound having no vinyl group, this seed particles ( polys iloxane having no vinyl group) and a hydrolyzable silicon compound having a vinyl group are hydrolyzed and condensed to introduce a vinyl group into polysiloxane . In the latter case, on the occasion of hydrolysis and condensation of the seed particles and the hydrolyzable silicon compound having a vinyl group, a radical polymerization reaction may be carried out with a polymeri z able component simultaneously. Although the above-mentioned hydrolysable silicon compounds are not especially limited, for example, silane compounds shown by the following general formula (4) and their derivatives can be used.

(wherein, R 3 may have a substituent and indicates at least one kind of group selected from the group consisting of an alkyl group, an aryl group, an aralkyl group, and unsaturated aliphatic groups, X indicates at least one kind of group selected from the group consi sting -of the hydroxyl group, an alkoxy

group, and an acyloxy group, 1 indicates an integer of 0 to 3. )

As silane compounds shown by the above-mentioned general formula (4), for example, the following compounds can be exemplified. As those of 1 = 0, tetrafunctional silanes such as tetramethoxys ilane , tetraethoxys ilane , tetrai sopropoxysilane , and tetrabutoxysilane; as those of 1 = 1, trifunctional silanes such as methyltrimethoxysilane , methyltriethoxys ilane , ethyItrimethoxys ilane , ethyltriethoxys ilane, hexyltriethoxys ilane, decyltrimethoxys ilane, phenyltrimethoxys ilane, benzyltrimethoxysilane, naphthyltrimethoxysilane, methyltriacetoxysilane , β- (3, 4 -epoxycyclohexyl ) ethyltrimethoxys ilane , 3-glycidoxy propyltrimethoxysilane, vinyltrimethoxys ilane, 3- (meth) acryloxypropyltrimethoxysilane , and 3 , 3 , 3-trifluoropropyltrimethoxys ilane ; as those of 1 = 2, bifunctional silanes such as dimethys ilane , dimethydiethoxys ilane , diacetoxy dimethyls ilane , and dimethoxy diphenylsilanediol ; as those of 1 =3, monofunctional silanes such as trymethy1s ilane , trimethylethoxys ilane , and trimethyl s ilanol . The above-mentioned silane compounds may be used only in one kind, and may be used in suitably combining

two or more kinds. Further, in cases where only one of silane compounds of 1 = 3 and its derivatives in the above-mentioned general formula (4) is used as a raw material, composite particles cannot be obtained .

The above-mentioned hydrolyzable silicon compounds having a vinyl group include, for example, those having a polymeri z able reactive group shown by, for example, the following general formulas (5) , (6) and (7) .

CH 2 = C(-R 4 )-COOR 5 - (5) wherein, R 4 indicates the hydrogen atom or the methyl group, and R5 indicates a divalent organic group that may have a substituent and has the carbon number of 1 to 20.

CH 2 = C(-R 6 )- (6) wherein, R6 indicates the hydrogen atom or the methyl group .

CH 2 = 0(-R 1 O-R B - (7) wherein, R 7 indicates the hydrogen atom or the methyl group, and R 8 indicates a divalent organic group that may have a substituent and has the carbon number of 1 to 20.

Polymeri zable reactive groups shown by the above-mentioned general formula (5) include, for

example, acryloxy groups and methacryl oxy groups, and silicon compounds that have such organic group and shown by the above-mentioned general formula (4) include, for example, γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropyltriethoxysilane, γ-acryloxypropyltrimethoxysilane, γ-acryloxypropyltriethoxysilane, γ-methacryloxypropyltriacetoxysilane, γ-methacryloxyethoxypropyltrimethoxys ilane (or, also called γ-trimethoxys ily Ipropyl-β-methacryloxyethyl ether) , ll-methacryloxyundecamethylenetrimethoxys ilane, γ-methacryloxypropylmethyldimethoxysilane, γ-methacryloxypropylmethyldi ethoxys i lane , and γ-acryloxypropylmethyldimethoxysilane.

Polymeri zable reactive groups shown by the above-mentioned general formula (6) include, for example, vinyl group and isopropenyl group, and silicon compounds that have such organic group and shown by the above-mentioned general formula (4) include, for example, vinylt rimethoxys ilane , vinyltriethoxysilane , vinyIt riacetoxys ilane , 4 -vinyltetramethylenetrimethoxys ilane, 8 -vinyloctamethylenetrimethoxysilane,

3 -1rimethoxys ilylpropy1 vinyl ether, vinylmethyldimethoxysilane, vinylmethyldiethoxys ilane , and vinyImethyldiacetoxys ilane . These compounds may be used only in one kind, and may be used in two or more kinds together.

Polymeri zable reactive groups shown by the above-mentioned general formula (7) include, for example, 1-alkenyl groups or vinyl phenyl group, and isoalkenyl group or isopropynyl phenyl group, and silicon compounds that have such organic group and shown by the above-mentioned general formula (4) include, for example, 1-hexenyltrimethoxys ilane ,

1-hexenyltriethoxys ilane, 1-octenyItrimethoxys ilane ,

1-decenyltrimethoxys ilane, γ-trimethoxysilylpropyl vinyl ether, ω-trimethoxys ilylunde canoic acid vinyl ester, p-trimethoxys ilyl styrene , p-triethoxysilylstyrene, p-trimethoxysiIyI-α-methylstyrene, p-triethoxysilyl-α-methyl styrene,

N-β- (N-vinylbenzylaminoethyl-γ-aminopropyl)trimeth oxysilane hydrochloride,

1-hexenylmethyldimethoxys ilane, and 1-hexenylmethyldiethoxysilane . These compounds may

be used only in one kind independently, and may be used in two or more kinds together.

The above-mentioned polys i loxane s are obtained through the hydrolysis and condensation of compounds included in the above-mentioned silicon compound group in a solvent containing water. As for the hydrolysis and condensation, any method of batch processing, division processing, continuous processing and the like can be adopted. Moreover, when hydrolysis and condensation are carried out, any of catalysts such as ammonia, urea, ethanolamine , tet ramethylammonium hydroxide, alkali metal hydroxides, and alkaline-earth metal hydroxides can be used. Moreover, in the solvent, an organic solvent may exist other than water and a catalyst.

Although the above-mentioned organic solvents are not especially limited, for example, the following solvents are preferably cited: alcohols such as methanol, ethanol, isopropanol, n-butanol, is.obutanol, sec-butanol, t-butanol, pentanol, ethylene glycol, propylene glycol, and 1 , 4 -but anediol ; ketones such as acetone and methyl ethyl ketone; esters such as ethyl acetate; ( cycl o ) paraffins such as isooctane and cyclohexane; ethers such as dioxane and diethyl ether; aromatic

hydrocarbons such as benzene and toluene. These solvents may be used only in one kind, and may be used in two or more kinds together.

Hydrolysis and condensation reactions are carried out by adding the above-mentioned silicon compounds and organic solvents and the like in a solvent containing water and stirring for 30 minutes to 100 hours at the temperature range of 0 to 100°C, preferably at 0 to 7O 0 C. Moreover, at this time, it is preferable that the water concentration is 10 to 99.99 % by mass, the catalyst concentration is 0.01 to 10 % by mass, the organic solvent concentration is 0 to 90 % by mass, the concentration of the above-mentioned silicon compound is 0.1 to 30 % by mass to the total amount of the reaction mixture. Further, it is preferable that the time of adding the above-mentioned silicon compounds is 0.001 to 500 hours and the reaction temperature is 0 to 100°C. In addition, in cases where particles obtained by previously carrying out the hydrolysis and condensation reactions are used as seed particles, the concentration of the seed particles is preferably set to be 0.1 to 30 % by mass to the total amount of the reaction mixture. Moreover, particles obtained by the hydrolysis

and the condensation reaction have been previously put in the synthesis system as the seed particles, and then the above-mentioned silicon compounds are added in the system to make the above-mentioned seed particles grow. Polysiloxane particles can thus be obtained. In this way, the above-mentioned silicon compounds are hydrolyzed and condensed under the suitable conditions in a solvent where water is contained and particles precipitate to form slurry. The precipitated particles become polysiloxane particles having vinyl groups because the particles are obtained by using the above-mentioned silicon compound having a vinyl group as the essential component. Here, although the suitable conditions are not especially limited, for example, it is preferable that the slurry containing the seed particles that were obtained by previously carrying out hydrolysis and condensation reaction (preferably 0.1 to 20 % by mass in concentration) has the concentration of the above-mentioned hydrolysable silicon compound of 20 % by mass or less to the total amount of the reaction mixture, the water concentration of 50 % by mass or more, and the catalyst concentration of 10 % by mass or less. The shapes of the above-mentioned polysiloxane

particles may be arbitrary shapes including a globular shape, a needle shape, a plate shape, a scale shape, a pulverized shape, a straw bag (cilinder) shape, a cocoon shape, and a confetti shape, and not especially limited.

