DESCRIPTION

ETHYLENICALLY UNSATURATED GROUP-CONTAINING ISOCYANATE

COMPOUND AND PROCESS FOR PRODUCING THE SAME, AND

REACTIVE MONOMER, REACTIVE (METH)ACRYLATE POLYMER AND

ITS USE

CROSS REFERENCES OF RELATED APPLICATION

This application is an application filed under 35

U.S.C. §111 (a) claiming benefit pursuant to 35 U.S.C.

§119 (e) (1) of the filing date of Provision Application

60/626,497 filed on November 10, 2004, 60/704,431 filed on

August 2, 2005, and 60/704,892 filed on August 3, 2005

pursuant to 35 U.S.C. §111 (b) .

TECHNICAL FIELD

The present invention relates to a novel isocyanate

compound containing two or more polymerizable functional

groups usable, for example, in coating materials, UV- and

heat-curable coating materials, molding materials,

adhesives, inks, resists, optical materials,

stereolithographic materials, printing plate materials,

dental materials, and polymer battery materials, and a

process for producing the same. Further, the present

invention relates to a reactive monomer, which is produced

from this isocyanate compound, and is particularly suitable

in optical materials, a curable composition comprising the

same, and a cured product thereof.

The present invention relates to a reactive polymer,

which can provide a curable composition with improved

sensitivity and developing properties in the field of a

photosensitive composition for color filters used in the

production of optical color filters used, for example, in

color televisions, liquid crystal display elements, solid

state imaging devices, and cameras, and can provide a

curable composition with improved flexibility, heat

resistance, chemical resistance, plating resistance and the

like in the field of a photosensitive composition for

solder resists used, for example, in insulating protective

films in printed wiring boards, and a process for producing

the same and use of said reactive polymer. More

particularly, the present invention relates to a reactive

polymer, which is obtained by reacting an isocyanate

compound with a polyhydroxy compound comprising repeating

units and can provide, for example, a curable composition

excellent in curing speed and sensitivity in curing upon

exposure to ultraviolet light or heat, or a curable

composition having high adhesion, high heat resistance

temperature, good chemical resistance and the like, a

process for producing the same and use of said reactive

polymer.

BACKGROUND OF THE INVENTION

Resins which have been rendered reactive have been

used in various fields. Ethylenically unsaturated group-

containing isocyanate compounds are useful for the

production of such resins. For example, an ethylenically

unsaturated group or isocyanate group can be introduced

into the resin through a reaction with a functional group

in the main chain of the resin.

On the other hand, functions such as high curing

speed and high crosslinking density in cured products

obtained therefrom are required of resins and resin

compositions. To impart such functions, ethylenically

unsaturated group-containing isocyanate compounds capable

of introducing a plurality of ethylenically unsaturated

groups into resin molecules and a process for producing the

same have been desired. Further, for applications and

fields where such compounds are used, typified by optical

materials, polyelectrolytes and the like, such compounds

should have high purity.

Regarding the production of such ethylenically

unsaturated group-containing isocyanate compounds, for

example, patent document 1 discloses the following two

production processes. The first process comprises reacting

an amino alcohol with ethyl chlorocarbonate to give ethyl

hydroxycarbamate, then reacting this compound with an

unsaturated carboxylic acid chloride to give an

urethanoester, and then thermally decomposing the

urethanoester in the presence of phosphorus pentachloride

or the like to give an unsaturated carboxylic acid

isocyanatoalkyl ester.

The second process comprises preparing a chloroalkyl

ester by transesterification from a methyl ester of an

unsaturated carboxylic acid and chloroalcohol, then

reacting this compound with an alkali metal isocyanate and

ethanol to give an urethanoester of an unsaturated

carboxylic acid, and then thermally decomposing this

compound in the presence of phosphorus pentachloride or the

like to give an isocyanatoalkyl ester of an unsaturated

carboxylic acid.

These processes, however, suffer from a problem that

phosphorus and sulfur are present as impurities . Further,

the resultant product contains a large amount of by¬

products which appear to derive from the unsaturated group

( for example, HCl adduct of unsaturated group) . Therefore,

these processes involve problems such as very low reaction

yield and the necessity of a large amount of labor for

purification .

Patent document 2 discloses a process which comprises

reacting an unsaturated carboxylic acid chloride with an

amino alcohol hydrochloride to synthesize an aminoalkyl

ester hydrochloride of an unsaturated carboxylic acid and

then reacting this compound with carbonyl chloride to give

an isocyanatoalkyl ester of an unsaturated carboxylic acid .

Patent document 3 discloses a process which comprises

reacting an imidazole derivative with carbonyl chloride,

reacting the resultant compound with a monoalkanolamine,

and then ester ifying the resultant compound using an

unsaturated carboxylic acid or its chloride or ester to

give an isocyanatoalkyl ester of an unsaturated carboxylic

acid .

Also in these processes disclosed in patent documents

2 and 3, however, the resultant compounds contain a large

amount of by-products which appear to derive from the

unsaturated group (for example, HCl adduct of the

unsaturated group) , posing problems such as low reaction

yield and the necessity of a large amount of labor for

purification.

Patent document 4 and patent document 5 disclose a

process in which a 2-alkenyl-2-oxazoline is reacted with

phosgene to give an isocyanatoalkyl ester of an unsaturated

carboxylic acid. This process is very advantageous from

the viewpoints of energy saving and safety and has been

carried out on a commercial scale. Furthermore, patent

document 6 to patent document 9 propose production

processes of 2~alkenyl-2-oxazolines as a precursor compound.

In these processes, however, expensive oxazoline

compounds are used as a starting compound, and, in addition,

the process is long. Therefore, these processes are cost-

ineffective. Further, since a large amount of HCl adducts

of the unsaturated group are contained as by-products,

disadvantageously, for example, a large amount of labor is

required for purification.

Further, patent document 10 discloses a process which

comprises reacting dimethyl carbonate, diethyl carbonate,

or dipropyl carbonate with ethanolamine to synthesize

hydroxy urethane, reacting this compound with an

unsaturated carboxylic acid or its chloride or ester to

give a urethanoester, and thermally decomposing this

compound to give an isocyanatoalkyl ester of an unsaturated

carboxylic acid.

In this process, the thermal decomposition of the

urethanoester is difficult, and the percentage

decomposition is 50% to 60%, for example, even at a high

temperature of 400°C. The unsaturated carboxylic acid isocyanatoalkyl ester contains an ethylenically unsaturated

group and thus is polymerized at this high temperature,

leading to problems of lowered yield and safety problems

such as clogging of the thermal decomposition reactor.

Therefore, the practice of this process on a commercial

scale is considered difficult.

Further, conventional processes are also

disadvantageous in that a large amount of by-produced

chlorine compounds and the like stay in the reaction

solvent. This is considered to affect, for example, the

stability of the contemplated compound at the time of

purification. Further, in the prior art documents, there

is no description on a technique albout a compound

containing in its molecule two or .more polymerizable

functional groups, that is, two or more ethylenically

unsaturated groups, and, at the same time, containing an

isocyanate group.

On the other hand, monomers, oligomers or polymers

containing a urethane bond with a reactive ethylenically

unsaturated group-containing isocyanate compound added

thereto have hitherto been used in. various fields such as

coating materials, UV- and heat-cixrable coating materials,

molding materials, adhesives, inks, resists, optical

materials, stereolithographic materials, printing plate

materials, dental materials, polyirLer battery materials, and

starting materials for polymers. IOr example, applications

of optical materials include optical lenses, films,

materials for optical antireflectLon films such as glass

for CRTs, materials for cladding materials for optical

fibers, or optical adhesives, for example, for optical

fibers and optical lenses.

Urea bond-containing monomers, oligomers, or polymers

to which a reactive ethylenically unsaturated group-

containing isocyanate compound was added have also been

used in the same applications.

Regarding compositions used in optical lenses,

comprising a urethane bond-containing compound, patent

document 12 discloses a curable composition comprising a

compound produced by reacting a diol such as a cycloolefin

diol with 2-methacryloyloxyethyl isocyanate.

Patent document 21 discloses a curable composition

comprising urethane (meth) acrylate produced by reacting a

bisphenol-type diol with a polyisocyanate and a hydroxy-

containing (meth) acrylate. In the technique disclosed in

this document, an aromatic ring or cycloolefin ring has

been introduced to enhance the refractive index or

transparency of the lens .

This, however, increases the rigidity of the polymer,

and, thus the adhesion to a mold base material for

providing dimensional accuracy is lowered. Further, upon

curing, the crystalline area is increased, leading to

lowered transparency.

In patent document 13, a fluorine-containing

composition comprising a compound produced by reacting a

carboxyl-containing ethylenically unsaturated monomer with

a copolymer of a f luoroethylenically unsaturated monomer

and glycidyl acrylate is disclosed as a fluorine-containing

f luoroethylenically unsaturated compound which is a low-

refractive index materials used, for example, in materials

for antiref lection films , materials for cladding of optical

fibers, and optical adhesives .

In patent document 14 , a photocurable composition

comprising a (meth) acrylate compound containing in its

structure a urethane bond-containing fluorine-containing

mono functional (meth) acrylate and a f luorinated polyether

is disclosed as a urethane bond-containing polymer or

monomer . Patent document 15 discloses a specific fluorine-

containing ethylenically unsaturated compound produced by

reacting a fluorohydroxy compound with a monofunctional

(meth) acrylate group-containing isocyanate compound .

In patent document 13, the reactivity and the

adhesion to base materials are enhanced by introducing a

reactive group into a polymer side chain by a glycidyl

group . In patent document 14 , a photocurable composition

comprising a fluorine-containing urethane (meth) acrylate

and a fluorine-containing polyether realizes a highly

transparent, low-refractive index ultraviolet-curable

composition. They, however, are monofunctional monomers

and suffer from problems of curability and adhesion.

Further, crystallization upon curing causes a problem of

opacity.

In patent document 15, a fluorine-containing hydroxyl

compound is reacted with acrylic acid and a monofunctional

(meth) acrylate group-containing isocyanate compound for

convertion to a polyfunctional monomer, whereby the

reactivity is enhanced and, at the same time, compatibility

with other monomer is improved. This technique, however,

is disadvantageous, for example, in that the fluorine

content is low and a further increase in fluorine content

causes a lowering in curability.

In the techniques disclosed in the above patent

documents, for the reason that the fluorine content affects

the refractive index, transparency, adhesion, heat

resistance or the like, a curing composition is produced by

mixing or reacting a fluoroethylenically unsaturated

monomer with other polymer, particularly a fluoropolymer.

However, problems of curability and adhesion remain

unsolved. Further, upon curing, a crystalline region is

formed, resulting in clouding.

Furthermore, in patent document 16, a polyfunctional

urethane acrylate produced by adding a diisocyanate to a

bisphenol-type acrylate is disclosed as hardcoat materials

for use in the protection of the surface of glass base

materials for various displays or the like, or plastic base

materials. Patent document 17 discloses a curable

composition comprising a urethane acrylate compound

produced by reacting a polyester polyol or a polycarbonate

polyol with a polyisocyanate and a hydroxyl-containing

(meth) acrylate.

In the techniques disclosed in patent document 16 and

patent document 17, curability, adhesion and surface

hardness are provided by adding a monofunctional isocyanate

to a polyol .

Regarding a urethane bond-containing compound, in

patent document 18, a photocurable composition comprising

an ethylenically unsaturated group-containing oligomer in

which bonding has been achieved through a urea bond, and a

specific photopolymerization initiator is disclosed as a

coating material for optical fibers, which contributes to

an improvement in photocurability and heat resistance of

the overcoat. In order to enhance the curability and heat

resistance, however, specific photopolymerization initiator

and composition are required.

In patent document 19, a thermally polymerized

material produced by allowing an isocyanate-terminated

prepolymer, obtained by reacting an aliphatic diisocyanate

with a diol, to react with an aromatic diamine is disclosed

as a transparent material suitable for optical applications.

In this technique, the transparency and heat resistance are

improved by producing a cured product through a reaction

betwe'en an isocyante group and an amine group.

Patent document 20 discloses a thiourethane having a

specific structure formed from an isocyanate group and a

thiol compound.

In these prior art techniques as well, however,

regarding urethane bond-, urea bond-, or thiourethane bond-

containing reactive monomers, oligomers, or polymers for

use in optical applications or other fields, problems of

curability, adhesion to base materials, transparency, and

heat resistance remain unsolved, and any satisfactory

material has not been developed.

Monomers, oligomers or polymers containing a urethane

bond with the reactive ethylenically unsaturated group-

containing isocyanate compound added thereto have hitherto

been used in various fields. As a result of detailed

review of these prior art techniques, it has been found

that, for the field of resist materials, the reactive

polymer has the following problems in the field of

photosensitive compositions for color filters used in the

production of color filters for LCDs. In conventional

color filters, a black matrix (K) is formed on a surface of

transparent substrate such as glass or a plastic sheet.

Subsequently, three or more different hues such as red (R) ,

green (G) , and blue (B) are formed successively in a color

pattern such as a stripe or mosaic form. The black matrix

is disposed in a lattice, stripe or mosaic form between R,

G, and B color patterns and functions to suppress color

mixing between colors for a contrast improvement or to

prevent light leakage-derived malfunction of a thin film

transistor (TFT) .

Therefore, a high level of light shielding properties

are required of the black matrix, and, as disclosed in

patent document 22, for example, a method in which the

content of light shielding pigments or dyes is increased

has been studied. This method, however, suffers from a

problem that the sensitivity, developability, resolution,

adhesion and the like of the photosensitive composition are

deteriorated. Accordingly, the productivity is lowered,

and, in addition, the accuracy and reliability required of

the color filter cannot be provided. That is, the

development of a curable composition which can exhibit good

sensitivity (curability) , adhesion, developability, and

resolution under thin film and high light shielding

conditions has been desired.

On the other hand, the same problems are involved in

the field of solder resists used in printed wiring boards.

Solder resists are used to protect a wiring (circuit)

pattern on a substrate against an external environment and

to coat a protective layer called a cover coat or a solder

mask onto a printed wiring board from the viewpoint of

preventing solder from being deposited onto an unnecessary

part in the step of soldering in mounting an electronic

component on a surface of a printed wiring board.

As disclosed in patent document 23, a polyfuntional

epoxy resin system has been mainly used. In this case, the

resultant cured film has good heat resistance, but on the

other hand, the flexibility is disadvantageously low.

Accordingly, the application of the above solder resist is

limited to a rigid plate where the flexibility is not

required of the cured film, and the use of the cured film

in flexible printed wiring boards (FPCs) which have become

more and more used in recent years is difficult.

Under these circumstances, in recent years, a number

of proposals have been proposed on flexible solder resists.

For example, patent document 24 discloses a composition

comprising a carboxyl-containing urethane (meth) acrylate

compound. The technique disclosed in this patent document

24 can improve flexibility, but on the other hand, due to

great influence of crosslinkability and adhesion of the

polymer, the chemical resistance, particularly gold plating

resistance, is unsatisfactory.

The above properties of the photosensitive

composition are mainly derived from the polymer used, and,

thus, the structure of the polymer should be improved.

[Patent document 1] U.S. Patent No. 2,718,516

[Patent document 2] U.S. Patent No. 2,821,544

[Patent document 3] Japanese Patent Laid-Open No.

129163/1990

[Patent document 4] U.K. Patent No. 1,252,099

[Patent document 5] Japanese Patent Laid-Open No.

010750/1988

[Patent document 6] Japanese Patent Laid-Open No.

010771/1988

[Patent document 7] Japanese Patent Laid-Open No.

010772/1988

[Patent document 8] Japanese Patent Laid-Open No.

010773/1988

[Patent document 9] Japanese Patent Laid-Open No.

010774/1988

[Patent document 10] Japanese Patent Laid-Open No.

195354/1987

[Patent Document 11] Japanese Patent Laid-Open No.

143220/1997

[Patent Document 12] Japanese Patent Laid-Open No.

104401/1998

[Patent Document 13] Japanese Patent Laid-Open No,

14221/1989

[Patent Document 14] Japanese Patent Laid-Open No.

43671/2004

[Patent Document 15] Japanese Patent Laid-Open No,

48856/2001

[Patent Document 16] Japanese Patent Laid-Open No,

296152/1997

[Patent Document 17] Japanese Patent Laid-Open No.

287718/1998

[Patent Document 18] Japanese Patent Laid-Open No.

200007/2001

[Patent Document 19] Japanese Patent Laid-Open No.

226806/2003

[Patent Document 20] Japanese Patent Laid-Open No.

104842/2005

[Patent Document 21] Japanese Patent Laid-Open No.

333902/2004

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300923/1998

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228688/1999

[Patent document 24] Japanese Patent Laid-Open No,

229201/2002

DISCLOSURE OF THE INVENTION

PROBLEMS TO BE SOLVED BY THE INVENTION

An object of the present invention is to provide a

novel ethylenically unsaturated group-containing isocyanate

compound and to provide a production process which can

suppress the■production of by-products and can produce the

ethylenically unsaturated group-containing isocyanate

compound of high purity in a safe and simple manner.

Another object of the present invention is to provide

a reactive monomer, which has excellent curability,

adhesion to base materials, and transparency and, at the

same time, high hardness, and has a urethane bond, a

thiourethane bond, or a urea bond, a curable composition

using the reactive monomer, and a cured product produced

from the curable composition.

An object of the present invention is to provide a

curable composition, which has a satisfactorily high level

of curing properties (sensitivity), can form a highly heat,

resistant and durable cured film while enjoying a high

level of light shielding properties, or to provide a

reactive polymer, which can provide a curable composition

capable of forming a cured film having flexibility and

possessing excellent heat resistance and chemical

resistance, and a production process and use thereof.

MEANS FOR SOLVING THE PROBLEMS

The present inventor has noticed that the isocyanate

compound used in the prior art has a structure containing

one (meth) acryloyl group per isocyanate group. Against

this, the present inventor has made studies on the

synthesis of a specific isocyanate compound having two

ethylenically unsaturated groups in its molecule.

The present inventor has further made studies on the

synthesis of reactive urethane compounds, reactive

thiourethane compounds, or reactive urea compounds produced

by reacting this isocyanate compound with an aliphatic,

aromatic, or heterocyclic group containing one or more

hydroxyl, mercapto, or amino groups as an active hydrogen-

containing functional group. Further, the present inventor

has made studies on the synthesis of reactive polymers

produced by reacting this isocyanate compound with a

polymer compound comprising repeating units with an active

hydrogen-containing functional group bonded thereto. As a

result, the present inventor has found that the above

compound can be actually produced and the above objects can

be attained, which has led to the completion of the present

invention.

The present invention will be summarized as follows

[1] An ethylenically unsaturated group-containing

isocyanate compound represented by formula (I)

(I)

wherein R ¹ represents a straight-chain or branched-chain

saturated aliphatic group having 1 to 10 carbon atoms; R ²

represents a hydrogen atom or a methyl group; R ³ represents

a straight-chain or branched-chain alkylene group having 0

to 5 carbon atoms; and R ⁴ represents a hydrogen atom, a

straight-chain or branched-chain alkyl group having 1 to 6

carbon atoms, or an aryl group.

[2] The ethylenically unsaturated group-containing

isocyanate compound according to the above item [1],

characterized in that R ¹ in formula (I) is a straight-chain

or branched-chain saturated aliphatic group having 1 to 5

carbon atoms .

[3] The ethylenically unsaturated group-containing

isocyanate compound according to the above item [1] or [2],

characterized in that R ³ in formula (I) is a straight-chain

or branched-chain alkylene group having 0 to 3 carbon atoms

[ 4 ] The ethylenically unsaturated group-containing

isocyanate compound according to any of the above items [ 1 ]

to [3 ] , characterized in that R ⁴ in formula ( I ) is a

hydrogen atom or a methyl or aryl group .

[ 5] The ethylenically unsaturated group-containing

isocyanate compound according to the above item [ 1 ] ,

characterized by being represented by formula ( II )

(i D wherein R ² represents a hydrogen atom or a methyl group.

[6] The ethylenically unsaturated group-containing

isocyanate compound according to the above item [1],

characterized by being represented by formula (III)

wherein R represents a hydrogen atom or a methyl group.

[7] The ethylenically unsaturated group-containing

isocyanate compound according to the above item [1],

characterized by being represented by formula (IV)

( I V)

wherein R ² represents a hydrogen atom or a methyl group.

[8] A process for producing an ethylenically

unsaturated group-containing isocyanate compound

characterized by comprising the steps of:

preparing a dihydroxyarαine mineral acid salt compound

represented by formula (VI)

wherein R ¹ is as defined below, and X ¹ represents a mineral

acid, from a dihydroxyamine compound represented by formula

(V)

NH ₂

HO >"OH (V)

wherein R ¹ represents a straight-chain or branched-chain

saturated aliphatic group having 1 to 10 carbon atoms, and

a mineral acid;

preparing an ester compound represented by formula

wherein R ¹ and X ¹ are as defined above and R ² to R ⁴ are as

defined below, from the dihydroxyamine mineral acid salt

compound and a compound represented by formula (VII)

wherein R ² represents a hydrogen atom or a methyl group; R ³

represents a straight-chain or branched-chain alkylene

group having 0 to 5 carbon atoms; R ⁴ represents a hydrogen

atom, a straight-chain or branched-chain alkyl group having

1 to .6 carbon atoms or an aryl group; and Y ¹ represents a

hydroxyl group, a chlorine atom, or R ⁶ O- wherein R ^δ

represents an alkyl group having 1 to 6 carbon atoms;

preparing an isocyanate compound represented by

formula (X)

wherein R ¹ to R ⁴ are as defined above, from the ester

compound and. a compound represented by general formula ( IX)

( I X) .

wherein Z ¹ and Z ² each independently represent a chlorine

atom; a bromine atom; R ⁷ O- wherein R ⁷ represents a

straight-chain or branched-chain alkyl group having 1 to 6

carbon atoms , a straight-chain or branched-chain alkenyl

group having 1 to 6 carbon atoms, or an optionally

substituted aryl group; a residue of imidazoles ; or a

residue of pyrazoles ; and

dehydrochlorinating the isocyanate compound in the

presence of a basic nitrogen compound to give an

ethylenically unsaturated group-containing isocyanate

compound represented by formula ( I )

(D

wherein R ¹ to R ⁴ are as defined above.

[9] The process for producing the ethylenically

unsaturated group-containing isocyanate compound according

to the above item [8], characterized in that the mineral

acid reacted with the dihydroxyamine compound represented

by formula (V) is sulfuric acid, nitric acid, hydrochloric

acid, carbonic acid, or phosphoric- acid.

[10] The process for producing an ethylenically

unsaturated group-containing isocyanate compound according

to the above item [8] or [9], characterized in that the

reaction in each of the steps is carried out in a solvent.

[11] The process for producing an ethylenically

unsaturated group-containing isocyanate compound according.

to any of the above items [8] to [10] , characterized in

that the reaction in the step of preparing the

dihydroxyamine mineral acid salt compound represented by

formula (VI) from the dihydroxyamine compound represented

by formula (V) and the mineral acid is carried out in a

solvent selected from water, alcohols, esters, ethers,

aromatic hydrocarbons, aliphatic hydrocarbons, and

halogenated hydrocarbons.

[12] The process for producing an ethylenically

unsaturated group-containing isocyanate compound according

to any of the above items [8] to [10], characterized in

that the reaction in the step of preparing the ester

compound represented by formula (VIII), the reaction in the

step of preparing the isocyanate compound represented by

formula (X) , and the reaction in the step of preparing the

ethylenically unsaturated group-containing isocyanate

compound represented by formula (I) are carried out in a

solvent selected from esters, ethers, aromatic hydrocarbons,

aliphatic hydrocarbons, and halogenated hydrocarbons.

[13] The process for producing an ethylenically

unsaturated group-containing isocyanate compound according

to any of the above items [8] to [12], characterized in

that, after the dihydroxyamine compound represented by

formula (V) is reacted with the mineral acid in the solvent

to give the dihydroxyamine mineral acid salt compound

represented by formula (VI), the reaction solvent is

removed by evaporation and the next step of carrying out

the reaction for preparing the ester compound represented

by formula (VIII) is carried out.

[14] The process for producing an ethylenically

unsaturated group-containing isocyanate compound according

to any of the above items [8] to [12], characterized in

that the reaction in the step of dehydrochlorinating the

isocyanate compound represented by formula (X) in the

presence of a basic nitrogen compound to give the

ethyleneically unsaturated group-containing isocyanate

compound represented by formula (I) is carried out at a

temperature of 0 ⁰ C to 150 ⁰ C.

[15] The process for producing an ethylenically

unsaturated group-containing isocyanate compound according

to any of the above items [8] to [14], characterized in

that basic nitrogen compound used in the step of

dehydrochlorinating the isocyanate compound represented by

formula (X) in the presence of a basic nitrogen compound to

give the ethyleneically unsaturated group-containing

isocyanate compound represented by formula (I) is

triethylamine.

[16] A process for producing an ethylenically

unsaturated group-containing isocyanate compound

characterized by comprising the steps of :

preparing a dihydroxyamine mineral acid salt compound

represented by formula (VI )

wherein R ¹ is as defined below, and X ¹ represents a mineral

acid, from a dihydroxyamine compound represented by formula

(V)

wherein R ¹ represents a straight-chain or branched-chain

saturated aliphatic group having 1 to 10 carbon atoms , and

a mineral acid;

preparing an ester compound represented by formula

(XII )

wherein R ¹ and X ¹ are as defined above and R ³ and R ⁴ are as

defined below, from the dihydroxyamine mineral acid salt

compound and a compound represented by formula (XI)

wherein R ³ represents a straight-chain or branched-chain

alkylene group having 0 to 5 carbon atoms; R ⁴ represents a

hydrogen atom, a straight-chain or branched-chain alkyl

group having 1 to 6 carbon atoms or an aryl group; and Y ¹

represents a hydroxyl group, a chlorine atom, or R ⁶ O-

wherein R ⁶ represents an alkyl group having 1 to 6 carbon

atoms; and

preparing an ethylenically unsaturated group-

containing isocyanate compound represented by formula

⁽ XIIi:

wherein R ¹ , R ³ , and R ⁴ are as defined above, from the ester ■

compound and a compound represented by general formula (IX)

(IX)

wherein Z ¹ and Z ² each independently represent a chlorine

atom; a bromine atom; R ⁷ O- wherein R ⁷ represents a

straight-chain or branched-chain alkyl group having 1 to 6

carbon atoms, a straight-chain or branched-chain alkenyl

group having 1 to 6 carbon atoms, or an optionally

substituted .aryl group; a residue of imidazoles; or a

residue of pyrazoles.