Although the average particle diameter of the above-mentioned polysiloxane particles is not especially limited, it is preferable to be 0.1 to 700 μm, more preferable to be 0.5 to 70 μm, and most preferable to be 1 to 50 μm . When the average particle diameter of the above-mentioned polysiloxane particles is within the above-mentioned range, such advantageous effects can be exhibited that the absorption of polymeri zable components as described later progresses efficiently. On the other hand, when the average particle diameter of the above-mentioned polysiloxane particles is too small, the absorption of polymeri zable components as described later may be insufficient, and when being too large, the mass of the particles becomes large and the sedimentation of polymer fine particles occurs in a reactor, and it becomes easy for the particles to cohere mutually.

Polysiloxane particles obtained as described above are such particles that they can easily absorb

polymer i zable components to be described later and hold the components in the siloxane skeleton constituting the particles. It can be said that this is because the above-mentioned polysiloxane particles are in the degree of condensation suitable for absorbing polymeri zable components to be described later.

Next, the polymeri zable components to be polymerized with the above-mentioned polysiloxane particles will be described. The above-mentioned polymeri zable components are not especially limited, but considering miscibility with the above-mentioned polysiloxane particles, it is preferable to use radical polymeri zable vinyl monomers and bifunctional oligomers having two (meth ) acryloy1 groups in one molecule.

Radical polymeri zable vinyl monomers are preferably monomers containing at least one ethyleninc unsaturated group within the molecule, and are sufficient to be properly selected so that the polymer particles can exhibit the desired physical properties. In concrete terms, the following monomers can be cited: monomers having the hydroxyl group such as 2 -hydroxyethy1 (meth ) acrylate , 2 -hydroxypropy1 (meth ) acrylate , and 2 -hydroxybutyl

(meth ) acrylat e ; monomers containing a polyethylene glycol component such as methoxypolyethylene glycol (meth ) acrylat e ; alkyl (meth ) acryl ates such as butyl (meth) acrylate, methyl (meth ) acrylates , ethyl (meth ) acrylat e , isoamyl acrylate, lauryl

(meth ) acrylat e , benzyl (meth ) acrylate , and t et rahydro furfury1 methacrylate ; fluorine-containing (meth ) acrylat es such as t rifluoroethy1 (meth) acrylate, t etrafluoropropy1 (meth ) acrylate , pentafluoropropyl (meth) acrylate, and octafluoroamyl (meth) acrylat e ; aromatic vinyl compounds such as styrene, α-methyl styrene, vinyltoluene , α-chlorostyrene , o-chloros t yrene , m-chlorostyrene , p-chloros tyrene , and p-ethyl styrene; glycidyl (meth ) aerylate , (meth ) acrylic acids, (meth ) acrylamides , and (meth ) acrylonit riles .

A bifunctional oligomer having two

(meth ) acryloyl groups in one molecule is preferably such one that the solubility in water at 25°C is 10 % by mass or less to the total amount of water and the bifunctional oligomer and the weight average molecular weight is 300 or more. Such a component is easily absorbed into the above-mentioned polysiloxane particle and greatly contributes to improving the properties of the polymer fine particle

(for example, flexibility, elasticity and the like) . The above-mentioned bifunctional oligomers are not especially limited as long as they meet the above-mentioned properties and include, for example, polyethylene glycol di (meth ) aerylate ; polypropylene glycol di (meth ) acrylate s such as propylene glycol di (meth ) aerylate ; tripolypropylene glycol di (meth ) acryIate ; polytetramethylene glycol di (meth ) aerylate ; neopentyl glycol di (meth ) acrylate ; 1, 3-butylene glycol di (meth) acrylate;

2 , 2 -bis [4- (methacryloxypolyethoxy) phenyl] propane di (meth ) acrylate s such as 2, 2-bis [4- (methacryloxyethoxy) phenyl] propane di (meth) acrylate ; EO modified di (meth ) acrylates of bisphenol A such as 2 , 2 -hydrogenated bis [4- (acryloxypolyethoxy) phenyl] propane di (meth) acrylate; isocyanuric acid EO modified di (meth) acrylates . Bifunctional oligomers having the above-mentioned structures include, for example, NK ester series manufactured by Shin-Nakamura Chemical Co., Ltd. such as λλ 9PG", "APG-200", "APG-400", "APG-700", "BPE-IOO", "BPE-200", and "BPE-500", products manufactured by Nippon Kayaku Co. , Ltd. such

as "KAYARAD HX-220" and "KAYARAD HX-620", and products manufactured by Kyoeisha Chemical Co., Ltd. such as "Lightacrylate PTMGA-250". In addition to these products, "KAYARAD MANDA" and "KAYARAD R-167" manufactured by Nippon Kayaku Co., Ltd. are also preferably used.

These polymeri zable components may be used independently, and may be used in two or more kinds together. In cases where the above-mentioned polymeri z able component is absorbed into polysiloxane particles, at the time of forming an emulsion by emulsifying and dispersing the above-mentioned polymeri zable component, hydrophobic radical polymeri zable vinyl monomers are preferably used to make the emulsion stable.

Moreover, in addition to the above-mentioned polymeri zable component, a crosslinking monomer may be used. In this case, it becomes easy to control the mechanical properties of the obtained polymer fine particles. The above-mentioned crosslinking monomers are not especially limited, and include, for example, divinylbenzene , 1 , 6-hexanediol di (meth ) aerylate , neopentyl glycol di (meth ) acrylat e , trimethylolpropane tri (meth) acrylate, tetramethylolmethane. tri (meth ) acrylat e ,

tetramethylolpropane tetra (meth) acrylate, dipentaerythritol hexacrylate, diallyl phthalate, ethylene oxide modified trimethylolpropane tri (meth ) acrylates and their isomers, and triallyl isocyanurate and its derivatives. These may be used independently, and may be used in two or more kinds together .

In the above-mentioned polymeri zable component, the above-mentioned hydrolyzable silicon compound may be contained. As a hydrolyzable silicon compound, both of those having a vinyl group and those having no vinyl group can be used. However, when polysiloxane particles having no vinyl group are used as the seed particles, it is necessary to add a hydrolyzable silicon compound in the polymeri zable component .

Although the blending ratio of the above-mentioned polymeri zable components is not especially limited and can be suitably set according to the desired properties, for example, the blending amount of the above-mentioned bifunctional oligomer is preferable to be 20 % by mass or more in 100 % by mass of the above-mentioned polymeri zable components

(that is, the total amount of the above-mentioned bifunctional oligomer and the above-mentioned

pol ymeri z able vinyl monomer) , more preferable to be 30 % by mass or more, and further preferable to be 40 % by mass. When the amount of the bifunctional oligomer is included within the above-mentioned range, it is easy to control the compressive deformation recovery factor of the obtained polymer fine particles. In addition, all of the polymeri z able components may be ones of the above-mentioned bifunctional oligomers. Moreover, the components derived from bifunctional oligomers in the polymer fine particle to be obtained are preferable to be 10 % by mass or more, more preferable to be 20 % by mass or more, and further preferable to be 30 % by mass or more, and preferable to be 99 % by mass or less, more preferable to be 95 % by mass or less, and further preferable to be 90 % by mass or less.

As the method of producing the above-mentioned polysiloxane particle, any of the following methods can be adopted:

[A] A method of producing the seed particles (polysiloxane having vinyl groups) by hydrolyzing and • condensing the above-mentioned hydrolyzable silicon compound having a vinyl group. [B] A method in which the seed particles (1)

( polys i1oxane having no vinyl group) are produced by hydrolyzing and condensing a hydrolyzable silicon compound having no vinyl group, after that, this seed particles (1) and a hydrolyzable silicon compound having a vinyl group are hydrolyzed and condensed to produce the seed particles (2) ( polys iloxane having vinyl groups ) .

[C] A method in which the seed particles (1) ( polys iloxane having no vinyl group) are produced by hydrolyzing and condensing a hydrolyzable silicon compound having no vinyl group, a hydrolyzable silicon compound having a vinyl group and a polymeri zable component described later are made to absorbed into this seed particles (1), at this time, the polysiloxane in the above-mentioned seed particles (1) and the hydrolyzable silicon compound having a vinyl group are hydrolyzed and condensed to produce the seed particles (2) (polysiloxane having vinyl groups ) . The above-mentioned polymer fine particle can be obtained through the absorption process where the above-mentioned polymerizable component in the state of being emulsified and dispersed in water is added and absorbed in the above-mentioned polysiloxane particles having vinyl groups, or the absorption

process where the polymer i zable components essentially containing the above-mentioned polymeri zable component and a polymeri zable monomer indispensably having a vinyl group and a hydrolyzable silyl group in the state of being emulsified and dispersed in water are added and absorbed in the above-mentioned polysiloxane particles having no vinyl group, and through the polymerization process where the radical polymerization of the above-mentioned polymeri z able components absorbed into the above-mentioned polysiloxane particles at the above-mentioned absorption process are performed .

The above-mentioned absorption process is not especially limited as long as the process progresses in the state that the above-mentioned polymeri z able components exist in the presence of the above-mentioned polysiloxane particles. In addition, although the above-mentioned polymeri zable component is absorbed into the structure of the above-mentioned polysiloxane particle in the absorption process, the absorption is preferably carried out after setting various kinds of conditions including the concentration of each of the above-mentioned polysiloxane particles and

polymeri zable components, the mixing ratio of the above-mentioned polysiloxane particles and polymeri zable component, the treating method and means of the mixing, the temperature and time when mixing them, and the treating method and means after the mixing so that the absorption process progresses rapidly .

The mass of the polymeri zable component added in the above-mentioned absorption process is preferable to be 0.01 to 100 times the mass of silicon compound used as a raw material of polysiloxane particle, more preferable to be 0.5 to 30 times, and further preferable to be 1 to 15 times. When the mass added is less than the above-mentioned range, the amount of the polymeri zable component absorbed into the polysiloxane particle becomes small and it may be difficult to obtain the polymer fine particle having the above-mentioned mechanical properties, and when the mass added is over the above-mentioned range, the complete absorption into the polysiloxane particle of the polymeri zable component added is apt to become difficult, and because unabsorbed polymeri zable components remain, it may become easy to generate the cohesion between the particles in the following polymerization stage.

As for the mixing of the polymer i zable component and polysiloxane particles, the above-mentioned polymeri z able component may be added in the solvent in which polysiloxane particles are dispersed, or polysiloxane particles may be added in the solvent containing the above-mentioned polymeri zable component. Among them, it is preferable to add the polymeri z able component in a solvent in which polysiloxane particles are dispersed in advance. And it is further preferable that without taking out polysiloxane particles from the polysiloxane particle dispersion liquid that was obtained by synthesizing the polysiloxane particles, the polymeri z able component is added in the dispersion liquid, because the process does not become complex and is excellent in productivity.

In the above-mentioned absorption process, the timing of adding the polymer i zable component is not especially limited, the polymeri zable component may be added in a lump, may be added dividing in several times, and may be fed at any speed. Moreover, at the time of adding the polymeri zable component, only the^ polymeri zable component may be added, and the solution of the polymeri zable component may be added. However, it is preferable to add the polymeri zable

component in the polysiloxane particles in advance in the state of being emulsified and dispersed with an emulsifying agent because the absorption into the polysiloxane particles is performed efficiently. The above-mentioned emulsifying agents are not especially limited and include, for example, anionic surfactants, cationic surfactants, nonionic surfactants, amphoteric surfactants, high-molecular surfactants, and polymeri zable surfactants having one or more polymeri z able unsaturated carbon-carbon bonds in the molecule. Among them, anionic surfactants and nonionic surfactants are preferable because they can stabilize the dispersion states of polysiloxane particles, of polysiloxane particles absorbed polymeri zable components, and of polymer fine particles. These emulsifying agents maybe used only in one kind, and may be used in two or more kinds together .

The above-mentioned anionic surfactants are not especially limited and include, in concrete terms, alkali metal alkyl sulfates such as sodium dodecyl sulfate, and potassium dodecyl sulfate; ammonium alkyl sulfates such as ammonium dodecyl sulfate; alkali metal salts such as sodium dodecyl polyglycolether sulfate, sodium sulfocynoate , and

sulfonated paraffin; alkylsulfonates such as ammonium salt of sulfonated paraffin; fatty acid salts such as sodium laurate, triethanolamine oleate, and triethano lamine abietate; alkylaryl sulfonates such as sodium dodecylbenz ene sulfonate , and alkali metal sulfate of alkaliphenol hydroxyethylene ; higher alkylnaphthalene sulfonate, naphthalenesulfonate formalin condensate, dialkyl sul fosuccinate , polyoxyethylene alkyl sul fate , and polyoxyethylene al kylaryl sul fate .

The above-mentioned cationic surfactants are not especially limited and include, for example, amine salts, quaternary ammonium salts, and oxyethylene addition type ammonium hydrochlorides. In concrete terms, trimethylal kylammonium hydrochlorides, dimethyldial kylammonium hydrochlorides, monoalkylamine acetates, alkylmethyl dipolyoxyethylene ammonium hydrochlorides, and the like can be exemplified. Alkyl groups containing in these cationic surfactants are preferable to be saturated aliphatic hydrocarbon groups or unsaturated aliphatic hydrocarbon groups of 4 to 26 in carbon number, for example, the octyl group, the dodecyl group, the tetradecyl group, the hexadecyl group, the octadecyl group, the behenyl

group, the oleyl group, the stearyl group, and the like can be cited.

The above-mentioned nonionic surfactants are not especially limited and include, in concrete terms, fatty acid monoglycerides such as polyoxyethylene alkyl ether, polyoxyethylene alkylaryl ether, sorbitan fatty acid ester, polyoxyethylene sorbitan fatty acid ester, and glycerol monolaurat e ; polyoxyethylene oxypropylene copolymer, and condensation products of ethyleneoxide and a fatty acid amine, amide or acid.

The above-mentioned amphoteric surfactants include amino acid type amphoteric surfactants and betaine type amphoteric surfactants. For example, al kyldi ( aminoethyl ) glycine, alkylpolyamino ethylglycine hydrochloride, 2-alkyl-N-carboxyethyl-N-hydroxyethyl imidazolynium betaine, N-tet radecyl-N , N-betaine type amphoteric surfactants (for example, "Amogen K" manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.), and the like can be cite.

The above-mentioned high-molecular surfactants- include, in concrete terms, polyvinyl alcohol, sodium poly (meth ) aerylate , potassium poly (meth ) acrylate , ammonium poly (meth ) acrylate , polyhydroxyethyl

(meth ) aerylate , polyhydroxypropyl (meth) acrylate, polyvinyl pyrrolidone, copolymers of two kinds or more of polymeri zable monomers that are constitutional units of these polymers or copolymers of any of these monomers with other monomers, phase-transfer catalysts of crown ethers, and the like .

The above-mentioned polymeri zable surfactants are not especially limited and include, for example, anionic polymeri zable surfactants such as propenyl-2 -ethylhexylbenzene sodium sul fosuccinate , sulfate ester of polyoxyethylene (meth ) acrylate , polyoxyethylene al kylpropenylether ammonium sulfate, and phosphate ester of polyoxyethylene (meth ) acrylate ; and nonionic polymeri zable surfactants such as polyoxyethylene alkylbenzeneether (meth) acrylate , and polyoxyethylene alkylether (meth ) acrylate .

The amount of the above-mentioned emulsifying agent used is not especially limited, and in concrete terms, the amount is preferable to be 0.01 to 10 % by mass to the total mass of the above-mentioned polymeri zable component, more preferable to be 0.05 to 8% by mass, and further preferable to be 1 to 5% by mass. When the amount of the above-mentioned

emulsifying agent used is less than 0.01 % by mass, the stable emulsified and dispersed product of the polymeri zable component may not be obtained, and when the amount is over 10 % by mass, emulsion polymerization and the like may be occurred at the same time as a side reaction. As for the above-mentioned emuls i fi cat ion and dispersion, generally, it is preferable to make the emulsion of the above-mentioned polymeri zable component with an emulsifying agent in water with the use of a homo mixer or an ultrasonic homogenizer.

And when a polymeri zable component is emulsified and dispersed with an emulsifying agent, it is preferable to use water or a water-soluble organic solvent 0.3 to 10 times the mass of the polymeri z able component. The above-mentioned water-soluble organic solvents include alcohols such as methanol, ethanol, isopropanol, n-butanol, isobutanol, sec-butanol, t-butanol, pentanol, ethylene glycol, propylene glycol, and 1,4-butandiol; ketones such as acetone and methyl ethyl ketone; and esters such as ethyl acetate .

The above-mentioned absorption process is preferably carried out at the temperature range of 0 to 60°C for 5 to 720 minutes while stirring. It is

sufficient to set these conditions suitably depending on polysiloxane particles and the kind of a polymeri zable component to be used. Only one of these conditions may be adopted, and two kinds or more of them may be adopted together.

In the above-mentioned absorption process, as for judging whether the polymiri zable component is absorbed, the particles are observed with a microscope before the polymeri zable component is added and after the end of the absorption stage and the judgment can be made easily by confirming the particle size being grown by absorbing the polymeri zable component and the like.