[17] The process for producing the ethylenically

unsaturated group-containing isocyanate compound according

to the above item [16], characterized in that the mineral

acid reacted with the dihydroxyamine compound represented

by formula (V) is sulfuric acid, nitric acid, hydrochloric

acid, carbonic acid, or phosphoric acid.

[18] The process for producing an ethylenically

unsaturated group-containing isocyanate compound according

to the above item [16] or [17], characterized in that the

reaction in each of the steps is carried out in a solvent.

[19] The process for producing an ethylenically

unsaturated group-containing isocyanate compound according

to any of the above items [16] to [18], characterized in

that the reaction in the step of preparing the

dihydroxyamine mineral acid salt compound represented by

formula (VI) from the dihydroxyamine compound represented

by formula (V) and the mineral acid is carried out in a

solvent selected from water, alcohols, esters, ethers,

aromatic hydrocarbons, aliphatic hydrocarbons, and

halogenated hydrocarbons.

[20] The process for producing an ethylenically

unsaturated group-containing isocyanate compound according

to any of the above items [16] to [19], characterized in

that the reaction in the step of preparing the ester

compound represented by formula (XII) and the reaction in

the step of preparing the ethylenically unsaturated group-

containing isocyanate compound represented by formula

(XIII) are carried out in a solvent selected from esters,

ethers, aromatic hydrocarbons, aliphatic hydrocarbons, and

halogenated hydrocarbons .

[21] The process for producing an ethylenically

unsaturated group-containing isocyanate compound according

to any of the above items [16] to [20] , characterized in

that, after the dihydroxyamine compound represented by

formula (V) is reacted with the mineral acid in the solvent

to give the dihydroxyamine mineral acid salt compound

represented by formula (VI) , the reaction solvent is

removed by evaporation and the next step of carrying out

the reaction for preparing the ester compound represented

by formula (XII ) is carried out .

[22 ] A reactive monomer represented by formula ( Ia)

)

wherein R ¹ represents a straight-chain or branched-chain

saturated aliphatic group having 1 to 10 carbon atoms ; R ²

represents a hydrogen atom or a methyl group; R ³ represents

a straight-chain or branched-chain alkylene group having 0

to 5 carbon atoms ; R ⁴ represents a hydrogen atom, a

straight-chain or branched-chain alkyl group having 1 to 6

carbon atoms , or an aryl group; R ⁵ represents an ether,

thioether, or NH group; X represents an aliphatic, aromatic,

or heterocyclic group; and n is an integer of 1 to 4 .

[23 ] The reactive monomer according to the above item

[ 22 ] , characterized by being represented by formula ( Ha)

wherein R ² , R ⁵ , and X are as defined above.

[24] The reactive monomer according to the above _^ item

[22], characterized by being represented by formula (Ilia)

wherein R ² , R ⁵ , and X are as defined above .

[ 25 ] The reactive monomer according to the above item

[22 ] , characterized by being represented by formula ( IVa)

)

wherein R ² , R ⁵ , and X are as defined above.

[26] The reactive monomer according to any of the

above items [22] to [25], characterized in that R ⁵ in

formula (Ia) is an ether group, X represents a fluorine-

containing group, and n = 1.

[27] The fluorine-containing reactive monomer

according to the above item [26] , characterized in that X

in formula (Ia) is a group represented by - (CH ₂ ) _ra (CF ₂ ) iF

wherein m is an integer of 0 to 2 and 1 is an integer of 0

to 8, provided that m and 1 are not simultaneously 0.

[28] The reactive monomer according to any of the

above items [22] to [25], characterized in that R ⁵ in

formula (Ia) is an ether group, X represents a fluorine-

containing group, and n = 2.

[29] The reactive monomer according to any of the

above items [22] to [25], characterized in that R ⁵ in

formula (Ia) is an ether group, X represents a group having

a fluorene skeleton, and n = 2.

[30] The reactive monomer according to the above item

[29], characterized in that X in formula (Ia) is a group

represented by formula (XVI)

wherein h is an integer of 1 to 4.

[31] The reactive monomer according to any of the

above items [22] to [25], characterized in that R ⁵ in

formula (Ia) is group NH, X represents a fluorine-

containing group, and n = 1.

[32] The reactive monomer according to the above item

[31], characterized in that X in formula (Ia) represents a

group represented by F(CF ₂ ) 8CH2-, or X-R ⁵ represents a

residue of 2, 6-difluoroaniline.

[33] The reactive monomer according to any of the

above items [22] to [25] , characterized in that R ⁵ in

formula (Ia) is group NH, X represents an alkyl, xylylene,

or norbornane group, and n = 2.

[ 34 ] The reactive monomer according to the above item

[33 ] , characterized in that X-R ⁵ in formula ( Ia) represents

a residue of m-xylylenediamine or a residue of 2, 3, 5, 6-

tetrafluoro-1, 4-xylylenediamine, or X is represented by

formula (XVII )

[35] The reactive monomer according to any of the

above items [22] to [25], characterized in that R ⁵ in

formula (Ia) represents a thioether group, X represents a

straight-chain or branched-chain saturated aliphatic group,

or a phenyl group.

[36] A process for producing a reactive

(meth) acrylate polymer, characterized in that an

ethylenically unsaturated group-containing isocyanate

compound represented by formula (I)

CD .

wherein R ¹ represents a straight-chain or branched-chain

saturated aliphatic group having 1 to 10 carbon atoms; R ²

represents a hydrogen atom or a methyl group; R ³ represents

a straight-chain or branched-chain alkylene group having 0

to 5 carbon atoms; and R ⁴ represents a hydrogen atom, a

straight-chain or branched-chain alkyl group having 1 to 6

carbon atoms, or an aryl group, is reacted with a polymer

compound comprising repeating units to which an active

hydrogen-containing functional group is attached.

[37] The process for producing a reactive

(meth) acrylate polymer according to the above item [36] ,

characterized in that said polymer compound is a

polyhydroxy compound comprising repeating units.

[38] The process for producing a reactive

(meth) acrylate polymer according to the above item [36] or

[37] , characterized in that said ethylenically unsaturated

group-containing isocyanate compound is represented by

formula (II)

(I I) wherein R ² represents a hydrogen atom or a methyl group.

[39] The process for producing a reactive

(meth) acrylate polymer according to the above item [ 36.] or

[ 37 ] , characterized in that -said ethylenically unsaturated

group-containing isocyanate compound is represented by

formula ( II I )

( 1 Ϊ I ) wherein R ² represents a hydrogen atom or a methyl group.

[40] The process for producing a reactive

(meth) acrylate polymer according to any of the above items

[37] to [39] , characterized in that said repeating unit-

containing polyhydroxy compound is a polyester polyol

compound, a polycarbonate polyol compound, a polyether

polyol compound, a polyurethane polyol compound, a homo- or

copolymer of hydroxyalkyl (meth) acrylate, or an

epoxy(meth) acrylate compound.

[41] The process for producing a reactive

(meth) acrylate polymer according to any of the above items

[37] to [40] , characterized in that said repeating unit-

containing polyhydroxy compound contains a carboxyl group.

[42] A reactive (meth) acrylate polymer produced in

that an ethylenically unsaturated group-containing

isocyanate compound represented by formula (I)

( D

wherein R ¹ represents a straight-chain or branched-chain

saturated aliphatic group having 1 to 10 carbon atoms ; R ²

represents a hydrogen atom or a methyl group; R ³ represents

a straight-chain or branched-chain alkylene group having 0

to 5 carbon atoms ; R ⁴ represents a hydrogen atom, a

straight-chain or branched-chain alkyl group having 1 to 6

carbon atoms, or an aryl group, is reacted with a polymer

compound comprising repeating units to which an active

hydrogen-containing functional group is attached.

[ 43 ] The reactive (meth) acrylate polymer according to

the above item [ 42 ] , characterized in that said polymer

compound is a repeating unit-containing polyhydroxy

compound .

[44 ] The reactive (meth) acrylate polymer according to

the above item [ 42 ] or [ 43 ] , characterized in that said

ethylenically unsaturated group-containing isocyanate

compound is represented by formula ( I I )

(J r)

[45] The reactive (meth) acrylate polymer according to

the above item [42] or [43] , characterized in that said

ethylenically unsaturated group-containing isocyanate

compound is represented by formula (III)

Cm)

[46] The reactive (meth) acrylate polymer according to

any of the above items [43] to [45], characterized in that

said repeating unit-containing polyhydroxy compound is a

polyester polyol compound, a polycarbonate polyol compound,

a polyether polyol compound, a polyurethane polyol compound,

a homo- or copolymer of a hydroxyalkyl (meth) acrylate, or an

epoxy(meth) acrylate compound.

[47] The reactive (meth) acrylate polymer according to

any of the above items [43] to [46] , characterized in that

said repeating unit-containing polyhydroxy compound

contains a carboxyl group.

[48] A curable composition characterized by

comprising the reactive monomer according to any of the

above items [22] to [35] and a polymerization initiator.

[49] A cured product produced by curing the curable

composition according to the above item [48] .

[50] A -curable composition characterized by

comprising a reactive (meth) acrylate polymer (A) according

to any of the above items [43] to [47] and a pigment (B) .

[51] The curable composition according to the above

item [50] , characterized by further comprising a

photopolymerization initiator (D) .

[52] The curable composition according to the above

item [51] , characterized by further comprising an

ethylenically unsaturated monomer (F) .

[53] The curable composition according to the above

item [52], characterized by comprising 10 to 40% by mass of

the reactive (meth) acrylate polymer (A), 25 to 60% by mass

of the pigment (B) , 2 to 25% by mass of the

photopolymerization initiator (D) , 5 to 20% by mass of the

ethylenically unsaturated monomer (F) , and an organic

solvent (G) .

[54] The curable composition according to the above

item [52], characterized by comprising 10 to 40% by mass of

the reactive (meth) acrylate polymer (A), 25 to 60% by mass

of the pigment (B) , 2 to 20% by mass of the

photopolymerization initiator (D) , 5 to 20% by mass of the

ethylenically unsaturated monomer (F) , the organic solvent

(G) , and 2 to 20% by mass of a polyfunctional thiol (H) .

[55] The curable composition according to any of the

above items [52] to [54], characterized in that said

curable composition is used for color filter formation.

[56] The curable composition according to the above

item [55] , characterized in that the pigment (B) is carbon

black.

[57] A curable composition characterized by

comprising the reactive (meth) acrylate polymer (A)

according to any of the above items [43] to [47], a heat-

curable polymer (C) , a photopolymerization initiator (D) ,

and a thermal polymerization catalyst (E) .

[58] The curable composition according to the above .

item [57], characterized in that said curable composition

is used as a solder resist.

[59] An insulating protective film having been formed

using the curable composition according to the above item

[58] .

[60] A printed wiring board comprising the insulating

protective film according tσ the above item [59] .

The isocyanate compound represented by formula (I)

containing in its molecule two or more polymerizable

functional groups, that is, containing two or more

ethylenically unsaturated bonds, is suitable as starting

reactive monomers for resins used, for example, in a wide

variety of fields such as coating materials, UV- and heat-

curable coating materials, molding materials, adhesives,

inks, resists, optical materials, stereolith.ograph.ic

materials, printing plate materials, dental materials, and

polymer battery materials.

Further, in various fields, the isocyanate compound

represented by formula (I) can be used in the production of

resins with a reactive functional group, that is, an

ethylenically unsaturated group or an isocynate giroup,

introduced thereinto. For example, isocyanate groiip-

containing functional polymer materials can be produced by

copolymerizing the isocyanate compound represented by

formula (I), for example, with (meth) acrylates such as

methyl methacrylate or methylacrylate, or vinyl grroup-

containing compounds such as vinyl ether and styrene.

Further, reacting, e.g., monomers, oligomers, or polymers

containing active hydrogen such as hydroxyl, amino or

carboxyl groups, with an isocyanate group can realize the

introduction of a polymerizable unsaturated group into the

monomers, oligomers, polymers or the like to produce

materials which are curable upon exposure to ultraviolet

light, electron beams, heat or the like.

Further, the isocyanate compound represented by

formula (I) can provide a curable composition which can

realize a high curing speed. Furthermore, a curable

composition which can provide a cured product having high

crosslinking density can be provided.

On the other hand, the use of the reactive monomer

represented by formula (Ia) is advantageous in that, since

there are two adjacent reactive ethylenically unsaturated

groups, the radical reactivity between the ethylenically

unsaturated groups is high, and, at the same time, the

adhesive strength to the base material is excellent. This

increase in adhesive strength is considered attributable to

a high level of reactivity and a high level of

crosslinkability.

Since the ethylenically unsaturated groups are

adjacent to each other, upon exposure to light or heat,

curing proceeds in an amorphous manner and the proportion

of the crystalline region is reduced. As a result, good

transparency can be realized.

Further, because of polyfunctionality, the compound

functions as a crosslinking component to provide a heat-

curable or photocurable curing composition. This curable

composition can be cured at a high curing speed. Further,

this curing composition can provide a cured product having

high crosslinking density..

The two reactive ethylenically unsaturated groups can

be copolymerized, for example, with (meth) acrylates such as

methyl methacrylate and methyl acrylate, or ethylenically

unsaturated group-containing compounds such as vinyl ether

and styrene and can also be used as monomers for polymer

production.

The reactive monomer represented by formula (Ia) is •

suitable for use in a wide variety of fields such as

coating materials, UV- and heat-curable coating materials,

molding materials, adhesives, inks, resists, optical

materials, stereolithographic materials, printing plate

materials, dental materials, and polymer battery materials.

In particular, by virtue of features such as curing

reactivity, adhesion to base materials, and transparency,

the reactive monomer represented by formula (Ia) is

suitable for use, for example, in optical materials,

coating materials, resists, and UV curing coating materials

[Effect of the Invention]

The present invention provides a novel isocyanate

compound containing in its molecule two or more

polymerizable functional groups, that is, two or more

ethylenically unsaturated groups.

In the production of the ethylenically unsaturated

group-containing isocyanate compound, the production

process of the present invention can suppress the

production of by-products and, at the same time, can

produce a high-purity ethylenically unsaturated group-

containing isocyanate compound in a safe and simple manner.

The present invention can provide a reactive monomer .

containing a urethane bond, a thiourethane bond, or a urea

bond, which is excellent in curability, adhesion to base

materials, and transparency, and, at the same time, has

high hardness, a curable composition using the reactive

monomer, and a cured product produced from the curable

composition.

The production process of the present invention using

an ethylenically unsaturated group-containing isocyanate

can provide a curable composition, which has a

satisfactorily high level of curing properties

(sensitivity) , can form a highly heat resistant and durable

cured film while enjoying a high level of light shielding

properties, or can provide a reactive (meth) acrylate

polymer which can provide a curable composition capable of

forming a cured film having flexibility and possessing

excellent heat resistance and chemical resistance.

The reactive (meth) acrylate polymer according to the

present invention can provide a curable composition which

has a satisfactorily high level of curing properties

(sensitivity) , can form a highly heat resistant and durable

cured film while enjoying a high level of light shielding

properties, or a curable composition capable of forming a •

cured film having flexibility and possessing excellent heat

resistance and chemical resistance.

The curable composition comprising a reactive

(meth) acrylate polymer according to the present invention

has a satisfactorily high level of curing properties

(sensitivity) and can form a cured film which has high heat

resistance and durability while enjoying a high level of

light shielding properties and is suitable for use in a

color filter.

Further, the curable composition can form a cured

film which is flexible and, at the same time, possesses

excellent heat resistance and chemical resistance, and is

suitable for a solder resist.

[BRIEF DESCRIPTION OF THE DRAWING]

[Fig. 1] Fig. 1 is an X-ray analysis chart for

Example 7 and Comparative Example 8.

[BEST MODE FOR CARRYING OUT THE INVENTION]

The present invention will be described in more

detail.

(i) Ethylenically unsaturated group-containing isocyanate

compound

The ethylenically unsaturated group-containing

isocyanate compound according to the present invention is

represented by formula (I) . All general formulae in the

present specification embrace all stereoisomers such as cis

and trans isomers.

( I )

wherein R ¹ represents a straight-chain or branched-

chain saturated aliphatic group having- 1 to 10 carbon atoms ,

preferably 1 to 5 carbon atoms , and R ² represents a

hydrogen atom or a methyl group . More preferably, R ¹

represents a branched saturated aliphatic group having 3 or

4 carbon atoms from the viewpoint of easiness in

synthesizing the isocyanate group . R ³ represents a

straight-chain or branched-chain alkylene group having 0 to

5 carbon atoms , preferably 0 to 3 carloon atoms . R ⁴

represents a hydrogen atom, a straight-chain or branched-

chain alkyl group having 1 to 6 carbon atoms , or an aryl

group . Preferably, R ⁴ represents a hydrogen atom, a methyl

group, or an aryl group .

Specific examples of preferred ethylenically

unsaturated group-containing isocyanate compounds according

to the present invention include comp ounds represented by

formulae ( II ) to ( IV) .

(I I)

(TII)

ClV)

In formulae (II) to (IV), R ² represents a hydrogen

atom or a methyl group.

The production process of an ethyleniLcally

unsaturated group-containing isocyanate compound according

to the present invention will be described,

(ii) First production process of the ethylenically

unsaturated group-containing isocyanate compound

The first production process of the ethylenically

unsaturated group-containing isocyanate compound according

to the present invention comprises the following first to

fourth steps.

[First step]

A step of preparing a dihydroxyamine mineral acid

salt compound represented by formula (VI)

wherein R ¹ is> as defined below, and X ¹ represents a miner ^~ al

acid, from a dihydroxyamine compound represented by formilla

(V)

wherein R ¹ represents a straight-chain or branched-chain

saturated aliphatic group having 1 to 10 carbon atoms, and

a mineral acid.

[Second step]

A step of preparing an ester compound represented 3oy

formula (VIII)

wherein R ¹ and X ¹ are as defined above and R ² to R ⁴ are as

defined below, from the dihydroxyamine mineral acid salt

compound and a compound represented by formula (VI I ]

wherein R ² represents a hydrogen atom or a methyl group/ R ³

represents a straight-chain or branched-chain alkylene

group having 0 to 5 carbon atoms; R ⁴ represents a hydrogen

atom, a straight-chain or branched-chain alkyl group having

1 to 6 carbon atoms or an aryl group; and Y ¹ represents a

hydroxyl group, a chlorine atom, or R ⁵ O- wherein R ⁶

represents an alkyl group having 1 to 6 carbon atoms.

[Third step]

A step of preparing an isocyanate compound

represented by formula (X)

wherein R ¹ to R ⁴ are as defined above, from the ester

compound and a compound represented by general formula (IX)

(IX)

wherein Z ¹ and Z ² each independently represent a chlorine

atom; a bromine atom; R ⁷ O- wherein R ⁷ represents a

straight-chain or branched-chain alkyl group having 1 to 6

carbon atoms, a straight-chain or branched-chain alkenyl

group having • 1 to 6 carbon atoms, or an optionally

substituted aryl group; a residue of imidazoles ; or a

residue of pyrazoles .

[Fourth step]

A step of dehydrochlorinating the isocyanate compound

in the presence of a basic nitrogen compound to give an

ethylenically unsaturated group-containing isocyanate

compound represented by formula ( I )

( I )

wherein R ¹ to R ⁴ are as defined above ,

(ii-a) First step

Mineral acids usable in the first step include, for

example, sulfuric acid, nitric acid, hydrochloric acid,

phosphoric acid, and carbonic acid . Among them,

hydrochloric acid and carbonic acid are preferred . More

preferred is hydrochloric acid. The use of dry hydrogen

chloride gas is particularly preferred.

Dihydroxyamine compounds represented by formula (V)

used in the first step are easily commercially available.

Specific examples of dihydroxyamine compounds represented

by formula (V) include aminomethanediol, 2-amino-l, 1-

ethanediol, 1-amino-l, 2-ethanediol, 1-amino-l, 1-propanediol,

1-amino-l,2-propanediol, 1-amino-l, 3-propanediol, 2-amino-

1, 2-propanediol, 2-amino-l, 3-propanediol, 3-amino-l, 1-

propanediol, 3-amino-l, 2-propanediol, 1-amino-l, 4-

butanediol, l-amino-2, 3-butanediol, 2-amino-l, 3-butanediol,

2-amino-l, 4-butanediol, 3-amino-l, 2-butanediol, 4-amino-

1,2-butanediol, 4-amino-l, 3-butanediol, l-amino-2-methyl-

1, 3-propanediol, 3-amino-2-methyl-l, 2-propanediol, 2-

aminomethyl-1, 3-propanediol, 2-amino-2-methyl-l, 3-

propanediol, 2-aminomethyl-l, 2-butanediol, 2-amino-l, 3-

pentanediol, 2-amino-l, 4-pentanediol, 2-amino-l, 5-

pentanediol, 3-amino-l, 2-pentanediol, 3-amino-l, 5-

pentanediol, 3-amino-2, 4-pentanediol, 4-amino-l,2-

pentanediol, 5-amino-l, 2-pentanediol, 5-amino-l,3-

pentanediol, 2-aminomethyl-2-methyl-l, 3-propanediol, 2-

amino-2-methyl-l, 3-butanediol, 2-amino-2-ethyl-l, 3-

propanediol, 2-amino-2-methyl-l, 4-butanediol, 2-amino-3-

methyl-1, 3-butanediol, 2-amino-3-methyl-l, 4-butanediol, 2-

[hydroxy (1-methylethyl) amino] -ethanol, 2- (2 -amino ethyl) -

1, 3-propanediol, 3-amino-2, 2-dimethyl-l, 4-butanediol, 2-

(aminomethyl) -2-ethyl-l, 3-propanediol, 2-amino-3-ethyl-l, 4-

butanediol, 2-amino-2-ethyl-l, 4-butanediol, 3-

( aminomethyl ) -1, 5-pentanediol, 2- (2-amino-l-methylethyl) -

1, 3-propanediol, 3-amino-3-methyl-2, 4-pentanediol, 2-amino-

1, 3-hexanediol, 2-amino-l, 6-hexanediol, 2-amino-3, 4-

hexanediol, 3-amino-l, 2-hexanediol, 4-amino-2, 3-hexanediol,

6-amino-l,2-hexanediol, 6-amino-l, 3-hexanediol, 6-amino-

1, 4-hexanediol, l-amino-4-methyl-2, 4-pentanediol, 3-amino-

2-methyl-2, 4-pentanediol, 4 -amino- 2 -methyl- 2, 3-pentanediol,

4-amino-4-methyl-2, 3-pentanediol, 2-amino-4 -methyl- 1, 3-

pentanediol, 3-amino-3-methyl-2, 4-pentanediol, 3-amino-4-

methyl-1, 2-pentanediol, 2-amino-2-hydroxymethyl-3-

methylbutanol, 5-amino-2-hydroxymethylpentanol, 2-amino-2-

isopropyl-1, 3-propanediol, 3- (2-aminomethyl) -1, 5-

pentanediol, 5- (dime thylamino) -1, 2-pentanediol, 2-

(dimethylamino) -1, 5-pentanediol, 2-amino-3-ethyl-l, 5-

pentanediol, 4-amino-3, 5-heptanediol, 2-amino-2-ethyl-l, 5-

pentanediol, 2- (3-amino-2-methylpropyl) -1, 3-propanediol, 2-

i (4-aminobutyl) -1, 3-propanediol, 2-amino-l, 7-heptanediol, 3-

amino-5-methyl-l, 2-hexanediol, 2-amino-butyl-l, 3-

propanediol, 3-amino-3-ethyl-2, 4-pentanediol, l-amino-4-

methyl-2, 4-hexanediol, 2-amino-4, 4-dimethyl-l, 3-pentanediol,

2-amino-5-methyl-l, 3-hexanediol, 2-amino-5-methyl-3, A-

hexanediol, 4-amino-l _A 7-heptanediol, 2-amino-l, 3-

heptanediol, 5-amino-2-methyl-3, 4-heptanediol, 3-amino-1, 2-

octanediol, 2-amino-6-methyl-3, 4-heptanediol, 2- (2-amino-l-

methylethyl) -1, 5-pentanediol, 3- (2-aminopropyl) -1, 5-

pentanediol, 2-amino-2-pentyl-l, 3-propanediol, 6-amino-2-

methyl-1, 2-heptanediol, 2-amino-l, 3-octanediol, 2-amino-

3, 4-octanediol, 2-amino-l, 8-octanediol, 4- (aminomethyl) -

2, 6-heptanediol, 2-amino-2-hexyl-l, 3-propanediol, 5-

(aminomethyl) -2-methy1-3, 5-heptanediol, 1-amino-4, 5,5-

trimethyl-2, 4-hexanediol, 2-amino-l, 3-nonanediol, 2-amino-

7-methyl-3, 4-octanediol, 2-amino-3, 4-nonanediol, 8-amino-

2, 5-nonanediol, 3- (2-aminopropyl) -2-methyl-l, 5-pentanediol,

3-amino-l, 2-decanediol, 5- (aminomethyl) -2-methyl-3, 5-

octanediol, 3- (aminomethyl) -2, 2-dimethyl-3, 5-heptanediol,

2-amino-3, 7-dimethyl-l, 3-octanediol, l-amino-3, 7-dimethyl-

2, 3-octanediol, 2-amino-l, 10-decanediol, 2-amino-l, 3-

decanediol, 8-amino-2, 3-dimethyl-2, 3-octanediol, 2-amino-

1 , 3-decanediol .

The reaction temperature in the first step may vary

depending upon the type of the compound used . The reaction

temperature is generally 0 to 150°C, preferably 15 to 120°C,

more preferably 30 to 100°C . When the reaction temperature is excessively low, the reaction rate is likely to be

lowered . On the other hand, when the reaction temperature

is excessively high, the produced salt is likely to be

thermally decomposed.