After the end of the absorption process, it is preferable to add water in the dispersion liquid of polysiloxane particles so that the concentration of polysiloxane particles in which the polymeri zable component has been absorbed is diluted to 40 % by mass or less to the total amount of the dispersion liquid and water. The concentration is more preferable to be 30 % by mass or less and further preferable to be 20 % by mass or less. When the particle concentration in the above-mentioned dispersion liquid is too high, in the following polymerization process, the temperature control may be difficult because of the

heat generation accompanied by the polymerization reaction. And, at this time, the above-mentioned surfactant may additionally be added to improve the dispersion stability of the particles. In the polymerization process, methods for performing the radical polymerization are not especially limited and include, for example, a method of using a radical polymerization initiator, a method of irradiating ultraviolet or radiation, and a method of heating. The above-mentioned radical polymerization initiators are not especially limited and preferably include, for example, persulfates such as potassium persulfate; peroxide type initiators such as hydrogen peroxide, peracetic acid, benzoyl peroxide, lauroyl peroxide, orthochloro benzoyl peroxide, orthomethoxy benzoyl peroxide, 3, 5, 5-trimethylhexanoyl peroxide, t-butylperoxy-2-ethylhexanoate, di-t-butylperoxide, benzoyl peroxide, 1, 1 -bis (t-butylperoxy) -3, 3, 5-trimethylcyclohexane, and t-butylhydroperoxide ; azo type compounds such as azobisisobutyronitri.Ie, a zobi s cyclohexacarbonitrile , azobis (2, 4-dimethylvaleronitrile) , 2 ' -azobisispobutyronitrile ,

2 , 2 ' -azobis (2-amidinopropane) dihydrochloride, 4 , 4 ' -azobis (4-cyanopentanoic acid) , 2,2' -azobis (2-methylbutyronitrile) , 2 , 2 ' -azobisisobutyronitrile , and 2 , 2 ' -azobis ( 2 , 4 -dimethylvaleronitri Ie ) . These radical polymerization initiators may be used independently, and may be used in two or more kinds together .

The amount of the above-mentioned radical polymerization initiator used is preferable to be 0.001 % by mass to 20 % by mass to the total amount of the above-mentioned polymeri zable component, more preferable to be 0.01 % by mass to 10 % by mass, and further preferable to be 0.1 % by mass to 5 % by mass. When the amount of the above-mentioned radical polymerization initiator used is less than 0.001 % by mass, the polymerization degree of the polymeri zable component may not be risen. The method of feeding the above-mentioned radical polymerization initiator into the above-mentioned solvent is not especially limited and any of such heretofore known techniques can be adopted that a method of feeding the whole amount at the beginning (before starting the reaction) (a mode that a radical polymerization initiator is emulsified and dispersed

together with the polymer i zable component, a mode that a radical polymerization initiator is fed after the polymeri z able component is absorbed) ; a method of feeding a part of the initiator at the beginning and adding the remaining with continuous feeding or with intermittent pulsing, or the technique of combining these methods.

When the above-mentioned radical polymerization is carried out, the reaction temperature is preferable to be 40 to 100°C and more preferable to be 50 to 80°C. When the reaction temperature is too low, it is apt to become difficult to obtain the mechanical properties of the polymer fine particle because the degree of .polymerization does not rise sufficiently. On the other hand, when the reaction temperature is too high, the polymer particles are apt to easily cohere mutually during the polymerization reaction. In addition, when. the above-mentioned radical polymerization is carried out, though the reaction time can be suitably changed depending on the kind of the polymerization initiator to be used, generally,, the reaction time is preferable to be 5 to 600 minutes and more preferable to be 10 to 300 minutes. When the reaction time is too short, the degree of polymerization may do not rise

sufficiently, and when the reaction time is too long, the polymer particles are apt to easily cohere mutually .

Next, the method of manufacturing the coated fine particle included in the present invention will be described. The manufacturing method included in the present invention is a manufacturing method of the coated fine particle having polymer coated layer on the surface of the core fine particle comprising of an organic material or an organic and inorganic composite material, and the method is characterized in that the above-mentioned polymer coated layer is formed by ring-opening reaction and/or polycondensat ion reaction in a water-based medium in which the above-mentioned core particles are dispersed, and in the presence of a surfactant.

Through adopting the manufacturing method like this, uniform polymer coated layer can be formed around the core fine particle. Moreover, when a compound shown by the above-mentioned formula (1) as a surfactant, polymer coated layer that the surfactant is contained in the insoluble reaction product derived from the above-mentioned compound (A) and/or compound (B) can be formed on the surface of the core fine particle. That is, the manufacturing

method of the present invention is to form polymer coated layer for coating the core fine particles by utilizing int ermolecular force such as hydrophobic interaction acting between the core fine particles and the surfactant, what is more, between the surfactant and the above-mentioned compound (A) and/or compound (B) . That is, the surfactant added in a water-base medium is cohered on the surfaces of the core fine particles and the mutual coherence of the core fine particles is, as a result, controlled to make the state of the core fine particles dispersing in the water-based _ medium . Next, the above-mentioned compound (A) (an initial condensation compound) and/or compound (B) (an epoxy compound) are added here, and the ring-opening and/or polycondensat ion reaction progresses in such a situation that these compounds surround the surfactant, that is, the core fine particle. As a result, uniform polymer coated layer is formed on the surface of the core fine particle.

Moreover, although chemical bonds are formed between the compound (A) or the epoxy compound and the surfactant by the above-mentioned ring-opening and/or polycondens at ion reaction to produce a polymer coated layer (when a- surfactant shown by the

above-mentioned formula (1) is used) , only intermolecular forces such as hydrophobic interactions and hydrogen bonds act between the core fine particle and the polymer coated layer and no chemical bond is formed between the core fine particle and the polymer coated layer even by the progress of the above-mentioned reaction.

The formation of the polymer coated layer included in the present invention is carried out in a water-based medium. The above-mentioned water-based mediums include a mixed solvent of water and an organic solvent as well as the case of using only water as a reaction solvent. Organic solvents are preferable to be hydrophilic and include, for example, alcohols such as methanol, ethanol, isopropyl alcohol, n-propyl alcohol, and allyl alcohol; glycols such as ethylene glycol, propylene glycol, butylene glycol, hexylene glycol, pentanediol, hexanediol, heptanediol, and dipropylene glycol; ketones such as acetone, methyl ethyl ketone, and methyl propyl ketone; esters such as methyl formate, ethyl formate, methyl acetate, and methyl acetoacetate ; ethers such as diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol dimethy ether, ethylene glycol

monomethyl ether, and ethylene glycol monoethyl ether These solvents may be used independently, and may be used in two or more kinds together. Further, in case of that the above-mentioned initial condensation compound is hard to dissolve in water, it is preferable to use the above-mentioned mixed solvent. In this case, the blending amount of an organic solvent is preferable to be 50 % by mass or less to the total amount of the organic solvent and water, and more preferable to be 40 % by mass or less.

Further, organic solvents (other solvent) other than the above-mentioned hydrpphilic organic solvents may be used. In concrete terms, dioxane, hexane, cyclopentane , pentane, isopentane, octane, benzene, toluene, xylene, ethylbenzene , petroleum ether, terpene, ricinus, soy oil, paraffin, kerosene and the like can be exemplified. In case of using these other organic solvents, the amount used is preferable to be 30 % by mass or less in the mixed solvent consisting of the above-mentioned water-a hydrophilic organic solvent, more preferable to be 25 % by mass or less, and further preferable to be 20 % by mass or less.

The concentration of the core fine particles in a water-based medium- is preferable to be 1 % by mass

or more and more preferable to be 2 % by mass or more, and preferable to be 60 % by mass or less and more preferable to be 50 % bymass or less. When the amount of the core fine particles is too much, the coherence of the core fine particles may occur in the coating process, and when the amount is too little, the polymer component derived from compound (A) and compound (B) that having no core fine particle may precipitate in the medium. The amount of the above-mentioned surfactant added is preferable to be 1 % by mass or more to the core fine particles, more preferable to be 3 % by mass or more and further preferable to be 5 % by mass or more, and preferable to be 50 % by mass or less, more preferable to be 30 % by mass or less and further preferable to be 25 % by mass or less. When the blending amount of the surfactant is too little, the dispersion state of the core fine particles may not be held sufficiently stable and the core fine particles may be cohered mutually . On the other hand, when the blending amount is too much, the viscosity of the whole reaction system rises rapidly and stirring may become difficult. Moreover, from the viewpoint of the physical properties of coated fine particle to be obtained, when the blending amount of

a surfactant is within the above-mentioned range, suitable flexibility can be given to the polymer coated layer and the mechanical strength of the polymer coated layer can be consequently improved. In the manufacturing method of the present invention, the method of dispersing the core fine particles in a water-based medium is not limited and heretofore known dispersion methods can be adopted. For example, a water-based medium and a mixture containing the core fine particles and a surfactant are strongly stirred mechanically and dispersed with a machine of an ultrasonic disperser, a disper, a homomixer (manufactured by Tokushu Kikai Kogyo Co., Ltd.), a homogenizer (manufactured by Nippon Seiki Co., Ltd.) or the like.

Further, the above-mentioned surfactant may be dissolved in the water-based medium before the core fine particles are dispersed in the water-based medium, or may be dissolved at the same time or after of the dispersion. The timing of the addition is not especially limited.

After that, an initial condensation compound is added in the water-based medium in which the core fine particles have been dispersed. Although the amount of the above-mentioned initial condensation compound

added is not limited, the amount is preferable to be 0.1 parts by mass or more to 1 parts by mass of the above-mentioned surfactant, more preferable to be 0.2 parts by mass or more and further preferable to be 0.3 parts by mass or more, and preferable to be 10 parts by mass or less, more preferable to be 5 parts by mass or less and further preferable to be 3 parts by mass or less. The thickness of the polymer coated layer can be easily controlled by adjusting the amount of the initial condensation compound added. When the added amount of the above-mentioned initial condensation compound is too little, the polymer coated layer with sufficient thickness is hard to be formed. When the amount is too much, large deviation is produced in the component composition of the polymer coated layer. As a result, the strength of the polymer coated layer may be lowered and the adhesion with metals may be deteriorated.