Whether or not the solvent is to be used in the first

step depends upon the type of the compound used or the like .

When the amine compound represented by formula (V) and/or

the amine mineral acid salt compound represented by formula

(VI ) is liquid or melts, the reaction may be carried out in

the absence of a solvent . On the other hand, when the

amine compound represented by formula (V) and/or the amine

mineral acid salt compound represented by formula (VI ) is .

solid or does not melt, the reaction is preferably carried

out in the presence of a solvent .

Specific examples of solvents usable herein include

water; alcohols such as methanol , ethanol , n-propanol,

isopropanol , n-butanol and n-hexanol ; esters such as methyl

i acetate, ethyl acetate, propyl acetate, isopropyl acetate

and butyl acetate; chain ethers such as diethyl ether,

dipropyl ether, and dibutyl ether; cyclic ethers such as

dioxane, dioxolane and tetrahydrofuran; aromatic

hydrocarbons _' such as toluene, xylene, ethylbenzene,

mesitylene, and cumene; aliphatic hydrocarbons such as

propane, hexane, heptane, and cyclohexane; and halogenated

hydrocarbons such as methylene chloride, 1, 2-dichloroethane

and 1, 2-dichlorobenzene.

When the solvent is used, the amount of the solvent

used is such that the concentration of the amine compound

represented by formula (V) based on the total amount of the

amine compound of formula (V) , the mineral acid and the

solvent is generally 1 to 50% by weight, preferably 5 to

30% by weight, more preferably 10 to 20% by weight. When

the amount of the solvent used is excessively small,

stirring in the reaction cannot be successfully carried out

and, in this case, the use of an excessive amount of

mineral acid is sometimes necessary. On the other hand,

when the amount of the solvent used is excessively large,

the reaction rate is likely to be significantly lowered and,

in this case, the use of an excessive amount of mineral

i acid is sometimes necessary for accelerating the reaction

rate. The use of the excessive amount of mineral acid is

likely to cause a load on wastewater treatment. Further,

when the mineral acid is volatile, disadvantageously, a

special removal apparatus or the like is sometimes

necessary.

The amount of the mineral acid used may vary

depending upon the type of the compound used. Generally,

the amount of the mineral acid may be 1 to 5 times by mole,

preferably 1 to 1.2 times by mole, the amount of the amine

compound represented by formula (V) . When the amount of

the mineral acid used is excessively small, the yield is

likely to be lowered. Further, this is likely to affect

the next second step. Specifically, there is a possibility

that the amino group which does not form any salt of the

amine compound represented by formula (V) remains and is

reacted with the compound represented by formula (VII) used

in the next second step to give impurities. On the other

hand, when the amount of the mineral acid used is

excessively large, in some cases, a load is applied to

wastewater treatment. Further, when the mineral acid is

volatile, disadvantageously, a special removal apparatus or

the like is possibly necessary.

The amine mineral acid salt compound represented by

formula (VI) obtained in the first step may be purified by

a conventional procedure, for example, by extraction and

recrystallization, or alternatively as such may be used in

the reaction in the next second step without any

purification,

(ii-b) Second step

The compounds represented by formula (VII) used in

the second step are easily commercially available.

Specific examples of the compounds represented by formula

(VII) include 3-chloropropionic acid, 3-chlorobutyric acid,

4-chlorobutyric acid, 3-chloro-2-methylpropionic acid, 5-

chlorovaleric acid, 4-chlorovaleric acid, 3-chlorovaleric

acid, 4~chloro-3-methylbutyric acid, 3-chloro-3-

methylbutyric acid, 6-chlorohexanoic acid, 5-chlorohexanoic

acid, 4-chlorohexanoic acid, 3-chlorohexanoic acid, 5-

chloro-4-methylvaleric acid, 4-chloro-4-methylvaleric acid,

5-chloro-3-methylvaleric acid, 4-chloro-3-rαethylvaleric

acid, 5-chloro-2-methylvaleric acid, 4-chloro-2-

methylvaleric acid, 3-chloro-2-methylvaleric acid, 4-

chloro-2, 3-dimethylbutyric acid, 3-chloro-2, 3-

i dimethylbutyric acid, 4-chloro-3-ethylbutyric acid, 3-

chloro-3-ethylbutyric acid, 4 — chloro-2-ethylbutyric acid,

3-chloro-2-ethylbutyric acid, 7-chloroenanic acid, 6-

chloroenanic acid, 5-chloroen.anic acid, 4-chloroenanic acid,

3-chloroenanic acid, 6-chloro — 5-methylhexanoic acid, 5-

chloro-5-iαethylhexanoic acid, 4-chloro-5-methylhexanoic

acid, 3-chloro-5-methylhexano ic acid, 6-chloro-4-

methylhexanoic acid, 5-chloro -4-iαethylhexanoic acid, 4-

chloro-4-methylhexanoic acid, 3-chloro-4-rαethylhexanoic

acid, 6~chloro-3-inethylh.exano ic acid, 5-chloro-3-

methylhexanoic acid, 4-chloro -3-methylhexanoic acid, 3-

chloro-3-methylhexanoic acid, 6-chloro-2-methylhexanoic

acid, 5-chloro-2-methylhexano ic acid, 4-chloro-2-

methylhexanoic acid, 3-chloro-2-methylhexanoic acid, 5-

chloro-3 , 4-dimethyl valeric acid, 4-chloro-3 , 4-

dimethylvaleric acid, 3-chlorro-3 , 4-dirαethylvaleric acid, 3-

chloro-4, 4-dirαethylvaleric acid, 5-chloro- 2 , 4-

dime thy 1 valeric acid, 4-chlorro-2 , 4-dimethylvaleric acid, 3-

chloro-2 , 4-dimethyl valeric acid, 5-chloro-2 , 3-

dimethylvaleric acid, 4-chloαro-2 , 3-dimeth.ylvaleric acid, 5-

chloro-3 , 3-dimethylvaleric acid, 5-chloro-2 , 2-

dimethylvaleric acid, 4-chloiro-2 , 2-dimethyl valeric acid, 4-

J chloro-2 , 2 , 3-trimethylbutyric acid, 5-chloro-3-ethylvaleric

acid, 4-chloro-3-ethylvaleric acid, 3-chloro-3-ethylvaleric

acid, 5-chloro-2-ethylvaleric acid, 4-chloro-2-ethyl valeric

acid, 3-chloro-2-ethylvaleric acid, 4-chloro-2-ethyl-3-

methylvaleri.c acid, 3-chloro-2-ethyL -3-methylvaleric acid,

4-chloro-2-ethyl-2-irιethyl valeric acid, 4-chloro-2-

propylbutyric acid, 3-chloro-2-prop^lbutyric acid, 3-

chloro-3-phenylpropionic acid, 3-chLoro-3-phenyl-2-

methylpropionic acid, 4-chloro-4-phenylbutyric acid, 4-

chloro-4-phenyl-3-methylbutyric acid, and acid chloride

compounds of the above carboxylic acids , or ester compounds

of the above carboxylic acids with straight-chain or

branched-chain alcohol compounds having 1 to 6 carbon atoms ,

for example, methyl esters , ethyl esters , propyl esters,

isopropyl esters, butyl esters , isobutyl esters , pentyl

esters, hexyl esters, and cyclohexyl. esters .

Regarding the compounds repres ented by formula (VII ) ,

before use, the above carboxylic acids may be converted to

carboxylic acid chloride compounds . Methods for converting

carboxylic acids to carboxylic acid chloride compounds are

generally known, and, for example, Japanese Patent

Publication No . 026497 / 1982 , Japanese Patent Laid-Open Nos .

089617/1977 and 199540/1999 disclose methods for producing

carboxylic acid chloride compounds from carboxylic acids

and thionyl chloride, phosphorus pentachloride, phosgene or

the like.

The reaction temperature in the second step may var;y

depending upon the type of the compound used. The reaction

temperature is generally 30 to 150 ⁰ C, preferably 50 to

120°C. When the reaction temperature is excessively low, the reaction rate is likely to be lowered. On the other

hand, when the reaction temperature is excessively high,

the salt produced in the first step is likely to be

thermally decomposed.

Whether or not the solvent is to be used in the

second step depends upon the type of the compound used or

the like. When the amine mineral acid salt compound of

formula (VI) and/or the compound of formula (VII) and/or

the ester compound of formula (VIII) are liguid or melt,

the reaction may be carried out in the absence of a solv&nt.

On the other hand, when the amine mineral acid salt

compound of formula (VI) and/or the compound of formula

(VII) and/or the ester compound of formula (VIII) are soLid

or do not melt, the reaction is preferably carried out in.

the presence of a solvent.

Specific examples of solvents usable herein include

esters such as methyl acetate, ethyl acetate, propyl

acetate, isopropyl acetate and butyl acetate; chain ethers

such as diethyl ether, dipropyl ether, and dibutyl ether;

cyclic ethers such as dioxane, dioxolane and

tetrahydrofuran; aromatic hydrocarbons such as toluene,

xylene, ethylbenzene, mesitylene, and cumene; aliphatic

hydrocarbons such as propane, hexane, heptane, and

cyclohexane; and halogenated hydrocarbons such as methylene

chloride, 1, 2-dichloroethane and 1, 2-dichlorobenzene.

When the solvent is used, the amount of the solvent

used is such that the concentration of the amine mineral

acid salt compound of formula (VI) based on the total

amount of the amine mineral acid salt compound of formula

(VI), the compound of formula (VII), and the solvent is

generally 1 to 50% by weight, preferably 5 to 30% by weight,

more preferably 10 to 20% by weight. When the amount of

the solvent used is excessively small, stirring in the

reaction cannot be successfully carried out and the

reaction rate is likely to be lowered. On the other hand,

when the amount of the solvent used is excessively large,

this does not affect the reaction. In this case, however _^

the amount of the solvent to be discarded is increased, and

a load on environment is likely to be enhanced.

The amount of the compound represented by formula

(VII) based on the amine mineral acid salt compound

represented by formula (VI) may vary depending upon the

type of the compound used. Generally, the amount of the

compound represented by formula (VII) may be 2 to 10 times

by mole, preferably 2 to 5 times by mole, the amount of tlhe

amine mineral acid salt compound represented by formula

(VI) . When the amount of the compound represented by

formula (VII) used is excessively small, the yield is likely to be lowered and, in addition, the amount of

impurities is likely to be increased. On the other hand,

when the amount of the compound represented by formula

(VII) used is excessively large, this does not affect the

reaction at all. In this case, however, since the amount

of waste is increased, disadvantageously, the load on

environment is likely to be increased.

The ester compound represented by formula (VIII)

obtained in the second step may be purified by a

conventional procedure, for example, by extraction,

recrystalli zation or distillation, or alternatively as such

may be used in the reaction in the next third step without

any purification ,

(ii-c) Third step

The reaction temperature in the third step may vary

depending upon the type of the compound used . The reaction

temperature is generally 30 to 150 ⁰ C, preferably 50 to

120 ⁰ C . When the reaction temperature is excessively low, the reaction rate is likely to be lowered . On the other

hand, when the reaction temperature is excessively high,

the amount of impurities is likely to be increased.

Further, in this case, dehydrochlorination proceeds due to

the heat, possibly leading to, polymerization of the formed

unsaturated bond.

Whether or not the solvent is to be used in the third

step depends upon the type of the compound used or the like .

When the ester compound of formula (VIII ) is liquid or

melts, the reaction may be carried out in the absence of a

solvent . On the other hand, when the ester compound of

formula (VIII ) is solid or does not melt, the reaction is

preferably carried out in the presence of a solvent .

Specific examples of solvents usable herein include

esters such as methyl acetate, ethyl acetate, propyl

acetate, isopropyl acetate and butyl acetate; chain ethers

such as diethyl ether, dipropyl ether, and dibutyl ether;

cyclic ethers such as dioxane, dioxolane and

tetrahydrofuran; aromatic hydrocarbons such as toluene,

xylene, ethylbenzene, mesitylene, and cumene; aliphatic

hydrocarbons such as propane, hexane, heptane, and

cyclohexane; and halogenated hydrocarbons such as methylene

chloride, 1, 2-dichloroethane and 1, 2-dichlorobenzene.

When the solvent is used, the amount of the solvent

used is such that the concentration of the ester compound

of formula (VIII) based on the total amount of the ester

compound of formula (VIII) , the compound of formula (IX) ,

and the solvent is generally 0.5 to 80% by weight,

preferably 5 to 50% by weight. When the amount of the

solvent used is excessively small, stirring in the reaction

cannot be successfully carried out and the reaction rate is

likely to be lowered. On the other hand, when the amount

of the solvent used is excessively large, this does not

affect the reaciton. In this case, however, the amount of

the solvent to be discarded is increased, and a load on

environment is likely to be enhanced.

Specific examples of Z ¹ and Z ² in the compounds

represented by formula (IX) used in the third step include

a chlorine atom; a bromine atom; alkyloxy groups such as

methoxy, ethoxy, propyoxy, iso-propyoxy, butoxy, pentaoxy,

hexaoxy, and' cyclohexaoxy groups; alkenyloxy groups such as

vinyloxy and allyloxy groups; aryloxy groups such as

phenyloxy, tolyloxy, xylyloxy, biphenyloxy, naphthyloxy,

anthryloxy, and phenanthryloxy groups; residues of

imidazoles such as imidazole, 2-imidazoline, 3-imidazoline,

4-imidazoline, imidazolidine, imidazolidone, ethyleneurea,

and ethylenethiourea; residues of pyrazoles such as

pyrazole, 1-pyrazoline, 2-pyrazoline, 3-pyrazoline, and

pyrazolidone.

Dimers or trimers of the above compounds may also be

used. The dirαer referred to herein is a compound

comprising two molecules of a compound represented by

formula (IX) . For example, when Z ¹ and Z ² represent a

chlorine atom, the dimer is a compound represented by

formula (XIV)

(XIV)

Further, the trimer referred to herein is a compound

comprising three molecules of a compound represented by

formula (IX) . For example, when Z ¹ and Z ² represent a

chlorine atom, the trimer is a compound represented by

formula (XV) .

(XV) The amount of the compound represented by formula

(IX) based on the ester compound represented by formula

(VIII) may vary depending upon the type of the compound

used. Theoretically, the reaction between the ester

compound represented by formula (VIII) and the compound

represented by formula (IX) proceeds in a molar ratio of

1 : 1. In order to allow the reaction to proceed smoothly,

however, the use of an excessive amount of the compound

represented by formula (IX) is preferred. Generally, the •

amount of the compound represented by formula (IX) used may

be 1 to 10 times by mole, preferably 1 to 5 times by mole,

the amount of the ester compound represented by formula

(VIII) used. When the amount of the compound represented

by formula (IX) used is excessively small, a part of the

ester compound represented by formula (VIII) remains

unreacted. This is likely to lower the yield, and the

amount of impurities is likely to be increased. On the

other hand, when the amount of the compound represented by

formula (IX) ^used is excessively large, this does not

affect the reaction. In this case, however,

disadvantageously, a special removal apparatus or the like

is possibly necessary, and the load on environment is

likely to be increased.

The isocyanate compound represented by formula (X)

obtained in the third step may be purified by a

conventional procedure, that is, for example, by extraction,

recrystallization or distillation, or alternatively as such

may be used in the reaction in the next fourth step without

any purification,

(ii-d) Fourth step

The reaction temperature in the fourth step may vary •

depending upon the type of the compound used. However, the

reaction may be generally carried out at 0 ⁰ C to 15O ⁰ C,

preferably 20 ⁰ C to 100 ⁰ C. When the reaction temperature is excessively low, the reaction rate is likely to be lowered.

On the other hand, when the reaction temperature is

excessively high, disadvantageously, the unsaturated bond

produced by the dehydrochlorination is likely to be

polymerized.

Whether or not the solvent is to be used in the

fourth step depends upon the type of the compound used or

the like. When the isocyanate compound of formula (X) is

liquid or melts, the reaction may be carried out in the

absence of a solvent. On the other hand, when the

isocyanate compound of formula (X) is solid or does not

melt, the reaction is preferably carried out in the

presence of a solvent.

Specific examples of solvents usable herein include

esters such as methyl acetate, ethyl acetate, propyl

acetate, isopropyl acetate and butyl acetate; chain ethers

such as diethyl ether, dipropyl ether, and dibutyl ether;

cyclic ethers such as dioxane, dioxolane and

tetrahydrofuran; aromatic hydrocarbons such as toluene,

xylene, ethylbenzene, mesitylene, and cumene; aliphatic

hydrocarbons such as propane, hexane, heptane, and

cyclohexane; and halogenated hydrocarbons such as methylene

chloride, 1, 2-dichloroethane and 1, 2-dichlorobenzene.

When the solvent is used, the amount of the solvent

i used is such that the concentration of the isocyanate

compound of formula (X) based on the total amount of the

isocyanate compound of formula (X) , the ethylenically

unsaturated group-containing isocyanate compound of formula

(I), and the. solvent is generally 0.5 to 80% by weight,

preferably 5 to 50% by weight. When the amount of the

solvent used is excessively small, stirring in the reaction

cannot be successfully carried out and the reaction rate is

likely to be lowered. Further, in this case, the formed

salt could not be removed without difficulties. On the

other hand, when the amount of the solvent used is

excessively large, this does not affect the reaction. In

this case, however, the amount of the solvent to be

discarded is increased, and a load on environment is likely

to be enhanced.

Conventional basic nitrogen-containing compounds are

usable as the basic nitrogen compound used in the fourth

step. In this case, when a hydrogen atom stays on the

basic nitrogen, disadvantageously, this is likely to be

reacted with the isocyanate group in the isocyanate

compound represented by formula (X) , possibly leading to

lowered yield.

Accordingly, the basic nitrogen compound is

preferably a tertiary nitrogen-containing basic nitrogen

compound. Further, in order to efficiently carry out the

dehydrochlorination, weakly basic nitrogen compounds in

which an aromatic ring is attached directly to the nitrogen

atom, such as quinoline, are unsatisfactory, and the basic

nitrogen compound should have a certain level of basicity.

That is, preferably, the basic nitrogen compound contains a

tertiary nitrogen atom which contains at least one

substituent other than aromatic ring, for example, alkyl

group. Further, the number of aromatic rings substituted

by the tertiary nitrogen atom is preferably one or less.

Specific examples of basic nitrogen compounds used in

the fourth step include trimethylamine, triethylamine,

tripropylamine, dimethylethylamine, dimethylisopropylamine,

diethylmethylamine, dimethylbutylamine, dimethylhexylamine,

diisopropylethylamine, dimethylcyclohexylamine,

tetramethyldiaminomethane, dimethylbenzylamine,

tetramethylethylenediamine, tetramethyl-1, 4-diaminobutane,

tetramethyl-1, 3-diaminobutane, tetramethyl-1, 6-

diaminohexane, pentamethyldiethylenetriamine, 1-

methylpiperidine, 1-ethylpiperidine, N,N-methylpiperazine,

N-methylruorpholine, 1, 8-diazabicyclo [5.4.0. ] -7-undecene

(DBU), l,5-diazabicyclo[4.3.0]-5-nonene (DBN), 2 ,4-

diazabicyclo [2.2.2] octane (DABCO), N,N-dimethylaniline,

N,N-diethylaniline, and ion exchange resins containing

tertiary nitrogen.

Among them, trimethylamine, triethylamine,

tripropylamine, and tetramethylenediamine are preferred.

The above basic nitrogen compounds may be used solely or in

a combination of two or more compounds.

The amount of the basic nitrogen compound ^" used in the

fourth step may vary depending upon the type of the

compound used. In general, a method may be adop ^" ted in

which the reaction solution after the completion- of the

reaction in the third step is measured for alkaLi

decomposable chlorine and the basic nitrogen compound is

used in such an amount so as to be 0.5 to 10 tiin.es by mole,

preferably 0.8 to 5.0 times by mole, more preferably 0.9 to

2.0 times by mole, the amount of the alkali decomposable

chlorine. When the amount of the basic nitrogen compound

used is excessively small, disadvantageously, ttxe yield is

likely to be lowered. On the other hand, when tlhe amount

of the basic nitrogen compound used is excessively large,

the stability of the resultant ethylenically unsaturated

group-containing isocyanate compound represented by formula

(I) is possibly deteriorated and, further, the cost

reguired for production on a commercial scale is increased.

The amount of the alkali decomposable chlorine

referred to herein is one as measured by a method which

comprises diluting the reaction solution obtained in the

third step with a methanol/water mixed solvent, further

adding an aqueous sodium hydroxide solution to the diluted

solution, then heating the mixture, and then subjecting the

mixture to potentiometric titration with a silver nitrrate

solution to determine the amount of the alkali decomposable

chlorine.

The ethylenically unsaturated group-containing

isocyanate compound represented by formula (I) obtained in

the fourth step may be purified by a conventional procedure,

for example, filtration, extraction, recrystallization, or

distillation.

(iii) Second production process of ethylenically

unsaturated group-containing isocyanate compound

The second production process of the ethylenically

unsaturated group-containing isocyanate compound according

i to the present invention comprises the following first to

third steps.

[First step]

A step of preparing a dihydroxyamine mineral acid

salt compound represented by formula (VI)

wherein R ¹ is as defined below, and X ¹ represents a mineral

acid, from a dihydroxyamine compound represented by formula

(V)

NH ₂

>

HO^ OH (V)

wherein R ¹ represents a straight-chain or branohed-chain

saturated aliphatic group having 1 to 10 carbon atoms, and

a mineral acid.

[Second step]

A step of preparing an ester compound represented by

formula (XII)

(X 1 1 )

wherein R ¹ and X ¹ are as defined above and R ³ and R ⁴ are as

defined below, from the dihydroxyamine mineral acid salt

compound and a compound represented by formula (XI)

wherein R ³ represents a straight-chain or branched-chain

alkylene group having 0 to 5 carbon atoms; R ⁴ represents a

hydrogen atom, a straight-chain or branched-chain alkyl

group having 1 to 6 carbon atoms or an aryl group; and Y ¹

represents a hydroxyl group, a chlorine atom, or R ⁶ O-

wherein R ⁶ represents an alkyl group having 1 to 6 carbon

atoms .

[Third step]

A step of preparing an ethylenically unsaturated

group-containing isocyanate compound represented by formula

(XIII)

wherein R ¹ , R ³ , and R ⁴ are as defined above, from the ester

compound and a compound represented by general formula (IX)

(IX)

wherein Z ¹ and Z^ each independently represent a chlorine

atom; a bromine atom; R ⁷ O- wherein R ⁷ represents a

straight-chain or branched-chain alkyl group having 1 to 6

carbon atoms, a straight-chain or branched-chain alkenyl

group having 1 to 6 carbon atoms, or an optionally

substituted aryl group; a residue of imidazoles; or a

residue of pyrazoles.

(iii-a) _ First step

Details of the first step are as described in (ii-a) .

(iii-b) Second step

The compound of formula (XI) used in the second step

may be commercially available one and is easily available.

Specific examples of compounds represented by formula (XI)

include methacrylic acid, 3-methyl-3-butenoic acid, tiglic

acid, 4-rαethyl-4-pentenoic acid, α-methylcinnamic acid, and acid chloride compounds of the above carboxylic acids,

or ester compounds of the above carboxylic acids with

linear or branched alcohol compounds having 1 to 6 carbon

atoms, for example, methyl esters, ethyl esters, propyl

esters, isopropyl esters, butyl esters, isobutyl esters,

pentyl esters, hexyl esters, and cyclohexyl esters.

The compounds represented by formula (XI) may be used

after the carboxylic acid is converted to a carboxylic acid

chloride compound. Methods for converting carboxylic acids

to carboxylic acid chloride compounds are generally known,

and, for example, Japanese Patent Publication No.

026497/1982 and Japanese Patent Laid-Open Nos . 089617/1977

and 199540/1999 disclose methods for producing carboxylic

acid chloride compounds from carboxylic acids and thionyl

chloride, phosphorus pentachloride, phosgene or the like.

The reaction temperature in the second step may vary

depending upon the type of the compound used. Generally,

the reaction may be carried out at 30 ⁰ C to 150°C,

preferably 50°C to 12O ⁰ C. When the reaction temperature is excessively low, the reaction rate is likely to be lowered.

On the other hand, when the reaction temperature is

excessively high, disadvantageously, the amount of

impurities is likely to be increased, and, further, the

unsaturated bond is likely to be polymerized.

Whether or not the solvent is to be used in the

second step depends upon the type of the compound used or

the like. When the amine mineral acid salt compound of

formula (VI) and/or the compound of formula (XI) and/or the

ester compound of formula (XII) are liquid or melt, the

reaction may be carried out in the absence of a solvent.

On the other .hand, when the amine mineral acid salt

compound of formula (VI) and/or the compound of formula

(XI) and/or the ester compound of formula (XII) are solid

or do not melt, the reaction is preferably carried out in

the presence of a solvent.

Specific examples of solvents usable herein include

esters such as methyl acetate, ethyl acetate, propyl

acetate, isopropyl acetate and butyl acetate; chain ethers

such as diethyl ether, dipropyl ether, and dibutyl ether;

cyclic ethers such as dioxane, dioxolane and

tetrahydrofuran; aromatic hydrocarbons such as toluene,

xylene, ethylbenzene, mesitylene, and cumene; aliphatic

hydrocarbons such as propane, hexane, heptane, and

cyclohexane; and halogenated hydrocarbons such as methylene

chloride, 1, 2-dichloroethane and 1, 2-dichlorobenzene.

When the solvent is used, the amount of the solvent

used is such that the concentration of the amine mineral

acid salt compound of formula (VI) based on the total

amount of the amine mineral acid salt compound of formula

(VI), the compound of formula (XI), and the solvent is

generally 1 to 50% by weight, preferably 5 to 30% by weight,

more preferably 10 to 20% by weight. When the amount of

the solvent used is excessively small, stirring in the

reaction cannot be successfully carried out and the

reaction rate is likely to be lowered. On the other hand,

when the amount of the solvent used is excessively large,

this does not affect the reaction. In this case, however,

the amount of the solvent to be discarded is increased, and

a load on environment is likely to be enhanced.

The amount of the compound represented by formula

(XI) based on the amine mineral acid salt compound

represented by formula (VI) may vary depending upon the

type of the compound used. Generally, the amount of the

compound represented by formula (XI) may be 2 to 10 times

by mole, preferably 2 to 5 times by mole, the amount of the

amine mineral acid salt compound represented by formula

(VI) . When the amount of the compound represented by

formula (XI) used is excessively small, the yield is likely

to be lowered and, in addition, the amount of impurities is

likely to be increased. On the other hand, when the amount

of the compound represented by formula (XI) used is

excessively large, this does not affect the reaction at all

In this case, however, since the amount of waste is

increased, disadvantageously, the load on environment is

likely to be ,increased.

The ester compound represented by formula (VIII)

obtained in the second step may be purified by a

conventional procedure, for example, by extraction,

recrystallization or distillation, or alternatively as such

may be used in the reaction in the next third step without

any purification,

(iii-c) Third step

The reaction temperature in the third step may vary

depending upon the type of the compound used. The reaction

temperature is generally 30 to 150°C, preferably 50 to

120°C. When the reaction temperature is excessively low, the reaction rate is likely to be lowered. On the other

hand, when the reaction temperature is excessively high,

the amount of impurities is likely to be increased.

Further, in this case, polymerization of the formed

unsaturated bond is likely to take place.

Whether or not the solvent is to be used in the third

step depends upon the type of the compound used or the like.

When the ester compound of formula (XII) is liquid or melts,

the reaction may be carried out in the absence of a solvent.

On the other hand, when the ester compound of formula (XII)

is solid or does not melt, the reaction is preferably

carried out in the presence of a solvent.

Specific examples of solvents usable herein include

esters such as methyl acetate, ethyl acetate, propyl

acetate, isopropyl acetate and butyl acetate; chain ethers

such as diethyl ether, dipropyl ether, and dibutyl ether;

cyclic ethers such as dioxane, dioxolane and

tetrahydrofuran; aromatic hydrocarbons such as toluene,

xylene, ethylbenzene, mesitylene, and cumene; aliphatic

hydrocarbons such as propane, hexane, heptane, and

cyclohexane; and halogenated hydrocarbons such as methylene

chloride, 1, 2-dichloroethane and 1, 2-dichlorobenzene.

When the solvent is used, the amount of the solvent ■

used is such that the concentration of the ester compound

of formula (VIII) based on the total amount of the ester

compound of formula (XII), the compound of formula (IX),

and the solvent is generally 0.5 to 80% by weight,

preferably 5 to 50% by weight. When the amount of the

solvent used is excessively small, stirring in the reaction

cannot be successfully carried out and the reaction rate is

likely to be lowered. On the other hand, when the amount

of the solvent used is excessively large, this does not

affect the reaction. In this case, however, the amount of

the solvent to be discarded is increased, and a load on

environment is likely to be enhanced.

Specific examples of Z ¹ and Z ² in compounds

represented by formula (IX) used in the third step are as

described above. Further, as described above, a dimer or

trirαer of the compound of formula (IX) may also be used.

The amount of the compound represented by formula

(IX) based on the ester compound represented by formula

(XII) used may vary depending upon the type of the compound

used. Theoretically, the reaction between the ester

compound represented by formula (XII) and the compound

represented by formula (IX) proceeds in a molar ratio of

1 : 1. In order to allow the reaction to proceed smoothly,

however, the use of an excessive amount of the compound

represented by formula (IX) is preferred. Generally, the

amount of the compound represented by formula (IX) used may

be 1 to 10 times by mole, preferably 1 to 5 times by mole,

the amount of the ester compound represented by formula

(XII) used. When the amount of the compound represented by

formula (IX) used is excessively small, a part of the ester

compound represented by formula (XII ) remains unreacted.

This is likely to lower the yield, and the amount of

impurities is likely to be increased.. On the other hand,

when the amount of the compound represented by formula (IX)

used is excessively large, this does not affect the

reaction at all. In this case, however, disadvantageously,

a special removal apparatus or the Like is possibly

necessary, and the load on environment is likely to be

increased.

The ethylenically unsaturated group-containing

isocyanate compound represented by formula (XIII) obtained

in the third step may be purified by a conventional

procedure, that is, for example, by extraction,

recrystallization or distillation, or alternatively as such

may be used in the reaction in the next fourth step without

any purification,

(iv) Reactive monomer

The reactive monomer according" to the present

invention is produced using the above ethylenically

unsaturated group-containing isocyanate compound as a

starting compound and is represented by formula (Ia) . In

this reactive monomer, two ethylenically unsaturated groups

are bonded to one urethane, thiourethane, or urea group.

At least one- urethane, thiourethane, or urea, bond is

contained in the molecule.

In the formula, R ¹ represents a straight-chain or

branched saturated aliphatic group having 1 to 10 carbon

atoms , preferably 1 to 5 carbon atoms . Specific examples

of preferred substituents include those obt ained from the

dihydroxyamine compound of formula (V) in tlie production

process of the ethylenically unsaturated group-containing

isocyanate compound . Examples thereof include those

prepared from 2-amino-l, 3-propanediol , l-aiαino-2 , 3-

butanediol, and 2-amino-2-methyl-l , 3-butanediol .

R represents a hydrogen atom or a methyl group .

R ³ represents a straight-chain or branched-chain

alkylene group having 0 to 5 carbon atoms.

R ⁴ represents a hydrogen atom, a straig ^~ h.t-ch.ain or

branched-chain alkyl group having 1 to 6 cartoon atoms, or

an aryl group. R ⁴ preferably represents a hydrogen atom or

a methyl group from the viewpoint of the reactivity of the

ethylenically unsaturated group.

Specific examples of preferred substituents include

those obtained from the compound of formula (VII) or

formula (XI) in the production process of the ethylenically

unsaturated group-containing ioscynate compound. Examples

thereof include those prepared from (meth) ac_rylic acid

chloride, crotonic acid chloride, 3-chloropropionic acid

chloride, and 3-chlorobutanoic acid chloride .

R ⁵ represents an ether, thioether, or NTH group, X

represents an aliphatic, aromatic, or heterocyclic group

bonded thereto, and n is an integer of 1 to 4. The

molecular weight of X is generally less than 2000,

preferably 300 to 1000.

The aliphatic group as the substituten ^~ t X is a group

which comprises a straight-chain, branched-cliain or cyclic

carbon chain and has 1 to 4 positions which can be

substituted. Specific examples thereof include straight-

chain or branched-chain alkyl groups, straight-chain or

branched alkylene groups, and cyclic alkyl groups.

The aliphatic group as the substituent X furher may

have a substituent. Specific examples of such substituents

include alkyl groups such as ethyl, n-butyl, and n-hexyl

groups, -CH ₂ CH ₂ (CF ₂ ) _S F, 3Ud -CH ₂ CF ₂ CF ₂ CF ₂ CF ₂ CF ₂ CF ₂ CH _2- .; and

cyclic alkyl groups such as cyclohexyl, cycloalkenyl, and

norbornyl groups .

The aromatic group as the substituent X is an

aromatic group having 1 to 4 positions which can be

substituted. Specific examples thereof include phenyl,

xylylene, bisphenol, and fluorene groups.

The heterocyclic group as the substituent X is a

heterocyclic group having 1 to 4 positions which can be

substituted. Specific examples thereof include pyridyl,

thienyl, furyl, piperidyl, imidazolyl, and quinolyl groups■.

Specific examples of preferred reactive monomers

according to the present invention include compounds

represented by formulae (Ha) to (IVa) .

a )

In formulae (Ha) to (IVa), R", R and X are as

defined above.

In the reactive monomer according to the present

invention, the ethylenically unsaturated group can be

photocured or heat-cured, for example, by radical or cation

polymerization. In this case, as in the present invention,

when a structure containing adjacent reactive ethylenically

unsaturated groups is adopted, high reactivity and

increased degree of crosslinking can be mentioned as the

effect attained by the presence of the ethylenically

unsaturated group in the adjacent position. As a result,

when the reactive monomer has been brought to a curable

composition, the gelation speed becomes high. When the

curable composition is coated onto a reactive base material

followed by curing, the adhesive strength to the base

material is good. Further, the crosslinked structure is so

dense that the heat resistant temperature is good.

Further, the unfavorable phenomenon that the

ethylenically unsaturated group is sometimes crystallized

upon curing can be suppressed. At the same time, the

optical effect of good transparency can be attained. This

is considered attributable to the fact that, due to the

presence of adjacent ethylenically unsaturated groups,

crosslinking proceeds in an amorphous manner, making it

difficult to form a crystalline region upon curing. This

is a critical property for applications as optical

materials.

Specific examples of preferred reactive monomers in

the present invention will be described for a case where R ⁵

represents an ether group, a case where R ⁵ represents a

thioether group, and a case where R ⁵ represents an NH group.

It should be noted that the essential feature of the

present invention is that the effect is attained by the

fact that two adjacent reactive ethylenically unsaturated

groups are bonded to one urethane bond, thiourethane bond,

or urea bond, and at least one urethane bond, thiourethane

bond, or urea bond of this type is contained in its

molecule, and the substituent X is not limited to the

following exemplification.

Reactive monomer in which R ⁵ represents an ether group

In the reactive monomer in the first example, in

formula (Ia) , R ⁵ represents an ether group, X represents

fluorine-containing group, and n = 1. Specific examples of

the fluorine-containing group having one position which can

be substituted include fluoroalkyl groups. The fluoroalkyl

group preferably has 1 to 20 carbon atoms, more preferably

1 to 10 carbon atoms, and may have a straight-chain

structure (for example, -CF ₂ CF ₃ , -CH ₂ (CF ₂ ) ₄ H, -CH ₂ (CF ₂ ) ₈ CF ₃ , -

CH ₂ CH ₂ (CF ₂ ) ₄ H, or -CH ₂ CH ₂ (CF ₂ ) ₈ F) , a branched-chain structure

(for example, -CH(CF ₃ ) ₂ , -CH ₂ CF(CF ₃ ) ₂ , -CH(CH ₃ )CF ₂ CF ₃ , or -

CH(CH ₃ ) (CF ₂ ) ₅ CF ₂ H) , an alicyclic structure (preferably a

five-membered or six-membered ring, for example, a

perfluorocyclohexyl group, a perfluorocyclopentyl group, or

an alkyl group substituted by the above group) , or may have

an ether bond. Specific examples of ether bond-containing .

fluoroalkyl groups include -CH ₂ OCH ₂ CF ₂ CF ₃ , -CH ₂ CH ₂ OCH ₂ C ₄ F ₈ H, -

CH ₂ CH ₂ OCH ₂ CH ₂ C ₈ F ₁₇ , and -CH ₂ CH ₂ OCF ₂ CF ₂ OCF ₂ CF ₂ H.

A plurality of fluoroalkyl groups described above may

be contained in the same molecule.

An example of preferred X in formula (Ia) is a group

represented by - (CH ₂ ) _m (CF ₂ ) iF wherein m is an integer of 0

to 2 and 1 is an integer of 0 to 8, provided that m and 1

do not simultaneously represent 0.

The fluorine content is preferably not less than 30%

by weight based on the total amount of the reactive monomer,

more preferably not less than 40% by weight, still more

preferably not less than 50% by weight. When the fluorine

content is excessively low, the refractive index value is

increased. In this case, in some cases, properties as a

low-refractive index material cannot be provided when the

product is used as an antireflection film or a cladding

material. For example, when the fluorine content is less

than 40% by weight, in some cases, the refractive index is

not less than 1.45. This refractive index is not.

appropriate as a low-refractive index material. The

fluorine content based on the total amount of the

composition can be brought to not less than 50% by weight .

by preparing the composition using the reactive monomer as

one component.

In the reactive monomer in the second example, in

formula (Ia) , R ⁵ represents an ether group, X represents a

fluorine-containing group, and n = 2. The fluorine-

containing group having two positions which can be

subsituted is preferably a group obtained from a fluorine-

containing diol . Specific examples of fluorine-containing

diols include perf luoroalkyl diols such as 2,2,3,3,4,4-

hexaf luoro-1, 5-pentanediol, 2, 2, 3, 3, 4, 4, 5, 5-octaf luoro-1, 6-

hexanediol, and 2, 2, 3, 3, 4, 4, 5, 5, 6, 6, 7, 7-dodecaf luoro-1, 8-

octanediol; perf luoroalkylene glycols such as

perfluorotriethylene glycol and perf luorotetraethylene

glycol; polyperf luoroalkylene ether diols such as α-(l,l-

dif luoro-2-hydroxyethyl) -ω- (2, 2-dif luoroethanol) poly (oxy-

1, 1, 2, 2-tetraf luoroethylene) , α- (1, 1-dif luoro-2-

hydroxyethyl ) -ω- ( 2 , 2-dif luoroethanol ) poly ( oxy-

dif luoromethylene) , and α- (1, 1-dif luoro-2-hydroxyethyl ) -ω- (2, 2-dif luoroethanol) poly (oxy-dif luoromethylene) (oxy-

1, 1, 2, 2-tetrafluoroethylene) ; ring-opened diols of

f luoroalkyl epoxides such as 3-perf luorobutyl-1, 2-

epoxypropane, 3-perf luorooctyl-1, 2-epoxypropane, and 3-

perf luorobutyl-1, 2-epoxypropane; and 2,2-bis(4-

hydroxycyclohexyl)hexafluoropropane. A group obtained from

a diol comprising an alkylene oxide such as ethylene oxide

or propylene oxide added to the fluorine-containing diol

may also be used.

The preferred fluorine content range based on the

total amount of the reactive monomer is the same as

described above in connection with the first example.

In the reactive monomer in the third example, in

formula (Ia) ₇ R ⁵ represents an ether group, X represents a

group having a fluorene skeleton, and n = 2. A group

represented by formula (XVI) may be mentioned as the

fluorene skeleton-containing group.

In formula (XVI ) , h is preferably 1 to 4 , more

preferably 1 or 2 .

Reactive monomer in which R ⁵ represents NH group

In the reactive monomer in the first example, R ⁵ in

formula ( Ia) represents NH group, X represents a fluorine- ,

containing group, and n = 1 . The same group as in the case

where R ⁵ represents an ether group may be mentioned as the

fluorine-containing group having one position which can be

substituted . Specific examples of preferred fluorine-

containing groups include aromatic groups such as

F(CFz) ₃ CH ₂ -, F(CF ₂ ) ₆ CH ₂ -, F(CFz) ₇ CH ₂ -, F(CF ₂ ) ₈ CH ₂ -, and a

residue of 2, 6-dif luoroaniline.

In the reactive monomer in the second example, in

formula (Ia) , R ⁵ represents NH group, X represents a

saturated aliphatic group or aromatic group, and n = 2.

Saturated aliphatic groups include, for example, groups of

straight-chain, branched-chain or cyclic carbon chains

having two positions which can be substituted. Specific

examples thereof include groups having an alkylene

straight-chain structure such as ethylene, propylene,

butylene, hexamethylene, and polyoxyalkylene, and groups

having an alicyclic structure such as cyclohexyl and

norbornane .

Aromatic groups include phenylene, xylylene, 4,4'-

methylenebis (phenylamine) , 2,3,5, 6-tetraf luoro-phenyl, and

2,3,5, 6-tetraf luoro-1, 4-xylylenyl groups .

Reactive monomer in which R ⁵ represents thioether group

The substituent X in the case where R ⁵ represents a

thioether group may be the same group as described above in

connection with the case where R ⁵ represents an ether group

or NH group. Specific examples of the subsituent X include

those obtained by adding an isocyanate group in the

ethylenically unsaturated group-containing isocyanate

compound of formula (I) to the following compound

containing one or more merrcapto group. Specific examples

of compounds containing one or more mercapto groups include

methyl mercaptan, ethyl mercaptan, propyl mercaptan, butyl

mercaptan, amyl mercaptan^ hexyl mercaptan, heptyl

mercaptan, octyl mercaptan., nonyl mercaptan, cyclopentyl

mercaptan, cyclohexyl mercaptan, furfuryl mercaptan,

thiophenol, thiocresol, ethyl thiophenol, benzyl mercaptan,

1, 2-ethanedi thiol, 1, 2-propanedithiol, 1, 3-propanedithiol,

1, 4-butanedi thiol, 1, 6-he∑canedi thiol, 1, 2, 3-propanetrithiol,

1, 1-cyclohexanedithiol, l _r 2-cyclohexanedithiol,

bicyclo [2, 2, 1] hepta-exo-cis-2, 3-di thiol, 1,1-

bis (mercaptomethyl) cyclotαexane, bis (2-mercaptoethyl) ether,

ethyleneglycol bis (2-merca.ptoacetate) , ethyleneglycol

bis (3-mercaptopropionate) _r trimethylolpropanebis (2-

mercaptoacetate) , triiuethylolpropanebis (3-

mercaptopropionate) , pentaerythritol tetrakis (2-

mercaptoacetate) , pentaerythritol tetrakis (3-

mercaptopropionate) , 1,2-dimercaptobenzene, 1,3-

dimercaptobenzene, 1, 4-dimercaptobenzene, 1,2-

bis (mercaptomethyl) benzene, 1, 3-bis (mercaptomethyl) benzene,

1, 4-bis (mercaptomethyl)benzene, 1 , 2-bis (2-

mercaptoethyl)benzene, 1, 3-bis (2—mercaptoethyl) benzene,

1, 4-bis (2-mercaptoethyl)benzene, 1, 2-bis (2-

mercaptoethyleneoxy)benzene, 1, 3—bis (2-

mercaptoethyleneoxy)benzene, 1, 4—bis (2-

mercaptoethyleneoxy)benzene, 1,2, 3-trimercaptobenzene,

1, 2, 4-trimercaptobenzene, 1, 3, 5-fcrimercaptobenzene, 1,2,3-

tris (mercaptomethyl)benzene, 1,2, 4-

tris (mercaptomethyl)benzene, 1,3, 5-

tris (mercaptomethyl)benzene, 1,2, 3-tris (2-

mercaptoethyl)benzene, 1,2, 4-tris (2-mercaptoethyl)benzene,

1,3, 5-tris (2-mercaptoethyl)benzene, 1,2, 3-tris (2-

mercaptoethyleneoxy)benzene, 1,2, 4-tris (2-

mercaptoethyleneoxy)benzene, 1,3, 5-tris (2-

mercaptoethyleneoxy)benzene, 1,2 _Λ 3, 4-tetramercaptobenzene,

1,2,3, 5-tetramercaptobenzene, 1,2,4, 5-tetramercaptobenzene,

1, 2, 3, 4-tetrakis (mercaptomethyl)benzene, 1,2,3,5-

tetrakis (mercaptomethyl)benzene, 1,2,4,5-

tetrakis (mercaptomethyl) benzene, 1,2,3, 4-tetrakis (2-

mercaptoethyl)benzene, 1,2,3, 5-tetrakis (2-

mercaptoethyl)benzene, 1,2,4, 5-tetrakis (2-

mercaptoethyl)benzene, 1,2,3, 4-tetrakis (2-

mercaptoethyleneoxy) benzene, 1,2,3, 5-tetrakis (2-

mercaptoethyleneoxy)benzene, 1,2,4, 5-tetrakis (2-

mercaptoethyleneoxy)benzene, 2, 2 '-dimercaptobiphenyl, 4,4'—

thiobis-benzenethiol, 4, 4 '-dimercaptobiphenyl, 4,4'-

dimercaptobibenzyl, 2, 5-toluenedithiol, 3, 4-toluenedithiol,-

1, 4-naphthalenedithiol, 1, 5-naphthalenedithiol, 2,6-

naphthalenedithiol, 2, 7-naphthalenedithiol, 2,4-

dimethylbenzene-1, 3-dithiol, 4, 5-dimethylbenzene-l, 3-

dithiol, 9, 10-anthracenedimethanethiol, l,3-bis(2-

mercaptoethylthio)benzene, 1, 4-bis (2-

mercaptqethylthio)benzene, 1, 2-bis (2-

mercaptoethylthiomethyl)benzene, 1,3-bis (2-

mercaptoethylthiomethyl)benzene, 1, 4-bis (2-

mercaptoethylthiomethyl)benzene, 1,2, 3-tris (2-

mercaptoethylthio)benzene, 1,2, 4-tris (2-

mercaptoethylthio)benzene, 1, 3, 5-tris (2-

mercaptoethylthio)benzene, 1,2,3, 4-tetrakis (2-

rαercaptoethylthio)benzene, 1,2, 3,5-tetrakis (2-

mercaptoethylthio)benzene, 1,2,4, 5-tetrakis (2-

mercaptoethylthio)benzene, bis (2-mercaptoethyl) sulfide,

bis (2-mercaptoethylthio)methane, 1, 2-bis (2-

mercaptoethylthio) ethane, 1, 3-bis (2-

mercaptoethylthio)propane, 1,2, 3-tris (2-

mercaptoethylthio)propane, tetrakis (2-

mercaptoethylthiorαethyl)methane, 1, 2-bis (2-

mercaptoethylthio)propanethiol, 2, 5-dimercapto-l, 4-dithiane,

bis (2-mercaptoethyl) disulfide, 3, 4-thiophenedithiol, 1,2-

bis (2-mercaptoethyl) thio-3-mercaptopropane, and bis- (2-

mercaptoethylthio-3-mercaptopropane) sulfide. Among them,

octyl mercaptan, 1, 6-hexanedithiol, 2-mercaptoethyl sulfide,

and 1, 4-dimercaptobenzene are preferred,

(v) Production process of reactive monomer

The reactive monomer of formula (Ia) in the present

invention can be prepared by reacting the isocyanate

compound containing two reactive ethylenically unsaturated

groups represented by formula (I) with a compound

containing a hydroxyl, amino or mercapto group. In this

case, the reaction method is not particularly limited, and,

for example, the reactive monomer of formula (I) may be

produced by mere mixing.

In reacting the ethylenically unsaturated group-

containing isocyanate compound of formula (I) with the

hydroxyl group-containing compound, the use of a

urethanation catalyst is preferred. The use of this

catalyst can significantly accelerate the reaction.

Specific examples of urethanation catalysts include

dibutyltin dilaurate, copper naphthenate, cobalt

naphthenate, zinc naphthenate, triethylamine, 1,4-

diazabicyclo{2.2.2] octane, and 2, 6, 7-trimethyl-l, 4-

diazabicyclo [2.2.2] octane. These urethanation catalyst ma;y

be used either solely or in a combination of two or more.

The amount of the urethanation catalyst added is

preferably 0.01 to 5 parts by weight, more preferably 0.1

to 1 part by weight, based on 100 parts by weight of the

isocyanate compound. When the amount of the urethanation

catalyst added is less than 0.01 part by weight, the

reactivity is sometimes significantly lowered. On the

other hand, when the amount of the urethanation catalyst

added exceeds 5 parts by weight, in some cases, a side

reaction takes place in the reaction.

The reaction temperature in the reaction between the •

ethylenically unsaturated group-containing isocyanate

compound of formula (I) and the compound containing a

hydroxyl, amino, or mercapto group is preferably -10 to

100°C, more preferably 0 to 80°C. In the reaction with the amino group, the reaction rate is so high that mere mixing

can achieve a contemplated synthesis even in the absence of

a catalyst. When the reaction temperature is excessively

high, there is a fear that by-products are produced as a

result of a further reaction of the formed urea bond with

the isocyanate.

It is known that the above reaction proceeds even in

the case of groups other than the hydroxyl, amino, and

mercapto groups. For example, since the isocyanate group

can also be reacted with a carboxyl group or the like, the

reactive ethylenically unsaturated group can be introduced

by an addition reaction.

Further, the ethylenically unsaturated group-

containing isocyanate compound of formula (I) may be used

with an isocyanate compound containing one reactive

ethylenically unsaturated group for a reaction with a

hydroxyl-, amino-, or mercapto-containing compound.

Specific examples of isocyanate compounds containing one

reactive ethylenically unsaturated group include 2-

methacryloyloxyethylisocyanate, 2-

acryloyloxyethylisocyanate, 2- (2-ethylbutenoyloxy) -

ethylisocyanate, 2- (2-propylbutenoyloxy) ethylisocyanate,

methacryloyloxymethylisocyanate, acryloyloxymethyl-

isocyanate, (2-ethylbutenoyloxy)methylisocyanate, (2-

propylbutenoyloxy)methylisocyanate, 3-methacryloyloxy-

propylisocyanate, 3-acryloyloxypropylisocyanate, 3- (2-

ethylbutenoyloxy)propylisocyanate, 3- (2-propylbutenoyloxy) -

propylisocyanate, 4-methacryloyloxybutylisocyanate, 4-

acryloyloxybutylisocyanate, 4- (2-ethylbutenoyloxy) -

butylisocyanate, and 4- (2-propylbutenoyloxy)butylisocyanate,

(vi) Curable composition

The curable composition according to the present

invention comprises a reactive monomer of formula (Ia) and

a polymerization initiator. Photopolymerization initiators

may be used as the polymerization initiator. The

application of an actinic radiation such as ultraviolet

light or visible light can induce a polymerization reaction

of the reactive monomer to prepare a cured product.

Specific examples of such photopolymerization initiators

include 1-hydroxycyclohexyl phenyl ketone, 2, 2 '-dimethoxy- ■

2-phenylacetophenone, xanthone, fluorene, fluorenone,

benzaldehyde, anthraquinone, triphenyl amine, carbazole, 3-

methylacetophenone, 4-chlorobenzophenone, 4,4'-

dimethoxybenzophenone, 4, 4 '-diaminobenzophenone, Michler's

ketone, benzoylpropyl ether, benzoin ethyl ether,

benzyldimethylketal, 1- (4-isopropylphenyl) ^-hydroxyz¬

inethylpropan-1-one, 2-hydroxy-2-methyl-l-phenylpropan-l-one,

thioxanthone, diethylthioxanthone, 2-isopropylthioxanthone,

2-chlorothioxanthone, 2-methyl-l- [4- (methylthio)phenyl] -2-

morpholinopropan-1-one, 2,4,6-

trimethylbenzoyldiphenylphosphine oxide, 2-benzyl-2-

dimethylamino-1- (4-morpholinophenyl)butan-1-one, and l-[4-

(2-hydroxyethoxy) -phenyl] -2-hydroxy-2-methylpropan-l-one.