The method for adding the above-mentioned initial condensation compound in a water-bas ed medium is not limited. Addition in one lot will be accepted and addition in succession (continuous addition and/or intermittent addition) will be also accepted. In the manufacturing method of the present invention, temperature at the time of forming the

polymer coated layer (temperature of the water-based medium in which the core fine particles have been dispersed and a water soluble compound has been added) is preferable to be 25 to 85°C, more preferable to be 30 to 70°C, and further preferable to be 35 to 60°C. Besides, pH of the reaction liquid at the time of forming the polymer coated layer is preferable to be 2 to 13, more preferable to be 3 to 12, and further preferable to be 4 to 11. When pH of the reaction liquid is within the above-mentioned range, the coherence of the core fine particles is hard to be occurred and the reaction speed can be controlled easily. The reaction time is preferable to be 10 to 480 minutes, more preferable to be 30 to 360 minutes, and further preferable to be 60 to 300 minutes.

An aging period may be set after forming the above-mentioned polymer coated layer. Temperature during the aging period is not especially limited, but is preferable to be, for example, 200°C or less. The aging time is also not limited, and is preferable to be 1 to 5 hours and more preferable to be 1 to 3 hours. The pH of the solution during the aging period- is preferable to be in the range of 2 to 13. Moreover, aging may be carried out under pressure. In this case, pressure is not especially limited, but is preferable

to be, for example, in the range of atmospheric pressure to 20 atmosphere.

Further, when epoxy resin is contained in the polymer coated layer, although the amount of the epoxy compound added is not especially limited, the amount is preferable to be 0.5 parts by mass or more and 10 parts by mass or less to 1 parts by mass of the core fine particles. It becomes easy to control the thickness of the epoxy resin layer (polymer coated layer) to be formed by adjusting the amount of the epoxy compound added. In addition, when the amount added is too little, it may be difficult to obtain the effect of improving adhesion with metals by forming an epoxy resin layer. Although it does not especially hinder even if the amount added exceeds 10 parts by mass, the improvement of the adhesion with metals, which corresponds to the amount added, is not recognized, resulting in being economically inferior Consequently, more preferable upper limit is 5 parts by mass and further preferable limit is 3 parts by mas s .

Temperature at the time of forming the above-mentioned epoxy resin layer is preferable to be the same as that at the time of forming the above-mentioned polymer coated layer in cases where

the compound (A) is adopted.

In the manufacturing method of the present invention, an adjusted liquid in which coated fine particles are dispersed in a water-based medium is obtained after forming the above-mentioned polymer coated layer and after aging to be carried out as occasion demands.

In the manufacturing method of the present invention, a surfactant and the above-mentioned compound (A) and/or compound (B) are further added in the above-mentioned adjusted liquid as occasion demands, and the ring-opening and/or polycondensation reaction may be carried out. This leads to the formation of a similar polymer coated layer on the surface of the polymer coated layer formed previously. As a result, coated fine particles having a stratified polymer coated layer can be obtained. A coated polymer in which plural polymer coated layers are prepared, for example, can improve physical properties that have been obtained by the single polymer coated layer. In addition, changing the composition of the constituents in the outside layer and the inside layer in the polymer coated layer will reveal different physical properties. In concrete terms, in addition to have

the original property of the polymer coated layer, further, such effects can be obtained that physical properties including mechanical properties and hydrophilic property can be introduced easily. After the polymer coated layer is formed, the coated fine particles may be isolated as occasion demands. For example, after the coated fine particles are adjusted, the coated fine particles only have to be separated from the water-based medium and the like by suction filtration or spontaneous filtrat ion .

Moreover, in order to obtain coated fine particles with narrow particle size distribution, the coated fine particles after being isolated may be classified. As for classification, it is preferable to adopt a classification method in a wet state (wet classification) . The wet classification is a method of classifying coated fine particles on an adjusted liquid in which the coated fine particles are dispersed. Because classification is carried out on the above-mentioned adjusted liquid, it is a wet classification. The- wet classification is a method' that the above-mentioned adjusted liquid is subjected to classification treatment as it is or after diluting with any water-based medium to classify the coated

fine particles in the adjusted liquid so that the classified coated fine particles become to have the desired particle size or particle size distribution. The wet classification can be carried out with, for example, a method or device using a sieve method (a filter method), a centrifugal sedimentation method, a spontaneous sedimentation method or the like. As for coated fine particles having relatively large particle diameter, a sieve method can be used effectively.

Moreover, in order to remove impurities for improving the product quality, obtained coated fine particles are preferably washed.

Hereinafter, characteristics and various physical properties of the coated fine particle of the present invention will be described.

The coated fine particle of the present invention include such particle as the surface of the core fine particle are exposed on the part of coated fine particle as well as such particle as the whole of the surface of the core fine particle is covered with polymer coated layer. However, when the exposed part of the core fine particle is much, the adhesion with metals is lowered and forming a uniform conductor layer (described later) on the surface of the fine

particle may become difficult. Such defects cause bad continuity or lower the reliability of continuity when being used as conductive fine particle. Consequently, the coverage of the core fine particle with the polymer coated layer is preferable to be 40% or more, more preferable to be 50% or more, and further preferable to be 55% or more. Of course, the most preferable coverage is 100%.

As for the coated fine particle in the present invention, the form of a constituent derived from the above-mentioned surfactant may be that consisting of one molecule of the surfactant, or may be those of two or more molecules gathered such as a dimer and a trimer, and the form is not limited. Among these, only one kind may be contained in the polymer coated layer, two or more kinds may be contained in the polymer coated layer.

Although the content ratio of a constituent derived from the above-mentioned surfactant is not limited, it is preferable to be 5 % by mass or more to the whole amount of the polymer coated layer, more preferable to be 10 % by mass or more and further preferable to be 15 % by mass or more, and preferable to be 80 % by mass or less, more preferable to be 75 % by mass or less and further preferable to be 70 % by

mass. When the content ratio is low, flexibility is lowered and the polymer coated layer may become low in mechanical strength. When the content ratio is too high, the adhesion with metals may be lowered. Similarly, as the form of a constituent derived from an initial condensation compound (a compound (A) ) , that is the constituent of the polymer coated layer in the coated fine particle of the present invention, a wide variety of amino resins (urea type resins, melamine resin, guanamine type resins) can be cited. Among these resins, only one kind may be contained in the polymer coated layer, and two or more kinds may be contained in the polymer coated layer.

The content ratio of a constituent derived from a compound (A) and/or a compound (B) is preferable to be 20 % by mass or more to the whole amount of the polymer coated layer, more preferable to be 25 % by mass or more and further preferable to be 30 % by mass or more, and preferable to be 95 % by mass or less, more preferable to be 90 % by mass or less and further preferable to be 85 % by mass or less. When the content ratio is less than the above-mentioned range, the adhesion with metals may not be sufficient, and when the content ratio is over the above-mentioned range, the polymer coated layer may become poor in

flexibility and low in mechanical strength.

The polymer coated layer of the coated fine particle of the present invention may contain other component other than the above-mentioned component within the range where the effect of the present invention is not detracted. As the other constituents, for example, other constituents derived from the above-mentioned other compounds that can be used together with the above-mentioned surfactants can be cited. In concrete terms, constituents derived from polyvinyl alcohols, constituents derived from various surfactants other than the above-mentioned surfactants, components derived from natural high-molecular dispersants such as gelatin and gum arabic, components derived from synthetic high-molecular dispersants including styrene-maleic acid copolymer and its salts, and the like can be cited.

The shapes of the coated fine particle of the present invention are not especially limited and include, for example, a globular shape, a needle shape, a plate shape, a scale shape, a pulverized shape, a slanted shape, a cocoon shape, and a confetti shape. The coated fine particles of the present invention that have the above-mentioned constitution

is preferable to be 5O N / mm 2 or more in compressive elastic modulus (10% K value) and 5% or more in compressive deformation recovery factor when the diameter of the coated fine particle was transformed by 10%. Compressive elastic modulus is preferable to be 1000 N / mm 2 or more and further preferable to be 2450 N / mm 2 or more, and compressive deformation recovery factor is preferable to be 10% or more and further preferable to be 15% or more. Here, the above-mentioned compressive elastic modulus (10% K value) is an index of flexibility of the coated fine particle and compressive deformation recovery factor is an index of elastic force of the coated fine particle, respectively. Although the upper limits are not especially limited, the compressive elastic modulus is preferable to be 20000 N / mm 2 or less, more preferable to be 15000 N / mm 2 or less, and further preferable to be 10000 N / mm 2 or less. When compressive elastic modulus is too small, because the coated fine particle are too flexible, in case of being used as a gap holding material between various substrates, it may be difficult to keep the gap interval uniformly. On the other hand, the modulus is too large, because the coated fine particle are too hard, in case of being used as a gap holding

material, the surface of the substrate may be damaged.

The above-mentioned compressive deformation recovery factor is an index of elastic force of the coated fine particle. In cases where a constant load is applied on the coated fine particle and is removed, the compressive deformation recovery factor is obtained from the change in particle diameter of the coated fine particle before and after applying load. The compression deformation recovery factor in the coated fine particle of the present invention is preferable to be 5% or more, more preferable to be 10% or more, and further preferable to be 15% or more. The upper limit of the compression deformation recovery factor is not especially limited and, of course, it goes without saying that 100%, that is, the particle diameter of the coated fine particle preferably does not change before and after applying load.

Moreover, in the coated fine particles of the present invention, the amount of displacement at the time of 1 g load is preferable to be 5% or more to the diameter of the coated fine particle. The above-mentioned amount of displacement at the time of 1 g load is an index of easiness of deformation of the coated fine particle in the present invention,

especially easiness of deformation at the time of applying low load. The above-mentioned amount of displacement at the time of 1 g load is preferable to be 5% or more, more preferable to be 10% or more and further preferable to be 20% or more, and preferable to be 85% or less, more preferable to be 80% or less and further preferable to be 75% or less. Similarly to the compressive deformation recovery factor, when the amount of displacement at the time of 1 g load is not contained in the above-mentioned range, in case of being used in the application as a gap holding material between various substrates, it is apt to be difficult to keep the gap interval uniformly . Although the average particle diameter of the coated fine particles of the present invention is not especially limited, it is preferable to be 1.0 μm or more, more preferable to be 2.0 μm or more, and preferable to be 100 μm or less, more preferable to be 70 μm or less and further preferable to be 50 μm or less. When the particle diameter of the coated fine particle is too small, the particle may be polymer fine particle consisting of only initial condensate involving no core particle, and when the particle diameter is -too large, it may be difficult

to hold the physical properties required as normal coated fine particle.

Although the narrowness of the particle size distribution of the coated fine particles of the present invention is not especially limited, for example, the coefficient of variation (Cv value) of the particle diameter is preferable to be 10% or less, more preferable to be 5% or less, and further preferable to be 4% or less. When the coefficient of variation (Cv value) is within the above-mentioned range, in case of being used in the application as a gap holding material to make, gaps between various substrates uniform, the coated fine particle can exhibit the advantageous effect of keeping the gap interval uniformly. On the other hand, the coefficient of variation (Cv value) is over the above-mentioned range, in case of being used as a gap holding material, the particle may not be sufficient to keep the uniformity of the gap interval. Further, the above-mentioned properties

(elasticity and compressive elastic modulus) and particle diameter of the coated fine particles of the present invention, and its coefficient of variation (that is, narrowness of the particle size distribution) depend -s igni ficant Iy on the properties

of the core fine particle (particle diameter and particle size distribution) . Accordingly, the coated fine particle having the desired properties can be obtained by suitably adjusting manufacturing conditions of the core fine particle.

Although the thickness of the polymer coating of the present invention is not limited, it is preferable to be 0.001 μm or more, more preferable to be 0.005 μm or more and further preferable to be 0.008 μm or more, and preferable to be 10 μm or less. When the thickness of the polymer coating is too thin, not only the coating is in danger of lowering adhesion with metals, but also the strength of the coated fine particle may be lowered. On the other hand, when the thickness is too thick, because the rate of the core fine particle occupying in the coated fine particle becomes small, flexibility and elasticity may not be sufficient .

Next, the conductive fine particle included in the present invention will be described.

The conductive fine particle included in the present invention is made by forming conductor layer on the surface of the above-mentioned coated fine particle included in the present invention. The above-mentioned conductor layer only has to be formed

at least a part of the coated fine particle.

Although metals constituting the above-mentioned conductor layer are not especially limited, the metals include, for example, nickel, gold, silver, copper, indium, and their alloys. Among these metals, nickel, gold, and indium are preferable because of having high electric conductivity. Although the thickness of the above-mentioned conductor layer is not especially limited as long as there is enough electric conductivity, the thickness is preferable to be 0.01 μm or more and more preferable to be 0.02 μm or more, and preferable to be 5.0 μm or less and more preferable to be 2.0 μm or less. When the thickness of the conductor layer is too thin, the electric conductivity may become insufficient. On the other hand, when the thickness is too thick, the conductor layer may be apt to flake away because of the difference between coefficients of thermal expansion in the conductor layer and the polymer coated layer. The conductor layer may be one layer or two layers or more. In case of two layers or more, different kinds of metals may be laminated.

The method for forming conductor layer on the surface of the coated fine particle of the present

invention is not especially limited and heretofore known methods can be adopted. For example, the electroless plating (chemical plating) method, the coating method, the PVD (vacuum deposition, sputtering, ion plating, and the like) method, and the like can be cited. Among them, the electroless plating method is preferable because a conductor layer can be formed easily.

Generally, the above-mentioned electroless plating method is comprised of an etching process, an activating process, and an electroless plating process. Here, although the ab.ove-mentioned etching process is a process where concave and convexity are formed on the surface of the coated fine particle to improve the adhesion of the electroless plated layer, because the coated fine particle included in the present invention is provided with polymer coated layer having good adhesion with metals, the etching process is not an essential process and can be omitted In addition, when the etching process is carried out, it only has to use, for example, an alkali aqueous solution like caustic soda aqueous solution, or an aqueous solution of acids such as hydrochloric acid, sulfuric acid, and chromic anhydride as an etching solution. Further, following activating process and

electroless plating process only have to be carried out according to heretofore known methods.

Because the conductive fine particle of the present invention is those having the above-mentioned coated fine particle of the present invention as the base material particle, the conductive fine particle have necessary hardness and compressive deformation recovery factor to keep constantly the gap interval between one pair electrode base plates to be electrically connected and, in addition, is hard to give physical damage to the electrodes. Consequently, the gap interval between one pair electrode base plates is easily kept constantly, and the following troubles can be prevented: the exfoliation of a conductor layer owing to pres suri zat ion , a short-circuit between electrodes that should not be electrically connected, contact failure between electrodes that should be electrically connected, and others. The conductive particle thus obtained of the present invention has the same mechanical properties (hardness, breaking strength) as the above-mentioned coated fine particle of the present invention. Consequently, the conductive particle is especially useful as an electric connection material in

electronics such as a liquid crystal display panel, LSI, and a printed wiring board.

Example Hereinafter, the present invention will be described in detail based on examples. However, the following examples should not limit the present invention, and all changes and their implementation without departing from the above-mentioned purport and from that to be hereinafter described are included in the technical scope of the present invention. The measurement methods are as follows.

[Measurement of the thickness of a polymer coated layer] Particle diameters were measured before and after giving the coating layer with Coulter multicizer II (manufactured by Beckmann Coulter Inc. ) The thickness of the coated layer was calculated by dividing the difference of the particle diameters before and after giving the coating layer by 2. The particle diameters and coefficients of variation in the particle diameters of the coated fine particles are shown together in Table 1.

_ j^ . . _ . . ,„ N Standard deviation of particle diameter

Coefficient of vaπation(Cv) = x 100

Average particle diameter

[Evaluation of the surface aspect of a polymer coated layer]

The surface state of particle before and after the formation of the polymer coated layer was observed with a scanning electron microscope (SEM, S3500N manufactured by Hitachi, Ltd., and the results were evaluated by three stages according to the following criteria .

(Evaluation criteria) 1. The polymer coated layer on the surface of the core particle is very thin, or the polymer coated layer is not formed and the particle exists independently.

2. The surfaces of the core particle is covered with a uniform polymer coated layer, the particle exists independently.

3. The surface of the core particle is covered with much of resins, and particles are adhered each other by the resin. [Adhesion of plating]

Electroless plating treatment was performed on 10 g of coated fine particles obtained by the following manufacturing examples. The plated states of the surfaces of the particles after the treatment were observed with an electron microscope, and the

results were evaluated according to the following criteria .

(Evaluation criteria)

"o" (good) '• The surface of the particle is uniformly covered with nickel coated layer.

"x" (poor): No nickel coated layer is formed on the surface of the particle.

[Average particle diameter, and the coefficient of variation of particle diameters] As for the average particle diameters of polysiloxane particles and polymer fine particles, particle diameters of 30,000 pieces of particles were measured with Coulter multicizer (manufactured by Beckmann Coulter Inc.), and the average particle diameters were obtained.

The coefficients of variation of the particle diameter were obtained according to the following formula .

Coefficient of variation in particle diameter (%) = (σ/X) xlOO

Here, σ is standard deviation of particle diameter, X indicates average particle diameter.