Among them, 2, 4, 6-trimethylbenzoyldiphenylphosphine

oxide and 1-hydroxycyclohexyl phenyl ketone are preferred.

These photopolymerization initiators may be used

either solely or in a combination of two or more of them.

Further, the application of heat can induce a

polymerization reaction of the reactive monomer to prepare

a cured product. Specifically, a heat curable composition

can be produced by adding a thermal polymerization

initiator to a reactive monomer. Examples of such thermal ■

polymerization initiators include diacyl peroxides, ketone

peroxides, hydroperoxides, dialkyl peroxides, peroxy esters,

azo compounds, and persulfates. They may be used either

solely or in a combination of two or more of them.

The amount of the polymerization initiator used is

preferably 0.1 to 20 parts by weight, more preferably 0.5

to 10 parts by weight, based on 100 parts by weight of the

reactive monomer. When the amount of the polymerization

initiator used is less than 0.1 part by weight, in some

cases, the rate of polymerization of the reactive monomer

is lowered. Further, in this case, the reactive monomer is

sometimes likely to undergo inhibition of polymerization by

oxygen or the like. On the other hand, when the amount of

the polymerization initiator used exceeds 20 parts by

weight, the polymerization reaction is suppressed, often

resulting in lowered strength, adhesive strength and heat

resistance of the cured film. Further, this is causative

of coloring.

The curable composition according to the present

invention may contain a reactive monomer other than the

reactive monomer of formula (Ia) . The incorporation of

this reactive monomer can modify the viscosity of the

composition and, at the same time, can regulate properties

of the cured product, for example, mechanical properties

such as reactivity, hardness, elasticity, and adhesion, and

optical properties such as transparency.

Specific examples of such reactive monomers include

ethylenically unsaturated aromatic compounds such as

styrene, α-methylstyrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, p-tert-butylstyrene, diisopropenyl benzene,

o-chlorostyrene, m-chlorostyrene, p-chlorostyrene, 1,1-

diphenylethylene, p-methoxystyrene, N,N-dimethyl-p-

aminostyrene, N,N-diethyl-p-aminostyrene, ethylenically

unsaturated pyridine, and ethylenically unsaturated

imidazole; carboxyl group-containing compounds such as

(meth) acrylic acid, crotonic acid, maleic acid, fumaric

acid, and itaconic acid; alkyl (meth) acrylates such as

methyl (meth) acrylate, ethyl (meth) acrylate, propyl

(meth) acrylate, isopropyl (meth) acrylate, butyl

(meth) acrylate, isobutyl (meth) acrylate, tert-butyl

(meth) acrylate, pentyl (meth) acrylate, amyl (meth) acrylate,

isoamyl (meth) acrylate, hexyl (meth) acrylate, heptyl

(meth) acrylate, octyl (meth) acrylate, isooctyl

(meth) acrylate, 2-ethylhexyl (meth) acrylate, nonyl

(meth) acrylate, decyl (meth) acrylate, isodecyl

(meth) acrylate, undecyl (meth) acrylate, dodecyl

(meth) acrylate, lauryl (meth) acrylate, stearyl

(meth) acrylate, and isostearyl (meth) acrylate; fluoroalkyl

(meth) acrylates such as trifluoroethyl (meth) acrylate,

tetrafluoropropyl (meth) acrylate, hexafluoroisopropyl

(meth) acrylate, octafluoropentyl (meth) acrylate, and

heptadecafluorodecyl (meth) acrylate; hydroxyalkyl

(meth) acrylates such as hydroxyethyl (meth) acrylate,

hydroxypropyl (meth) acrylate, and hydroxybutyl

(meth) acrylate; phenoxyalkyl (meth) acrylates such as

phenoxyethyl (meth) acrylate, and 2-hydroxy-3-phenoxypropyl

(meth) acrylate; alkoxyalkyl (meth) acrylates such as

methoxyethyl (meth) acrylate, ethoxyethyl (meth) acrylate,

propoxyethyl (meth) acrylate, butoxyethyl (meth) acrylate,

and methoxybutyl (meth) acrylate; polyethylene glycol

(meth) acrylates such as polyethylene glycol

mono (meth) acrylate, ethoxydiethylene glycol (meth) acrylate,

methoxypolyethylene glycol (meth) acrylate,

phenoxypolyethylene glycol (meth) acrylate, and

nonylphenoxypolyethylene glycol (meth) acrylate;

polypropylene glycol (meth) acrylates such as polypropylene,

glycol mono (meth) acrylate, methoxypolypropylene glycol

(meth) acrylate, ethoxypolypropylene glycol (meth) acrylate,

and nonylphenoxypolypropylene glycol (meth) acrylate;

cycloalkyl (meth) acrylates such as cyclohexyl

(meth) acrylate, 4-butylcyclohexyl (meth) acrylate,

dicyclopentanyl (meth) acrylate, dicyclopentenyl

(meth) acrylate, dicyclopentadienyl (meth) acrylate, bornyl

(meth) acrylate, isobornyl (meth) acrylate, and

tricyclodecanyl (meth) acrylate; benzyl (meth) acrylate,

tetrahydrofurfuryl (meth) acrylate, ethylene glycol

di (meth) acrylate, diethylene glycol di (meth) acrylate,

triethylene glycol di (meth) acrylate, polyethylene glycol

di (meth) acrylate, propylene glycol di (meth) acrylate,

dipropylene glycol di (meth) acrylate, tripropylene glycol

di (meth) acrylate, polypropylene glycol di (meth) acrylate,

neopentyl glycol di (meth) acrylate, 1,3-propanediol

di (meth) acrylate, 1, 4-butanediol di (meth) acrylate, 1,6-

hexanediol di (meth) acrylate, hydroxy pivalic acid ester

neopentyl glycol di (meth) acrylate, bisphenol A

di (meth) acrylate, trimethylolpropane tri (meth) acrylate,

pentaerythritol tri (meth) acrylate, trimethylolpropane

trioxyethyl (meth) acrylate, tris (2-

hydroxyethyl) isocyanurate tri (meth) acrylate, and

dipentaerythritol hexa (meth) acrylate. These reactive

monomers may be used either solely or in a combination of

two or more of them.

In the production of the curable composition

i according to the present invention, mixing and regulation

may be carried out by mixing the reactive monomer of

formula (Ia) with a polymerization initiator at room

temperature or with heating in a mixing machine such as a

mixer, a ball mill or triple roll, or by adding and

dissolving a reactive monomer, a solvent or the like as a

diluent in the reaction system. Specific examples of

reactive monomers usable as the diluent include the above-

described reactive monomers. Specific examples of solvents

include esters such as ethyl acetate, butyl acetate and

isopropyl acetate; ketones such as acetone, methyl ethyl

ketone, methyl isobutyl ketone and cyclohexanone; cyclic

ethers such as tetrahydrofuran and dioxane; amides such as

N,N-dimethylformamide; aromatic hydrocarbons such as

toluene; and halogenated hydrocarbons such as methylene

chloride.

The curable composition according to the present

invention can be cured, for example, by coating a curable

composition onto a base material to form a coating film and

then applying a radiation or heat to the coating film.

Both the radiation and heat may also be simultaneously

applied for curing purposes.

The thickness of the coating film is preferably 1 to

200 μm for evaluation purposes but may be properly determined depending upon applications .

Coating methods usable herein include, for example,

coating by a _' die coater, a spin coater, a spray coatex, a

curtain coater, or a roll coater, coating by screen

printing, or coating by dipping.

An electron beam or light in the wavelength range of

ultraviolet light to infrared light is preferred as tlie

radiation for curing. For example, use may be made ozf:

ultrahigh pressure mercury light sources or metal hal ide

light sources for ultraviolet light; metal halide l±g\ht

sources or halogen light sources for visual light sources;

and halogen light sources for infrared light. In addzLtion

to the above light sources, light sources such as laser or

LEDs may be used. The dose of the radiation may be

properly determined depending upon the type of the IL ght

source, the thickness of the coating film and the likze.

The curable composition according to the presen-t

invention can be used in applications such as resists (for

example, solder resists, etching resists, color filter

resists, and spacers), sealing (for example, waterproof

sealing) , paints (for example, antifouling paints,

fluoropaints, and water-based paints), pressure-sensitive

adhesives and adhesives (for example, adhesives and dicing

tapes) , printing plates (for example, CTP plates and offset

plates), printing proofreading (for example, colorproof) ,

lenses (for example, contact lenses, microlenses, and

optical waveguides), dental materials, surface treatment

(for example, optical fiber coating and disk coating) , and

battery materials (for example, solid electrolytes) .

(vii) Reactive (meth) acrylate polymer (A)

The reactive (meth) acrylate polymer (A) according to

the present invention is a compound produced by reacting an

isocyanate compound represented by formula (I) containing

two adjacent ethylenically unsaturated groups in its

molecule with a polymer compound comprising repeating units

to which an active hydrogen-containing functional group is

attached. All general formulae in the present

specification embrace all stereoisomers such as cis and

trans isomers .

( I )

wherein R ¹ represents a straight-chain or branched-

chain saturated aliphatic group having 1 to 10, preferably

1 to 5 carbon atoms, and R ² represents a hydrogen atom or a

methyl group. More preferably, R ¹ represents a branched

saturated aliphatic group having 3 or 4 carbon atoms from

the viewpoint of easiness in synthesizing the isocyanate

group. R ³ represents a straight-chain or branched-chain

alkylene group having 0 to 5 carbon atoms, preferably 0 to

3 carbon atoms . R ⁴ represents a hydrogen atom, a straight-

chain or branched-chain alkyl group having 1 to 6 carbon

atoms, or an aryl group. Preferably, R ⁴ represents a

hydrogen atom, a methyl group, or an aryl group.

Specific examples of preferred isocyanate compounds •

include compounds represented by formulae (II) and (III) .

(I I)

In formulae (II) and (III), R ² represents a hydrogen atom

or a methyl group.

Here the polymer compound which is reacted with the

isocyanate compound of formula (I) comprises repeating

units to which an active hydrogen-containing functional

group such as a hydroxyl, amino, or mercapto group is

attached. The hydroxyl, amino, or mercapto group is

reacted with the isocyanate group in the isocyanate

compound of formula (I) to form a urethane, urea, or

thiourethane bond.

The repeating units to which an active hydrogen-

containing functional group is attached refer to repeating

units based on a monomer (s) containing this functional

group or capable of forming the functional group through a ^'

polymerization reaction. The above polymer compound is

obtained by polymerizing the monomer(s) . The polymer

compound may be a homopolymer prepared from an identical

type of monomer or a copolymer prepared from mutually

different monomers.

The above polymer compound is preferably a

polyhydroxy compound comprising repeating units.

The number average molecular weight (a value

determined in terms of polystyrene by gel permeation

chromatography (parts by mass; PC) ) of the reactive

(meth) acrylate polymer (A) according to the present

invention is generally 500 to 100,000, preferably 8,000 to

40,000.

(viii) Production process of reactive (meth) acrylate

polymer (A)

The reactive (meth) acrylate polymer (A) is prepared

by reacting the isocyanate compound of formula (I) with a

polymer compound comprising repeating units to which an

active hydrogen-containing functional group is attached.

The reaction method is not particularly limited, and, for

example, the reactive (meth) acrylate polymer (A) may be

prepared by merely mixing these compounds together.

In reacting the isocyanate group in the isocyanate

compound of formula (I) with the hydroxyl group in the

polyhydroxy compound, the use of a urethanation' catalyst is

preferred. The use of this catalyst can significantly

accelerate the reaction.

Specific examples of urethanation catalysts include

dibutyltin dilaurate, copper naphthenate, cobalt

naphthenate, zinc naphthenate, triethylamine, 1,4-

diazabicyclo [2.2.2] octane, and 2, 6, 7-trimethyl-l, 4-

diazabicyclo[2.2.2] octane. These urethanation catalyst may

be used either solely or in a combination of two or more.

The amount of the urethanation catalyst added is

preferably 0.01 to 5 parts by weight, more preferably 0.1

to 1 part by weight, based on 100 parts by weight of the

isocyanate compound of formula (I) . When the amount of the

urethanation catalyst added is less than 0.01 part by

weight, the reactivity is sometimes significantly lowered.

On the other hand, when the amount of the urethanation

catalyst added exceeds 5 parts by weight, in some cases, a

side reaction takes place in the reaction.

The reaction temperature in the reaction between the

isocyanate compound of formula (I) and the polyhydroxy

compound comprising repeating units is preferably -10 to

100°C, more preferably 0 to 8O ⁰ C.

(ix) Polyhydroxy compound comprising repeating units

Polyhydroxy compounds comprising repeating units

usable in the present invention include polyester polyol

compounds, polycarbonate polyol compounds, polyether polyol

compounds, polyurethane polyol compounds, homo- or co¬

polymers of hydroxyalkyl (meth) acrylate, or epoxy

(meth) acrylate compounds.

(ix-a) Polyester polyol compound

The polyester polyol compound used in the present

invention is a compound having two or more hydroxyl groups

and one or more ester bonds per molecule, and specific

examples thereof include polyester polyols prepared from

polyhydric alcohols and esters of polybasic acids, and

polylactonediols such as polycaprolactonediols and

polybutyrolactonediols . Further, polyester polyol

compounds which have been synthesized so that the carboxyl

group remains unchanged may also be used.

(ix-b) Polycarbonate polyol compound

The polycarbonate polyol used in the present

invention is a compound having two or more hydroxyl groups .

and one or more carbonate bonds per molecule. Among others,

compounds represented by formula (XVIII) are preferred:

HO- (R ⁸ -O-COO) _n - (R ⁹ -O-COO) _m -R ¹⁰ -OH

(XVIII)

wherein R ⁸ , R ⁹ , and R ¹⁰ each independently represent a

straight-chain, branched-chain or cyclic hydrocarbon group

which may contain a hydroxyl group and/or a carboxyl group

and have 2 to 30 carbon atoms; and m and n are each

indepdendently an integer of 0 to 100.

R ⁸ , R ⁹ ,, and R ¹⁰ preferably represent an alkylene group

having 2 to 12 carbon atoms, and specific examples thereof

include ethylene, trimethylene, tetramethylene,

pentamethylene, hexamethylene, propylene, 2, 2-dimethyl-l, 3-

propylen, 1, 2-cyclohexylene, 1, 3-cyclohexylene, and 1,4-

cyclohexylene groups.

The polycarbonate polyol compound may be prepared,

for example, by reacting a diaryl carbonate such as

diphenyl carbonate with a polyol such as ethylene glycol,

tetramethylene glycol, hexamethylene glycol,

trimethylolethane, trimethylolpropane, glycerin, or

sorbitol.

(ix-c) Polyether polyol compound

The polyether polyol compound used in the present

invention is preferably a compound having a structure

formed by dehydrocondensation of two or more alkylene

glycols. This compound is produced, for example, by

condensation of an alkylene glycol or ring-opening

polymerization of an alkylene oxide.

Specific examples of alkylene glycols include

ethylene glycol, propylene glycol, 1, 4-butanediol, 1,3-

butanediol, 1, 5-pentanediol, neopentylglycol, 3-methyl-l, 5-

pentanediol, • 1, 6-hexanediol, and 1, 4-cyclohexanedimethanol .

Specific examples of alkylene oxides include ethylene

oxide, propylene oxide, tetrahydrofuran, styrene oxide, and

phenyl glycidyl ether.

Specific examples of polyether polyol compounds

include polyethylene glycol, polypropylene glycol, ethylene

oxide/propylene oxide copolymer, polytetramethylene glycol,

and polyhexamethylene glycol,

(ix-d) Polyurethane polyol compound

The polyurethane polyol compound used in the present

invention has two or more hydroxyl groups and one or more

urethane bonds per molecule. They may be produced by

reacting a polyisocyanate with a polyol by any proper

method. In this reaction, the isocyanate compound of

formula (I) may also be charged into the reaction system to

produce the reactive (meth) acrylate polymer (A) .

Specific examples of polyisocyanates include

diisocyanates such as 2,4-toluene diisocyanate, 2,6-toluene

diisocyanate, isophorone diisocyanate, hexamethylene

diisocyanate, diphenylmethylene diisocyanate (o, m, or p)-

xylene diisocyanate, methylenebis (cyclohexylisocyanate) ,

trimethylhexamethylene diisocyanate, cyclohexane-1, 3-

dimethylene diisocyanate, cyclohexane-1, 4-dimethylene

diisocyanate, and 1, 5-naphthalene diisocyanate. These

polyisocyanates may be used either solely or in a

combination of two or more of them.

Specific examples of polyols include ethylene glycol,

propylene glycol, diol compounds such as 1, 4-butanediol,

1, 3-butanediol, 1, 5-pentanediol, neopentylglycol, 3-methyl-

1, 5-pentanediol, 1, 6-hexanediol, 1, 4-cyclohexanedimethanol,

glycerin, triol compounds such as trimethylol propane,

pentaerythritol, dipentaerythritol, and diglycerin.

Polyol compounds usable herein include carboxyl-

containing polyol compounds such as dihydroxy aliphatic

carboxylic acids. These compounds are preferred because an

alkali developing property can be imparted by introducing a

carboxyl group into the reactive (rαeth) acrylate polymer (A) .

Such carboxyl-containing polyol compounds include

dimethyolpropionic acid and dimethylolbutanoic acid. They

may be used either solely or in a combination of two or

more of them.

Polyester polyol compounds in the above (ix-a) ,

polycarbonate polyol compounds in the above (ix-b) , and

polyether polyol compounds in the above (ix-c) may be used

as the polyol.

(ix-e) Homo- or copolymer of hydroxyalkyl (meth) acrylate

The homo- or copolymer of the

hydroxyalkyl (meth) acrylate used in the present invention is

a polymer produced by homopolymerizing or copolymerizing

one or more hydroxyalkyl (meth) acrylates by any proper

method. Specific examples of hydroxyalkyl (meth) acrylates

usable herein include 2-hydroxyethyl (meth) acrylate,

hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate,

glycerin mono (meth) acrylate, glycerin di (meth) acrylate,

trimethylol propane mono (meth) acrylate, pentaerythritol

mono (meth) acrylate, dipentaerythritol mono (meth) acrylate,

ditrimethylol propane mono (meth) acrylate,

trimethylolpropane-alkylene oxide adduct-mono (meth) acrylate,

2-hydroxy-3-phenoxypropylacrylate, polyethylene glycol

(meth) acrylate, and 6-hydroxyhexanoyloxyethyl

(meth) acrylate.

Among them, 2-hydroxyethyl (meth) acrylate,

hydroxypropyl (meth) acrylate, and hydroxybutyl

(meth) acrylate are preferred, and 2-hydroxyethyl

(meth) acrylate is more preferred. These hydroxyl-

containing (meth) acrylates may be used either solely or in

a combination of two or more of them.

The constituent (s) other than the hydroxyalkyl

(meth) acrylate constituting the copolymer is an unsaturated

compound copolymerizable therewith, and specific examples

thereof include alkyl (meth) acrylates such as methyl

(meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate,

butyl (meth) acrylate, isobutyl (meth) acrylate, sec-butyl

(meth) acrylate, tert-butyl (meth) acrylate, hexyl

(meth) acrylate, octyl (meth) acrylate, isooctyl

(meth) acrylate, 2-ethylhexyl (meth) acrylate, decyl

(meth) acrylate, lauryl (meth) acrylate, and stearyl

(meth) acrylate; alicyclic (meth) acrylates such as

cyclohexyl (meth) acrylate, bornyl (meth) acrylate, isobornyl

(meth) acrylate, dicyclopentenyl (meth) acrylate, and

dicyclopentenyloxyethyl (meth) acrylate; aromatic

(meth) acrylates such as benzyl (meth) acrylate, phenyl

(meth) acrylate, phenyl carbitol (meth) acrylate, nonylphenyl

(meth) acrylate, nonylphenyl carbitol (meth) acrylate, and

nonylphenoxy (meth) acrylate; amino group-containing

(meth) acrylates such as 2-dimethylaminoethyl (meth) acrylate,

2-diethylaminoethyl (meth) acrylate, and 2-ter ^~ t-

butylaminoethyl (meth) acrylate; phosphorus-containing

methacrylates such as methacryloxy ethylphospliate, bis-

methacryloxy ethylphosphate, and methacryloxy ethyl phenyl

acid phosphate (phenyl P); glycidyl (meth) acrylates; allyl

(meth) acrylates; and phenoxyethyl acrylates.

Other unsaturated compounds usable herein include

carboxyl- or acid anhydride-containing unsatuxated

compounds such as (meth) acrylic acid, itaconic acid, maleic

anhydride, itaconic anhydride, polycaprolactoxie

(meth) acrylate, (meth) acryloyloxyethyl phthalate, and

(meth) acryloyloxyethyl succinate.

The expression ^λλ (meth) acrylate" or the Hike as used

herein refers to methacrylate and/or acrylate .

Further, N-vinyl compounds such as N-vinylpyrrolidone,

N-vinylformamide, N-vinylacetamide, and vinyl aromatic

compounds such as styrene and vinyltoluene are also

preferred.

(ix-f) Epoxy (meth) acrylate compound

The epoxy (meth) acrylate compound is a compound

comprising an unsaturated monocarboxylic acid added to an

epoxy group in an epoxy resin. In some cases, a polyb>asic

acid anhydride is further reacted. Specific examples of

epoxy resins usable herein include bisphenol A-type epoxy

resins, bisphenol F-type epoxy resins, bisphenol S-type

epoxy resins, novolac epoxy resins, (o~, m-, or p-)cresol

novolac epoxy resins, phenol novolac epoxy resins, na]phthol

modified novolac epoxy resins, and halogenated phenol

novolac epoxy resins.

Among them, carboxylic acid group-containing epoxy

(meth) acrylate resins prepared using, as a starting

material, novolac-type epoxy resins such as novolac e]poxy

resins, (o-, m-, or p-) cresol novolac epoxy resins, }phenol

novolac epoxy resins, naphthol modified novolac epoxy

resins, and halogenated phenol novolac epoxy resins aure

preferred from the viewpoint of photosensitivity.

The number average molecular weight (a value

determined in terms of polystyrene as determined by gel

permeation chromatography (parts by mass; PC) ) of the

reactive (meth) acrylate polymer (A) according to the

present invention is generally 500 to 100,000, preferably

8,000 to 40,000. When the number average molecular weight

is less than 500, the film strength is significantly

lowered. On the other hand, when the number average

molecular weight exceeds 40,000, the developing property

and flexibility are deteriorated.

When the reactive (meth) acrylate polymer (A)

according to the present invention is used in the resist,

the acid value is preferably 5 to 150 mgKOH/g, more

preferably 30 to 120 mgKOH/g. When the acid value is less

than 5 mgKOH/g, the alkali developing property is sometimes

deteriorated. On the other hand, when the acid value

exceeds 150 mgKOH/g, the alkali resistance, electrical

characteristics and the like of the cured film are

sometimes deteriorated.

For the carboxyl-containing compounds among the

polyhydroxy compounds comprising repeating units, the

isocyanate of formula (I) is reacted with the carboxyl

group under certain reaction conditions to form an amide

bond. The compound of formula (I) may also be added

through this reaction.

Further, the isocyanate compound of formula (I) may

be used with an isocyanate compound containing one reactive

ethylenically unsaturated group for a reaction with a

hydroxyl- (or amino- or mercapto-) containing polymer

compound. Specific examples of isocyanate compounds

containing one reactive ethylenically unsaturated group

include 2-methacryloyloxyethylisocyanate, 2-

acryloyloxyethylisocyanate, 2- (2-ethylbutenoyloxy) -

ethylisocianate, 2- (2-propylbutenoyloxy) ethylisocyanate,

methacryloyloxymethylisocyanate, acryloyloxymethyl-

isocyanate, (2-ethylbutenoyloxy)methylisocyanate, (2-

propylbutenoyloxy)methylisocyanate, 3-methacryloyloxy-

propylisocyanate, 3-acryloyloxypropylisocyanate, 3- (2-

ethylbutenoyloxy)propylisocyanate, 3- (2-propylbutenoyloxy) -

propylisocyanate, 4-methacryloyloxybutylisocyanate, 4-

acryloyloxybutylisocyanate, 4- (2-ethylbutenoyloxy) -

butylisocyanate, and 4- (2-propylbutenoyloxy)butylisocyanate.

(x) Curable composition

The curable composition is prepared by incorporating

other components in addition to the reactive (meth) acrylate.

polymer (A) according to the present invention. This

curable composition can be used in applications such as

resists (for example, solder resists, etching resists,

color filter resists, and spacers), sealing (for example,

waterproof sealing) , paints (for example, antifouling

paints, fluoropaints, and water-based paints), pressure-

sensitive adhesives and adhesives (for example, adhesives

and dicing tapes), printing plates (for example, CTP plates

and offset plates), printing proofreading (for example,

colorproof) , . lenses (for example, contact lenses,

microlenses, and optical waveguides) , dental materials,

surface treatment (for example, optical fiber coating and

disk coating) , and battery materials (for example, solid

electrolytes) .

Specific examples of curable compositions suitable

for color filters and curable compositions suitable for

solder resists are as follows. The reactive (meth) acrylate

polymer (A) which is particularly preferred for use in the

curable composition is a urethane (meth) acrylate polymer

prepared by reacting a polyhyroxy compound with an

isocyanate compound of formula (I) .

(x-a) Curable composition suitable for color filter

This curable composition contains a reactive

(meth) acrylate polymer (A) , a pigment (B) , a

photopolymerization initiator (D) , an ethylenically

unsaturated monomer (F) , and an organic solvent (G) .

(x-a-a) Reactive (meth) acrylate polymer (A)

The content of the reactive (meth) acrylate polymer

(A) in the curable composition is generally not less than

10% by mass, preferably not less than 20% by mass, more

preferably 30 to 90% by mass. The mass ratio of reactive

(meth) acrylate polymer (A) /other curable component such as

ethylenically unsaturated monomer (F) is preferably 30/70

to 90/10, more preferably 40/60 to 85/15, from the

viewpoints of balance between strength and photosensitivity.

When the mass ratio of the reactive (meth) acrylate polymer

(A) is smaller than 30/70, the film strength is lowered.

On the other hand, when the mass ratio of the reactive

(meth) acrylate polymer (A) is larger than 90/10, the cure

shrinkage is increased.

(x-a-b) Pigment (B)

Red, green, and blue pigments may be used as the

pigment (B) . Black pigments may be mentioned as pigments

which exhibits the maximum level of radiation shielding.

Such black pigments may be conventional black pigments, and

specific examples thereof include carbon black, acetylene

black, lamp black, carbon nanotubes, graphite, iron black,

iron oxide black pigments, aniline black, cyanine black,

and titanium black. Black-based pigments prepared by

mixing three organic pigments of red, green, and blue

together may also be used.

Among them, carbon black and titanium black are

preferred. Carbon black is particularly preferred from the

viewpoints of light shielding and image properties.

The carbon black may be commercially available one,

and the particle diameter of the carbon black is preferably

5 to 200 nm, more preferably 10 to 100 nm, from the

viewpoints of dispersibility and resolution. When the

particle diameter is less than 5 nm, homogeneous dispersion

is difficult. On the other hand, when the particle

diameter exceeds 200 nm, the resolution is lowered.

Specific examples of carbon blacks include Special

Black 550, Special Black 350, Special Black 250, Special

Black 100, Special Black 4 manufactured by Degussa, MA 100,

MA 220, MA 230 manufactured by Mitsubishi Chemical

Corporation, BLACKPEARLS 480 manufactured by Cabot

Corporation, and RAVEN 410, RAVEN 420, RAVEN 450, and RAVEN

500 manufactured by Columbian Carbon,

(x-a-c) Photopolymerization initiator (D)

The photopolymerization initiator (D) is a compound

that, upon excitation by an actinic radiation, generates

radicals which induce polymerization of the ethylenically

unsaturated bond. Such photopolymerization initiators are

required to generate radicals under high light shielding

conditions. Therefore, high-sensitivity

photopolymerization initiators are preferred. Specific

examples of photopolymerization initiators include

hexaarylbiimidazole compounds, triazine compounds,

aminoacetophenone compounds, a combination of a sensitizing

dye with an organic boron salt compound, titanocene

compounds, and oxadiazole compounds.

Among them, hexaarylbiimidazole compounds, triazine

compounds, aminoacetophenone compounds, glyoxy ester

compounds, bisacylphosphine oxide compounds, and

combinations thereof are preferred.

Specific examples of hexaarylbiimidazole compounds

include 2, 2'-bis (o-chlorophenyl) -4, 4' , 5, 5'-tetraphenyl-

1, 2' -biimidazole, 2, 2' -bis (o-bromophenyl) -4, 4' , 5, 5' -

tetraphenyl-1,2 ^r -biimidazole, 2,2' -bis (o-chlorophenyl) -

4,4' ,5, 5'-tetra (o,p-dichlorophenyl) -1,2' -biimidazole, 2,2'-

bis (o,p-dichlorophenyl) -4, 4' ,5, 5' -tetra (o,p-

dichlorophenyl) -1,2' -biimidazole, 2,2' -bis (o-chlorophenyl) -

4, 4' , 5, 5' -tetra (m-methoxyphenyl) -1,2' -biimidazole, and

2, 2'-bis (o-methylphenyl) -4,4' , 5, 5' -tetraphenyl-1, 2' -

biimidazole.

In order to further enhance the sensitivity, for

example, benzophenone compounds such as benzophenone,

2, 4, 6-trimethylbenzophenone, 4-phenylbenzophenone, 4,4'-

bis (dimethylamino) benzophenone, and 4, 4'-bis (diethylamino)

benzophenone, and thioxanthone compounds such as 2,4-

diethylthioxanthone, isopropylthioxanthone, 2,4-

diisopropylthioxanthone, and 2-chlorothioxanthone may be

added as sensitizers.

Specific examples of triazine compounds include

2,4, 6-tris (trichloromethyl) -s-triazine, 2, 4, 6-

tris (tribromomethyl) -s-triazine, 2-propionyl-4, 6-

bis (trichloromethyl) -s-triazine, 2-benzoyl-4, 6-

bis (trichloromethyl) -s-triazine, 2- (4-chlorophenyl) -4, 6-

bis (trichloromethyl) -s-triazine, 2, 4-bis (4-methoxyphenyl) -

β-trichloromethyl-s-triazine, 2- (4-methoxyphenyl) -2, 6-

bis (trichloromethyl) -s-triazine, 2- (4-methoxystyryl) -4, 6-

bis (trichloromethyl) -s-triazine, 2- (4-chlorostyryl) -4, 6-

bis (trichloromethyl) -s-triazine, 2- (4-aminophenyl) -4, 6-

bis (trichloromethyl) -s-triazine, 2, 4-bis (3-chlorophenyl) -6-

trichloromethyl-s-triazine, and 2- (4-aminostyryl) -4, 6-

bis (dichloromethyl) -s-triazine.

Specific examples of aminoacetophenone compounds

include 2-methyl-l- [4- (methyl thio ) phenyl ] -2-

morpholinopropan-1-one, and 2-benzyl-2-dimethylamino-l- (4-

morpholinophenyl) -butanone-1.

Specific examples of benzophenone compounds include

benzophenone, 4-methylbenzophenone, 2,4,6-

trimethylbenzophenone, benzoylbenzoic acid, 4-

phenylbenzophenone, 3, 3' -dimethyl-4-methoxybenzophenone, 4-

benzoyl-4' -methyldiphenylsulf ide, 4, 4' -

bis (dimethyl amino) benzophenone, 4,4'-

bis (diethylamino) benzophenone, (2-acryloyloxyethyl) (4-

benzoylbenzyl) dimethylammoniumbromide, 4- (3-dimethylamino-

2-hydroxypropoxy) -benzophenonemethochloride monohydrate,

and ( 4-benzoylbenzyl ) trimethylammoniumchloride .

Specific examples of thioxanthone compounds include

thioxanthone, 2, 4-diethyl thioxanthone,

isopropyl thioxanthone, 2, 4-diisopropyl thioxanthone, 2-

chlorothioxanthone, l-chloro-4-propoxythioxanthone, and 2-

(3-dimethylamimo-2-hydroxypropoxy) -3, 4-dimethyl-9H-

thioxanthen-9-one methochloride .

Specific examples of quinone compounds include 2-

ethyl anthraquinone and 9, 10-phenanthrenequinone .

Specific examples of titanocene compounds include

those described, for example, in Japanese Patent Laid-Open

Nos. 152396/1984, 151197/1986, 10602/1988, 41484/1988,

291/1990, 12403/1991, 20293/1991, 27393/1991, 52050/1991,

221958/1992, and 21975/1992. Specific examples thereof

include dicyclopentadienyl-Ti-dichloride,

dicyclopentadienyl-Ti-diphenyl, dicyclopentadienyl-Ti-

bis (2, 3, 4, 5, 6-pentaf luorophenyl) , dicyclopentadienyl-Ti-

bis (2, 3, 5, 6-tetraf luorophenyl) , dicyclopentadienyl-Ti-

bis (2,4, 6-trif luorophenyl) , dicyclopentadienyl-Ti-bis (2,6-

dif luorophenyl) , dicyclopentadienyl-Ti-bis (2, 4-

dif luorophenyl) , bis (methylcyclopentadienyl) -Ti-

bis (2, 3, 4, 5, 6-pentaf luorophenyl) ,

bis (methylcyclopentadienyl) -Ti-bis (2,3,5,6-

tetraf luorophenyl) , and bis (methylcyclopentadienyl) -Ti-

bis (2, 6-dif luorophenyl) .

Specific examples of oxadiazole compounds include

halomethyl-containing 2-phenyl-5-trichloromethyl-l, 3, 4-

oxadiazole, 2- (p-methylphenyl) -5-trichloromethyl-l, 3, 4-

oxadiazole, 2- (p-itiethoxyphenyl) -5-trichloromethyl-l, 3, 4-

oxadiazole, 2-styryl-5-trichloromethyl-l, 3, 4-oxadiazole, 2-

(p-methoxystyryl) -5-trichloromethyl-l, 3, 4 — oxadiazole, and

2- (p-butoxystyryl) -5-trichloromethyl-l, 3, 4 -oxadiazole .

Specific examples of glyoxy ester compounds include

benzyldimethylketal, benzoinethyl ether, and benzoin

isopropyl ether.

Specific examples of bisacylphosphirxe oxide compounds

include bis (2, 6-dimethoxybenzoyl) -2,4, 4-trrimethylpentyl

phosphineoxide, bis (2, 6-dichlorobenzoyl) -

phenylphosphineoxide, bis (2, 6-dichlorobenzoyl) -2, 5-

dimethylphenylphosphineoxide, and bis (2, A _r 6-

trimethylbenzoyl) phenylphosphineoxide .

(x-a-d) Ethylenically unsaturated monomer (F)

The ethylenically unsaturated monomer (F) is a

compound that causes crosslinking by radicals generated

from the photopolymerization initiator (D) upon exposure to

an actinic radiation and functions, for example, to modify

the viscosity of the composition. Specifically,

(me th) acrylic esters are preferred.

Specific examples of- (meth) acrylic esters include

alkyl (meth) acrylates such as methyl (meth.) acrylate, ethyl

(meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate,

isobutyl (meth) acrylate, sec-butyl (meth) acrylate, tert-

butyl (meth) acrylate, hexyl (meth) acrylate, octyl

(meth) acrylate, isooctyl (meth) acrylate, 2-ethylhexyl

(meth) acrylate, decyl (meth) acrylate, lauryl (meth) acrylate,

and stearyl (meth) acrylate; alicyclic (meth) a_crylates such

as cyclohexyl (meth) acrylate, bornyl (meth) acrylate,

isobornyl (meth) acrylate, dicyclopentenyl (meth) acrylate,

and dicyclopentenyloxyethyl (meth) acrylate; aromatic

(meth) acrylates such as benzyl (meth) acrylate , phenyl

(meth) acrylate, phenylcarbitol (meth) acrylate , nonylphenyl

(meth) acrylate, nonylphenylcarbitol (meth) acrrylate, and

nonylphenoxy (meth) acrylate; hydroxyl group-containing

(meth) acrylates such as 2-hydroxyethyl (meth) acrylate,

hydroxypropyl (meth) acrylate, hydroxybutyl (iαeth) acrylate,

butanediol mono (meth) acrylate, glycerol (meth.) acrylate,

phenoxyhydroxypropyl (meth) acrylate, polyethylene glycol

(meth) acrylate, and glycerol di (meth) acrylate; amino group-

containing (meth) acrylates such as 2-dimethyLaminoethyl

(meth) acrylate, 2-diethylaminoethyl (meth) acrrylate, and 2-

tert-butylaminoethyl (meth) acrylate; phosphorous atom-

containing methacrylates such as methacryloxyethyl

phosphate, bis-methacryloxyethyl phosphate, and

methacryloxyethylphenyl acid phosphate (phenyl-P) ;

diacrylates such as ethylene grycol di (meth) acrylate,

diethylene grycol di (meth) acrylate, triethylene grycol

di (meth) acrylate, tetraethylene di (meth) acrylate,

polyethylene glycol di (meth) acrylate, propylene glycol

di (meth) acrylate, dipropylene glycol di (meth) acrylate,

tripropylene glycol di (meth) acrylate, 1, 4-butanediol

di (meth) acrylate, 1, 3-butanediol di (meth) acrylate,

neopentyl glycol di (meth) acrylate, 1, 6-hexanediol

di (meth) acrylate, and bis-glycidyl (meth) acrylate;

polyacrylates such as trimethylolpropane tri (meth) acrylate,

pentaerythritol tri (meth) acrylate, and dipentaerythritol

hexa(meth) acrylate; modified polyol polyacrylates such as

ethylene oxide (4 mol) -modified diacrylate of bisphenol S,

ethylene oxide (4 mol) -modified diacrylate of bisphenol A,

fatty acid-modified pentaerythritol diacrylate, propylene

oxide (3 mol) -modified triacrylate of trimethylolpropane,

and propylene oxide (6 mol) -modified triacrylate of

trimethylolpropane; polyacrylates having an isocyanuric

acid skeleton, such as

bis (acryloyloxyethyl)monohydroxyethyl isocyanurate,

tris (acryloyloxyethyl) isocyanurate, and ε-caprolactone- modified tris (acryloyloxyethyl) isocyanurate; polyester

acrylates such as α,ω-diacryloyl- (bisethylene glycol) -

phthalate, or α, ω-tetraacryloyl- (bistrimethylolpropane) - tetrahydrophthalate; glycidyl (meth) acrylate; allyl

(meth) acrylate; ω-hydroxyhexanoyloxyethyl (meth) acrylate; polycaprolactone (meth) acrylate; (meth) acryloyloxyethyl

phthalate; (meth) acryloyloxyethyl succinate; 2-hydroxy-3-

phenoxypropyl acrylate; and phenoxyethyl acrylate. Further,

for example, N-vinyl compounds such as N-vinyl pyrrolidone,

N-vinylformamide, or N-vinylacetamide, and polyester

acrylate, urethane acrylate or epoxy acrylate may also be

used as the ethylenically unsaturated monomer (F) .

Among these compounds, hydroxyl-containing

(meth) acrylate, glycidyl (meth) acrylate, and urethane

acrylate are preferred. From the viewpoint of increased

curability and heat resistance, the above compounds

containing three or more ethylenically unsaturated groups

are preferred.

(x-a-e) Organic solvent (G)

Specific examples of the organic solvent (G) include

ethers such as diisopropyl ether, ethyl isobutyl ether, and

butyl ether; esters such as ethyl acetate, isopropyl

acetate, butyl acetate (n, sec, tert) , amyl acetate, -3-

ethoxy ethyl propionate, 3-methoxy methyl propionate, 3-

methoxy ethyl propionate, 3-methoxy propyl propionate, and

3-methoxy butyl propionate; ketones such as methyl ethyl

ketone, isobutyl ketone, diisopropyl ketone, ethylamyl

ketone, methyl butyl ketone, methyl hexyl ketone, methyl

isoamyl ketone, methyl isobutyl ketone, and cyclohexanone;

and glycols such as ethylene glycol monomethyl ether,

ethylene glycol monoethyl ether, ethylene glycol diethyl

ether, ethylene glycol monomethyl ether acetate, ethylene

glycol monoethyl ether acetate, diethylene glycol monoethyl

ether acetate, propylene glycol mono-t-butyl ether,

propylene glycol monomethyl ether, propylene glycol

monoethyl ether, propylene glycol monomethyl ether acetate,

propylene glycol monoethyl ether acetate, dipropylene

glycol monoethyl ether, dipropylene glycol monomethyl ether,

dipropylene glycol monomethyl ether acetate, dipropylene

glycol monoethyl ether acetate, ethylene glycol monobutyl .

ether, and tripropylene glycol methyl ether; and mixtures

of the above compounds.

The organic solvent (G) can dissolve or disperse

other components and has a boiling point of preferably 100

to 200°C, more preferably 120 to 170°C. The amount of the

organic solvent (G) used is such that the solid content of

the curable composition is brought to 5 to 50% by mass,

preferably 10 to 30% by mass,

(x-a-f) Polyfunctional thiol (H)

The curable composition may contain a polyfunctional

thiol (H) . The polyfunctioinal thiol (H) is a compound

containing two or more thiol groups, and specific examples

thereof include hexanedithiol, decanedithiol, butanediol

bisthiopropionate, butanediol bisthioglycolate, ethylene

glycol bisthioglycolate, ethylene glycol bisthiopropionate,

trimethylolpropane tristhioglycolate, trimethylolpropane

tristhiopropionate, pentaerythritol tetrakisthioglycolate,

pentaerythritol tetrakisthiopropionate,

trimercaptopropionate tris (2-hydroxyethyl) isocyanurate,

1, 4-dimethylmercaptobenzene, 2, 4, β-trimercapto-s-triazine,

and 2- (N,N-dibutylamino) -4, 6-dimercapto-s-triazine.

(x-a-g) Content of each component

Preferably, in the curable composition, the

components other than the organic solvent (G) have the

following respective contents.

The content of the reactive (meth) acrylate polymer

(A) is preferably 10 to 40% by mass, more preferably 15 to

35% by mass based on the total amount of the composition.

When the content is less than 10% by mass, the film

strength is sometimes lowered. On the other hand, when the

content exceeds 40% by mass, in some cases, the optical

density is unsatisfactory.

The content of the pigment (B) is preferably 25 to

60% by mass, more preferably 30 to 55% by mass, based on

the total amount of the composition. When the content is

less than 25% by mass, the optical density is sometimes

unsatisfactory. On the other hand, when the content

exceeds 60% by mass, in some cases, the film strength is

lowered.

The content of the photopolymerization initiator (D)

is preferably 2 to 25% by mass, more preferably 5 to 20% by

mass, based on the total amount of the composition. When

the content is less than 2% by mass, the photosensitivity

is sometimes unsatisfactory. On the other hand, when the

content exceeds 25% by mass, the photosensitivity is so

high that the resolution is disadvantageously sometimes

lowered.

The content of the ethylenically unsaturated monomer

(F) is preferably 5 to 20% by mass, more preferably 8 to

18% by mass, based on the total amount of the composition.

When the content is less than 5% by mass, the

photosensitivity is sometimes unsatisfactory. On the other

hand, when the content exceeds 20% by mass, in some cases,

the optical density is unsatisfactory.

When the polyfuntional thiol (H) is added, the

content of the photopolymerization initiator (D) is

preferably 2 to 20% by mass, more preferably 3 to 15% by

mass, based on the total amount of the composition. When

the content is less than 2% by mass, the photosensitivity

is sometimes unsatisfactory. On the other hand, when the

content exceeds 20% by mass, in some cases, the

photosensitivity is so high that the resolution is

disadvantageously lowered. The content of the

polyfunctional thiol (F) is preferably 2 to 20% by mass,

more preferably 3 to 15% by mass, based on the total amount

of the composition. When the content is less than 2% by

mass, the effect of the polyfunctional thiol does not

sometimes occur. On the other hand, when the content

exceeds 20% by mass, in some cases, the photosensitivity is

so high that the resolution is disadvantageously lowered.

In addition to the above components, for example,

pigment dispersants, adhesion improvers, leveling agents,

development improvers, antioxidants, and thermal

polymerization inhibitors may be added to the curable

composition. In particular, since what is important for

quality stabilization is to finely disperse the coloring

material and to stabilize the dispersion state, preferably,

the pigment dispersant is incorporated according to need,

(x-a-h) Production process of curable composition

The curable composition may be produced by mixing the

components together by any proper method. The mixing may

be carried by either a method in which the components are

simultaneously mixed together or a method in which the

components are successively mixed.

Mixing of all the formulating components together at

a time followed by dispersion treatment leads to a fear of

causing denaturation of highly reactive components due to

heat generation during dispersion treatment. To avoid this

unfavorable phenomenon, mixing is preferably carried out by

a method in which the pigment (B) such as a black pigment,

either together with the solvent (G) and the pigment

dispersant, or together with a mixture of the solvent (G)

and the pigment dispersant with the reactive (meth) acrylate

polymer (A) , is previously dispersed and the remaining

components are then mixed.

The dispersion treatment may be carried out with a

paint conditioner, a bead mill, a ball mill, a triple roll

mill, a stone mill, a jet mill, a homogenizer or the like.

When the dispersion is carried out with a bead mill,

glass beads or zirconia beads having a diameter of 0.1 to

several millimeters are preferred. The dispersion is

^' generally carried out at a temperature of 0 to 100 ⁰ C,

preferably room temperature to 80°C. A proper dispersion time is determined by taking into consideration, for

example, the formulation of the colored composition

(coloring materials, solvents, dispersant, and binder

polymer), and apparatus size of the bead mill.

When the dispersion is carried out with a triple roll

mill, the dispersion temperature is generally 0 to 60°C. When the frictional heat of the rolls is so large that the.

temperature exceeds 60°C, the inside of the roll is cooled with circulating water. The number of times of passage of

the ink through the triple roll mill depends upon

conditions such as linear velocity of rolls, pressure

between rolls, and the viscosity of the materials and may

be, for example, 2 to 10 times.

The composition prepared by the dispersion treatment

is mixed with the remaining components by any proper method

to produce the curable composition,

(x-a-i) Production process of color filter

A color filter is produced by coating the curable

composition onto a transparent substrate, drying the

solvent in an oven or the like, then exposing and

developing the dried coating to form a pattern, and then

postbaking the patterned coating.

Specific examples of the transparent substrate

include films or sheets of inorganic glasses such as quartz

glass, borosilicate glass, and lime-soda glass with a

silica-coated surface; thermoplastics, for example,

polyesters such as polyethylene terephthalate, polyolefins

such as polypropylene and polyethylene, polycarbonate,

polymethyl methacrylate, and polysulfone; and thermosetting

plastics such as epoxy polymers and polyester polymers .

In order to improve properties such as surface adhesion,

such transparent substrates may be previously subjected to

corona discharge treatment, ozone treatment, and thin film

treatment with siliane coupling agents, urethane polymers

or other various polymers.

The curable composition may be coated onto the

transparent substrate with a coater such as a dip coater, a

roll coater, a wire bar, a flow coater, a die coater, a

spray coater, or a spin coater.

After coating, the coating may be dried by any proper

method to remove the solvent. A drying device such as a

hot plate, an IR oven, or a convection oven may be used for

drying. The drying temperature is preferably 40 to 150°C, and the drying time is preferably 10 sec to 60 min. The

solvent may be removed by drying in vacuum.

The exposure is carried out by placing a photomask on

a sample and then exposing the dried coating image-wise

through the photomask. Specific examples of light sources

usable in the exposure include lamp light sources such as

xenon lamps, high-pressure mercury lamps, ultrahigh-

pressure mercury lamps, metal halide lamps, medium-pressure

mercury lamps, and low-pressure mercury lamps, and laser

beam sources such as argon ion lasers, YAG lasers, excimer

lasers, and nitrogen lasers. When only irradiating light

with a specific wavelength is used, an optical filter may

be utilized.

The development treatment is carried out with a

developing solution, and the resist: is developed, for

example, by a dipping, shower or paddle method. The

developing solution may be a solvent that can dissolve the

resist film in its unexposed areas , and specific examples

thereof include organic solvents such as acetone, methylene

chloride, trichlene, and cyclohexanone.

Further, an alkali developing solution may be used as

the developing solution. Specific examples of such alkali

developing solutions include aqueous solutions containing

inorganic alkali chemicals such as sodium carbonate,

potassium carbonate, sodium silicate, potassium silicate,

sodium hydroxide, and potassium hydroxide, or organic

alkali chemicals such as diethanolamine, triethanolamine,

and tetraalkylammonium hydroxide. The alkali developing

solution may if necessary contain, for example, surfactants,

water soluble organic solvents, hydroxyl- or carboxyl-

containing low-molecular compounds . In particular, a

number of surfactants have the effect of improving

developing properties, resolution, smudge and the like, and,

thus, the addition of such surfactants is preferred.

Specific examples of surfactants usable for the

developing solution include anionic surfactants containing ^"

sodium naphthalenesulfonate, sodium benzenesul fonate or

other groups , nonionic surfactants containing

polyalkyleneoxy groups , and cationic surfactants containing

tetraalkylammonium. groups .

The development treatment is generally carried out a_t

a development temperature of 10 to 50 ⁰ C, preferably 15 to

45°C, for example, by dip development, spray development, brush development, or ultrasonic development .

Postbaking is generally carried out with the same

apparatus as drying for solvent removal at a temperature of

150 to 300°C for 1 to 120 ruin . The film thickness of the

matrix thus obtained is preferably 0 . 1 to 2 μm, more

preferably 0 . 1 to 1 . 5 μm, still more preferably 0 . 1 to 1 μuα. In order that the film functions as the matrix, the optical

density in the above thickness range is preferably not less

than 3 .

In the black matrix pattern produced by the above

method, in general , an opening having a size of about 20 to

200 μm is provided between patterns . In the post-process , pixels of R, G, and B are formed in this space . In general,

the pixels are of three colors of R, G, and B and may be

formed using a curable composition comprising a reactive

(meth) acrylate polymer (A) and colored with the above

pigment or dye in the same manner as in the formation of

the black matrix.

(x-b) Curable composition suitable for solder resist

This curable composition comprises a reactive

(meth) acrylate polymer (A), a thermosetting polymer (C), a

photopolymerization initiator (D) , an ethylenically

unsaturated monomer (F) , and a thermal polymerization

catalyst (E) .

(x-b-a) Heat-curable polymer (C)

The heat-curable polymer (C) is incorporated as a

thermosetting component in the composition. The heat-

curable polymer (C) per se may be cured by heating, or

alternatively may be thermally reacted with the carboxyl

group in the reactive (meth) acrylate polymer (A) .

Specific examples of the heat-curable polymer (C)

include epoxy polymers; phenol polymers; silicone polymers;

melamine derivatives such as hexamethoxymelamine,

hexabutoxymelamine, and condensed hexamethoxymelamine; urea

compounds such as dimethylolurea; bisphenol A compounds

such as tetramthylol-bisphenol A; oxazoline compounds; and

oxetane compounds. They may be used either alone or in a

combination of two or more of them.

Among them, epoxy polymers are preferred. Specific

examples of epoxy polymers include epoxy compounds

containing two or more epoxy groups per molecule such as

bisphenol A epoxy polymers, hydrogenated bisphenol A epoxy

polymers, brominated bisphenol A epoxy polymers, bisphenol

F epoxy polymers, novolak epoxy polymers, phenol novolak

epoxy polymers, cresol novolak epoxy polymers, N-glycidyl

epoxy polymers, bisphenol A novolak epoxy polymers, chelate

epoxy polymers, glyoxal epoxy polymers, amino-containing

epoxy polymers, rubber-modified epoxy polymers,

dicyclopentadiene phenolic epoxy polymers, silicone-

modified epoxy polymers, and ε-caprolactone-modified epoxy polymers; and bisphenol S epoxy polymers, diglycidyl

phthalate polymers, heterocyclic epoxy polymers, bixylenol

epoxy polymers, biphenyl epoxy polymers, and

tetraglycidylxylenoylethane polymers .