[10% Compressive elastic modulus (10% K value: hardne s s ) ] On one of the sample particles which was

scattered on a sample stage (material: SKS flat place) with a Shimazu mi crocompre s s ion testing machine (MCTW-500, manufactured by Shimazu Corporation) at room temperature (25°C) , load is applied toward the center of the particle at the constant load speed (2.275 rriN / second) by the use of a circular flat plate indenter (material: diamond) of 50 μm in diameter, and the load and the amount of displacement (mm) are measured when the particle is deformed until the compressive displacement is 10% of the particle diameter. The measured compressive load, compressive displacement of particle, and particle diameter are substituted in the following formula to calculate the value:

(wherein, E: Compressive elastic modulus (N / mm 2 ), F: Compressive load (N), S: Compressive displacement (mm) , and R: Radius of particle) . This operation is performed on different 3 pieces of particles and the average value is referred to as 10% compressive elastic modulus.

[Compressive deformation recovery factor (recovery factor) ]

After sample particle is compressed to the

inversion load of 9.8 mN with the use of a mi crocompres s ion testing machine (MCTW-500, manufactured by Shimazu Corporation), when the load is being decreased, a value obtained by measuring the relationship between the load value and the compression displacement is the compression deformation recovery factor. The terminal point of load removing is set as the starting point load value of 0.098 mN and compression speed at load applying and load removing is set as 1.486 mN / second and then the measurement is carried out. The value shown as the ratio of the displacement .(L 1) to the point of inversion and the displacement (L 2) from the point of inversion to the point of starting point load value (L 1 / L 2) is the recovery factor [%] .

[Amount of displacement (compressibility) at the time of 1 g load]

On one of the sample particles which was scattered on a sample stage (material: SKS flat place) with a microcompres s ion testing machine (MCTW-500, manufactured by Shimazu Corporation) at room temperature (25°C) , load is applied toward the center of the particle at the constant load speed by the use of a circular flat plate indenter (material: diamond) of 50 μm in diameter. And the value (L 3 / D) [%] that

the amount of displacement of the particle (L 3) at the point load is applied to 0.098 mN (Ig load) is shown as the ratio to particle diameter (D) is referred to as the amount of displacement. Synthesis example (1) : Synthesis of an initial condensation compound; Synthesis of (compound (a)) . In a 50 ml separable flask, 3 g of urea, 7 g of melamine, 20 g of 37 mass % formalin, and 1.5 g of 25 mass % aqueous ammonia were fed and the mixture was heated to 7O 0 C while stirring. After keeping at the temperature for 15 minutes, the mixture was cooled to room temperature and compound (a) of homogeneous solution (the concentration of solid content: 55 % by mass to the total amount of the compound (a) of homogeneous solution) that was an initial condensation compound of melamine, urea and formaldehyde was obtained.

Synthesis example (2) : Synthesis of a surfactant ( compound ( b ) ) In a 300 ml separable flask, 14.5 g of polyethylene imine ("Epomine SP006", the weight average molecular weight = 600, manufactured by Nippon Shokubai Co., Ltd.) and 43.5 g of water fed initially. After that, 97.2 g of 25 mass % of epoxy compound (lauryl polyoxyethylene (n=22) glycidyl

ester, the solubility in water: 100%) prepared in advance was dropped for 10 minutes while stirring.

Liquid temperature was kept at 25°C or less during the dropping. After the end of dropping, the mixture was continuously stirred for about 30 minutes and then heated to 70°C. After being kept at the temperature for 2 hours, the mixture was cooled to ordinary temperature to give compound (b) having dispersibility (the concentration of solid content: 25 % by mass to the total amount of the mixture) .

Synthesis example (3) : Synthesis of core fine particle (organic and inorganic composite fine particle)

In a four-neck flask with a condenser, a thermometer and a dropping funnel, a mixed solution of 250 parts of water and 10 parts of 25% aqueous ammonia was put and a mixed solution of 30 parts of γ-methacryloxy propyltrimethoxys ilane and 125 parts of methanol was dropped through the dropping funnel while stirring. γ-Methacryloxy propyltrimethoxys ilane was thus hydrolyzed and condensed to prepare polysiloxane particles (inorganic particle) . After one hour from the start of the reaction, 250 parts of water was dropped through the dropping funnel to dilute the

polysiloxane particles dispersion liquid. Stirring was continued for 2 hours from the start of the reaction and the polysiloxane particles dispersion liquid was obtained (the average particle diameter: 1.83 μm, the coefficient of variation: 3.17%) .

In a flask different from the above-mentioned four-neck flask, 0.7 parts of anionic emulsifying agent (LA-IO, manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.), 70 parts of water, and 100 parts of NK ester APG-400 ( Shin-Nakamura Chemical Co. , Ltd. ) , 20 parts of 1 , 6-hexanediol dimethacrylate and 0.5 parts of 2 , 2-azobis (2, 4 -dimethylovaleronit rile ) ("V-65", manufactured by Wako Pure Chemical Industries, Ltd.) were mixed, and the mixture was emulsified and dispersed with a homogenizer for 5 minutes to prepare a monomer emulsion.

After the above-mentioned organic and inorganic composite particle dispersion liquid was stirred for 30 minutes, the above-mentioned monomer emulsion was added in the dispersion liquid in 15 seconds and the mixture was further stirred for 30 minutes. At this time, the polysiloxane particle was observed with a microscope, and it was confirmed that the inorganic particle had absorbed the monomer because the particle diameter was' increased. After one hour from

the addition of the monomer emulsion, 1000 parts of water was added in the dispersion liquid of the organic and inorganic composite particles in which the monomer had been absorbed. The reaction, liquid was heated to 75°C under the nitrogen atmosphere and kept at the temperature for 30 minutes. As a result, the radical polymerization was performed in the reaction liquid to give a core fine particle emulsion (the average particle diameter: 3.8 μm, the coefficient of variation: 2.9%) .

After the obtained core fine particle emulsion was filtered and washed with ethanol, the particles were dried under vacuum at 100°C for 4 hours and core fine particles were obtained. The properties of the obtained core fine particles are shown in Table 1. Synthesis example (4) : Synthesis of polystyrene parti cle s

In a four-neck flask with a condenser, a thermometer and a dropping funnel, 2 parts of polyvinylpyrrolidone (the weight average molecular weight (Mw) is 30,000), and 1 part of a zobi smethylvaleronitrile were dissolved in 150 parts .of isopropanol. While stirring the solution under nitrogen, 15 parts of styrene was put into the solution. Then, the ' solution was heated to 60°C and

the polymerization reaction was performed for 24 hours to give polystyrene particle dispersion liquid (the average particle diameter: 5.1 μm, the coefficient of variation: 7.3%) .

Polystyrene particles were separated from the obtained dispersion liquid and washed, classified, and dried to give polystyrene particles (the average particle diameter is 5.1 μm and the coefficient of variation is 4.8%) . The properties of the obtained polystyrene particles are shown in Table 1.

Table 1

Manufacturing example 1 In a 300 ml beaker, 10 g of the solution of compound (b) obtained in Synthesis example (2) and 2Og of the core fine particles obtained in Synthesis example (3) were put and mixed with a spatula, and then 50 g of water was added in the mixture. After

that, the mixture was subjected to ultrasonic and the core fine particles were dispersed (dispersion liquid Cl) .

In 300 ml a flat-bottom separable flask with a stirrer, the above-mentioned dispersion liquid Cl was put and 6 g of the solution of compound (a) was added while stirring (at the number of revolutions of 200 rpm) , and then the mixture was heated to 40°C. After being kept at the temperature for 2 hours (a, pH of the reaction liquid was 10 at this time) , 150 ml of water was added in the liquid to cool it to room temperature and coated fine particles Dl was obtained The thickness of the polymer coated layer and the evaluation result on the surface aspect of the coated fine particles Dl are shown in Table 2. Moreover, electron microscopic (SEM) pictures of the core fine particles and the coated fine particles Dl used at this time are shown in Fig. 3 and Fig. 4, respectively.

The obtained coated fine particles Dl was plated with Ni by the electroless plating method, and the adhesion of plating was evaluated. The result is shown in addition in Table 2.

Further, Ni plating was carried out as follows. Ten grams of the coated fine particles (Dl) was dispersed in 200 g of 1 mass % aqueous sodium hydroxide

solution and etched by being stirred at 60°C for 2 hours. After being filtered and dried, the coated fine particles (Dl) were dipped into 1 g/1 aqueous solution of stannous chloride at room temperat . ure for 5 minutes and intensified. The coated fine particles after being intensified was added in a catalyzed liquid consisting of 0.1 ml/1 aqueous palladium chloride solution and 0.1 ml/1 hydrochloric acid while stirring and further stirred for 5 minutes to make the coated fine particles catch palladium ions. Then, the coated fine particles were filtered, washed, and further dipped into 1 g/1 -aqueous sodium hypophosphite solution at room temperature for 5 minutes and reduced. Thus, base material particles that palladium was supported on the surfaces of coated fine particles were obtained. Next, the base material particles were added and dispersed in aqueous glycine solution (20 g/1) heated to 65°C under stirring to prepare slurry. In this slurry under stirring, a nickel electroless plating liquid containing aqueous nickel sulfate solution, aqueous sodium hypochlorite solution, and aqueous sodium hydroxide solution was added at the rate of 5 ml/minute. After the whole amount of the nickel electroless plating liquid was added, the liquid

temperature was kept at 65°C and stirring was continued until hydrogen bubbling was stopped. After the stop of hydrogen bubbling, fine particles were filtered and washed, and dried in a vacuum dryer (at 100 0 C) to give conductive fine particles having nickel coating.