In order to impart flame retardancy, use may be made

of epoxy polymers in which a halogen such as chlorine or

bromine, phosphorus or other atom has been introduced into

the structure in such a bound state that is less likely to

be decomposed by heat or water. These epoxy polymers may

be used either solely or in a combination of two or more of

them.

The content of the heat-curable polymer (C) is

preferably 10 to 150 parts by mass, more preferably 10 to

50 parts by mass, based on 100 parts by mass in total of

the photocurable components. When the content of the heat-

curable polymer (C) is less than 10 parts by mass,

soldering heat resistance of the cured film is sometimes

unsatisfactory. On the other hand, when the content of the

heat-curable polymer (C) exceeds 150 parts by mass, the

shrinkage of the cured film is increased. In this case,

when the cured film is used in an insulating protective

film in an FPC substrate, the- warpage is likely to be

increased,

(x-b-b) Photopolymerization initiator (D)

The same photopolymerization initiators as used in

the curable composition suitable for color filters may be

used as the photopolymerization initiator (D) .

The content of the photopolymerization initiator (D)

is preferably 0.1 to 20 parts by mass, more preferably 0.2

to 10 parts by mass, based on 100 parts by mass in total of

the urethane (meth) acrylate polymer (A) , the ethylenically

unsaturated monomer (F) , and the carboxyl-containing epoxy

(meth) acrylate compound which is optionally incorporated.

When the content of the photopolymerization initiator (D)

is less than.0.1 part by mass, in some cases, the curing of

the composition is unsatisfactory,

(x-b-c) Thermal polymerization catalyst (E)

The thermal polymerization catalyst (E) functions to

thermally cure the heat-curable polymer (C) , and specific

examples thereof include amines; amine salts or quaternary

ammonium salts such as chlorides of the amines; acid

anhydrides such as cyclic aliphatic acid anhydrides,

aliphatic acid anhydrides, and aromatic acid anhydrides;

nitrogen-containing heterocyclic compounds such as

polyamides, imidazoles, and triazine compounds; and

organometal compounds. They may be used either solely or

in a combination of two or more of them.

Specific examples of amines include aliphatic or

aromatic primary, secondary, and tertiary amines.

Specific examples of aliphatic amines include

polymethylenediamine, polyetherdiamine, diethylenetriamine,

triethylenetriarαine, tetraethylenepentamine,

triethylenetetramine, dimethylaminopropylamine,

menthenediamine, aminoethylethanolarαine,

bis (hexamethylene) triarαine, 1, 3, 6-trisaminomethylhexane,

tributylamine, 1, 4-diazabicyclo [2,2, 2] octane, and 1,8-

diazabicyclo{5, 4, 0]undecen-7-ene.

Specific examples of aromatic amines include

metaphenylenediamine, diaminodiphenylmethane, and

diaminodiphenylsulfone.

Specific examples of acid anhydrides include aromatic

acid anhydrides such as phthalic anhydride, trimellitic

anhydride, benzophenone tetracarboxylic acid anhydride,

ethylene glycol bis (anhydro trimellitate) , and glycerol

tris (anhydro trimellitate) , and maleic anhydride, succinic

acid anhydride, methylnadic anhydride, hexahydrophthalic

anhydride, tetrahydrophthalic anhydride, polyadipic acid

anhydride, chlorendic anhydride, and tetrabromophthalic

anhydride.

Specific examples of polyamides include primary

amino- or secondary amino-containing polyaminoarαides

produced by condensing a dimeric acid with a polyamine such

as diethylenetriamine or triethylenetetramine.

Specific examples of imidazoles include imidazole, 2-

ethyl-4-methylimidazole, N-benzyl-2-methylimidazole, 1-

cyanoethyl-2-undecylimidazolium-trirαellitate, and 2-

methylimidazolium-isocyamurate .

The triazine compound is a compound with a six-

membered ring containing three nitrogen atoms , and speci fic

examples thereof include melamine compounds such as

melamine, N-ethylenemelamine, and N, N ^T , N ' ^? -

triphenylmelamine ; cyanuric acid compounds such as cyanuric

acid, isocyanuric acid, trimethyl cyanurate, isocyanurate,

triethyl cyanurate, trisethyl isocyanurate, tri (n-

propyl ) cyanurate, tris (n-propyl ) isocyanurate, diethyl

cyanurate, N, N' -diethyl isocyanurate, methyl cyanurate, and

methyl isocyanurate ; and cyanuric acid melamine compounds

such as a reaction product between equimolar amounts of a

melamine compound and a cyanuric acid compound .

Specific examples of organometallic compounds include

metal salts of organic acids such as dibutyltin dilaurate, .

dibutyltin maleate, and zinc 2-ethylhexanoate; 1, 3-diketone

metal complex salts such as nickel acetyl acetonate, zinc

acetylacetonate ; and metal alkoxides such as titanium

tetrabutoxide, zirconium tetrabutoxide, and aluminum

butoxide .

The amount of the thermal polymerization catalyst (E)

used is preferably 0.5 to 20 parts by mass, more preferably

1 to 10 parts by mass, based on 100 parts by mass of the

heat-curable polymer (C) . When the amount of the thermal

polymerization catalyst (E) used is less than 0.5 part by

mass, the curing reaction does not proceed satisfactorily.

In this case, in some cases, the heat resistance is

deteriorated. Further, curing at an elevated temperature

for a long period of time is necessary, and this is

sometimes causative of lowered working efficiency. On the

other hand, when the amount of the thermal polymerization

catalyst (E) used exceeds 20 parts by mass, the thermal

polymerization catalyst (E) is likely to react with the

carboxyl group in the composition to cause gelation, often

leading to a problem of deteriorated storage stability,

(x-b-d) Ethylenically unsaturated monomer (F)

The same ethylenically unsaturated monomer as used in

the curable composition suitable for color filters may be

used as the ethylenically unsaturated monomer (F) .

The mixing ratio of the reactive (meth) acrylate

polymer (A) to other ethylenically unsaturated monomer (F)

is preferably 95 : 5 to 50 : 50, more preferably 90 : 10 to

60 to 40, still more preferably 85 : 15 to 70 : 30, in

terms of mass ratio. When the mixing ratio of the reactive

(meth) acrylate polymer (A) exceeds 95, the heat resistance

of the cured film formed of the composition is sometimes

deteriorated.' On the other hand, when the mixing ratio of

the reactive (meth) acrylate polymer (A) is less than 5, the

solubility of the composition in alkali is likely to be

lowered.

If necessary, carboxyl-containing epoxy

(meth) acrylate compounds may be used as the curable

component. Such carboxyl-containing epoxy (meth) acrylate

compounds include, for example, those described in the

above (iv-f) . The acid value of these carboxyl-containing

epoxy (meth) acrylate compounds is preferably not less than

10 mgKOH/g, more preferably 45 to 160 mgKOH/g, still more

preferably 50 to 140 mgKOH/g. The use of the epoxy

(meth) acrylate compounds having the above acid value can

improve balance between the alkali solubility of the

composition and the alkali resistance of the cured film.

When the acid value is less than 10 mgKOH/g, the alkali

solubility is deteriorated. On the other hand, when the

acid value is excessively large, in some cases, for some

formulation of the composition, the alkali resistance of

the cured film and properties as a resist such, as

electrical characteristics are deteriorated. When the

carboxyl-containing epoxy (meth) acrylate compound is used,

preferably, this compound is used in an amount of not more

than 100 parts by mass based on 100 parts by mass of the

carboxyl-containing reactive (meth) acrylate polymer (A) .

(x-b-e) Production process of curable composition

As with the curable composition suitable for color

filters, the above curable composition may be produced by

mixing the above-described components together by a

conventional method. The mixing method is not particularly

limited, and examples thereof include a method in which a

part of the components is mixed and the remaining

components are then mixed and a method in which all the

components are mixed at a time.

An organic solvent may be if necessary added to the .

composition for viscosity modification purposes or the like.

The viscosity modification facilitates coating or printing

onto an object, for example, by roller coating, spin

coating, screen coating, or curtain coating. Organic

solvents usable herein include ketone solvents such as

ethyl methyl ketone, methyl isobutyl ketone, and

cyclohexanone; ester solvents such as ethyl acetoacetate,

γ-butyrolactone, and butyl acetate; alcohol solvents such as butanol and benzyl alcohol; cellosolve solvents and

carbitol solvents such as carbitol acetate and

methylcellosolve acetate, and their ester and ether

derivative solvents; amide solvents such as N,N-

dimethylformamide, N,N-dimethylacetamide, N,N-

dimethylformamide, and N-methyl-2-pyrrolidone; dimethyl

sulfoxide; phenol solvents such as phenol and cresol; nitro

compound solvents; and aromatic or alicylic solvents of

hydrocarbons such as toluene, xylene, hexamethylbenzene,

cumene aromatic solvents, tetralin, decalin and dipentene.

They may be used either solely or in a combination of two

or more of them.

The amount of the organic solvent used is preferably

such that the viscosity of the composition is 500 to

500,000 mPa-s, more preferably 1,000 to 500,000 mPa-s (as

measured at 25°C with Brookfield viscometer) . When the viscosity of the composition is in the above-defined range,

the composition is more suitable and easier to use for

coating or printing on an object. The amount of the

organic solvent used for bringing the viscosity to frail

within the above-defined range is preferably not morre than

1.5 times by mass the amount of the solid matter otrαer than

the organic solvent. When the amount of the organic

solvent exceeds 1.5 times by mass, the solid content is

lowered. In this case, when the composition is printed on

a substrate or the like, a satisfactory film thickness

cannot be provided by single printing and, thus, in some

cases, printing should be carried out a plurality off times.

Further, a colorant may be added to the composition

for use of the composition as ink. Specific example:s of

colorants usable herein include phthalocyanine blue^

phthalocyanine green, iodine green, disazo yellow, crystal

violet, titanium oxide, carbon black, and naphthalene black.

Also when the composition is used as ink, the viscosity is

preferably 500 to 500,000 mPa-s.

A flow modifier may be further added to the

composition for flow modification purposes. The addition

of the flow modifier can realize proper modification of the

fluidity of the composition, for example, in the case where

the composition is coated onto an object by roller coating,

spin coating, screen coating, curtain coating or the like.

Specific examples of flow modifiers include inorganic

or organic fillers, waxes, and surfactants. Specific

examples of inorganic fillers include talc, barium sulfate,

barium titanate, silica, alumina, clay, magnesium carbonate,

calcium carbonate, aluminum hydroxide, and silicate

compounds. Specific examples of organic fillers include

silicone resins, silicone rubbers, and fluororesins.

Specific examples of waxes include polyamide wax and

polyethylene oxide wax. Specific examples of surfactants

include silicone oils, higher fatty acid esters, and amides .

These flow modifiers may be used either solely or in a

combination of two or more.

If necessary, additives such as thermal

polymerization inhibitors, thickeners, defoamers, level-ing

agents, and tackifiers can be added to the composition.

Specific examples of thermal polymerization inhibitors

include hydroquinone, hydroquinone monomethyl ether, tert- .

butyl catechol, pyrogallol, and phenothiazine. Specific

examples of thickeners include asbestos, orben, bentone,

and montmorillonite. The antifoamer is used to remove foam

formed during printing, coating or curing, and specific

examples thereof include surfactants such as acrylic and

silicone surfactants. The leveling agent is used to rende x

a film surface with concaves and convexes formed by

printing or coating even, and specific examples thereof

include surfactants such as acrylic and silicone

surfactants.. Specific examples of tackifiers include

imidazole, thiazole, and triazole tackifiers and silane

coupling agents.

Other additives usable herein include, for example,

ultraviolet absorbers and plasticizers for storage

stabilization purposes.

A coating film may be formed by coating the above

curable composition onto a substrate or the like by screen

printing to a suitable thickness and heat drying the

coating. Thereafter, the coating film can be brought to a

cured product by exposing and developing the coating film

and heat curing the developed coating film.

The above curable composition can be used in various .

applications. In particular, the curable composition is

excellent in photosensitivity and developing properties.

Further, the curable composition can be cured to form a

thin film which is also excellent in adhesion to substrate,

insulating properties, heat resistance, warpage deformation,

flexibility and appearance and thus is suitable for us e as

an insulating protective film in printed wiring boards .

The insulating protective film may be formed by coating the

composition or ink onto a substrate with a circuit formed

thereon to a■ thickness of 10 to 100 μm and then heat

treating the coating at a temperature of 60 to 100 ⁰ C for about 5 to 30 min to dry the coating and thus to bringr the

thickness to 5 to 70 μm. Next, the dried coating is exposed through a negative mask having a desired exposure

pattern and is then developed with a developing solutLon to

remove unexposed areas, followed by heat curing at a

temperature of 100 to 18O ⁰ C for about 10 to 40 min.

This curable composition can be cured to form a cured

product which is excellent particularly in flexibility. By

virtue of excellent flexibility, the cured product is

particularly suitable for use as an insulating protective

film in an FPC substrate and can provide an FPC substrrate .

which is less likely to curl and has good handleability.

Further, the cured product may also be used as an

insulating resin layer between layers, for example, in a

multilayer printed wiring board.

Actinic light generated, for example, from

conventional actinic light sources, for example, carbon arc,

mercury vapor arc, and xenon arc may be used as an actinic

light source used in the exposure.

Developing solutions usable herein include aqueous

solutions of. alkalis such as potassium hydroxide, sodium

hydroxide, sodium carbonate, potassium carbonate, sodium

phosphate, sodium silicate, ammonia, and amines.

Further, the curable composition may be used in a

photosensitive layer in a dry film resist. The dry film

resist comprises a photosensitive layer formed of the

composition on a support formed of a polymer film or the

like. The thickness of the photosensitive layer is

preferably 10 to 70 μm. Specific examples of polymer films suitable as the support include films of polyester resins

such as polyethylene terephthalate and aliphatic polyesters

and polyolefin resins such as polypropylene and low-density

polyethylene.

The dry film resist may be formed by coating the

curable composition onto a support and then drying the

coating to form a photosensitive layer. Further, a dry

film resist, which comprises a support, a photosensitive

layer, and a cover film stacked on top of one another, that

is, which has films provided respectively on both sides of

the photosensitive layer, may be formed by providing a

cover film on the formed photosensitive layer. In use of

the dry film resist, the cover film is peeled off. Until

use of the dry film resist, the cover film provided on the

photosensitive layer can protect the photosensitive layer,

that is, the dry film resist has an excellent pot life.

In the formation of an insulating protective film on

a printed wiring board using the dry film resist, the dry

film resist is first laminated onto a substrate so that the

photosensitive layer faces the substrate. Here when the

dry film resist provided with the cover film is used, the

cover film is removed to expose the photosensitive layer

before contact with the substrate.

Next, the photosensitive layer and the substrate are

thermocompression bonded to each other through a pressure

roller or the like at about 40 to 120°C to stack the photosensitive layer onto the substrate. Thereafter, the

photosensitive layer is exposed through a negative mask

having a desired exposure pattern, and the support is

removed from the photosensitive layer. Development is

carried out with a developing solution to remove the

unexposed areas , and the photosensitive layer is then heat

cured to prepare a printed wiring board comprising an

insulating protective film provided on the surface of the

substrate . Further, the above dry film resist may be used

to form an insulating resin layer between layers in a

multilayer printed wiring board .

Examples

The following Examples further illustrate the present

invention . However, it should be noted that the present

invention is not limited to these Examples only .

Analytical instruments and analytical conditions used in

Examples 1 to 6 were as follows .

• Gas chromatography (GC)

Analytical instrument : GC 14A, manufactured by

Shimadzu Seisakusho Ltd .

Column: DB-I , manufactured by J & W, 30 m x 0 . 53 mm x

1 . 5 μm

Column temperature : 70°C, temperature rise at

10°C/min to 250°C, holding _. for 18 min

Integrator : CR7A, manufactured by Shimadzu Seisakusho

Ltd .

Inj ection temperature : 220°C

Detector temperature: 270 ⁰ C FID

Detector: FID, H ₂ 40 ml/min, Air 400 ml/rαin

Carrier gas: He 10 ml/min

^• Automatic titrator

Analytical equipment: COM-550, manufactured by

HIRANUMA SANGYO Co., Ltd.

[Example 1]

First step

2-Amino-l, 3-propanediol (20.0 g, 0.22 mol) and 200 ml

of toluene were charged into a 500-ml four-necked flask

equipped with a stirrer, a thermometer, a dropping funnel,

and a reflux condenser under a nitrogen atmosphere. The

contents of the flask were heated to 50°C, and 2-amino-l, 3- propanediol was dissolved, and hydrogen chloride gas was

fed into the flask at a flow rate of 100 ml/min over a

period of one hr.

Second step

The solution prepared in the first step was heated to

90°C. 3-Chloropropionic acid chloride (62.6 g, 0.49 mol) was fed to the solution over a period of 1.5 hr, and

heating was continued at 90°C for additional one hr. Third step

Carbonyl chloride (47.5 g, 0.48 mol) was fed to the

solution prepared in the second step over a period of 4 hr

while maintaining the temperature of the solution at 90 ⁰ C,

and heating was continued at 90°C for additional one hr. Thereafter, carbonyl chloride remaining dissolved in the

reaction solution was removed by introducing nitrogen. The

solution was then analyzed by gas chromatography. As a

result, it was found that l,3-bis-3-

chloropropionyloxypropane-2-isocyanate was obtained (59.0 g,

0.20 mol, yield 90%) .

Fourth step

The solution obtained in the third step was analyzed

for alkali decomposable chlorine by the following method.

About 0.5 g of a sample was accurately weighed into a 300-

ml stoppered conical flask, and 100 ml of a mixed liquid

composed of methanol and purified water at 70 : 30 volume

ratio was added to the sample. Next, 10 ml of a 30%

aqueous sodium hydroxide solution was added thereto. A

cooling pipe was attached to the flask, and the contents of

the flask were heated on a water bath of 80°C under reflux for one hr. After cooling, the solution in the flask was

transferred to a 200-ml measuring flask and was measured up

with purified water. Next, 10 ml of the solution was

accurately placed in a 200-ml beaker, 100 ml of purified

water was added, 1 ml of (1 + 1) nitric acid was added

thereto, and potentiometric titration was carried out with

a 1/50 N silver nitrate solution.

As a result, it was found that the concentration of

the alkali decomposable chlorine in the solution obtained

in the third step was 8.7% and 220 g of the solution

contained 19.1 g (0.54 mol) of alkali decomposable chlorine,

This solution was charged into a 500-ml flask, and 0.05 g

of phenothiazine and 0.05 g of 2, 6-bis-t-butylhydroxy

toluene were added to the solution. Thereafter, 57.6 g

(0.52 mol) of triethylamine was added dropwise thereto over

a period of one hr. When the dropwise addition was

initiated, the temperature of the solution was 25°C. The dropwise addition caused heat generation of the solution,

resulting in a temperature rise to 60 ⁰ C. The solution was ■

stirred with heating at 60°C for 4 hr and was then cooled to room temperature. The resultant solid matter was

collected by filtration and was washed with toluene. The

weight of the filtrate thus obtained was 230 g. The

filtrate was analyzed by gas chromatography. As a result,

it was found that 1, 3-bisacryloyloxypropane-2-isocyanate

was obtained (36.8 g, 0.16 mol, yield 73%) .

Purification step

To the filtrate were added 0.05 g of phenothiazine

and 0.05 g of 2, 6-bis-t-butylhydroxy toluene. The pressure

was reduced by a vacuum pump to 10 kPa, and the solvent was

removed by evaporation. The resultant concentrate was

charged into a 100-ml flask, and 0.05 g of phenothiazine

and 0.05 g of 2, 6-bis-t-butylhydroxy toluene were added

thereto. The pressure was reduced to 0.5 kPa, followed by

distillation to collect a distillate of 120 to 123°C. As a result, it was found that 1, 3-acryloyloxypropane-2-

isocyanate was obtained (30.2 g, 0.13 mol, yield 61%) .

[Example 2]

First step

2-Amino-2-methyl-l, 3-propanediol (20.0 g, 0.19 mol)

and 200 ml of toluene were charged into a 500-ml four-

necked flask equipped with a stirrer, a thermometer, a

dropping funnel, and a reflux condenser under a nitrogen

atmosphere. Hydrogen chloride gas was fed into the flask

at a flow rate of 100 ml/min over a period of one hr.

Second step

The solution prepared in the first step was heated to

95°C. 3-Chloropropionic acid chloride (54.3 g, 0.43 mol) was fed to the solution over a period of one hr, and

heating was continued at 95°C for additional one hr. Third step

Carbonyl chloride (43.O g, 0.43 mol) was fed to the

solution prepared in the second step over a period of 4 hr

while maintaining the temperature of the solution at 90 ⁰ C,

and heating was continued at 90°C for additional one hr. Thereafter, carbonyl chloride remaining dissolved in the

reaction solution was removed by introducing nitrogen.

Fourth step

The concentration of the alkali decomposable chlorine

in the solution obtained in the third step was 7.9%, and

200 g of the solution contained 15.8 g (0.45 mol) of alkali

decomposable chlorine. This solution was charged into a

500-ml flask, and 0.05 g of phenothiazine and 0.05 g of

2, 6-bis-t-butylhydroxy toluene were added as a

polymerization inhibitor to the solution. Thereafter, 45.0

g (0.45 mol) of triethylamine was added dropwise thereto

over a period of one hr. When the dropwise addition was

initiated, the temperature of the solution was 25°C. The

dropwise addition caused heat generation of the solution,

resulting in a temperature rise to 6O ⁰ C. The reaction

solution was heated to 70°C, and stirring was continued at that temperature for 5 hr, followed by cooling to room

temperature.. The solid matter thus obtained was collected

by filtration and was washed with toluene to give 200 g of

the filtrate. The filtrate was analyzed by gas

chromatography. As a result, it was found that 1,3-

bisacryloyloxy-2-methyl-propane-2-isocyanate was obtained

(32.2 g, 0.13 mol, yield 71%) .

Purification step

To the filtrate were added 0.05 g of phenothiazine

and 0.05 g of 2, 6-bis-t-butylhydroxy toluene. The pressure

was reduced by a vacuum pump to 0.7 kPa, and the solvent

was removed by evaporation. The pressure was trien reduced

to 0.3 kPa, followed by distillation to collect a

distillate of 105 to 110 ⁰ C. As a result, it was found that. 1, 3-bisacryloyloxy-2-methyl-propane-2-isocyanate was

obtained (26.2 g, 0.11 mol, yield 58%) .

[Example 3]

First step

2-Amino-2-methyl-l,3-propanediol (20.O g, 0.19 mol)

and 40 ml of methanol were charged into a 200-ml fouir-

necked flask equipped with a stirrer, a thermometer, and a

reflux condenser under a nitrogen atmosphere. Hydrocfen

chloride gas was fed into the flask at a flow rate of 100

ml/min over a period of one hr. Methanol was removed, by

evaporation under reduced pressure to give a white crystal

of 2-amino-2-methyl-l, 3-propanediol hydrochloride (2 ^" 7.0 g,

0.19 mol) .

Second step

2-Amino-2-methyl-l, 3-propanediol hydrochloride (27.0

g) prepared above and 200 ml of toluene were charged into a

200-ml four-necked flask equipped with a stirrer, a

thermometer, a dropping funnel, and a reflux condenser

under a nitrogen atmosphere. The contents of the flask

were heated to 95°C. 3-Chloropropionic acid chloride (54.3 g, 0.43 mol) was fed to the solution over a period o_f one

hr, and heating was then continued at 95°C for additional one hr.

Third step

Carbonyl chloride (43.0 g, 0.43 mol) was fed to the

solution prepared in the second step over a period o_f 4 hr

while maintaining the temperature of the solution at 90 ⁰ C

and heating was continued at 9O ⁰ C four one hr. Thereafter, carbonyl chloride remaining dissolved in the reaction

solution was removed by introducing nitrogen. The solution

was then analyzed by gas chromatography. As a result, it

was found that 1, 3-bis-3-chloropropi_onyloxy-2-

methylpropane-2-isocyanate was obtained (52.2 g, 0.17 mol,

yield 88%) .

Fourth step

The solution obtained in the third step was analyzed

for alkali decomposable chlorine. As a result, it was

found that the concentration of the alkali decomposable

chlorine in the solution obtained in the third step was

7.9% and 200 g of the solution contained 15.8 g (0.45 mol)

of alkali decomposable chlorine. This solution was charged

into a 500-ml flask, and 0.05 g of phenothiazine and 0.05 g

of 2, 6-bis-t-butylhydroxy toluene were added to the

solution. Thereafter, 45.0 g (0.45 mol) of triethylamine .

was added thereto over a period of one hr. When the

dropwise addition was initiated, the temperature of the

solution was 25°C. The dropwise addition caused heat generation of the solution, resulting in a temperature rise

to 60°C. Stirring of the solution was continued with

heating at 60°C for 5 hr and was then cooled to room temperature. The resultant solid matter was collected by

filtration and was washed with toluene. Ttie weight of the

filtrate thus obtained was 200 g. The filtrate was

analyzed by gas chromatography. As a result, it was found

that 1, 3-bisacryloyloxy-2-methylpropane-2—isocyanate was

obtained (33.5 g, 0.14 mol, yield 74%) .

Purification step

To the filtrate were added 0.05 g of phenothiazine

and 0.05 g of 2, 6-bis-t-butylhydroxy toluene. The pressure

was reduced by a vacuum pump to 0.7 kPa, and the solvent

was removed by evaporation. Subsequently, the pressure was

reduced to 0.3 kPa, followed by distillation to collect a

distillate of 105 to 110 ⁰ C. As a result, ±t was found that 1, 3-bisacryloyloxy-2-methylpropane-2-isocy ^r anate was

obtained (25.8 g, 0.11 mol, yield 57%) .

[Example 4]

First step

2-Amino-2-methyl-l, 3-propanediol (30.O g, 0.29 mol)

and 300 ml of dioxane were charged into a 500-ml four-

necked flask equipped with a stirrer, a trαermometer, a

dropping funnel, and a reflux condenser under a nitrogen

atmosphere. Hydrogen chloride gas was fed into the flask

at a flow rate of 100 iαl/min over a period of one hr.