Manufacturing example 2

In 300 ml a flat-bottom separable flask with a stirrer, the dispersion liquid Cl was put and 6 g of the solution of compound (a) was added while stirring

(at the number of revolutions of 200 rpm) , and then the mixture was heated to 40°C. After being kept at the temperature for 3 hours, 150 ml of water was added in the mixture to cool it to room temperature and coated fine particles D2 was obtained. And, the coated fine particles D2 were plated with Ni by the same method as that in the above-mentioned Manufacturing example 1. The evaluation results on the properties (the thickness, the surface aspect and the adhesion of plating of the polymer coated layer) of the obtained coated fine particles D2 are shown in Table 2.

Manufacturing example 3

In a 300 ml beaker, 5 g of the solution of compound (b) obtained in Synthesis example (2) and 20g of the

organic and inorganic composite particles obtained in Synthesis example (3) were put and mixed with a spatula, and then 50 g of water was added in the mixture After that, the mixture was subjected to ultrasonic and the core fine particles were dispersed (dispersion liquid C2) .

In 300 ml a flat-bottom separable flask with a stirrer, the dispersion liquid C2 was put and 6 g of the solution of compound (a) was added while stirring (at the number of revolutions of 200 rpm) , and then the mixture was heated to 40 0 C. After being kept at the temperature for 3 hours, 150 ml of water was added in the mixture to cool it to room temperature and coated fine particles D3 was obtained. And, the coated fine particles D3 were plated with Ni by the same method as that in the above-mentioned Manufacturing example 1. The properties of the obtained melamine coated particles D3 are shown in Table 2. Manufacturing example 4

In 300 ml a flat-bottom separable flask with a stirrer, the dispersion liquid Cl was put and 6 g of the solution of compound (a) was added while stirring (at the number of revolutions of 200 rpm) , and then the mixture was heated to 50 0 C. After being kept at

the temperature for 1 hour, 150 ml of water was added in the mixture to cool it to room temperature and coated fine particles D4 was obtained. And, the coated fine particles D4 were plated with Ni by the same method as that in the above-mentioned

Manufacturing example 1. The properties of the obtained coated fine particles D4 are shown in Table 2.

Manufacturing example 5 In a 300 ml beaker, 10 g of the solution of compound (b) obtained in Synthesis example (2) and 2Og of polystyrene particles obtained in Synthesis example (4) were put and mixed with a spatula, and then 50 g of water was added in the mixture. After that, the mixture was subjected to ultrasonic and the core fine particles were dispersed (dispersion liquid C3) .

In 300 ml a flat-bottom separable flask with a stirrer, the dispersion liquid C3 was put and 6 g of the solution of compound (a) was added while stirring (at the number of revolutions of 200 rpm) , and then the mixture was heated to 50°C. After being kept at the temperature for 1 hour, 150 ml of water was added in the mixture to cool it to room temperature and coated fine particles D5 was obtained. And, the

coated fine particles D5 were plated with Ni by the same method as that in the above-mentioned Manufacturing example 1. The properties of the obtained coated fine particles D5 are shown in Table 2.

Manufacturing example 6: Formation of a conductive layer

The coated fine particles D3 obtained in Manufacturing example 3 were plated with Ni by the electroless plating method without being etched, and then nickel-gold plating layer was formed on the fine particles by a substitution reaction with gold and conductive fine particles were obtained.

The gold plated layer was formed in the following manner. In an electroless plating liquid (an aqueous solution that has a composition of 10 g/1 of ethylenediaminetetraacetic acid-4Na, 10 g/1 of citric acid-2Na, 3.0 g/1 of potassium cyanide, and further 2.1 g/1 of Au and pH is adjusted to be 6 with aqueous sodium hydroxide solution) , in which liquid temperature was kept at 60°C, nickel plated fine particles were added and plated with Au while stirring. After plating, Au plated fine particles were filtered, washed, and dried in a vacuum dryer (at 100 0 C) to give conductive fine particles having Au plated nickel

c o a t i ng .

When the adhesion of plating of obtained conductive fine particles was observed with SEM (scanning electron microscope) and XMA (X-ray micro analyzer) , it was confirmed that the surfaces of the coated fine particles were covered with Ni and further gold plated layer was formed on the Ni layer. Manufacturing example 7 In a 300 ml beaker, 10 g of the solution of compound (b) obtained in Synthesis example (2) and 2Og of the organic and inorganic composite particles obtained in Synthesis example (3) were put and mixed with a spatula, and then 30 g of water and 20 g of methanol was added in the mixture. After that, the mixture was subjected to ultrasonic and the organic and inorganic composite particles were dispersed (dispersion liquid C4) .

In 300 ml a flat-bottom separable flask with a stirrer, the dispersion liquid C4 was put and heated to 7O 0 C while stirring (at the number of revolutions of 200 rpm) , and then 3g of glycerol polyglycidyl ether (Denacol EX-145, manufactured by Nagase Chemtex Corporation) was added. After being kept at the temperature for 1 hour, 150 ml of water was added in the liquid to cool it to room temperature and epoxy

coated particles were obtained. The obtained particles were washed, classified, and dried to give epoxy coated fine particles Dβ. And, the coated fine particles D6 were plated with Ni by the same method as that in the above-mentioned Manufacturing example 1. The properties of the obtained coated fine particles D6 are shown in Table 2. Manufacturing example 8 With the use of the core fine particles (organic and inorganic composite particles) obtained in

Synthesis example (3), electroless Ni plating and a substitution reaction with gold were performed by the same methods as those in the above-mentioned Manufacturing example 6 and conductive fine particles on which nickel-gold plated layer had been formed were obtained. The evaluation result on the adhesion of plating of the obtained conductive fine particles is shown in Table 2.

Manufacturing example 9 With the use of the polystyrene particles obtained in Synthesis example (4), electroless Ni plating and a substitution reaction with gold were performed by the same methods as those in the above-mentioned Manufacturing example 6 and conductive fine particles on which nickel-gold plated

layer had been formed were obtained. The evaluation result on the adhesion of plating of the obtained conductive fine particles is shown in Table 2.

Manufacturing example 10 In a 300 ml beaker in which 50 g of water had been put, 20 g of the core fine particles obtained in Synthesis example (3) , and the mixture was subjected to ultrasonic and the core fine particles were dispersed (dispersion liquid C5) . In 300 ml a flat-bottom separable flask with a stirrer, the above-mentioned dispersion liquid C5 was put and 6 g of the solution of compound (a) was added while stirring (at the number of revolutions of 200 rpm) , and then the mixture was heated to 40°C. As a result, when 30 minutes passed from the start of the reaction, cohered substances and precipitation were produced. When precipitates were observed with a optical microscope, it was confirmed that the core fine particles were cohered together with a lot of scaly deposits. Further, because single particle could not take out from the precipitates, no evaluation on the adhesion of plating was carried out. Manufacturing example 11 In a 300 ml beaker, 20 g of the core fine particles (organic and inorganic composite particles) obtained

in Synthesis example (3) and 0.5g of sodium dodecylbenzenesul fonate were put and mixed with a spatula, and then 30 g of water was added in the mixture, After that, the mixture was subjected to ultrasonic and the core fine particles were dispersed (dispersion liquid C6) .

In 300 ml a flat-bottom separable flask with a stirrer, the dispersion liquid C6 was put and heated to 90°C while stirring (at the number of revolutions of 200 rpm) , and then 6 g of the solution of compound

(a) that was obtained in Synthesis example (1) and

5 g of 10 % by mass aqueous dodecylbenzene sul fonic acid solution were added. After being kept at the temperature for 8 hour, 150 ml of water was added in the liquid to cool it to room temperature and polymer coated particles were obtained. Because the obtained particles were cohered, after being washed and dried, the particles were pulverized, and then classified and refined. As a result, polymer coated particles D7 were obtained.

The coated fine particles D7 were plated with Ni by the same method as that in the above-mentioned' Manufacturing example 1. The properties of the obtained coated fine particles D7 are shown in Table 2.

Table 2

O

From Table 2, it is understood that the coated fine particle having polymer coated layer included in the present invention exhibit good adhesion of plating. In contrast with this, the fine particle having no polymer coated layer in Manufacturing examples 8 and 9 were poor in adhesion of plating.

INDUSTRIALAPPLICABILITY

According to the present invention, it is possible to obtain coated fine particle that properties of the fine particle such as flexibility and elasticity can be controlled and adhesion to metals are also good. Moreover, since conductive fine particle included in the present invention have the above-mentioned coated fine particle as the base material, the conductive fine particle have also good adhesion to metals and, for example, in case of being used as such conductive fine particle as to be used in an anisotropic conductive material, the peeling of the conductive layer are hard to occur.