Second step

The solution prepared in the first step was heated to

95°C. 3-Chloropropionic acid chloride (90.5 g, 0.71 mol) was fed to the solution over a period of one hr, and

heating was then continued at 95°C for additional one hr. Third step

Carbonyl chloride (82.5 g, 0.83 mol) was fed to the

solution prepared in the second step over a period of 6 hr

while maintaining the temperature of the solution at 90 ⁰ C,

and heating was continued at 90 ⁰ C for additional one hr. Thereafter, carbonyl chloride remaining dissolved in the

reaction solution was removed by introducing nitrogen. The

solution was then analyzed by gas chromatography. As a

result, it was found that 1, 3-bis-3-chloropropionyloxy-2-

methylpropane-2-isocyanate was obtained (53.6 g, 0.17 mol,.

yield 90%) .

Fourth step

The solution obtained in the third step was analyzed

for alkali decomposable chlorine. As a result, it was

found that the concentration of the alkali decomposable

chlorine in the solution obtained in the third step was

8.1% and 353.5 g of the solution contained 28.6 g (0.81

mol) of alkali decomposable chlorine. This solution was

charged into a 500-ml flask, and 0.20 g of phenothiazine

and 0.20 g of 2, 6-bis-t-butylhydroxy toluene were added to

the solution. Thereafter, 80.0 g (0.79 mol) of

triethylamine was added dropwise thereto over a period of

1.5 hr. After the completion of the dropwise addition,

stirring with heating was continued at 50 ⁰ C for 5 hr and was then cooled to room temperature. The resultant solid

matter was collected by filtration and was washed with

toluene. The weight of the filtrate thus obtained was

383.5 g. The filtrate was analyzed by gas chromatography.

As a result, it was found that 1, 3-bisacryloyloxy-2-

methylpropane-2-isocyanate was obtained (35.6 g, 0.15 mol,

yield 78%) .

Purification step

To the filtrate were added 0.20 g of phenothiazine

and 0.20 g of 2, 6-bis-t-butylhydroxy toluene. The pressure

was reduced by a vacuum pump to 0.7 kPa, and the solvent

was removed by evaporation. Subsequently, the pressure was

reduced to 0.3 kPa, followed by distillation to collect a

distillate of 105 to 110 ⁰ C. As a result, it was found that 1, 3-bisacryloγloxy-2-methylpropane-2-isocyanate was

obtained (26.2 g, 0.11 mol, yield 58%) .

[Example 5]

First step

l-Amino-2, 3-propanediol (20.0 g, 0.22 mol) and 200 ml

of toluene were charged into a 500-ml four-necked flask

equipped with a stirrer, a thermometer, a dropping funnel,

and a reflux condenser under a nitrogen atmosphere.

Hydrogen chloride gas was fed into the flask at a flow rate

of 100 ml/min over a period of one hr.

Second step

The solution prepared in the first step was heated to

95°C. 3-Chloropropionic acid chloride (70.4 g, 0.55 mol) was fed to the solution over a period of 1.5 hr, and

heating was then continued at 95°C for additional 3 hr. Third step

Carbonyl chloride (50.8 g, 0.51 mol) was fed to the

solution prepared in the second step over a period of 4.5

hr while maintaining the temperature of the solution at

90°C, and heating was continued at 90°C for additional one hr. Thereafter, carbonyl chloride remaining dissolved in

the reaction solution was removed by introducing nitrogen.

The solution was then analyzed by gas chromatography. As a

result, it was found that l,2-bis-3-

chloropropionyloxypropane-1-isocyanate was obtained (52.2 g,

0.18 mol, yield 80%) .

Fourth step

The alkali decomposition concentration of the

solution obtained in the third step was 9.2% and 216 g of

the solution contained 19.9 g (0.56 mol) of alkali

decomposable chlorine. This solution was charged into a

500-ml flask, and 0.05 g of phenothiazine as a

polymerization inhibitor and 0.05 g of 2, 6-bis-t-

butylhydroxy toluene were added to the solution.

Thereafter, 55.6 g (0.55 mol) of triethylamine was added

dropwise thereto over a period of 1 hr. When the dropwise

addition was initiated, the temperature of the solution was

25°C. The dropwise addition caused heat generation of the •

solution, resulting in a temperature rise to 60 ⁰ C. The

solution was heated to 70°C, and stirring with heating was continued for 5 hr and was then cooled to room temperature.

The resultant solid matter was collected by filtration and

was washed with toluene. The weight of the filtrate thus

obtained was 220 g. The filtrate was analyzed by gas

chromatography. As a result, it was found that 1,2-

bisacryloyloxypropane-1-isocyanate was obtained (30.2 g,

0.13 moI, yield 61%) .

Purification. step

To the filtrate were added 0.05 g of phenothiazine

and 0.05 g of 2, 6-bis-t-butylhydroxy toluene. The pressure

was reduced by a vacuum pump to 0.7 kPa, and the solvent

was removed by evaporation. Subsequently, the pressure was

reduced to 0.5 kPa, followed by distillation to collect a

distillate of 114 to 122°C. As a result, it was found that 1,2-bisacryloyloxypropane-l-isocyanate was obtained (25.4 g,

0.11 mol, yield 50%) .

[Example 6]

First step

2-Amino-l,3-propanediol (20.0 g, 0.22 mol) and 200 ml

of toluene were charged into a 500-rαl four-necked flask

equipped with a stirrer, a thermometer, a dropping funnel,

and a reflux condenser under a nitrogen atmosphere.

Hydrogen chloride gas was fed into the flask at a flow rate

of 100 ml/min over a period of one hr.

Second step

The solution prepared in the first step was heated to

90°C. Methacrylic acid chloride (49.2 g, 0.47 rαol) was fed to the solution over a period of 1.5 hr, and heating was

continued at 90°C for additional 2 hr. Third step

Carbonyl chloride (61.1 g, 0.62 mol) was fed to the

solution prepared in the second step over a period of 4 hr

while maintaining the temperature of the solution at 90 ⁰ C,

and heating was continued at 90 ⁰ C for additional one hr. Thereafter, carbonyl chloride remaining dissolved in the

reaction solution was removed by introducing nitrogen. The

solution was then analyzed by gas chromatography. As a

result, it was found that 1, 3-bis-methacryloyloxypropane-2-

isocyanate was obtained (38.1 g, 0.15 mol, yield 68%) .

Purification step

To the solution prepared in the third step were added

0.05 g of phenothiazine and 0.05 g of 2, 6-bis-t-

butylhydroxy toluene. The pressure was reduced by a vacuum

pump to 0.7 kPa, and the solvent was removed by evaporation.

Subsequently, the pressure was reduced to 0.3 kPa, followed

by distillation to collect a distillate of 133 to 140 ⁰ C. As a result, it was found that 1,3-

bismethacryloyloxγpropane-2-isocyanate was obtained (29.0 g,

0.11 mol, yield 52%) .

[Examples 7 to 22 and Comparative Examples 1 to 13]

(1) Preparation of curable compositions and preparation of

evaluation samples

1-Hydroxy-cyclohexyl-phenyl-ketone (Irgacure 184

manufactured by Ciba Specialty Chemicals, K.K.) as a

photopolymerization initiator for the reactive monomer (as

described in Table 1 to Table 9) was mixed in the mixing

amount as described in Tables 1 to 9 into 20 g of

dichloromethane (manufactured by Junsei Chemical

Corporation) with stirring at room temperature to give

homogeneous curable composition solutions. Further, these

curable composition solutions were coated onto a glass

substrate (size 50 mm x 50 mm) to a film thickness of about

200 μrα on a dry basis, the coated glass substrate was dried

at 50°C for 30 min to prepare evaluation samples of Examples 7 to 22, Comparative Examples 1 to 7 and

Comparative Examples 9 to 13.

(2) Evaluation of curable composition

<Curability>

The evaluation samples of Examples 7 to 22,

Comparative Examples 1 to 7, and Comparaizive Examples 9 to

13 prepared in the above (1) was exposed using an exposure

system (MULTILIGHT ML-251A/B, Ushio Inc. ) with a built-in

ultrahigh pressure mercury lamp, and an ethylenically

unsaturated group absorption peak (810 cirf ¹ ) was measured

with an infrared spectrophotometer (FT/IH7000 manufactured

by Japan Spectroscopic Co., Ltd.) . Exposure was carried

out at such an exposure that the reaction was brought to a

steady state (500 mj/cm ² ) . The conversion of the

ethylenically unsaturated group was measured from the level

of a change in the ethylenically unsaturated group

absorption peak (absorption peak intensity after

exposure) /absorption peak intensity before exposure x

100: %) at that time. The results are sliown in Tables 10

to 13.

<Change in viscosity>

The curable composition solutions prepared in the

above .(1) as such were provided, and, irx order to evaluate

the curability as a function of a change; in viscosity,

measurement was carried out with a rheometer with an

ultrahigh pressure mercury lamp for lightt irradiation. In

this case, while conducting light irradiation, the exposure

at which the viscosity begins to increase was measured at

25 ⁰ C. The results are shown in Tables 10 to 13. <Adhesive strength>

Evaluation samples of Examples 7 to 22, Comparative

Examples 1 to I ₁ and Comparative Examples 9 to 13 prepared

in the above (1) were exposed at an exposure of 3 j/cm ²

using an exposure system with a built-in ultrahigh pressure

mercury lamp. The surface of the cured film for each

sample was polished with sandpaper. Further, a hoILding

tool in an adhesion tester (Elcometor manufactured by

Elcometer Instrument Ltd) was cured with an epoxy adhesive

(HC-1210 manufactured by Mitsui Chemicals Inc.), and the

adhesive strength was measured with an adhesion tester.

The results are shown in Tables 10 to 13.

<Transmittance>

Evaluation samples of Examples 7 to 22, Comparative

Examples 1 to 7, and Comparative Examples 9 and 10 prepared

in the above (1) were exposed at an exposure of 3 j/cm ²

using an exposure system with a built-in ultrahigh, pressure

mercury lamp. For each of the cured samples, the

transmittance at 550 nm was measured with a

spectrophotometer (UV3100, manufactured by Japan

Spectroscopic Co., Ltd.) . The results are shown in Tables

10 to 13.

<Heat resistance>

Evaluation samples of Examples 7 to 22, Comparative

Examples 1 to 7, and Comparative Examples 9 to 13 prepaxed

in the above (1) were exposed at an exposure of 3 j/cm ²

using an exposure system with a built-in ultrahigh pres sure

mercury lamp. For each of the cured samples, the

decomposition temperature was measured with a different ial

scanning calorimeter (EXSTAR6000, manufactured by Seiko

Instrument Inc.) for comparison about the heat resistan.ce

among the samples. The results are shown in Tables 10 "to

13.

<Refractive index>

Each of the curable composition solutions prepared, in

the above (1) was coated onto a PET film to a film

thickness of about 200 μm on a dry basis. The coating v^as .

dried at 50°C for 30 min to prepare evaluation samples of Examples 7 to 14 and Comparative Examples 1 to 7. Each of

the samples thus obtained was exposed at an exposure off 3

j/cm ² using an exposure system with a built-in ultrahigh

pressure mercury lamp. Each of the cured samples was

peeled off as a film, and the refractive index of each of

the cured films was measured with an Abbe's refractometer.

The results are shown in Tables 10 and 12.

<X-raγ analysis>

Evaluation samples of Example 7 and Comparative

Example 8 were prepared, and each of the samples thus

obtained was exposed at an exposure of 3 j/cm ² using an

exposure system with a built-in ultrahigh pressure mercury

lamp. Each of the cured samples were measured with an X-

ray analyzer (RU-200B, manufactured by R±gaku International

Corporation) . The results are shown in Fig. 1.

[Production Example 1] : Synthesis of ure"thane

(meth) acrylate (UB-I)

Polycaprolactonediol (PLACCEL 212, molecular weight

1,250, manufactured by Daicel Chemical Industries, Ltd.)

(625 g, 0.5 mol) as a polyester polyol and BEI (239 g, 1.0

mol) , a compound listed in Table 14 were introduced into a.

reaction vessel equipped with a stirrer, a thermometer, and

a condenser. p-Methoxyphenol and di-t-butyl-hydroxytoluene

(each 1.0 g) were introduced thereinto. The mixture was

heated to 60°C with stirring. Thereafter:, heating was stopped, and 0.2 g of dibutyltin dilaurate was added

thereto. When the temperature within the reaction vessel

began to drop, heating was again carried out. Stirring was

continued at 80°C, and the reaction was terminated when the infrared absorption spectrum showed substantial

disappearance of an absorption spectrum (2280 cm ^"1 )

attributable to an isocyanate group. Thus, a urethane

(meth) acrylate polymer (UB-I) as a viscose liquid was

prepared. The urethane (meth) acrylate had an average

molecular weight of 1,800.

[Production Example 2] : Synthesis of urethane

(meth) acrylate (UB-2)

A urethane (meth) acrylate polymer (UB-2) was

synthesized in the same manner as in Production Example 1,

except that polycarbonatediol (PLACCEL CD 210PL (tradename) ,

average molecular weight 1,000, manufactured by Daicel

Chemical Industries, Ltd.) (500 g, 0.5 mol) was used

instead of polycaprolactonediol. The urethane

(meth)acrylate had a number average molecular weight of

1,500.

[Production Example 3: Synthesis of urethane (meth) acrylate

(UB-3)

A urethane (meth) acrylate polymer (UB-3) was

synthesized in the same manner as in Production Example 1 ,

except that polytetramethylene glycol ( PTMG-850, molecular

weight of 850 , manufactured by Hodogaya Chemical Co . , Ltd . )

( 425 g, 0 . 5 mol ) was used instead of polycaprolactonediol .

The urethane ^ acrylate had a number average molecular weight

of 1 , 350 .

[Production Example 4 ] : Synthesis of urethane

(meth) acrylate (UB-4 )

Polytetramethylene glycol (PTMG-850, molecular weight

of 850, manufactured by Hodogaya Chemical Co., Ltd.) (255 g,

0.3 mol), dimethylolpropionic acid (67 g, 0.5 mol),

isophorone diisocyanate (133 g, 0.6 mol), BEI, a compound

listed in Table 14 (95.6 g, 0.4 mol), 0.1 g of p-

methoxyphenol and 0.1 g of di-t-butyl-hydroxytoluene were

introduced thereinto. The mixture was heated to 60 ⁰ C with stirring. Thereafter, heating was stopped, and 0.1 g of

dibutyltin dilaurate was added thereto. When the

temperature within the reaction vessel began to drop,

heating was again carried out. Stirring was continued at

8O ⁰ C, and the reaction was terminated when the infrared

absorption spectrum showed substantial disappearance of an

absorption spectrum (2280 cm ^"1 ) attributable to an

isocyanate group. Thus, a urethane (meth) acrylate polymer

(UB-4) as a viscose liquid was prepared. The urethane

acrylate had a number average molecular weight of 23,000

and an acid value of 45 mgKOH/g.

[Production Example 5] : Synthesis of urethane

(meth) acrylate (UB-5)

A urethane (meth) acrylate polymer (UB-5) was

synthesized in the same manner as in Production Example 1,

except that polycarbonatediol (PLACCEL CD 210PL (tradename) ,

average molecular weight 1,000, manufactured by Daicel

Chemical Industries, Ltd.) (500 g, 0.5 mol) and BMI, a

compound listed in Table 14 (225 g, 1.0 mol) were used

instead of polycaprolactonediol. The urethane acrylate had

a number average molecular weight of 1,500.

[Production Example 6] : Synthesis of urethane

(meth) acrylate (UB-6)

Methacrylic acid (12.0 g) , 2-hydroxyethylacrylate

(6.0 g) , and propylene glycol monomethyl ether acetate

(225.0 g) were charged into a four-necked flask equipped

with a dropping funnel, a thermometer, a cooling pipe, and

a stirrer, and the air in the four-necked flask was

replaced by nitrogen for one hr. The flask was heated to

9O ⁰ C on an oil bath, and a mixed liquid composed of methacrylic acid (12.0 g) , methyl methacrylate (14.0 g) ,

butyl methacrylate (43.0 g) , 2-hydroxyethylacrylate (6.0

g) , propylene glycol monomethyl ether acetate (225.0 g) ,

and azobisispbutyronitrile (3.2 g) was then added dropwise

thereto over a period of one hr. After polymerization for

3 hr, a mixed liquid composed of azobisisobutyronitrile

(1.0 g) and propylene glycol monomethyl ether acetate (15.0

g) was added thereto. The mixture was heated to 100°C, polymerization was allowed to proceed for 1.5 hr, and the

reaction solution was then allowed to cool. BEI (20.3 g)

listed in Table 14 was gradually added to the solution, and

the mixture was stirred at 80 ⁰ C for 4 hr to synthesize a copolymer (UB- 6) . The copolymer thus obtained had an acid

value of 90 mgKOH/g and a mass average molecular weight of

25,000 in terms of polystyrene as measured by GPC.

[Comparative Production Example 1] : Synthesis of urethane .

(meth) acrylate (UA-I)

A urethane (meth) acrylate polymer (UA-I) was prepared

in the same manner as in Production Example 1, except that

2-acryloyloxyethyl isocyanate (142 g, 1.0 mol) was used

instead of the compound BEI listed in Table 14 for the

reaction. The urethane acrylate thus obtained had an

average molecular weight of 1,600.

[Comparative Production Example 2] : Synthesis of urethane

(meth) acrylate (UA-2)

A urethane (meth) acrylate polymer (UA-2) was prepared

in the same manner as in Production Example 2, except that

2-acryloyloxyethyl isocyanate (142 g, 1.0 mol) was used

instead of the compound BEI listed in Table 14 for the

reaction. The urethane acrylate thus obtained had an

average molecular weight of 1,300.

[Example 23]

UB-I (30.0 g, solid content 7.0 g) produced in

Production Example 1, propylene glycol monomethyl ether

acetate (5.0 g) , a dispersant (Flowlen DOPA-33, solid

content 30%, manufactured by Kyoeisha Chemical Co., Ltd.)

(3.5 g) , and carbon black (Special Black 4, manufactured by

Degussa) (7.0 g) were mixed together, and the mixture was •

then allowed to stand overnight. Next, this mixture was

stirred for one hr and was passed through a three-roll mill

(R III-l RM-2, manufactured by Kodaira Seisakusho Co.,

Ltd.) four times. Cyclohexanone was added to the black

mixture thus obtained for concentration adjustment to

prepare a black colored composition having a solid content

of 18.0%.

The colored composition prepared above and other

ingredients were mixed together in a mixing ratio as

described in. Table 2 to prepare a black curable composition

which was then filtered through a filter with a pore

diameter of 0.8 μm (Kiriyama filter paper for GFP) . The filtrate was evaluated for photosensitivity and resist

properties (OD value (optical density) , reflectance, and

pencil hardness) by the following methods.

Evaluation of photosensitivity

The curable composition was spin coated onto a glass

substrate (size: 100 x 100 mm), and the coating was dried

at room temperature for 30 min and was then prebaked at

70°C for 20 min. The film thickness of the resist was previously measured with a film thickness meter (SURFCOM

130A, manufactured by TOKYO SEIMITSU) , and the resist was .

photocured with an exposure system with an ultrahigh

pressure mercury lamp incorporated therein (MULTILIGHT ML-

251 A/B (tradename) , manufactured by Ushio Inc.) with

varied exposure. Further, the resist was developed with an

alkali developing agent (a 0.1% aqueous potassium carbonate

solution, Developer 9033, manufactured by Shipley Far East

Ltd.) at 25°C for a predetermined period of time. After alkali development, the coated glass substrate was washed

with water and was dried by air spraying, and the film

thickness of. the remaining resist was measured. The

exposure at which the value (remaining film sensitivity)

calculated by the following equation:

Remaining film sensitivity (%) = "(film thickness after

alkali development) / (film thickness before alkali

development) " x 100

was not less than 95% was regarded as the photosensitivity

of the curable composition. The results are shown in Table

16.

Evaluation of resist properties

The curable composition was spin coated onto a glass

substrate (size: 100 x 100 mm), and the coating was dried

at room temperature for 30 min and was then prebaked at

70°C for 20 min. The coating was then photocured using an ultrahigh pressure mercury lamp at an exposure of twice the

photosensitivity of the composition and was then post-baked

at 200°C for 30 min. The resist coated glass substrate thus obtained was used for the following evaluation.

OD value (optical density)

A calibration curve was prepared by measuring the

transmittance at 550 run with a standard plate having a

known OD value. Next, the transmittance at 550 nm of the

resist-coated glass substrate prepared in each of the

Examples and Comparative Examp-Les was measured to determine

the OD value. The results are shown in Table 16.

Reflectance

For each of the resists, the reflectance at 550 nm

was measured with a spectrophotometer (UV-3100 PC,

manufactured by Shimadzu Seisak:usho Ltd.), and the pencil

hardness was measured according to JIS K 5400. The results

are shown in Table 16.

[Examples 24 to 28 and Comparative Examples 14 and 15]

Evaluation was carried out in the same manner as in

Example 23, except that the ingredients were used according

to formulations shown in Table 15. The results are shown

in Table 16.

[Examples 29 to 34 and Comparative Examples 16 and 17]

The ingredients were mixed together according to

formulations (parts by mass) shown in Table 17 to prepare

compositions. A bisphenol A-t^pe epoxy resin EPICLON 860

(manufactured by Dainippon Ink and Chemicals, Inc.) was

used as a heat-curable resin (C) . 2, 4, 6-Trimethyl benzoyl

phenyl phosphine oxide TPO (manufactured by BASF) and 4,4'-

bis (diethylamino)benzophenone EAB-F (manufactured by

Hodogaya Chemical Co., Ltd.) were used as a

photopolymerization initiator (D) . Melamine PC-I

(manufactured by Nissan Chemical Industries Ltd..) was used

as a thermal polymerization catalyst (E) .

(Preparation of curable composition coating film)

The viscosity of each of the curable compositions

prepared according to the formulations shown in Table 4 was

modified to 5,000 mPa-s by the addition of metriyl cellosolve acetate, and each of the viscosity modified

curable compositions was screen printed to a thickness of

30 μm onto a printed board comprising a 35 μm-"thick copper

foil stacked onto one side of a 50 μm-thick polyimide film (UPISEL (registered trademark) N, manufactured, by UBE

Industries, Ltd. which had been washed with a 1% aqueous

sulfuric acid solution, was washed with water, and was

dried with an air stream) , and the coating was dried at

70°C to prepare a substrate. (Exposure and development)

A test piece of each of the laminates thus obta.ined

was exposed at 500 mJ/cπr with an exposure system equipped

with a metal halide lamp (HMW-680 GW, manufactured by Ore

manufacturing Corporation) through a negative pattern,

having squares of 1 cm x 1 cm in an area of 4 cm x 6 cm.

Next, the exposed laminates were developed by spraying 1

mass% aqueous sodium carbonate solution at 30°C for 60 sec to remove unexposed areas. The developed laminates were

then heat treated at 150 ⁰ C for 30 min. Thus, copper-clad laminates with a copper foil of 1 cm x 1 cm square exposed

thereon were prepared.

(Gold plating resistance)

Electroless gold plating was carried out using the

copper-clad laminates prepared above by the following step.

For the test pieces, a change in appearance was judged, and

the state of peeling of the resist was judged by a peeling

test using Cello-Tape (R) . The results are shown in Table .

17.

O — Neither change in appearance nor resist peeling was observed at all.

Δ ••• Slight peeling of resist was observed although no change in appearance was observed.

I X ••• Lifting of resist was observed, plating got in between resist and copper foil, ancL resist peeling was

significant in peeling test.

(Step of electroless gold plating)

Degreasing: The test piece was immersed in an acidic

degreasing liguid (20 vol% aqueous solution of Metex L-5B,

manufactured by MacDermid Japan) off 30°C for 3 min.

Water washing: The test piece was immersed in running

water for 3 min.

Soft etching: The test piece was immersed in a 14.3

wt% aqueous ammonium persulfate solution at room

temperature for one min.

Water washing: The test piece was immersed in running

water for 3 min.

Immersion in acid: The test piece was immersed in a

10 vol% aqueous sulfuric acid solution at room temperature

for one min.

Water washing: The test piece was immersed in running

water for 30 sec to one min.

Application of catalyst: The test piece was immersed

in a catalyst liquid (10 vol% aqueous solution of Melplate

Activator 350, manufactured by Meltex Inc.) of 30 ⁰ C for 7

rum .

Water washing: The test piece was immersed in running

water for 3 rain.

Electroless nickel plating (gold plating substrate

layer) : The test piece was immersed in a nickel plating

solution (85°C, pH = 4.6) (20 vol% aqueous solution of Melplate Ni-865 M, manufactured by Meltex Inc.) for 20 rain.

Immersion in acid: The test piece was immersed in a

10 vo1% aqueous sulfuric acid solution at room temperature

for one rain.

Water washing: The test piece was immersed in running

water for 30 sec to one min.

Electroless gold plating: The test piece was immersed

in a gold plating solution (95°C, pH = 6) (aqueous solution containing 15 vol% Aurolectroless UP, manufactured by

Meltex Inc., and 3 vol% of aqueous gold potassium cyanide

solution) for 10 min.

Water washing: The test piece was immersed in running

water for 3 min.

Hot-water washing: The test piece was immersed in hot

water of 60°C, thoroughly washed with water for 3 min, was then satisfactorily dehydrated and was dried to prepare an

electroless gold plated test piece.

[Table 1]

00

[Table 2]

[Table 3]

Reactive Polymerization

Reactive urethane compound urethane initiator compound, g (Irgacure 184) , g

Ex. 13 10 0.10

Ex. 14 10 0.10 K)

O O

Ex. 15 10 0.10

[Table 4]

[Table 5]

Reactive Polymerization

Reactive urethane compound urethane initiator compound, g (Irgacure 184) , q

Ex. 19 10 0.10

Ex. 20 10 0.10

K>

O κ>

Ex. 21 10 0.10 ^A

Ex. 22 10 0.10

[Table 6]

Reactive Polymerization

Reactive urethane compound urethane initiator compound, g (Irgacure 184) , g

Comp. Ex. 1 10 0.10

Comp. Ex. 2 10 0.10

K>

O

Comp. Ex. 3 10 0.10

[Table 7]

Reactive Polymerization

Reactive urethane compound urethane initiator compound, g (Irgacure 184) , g

Comp . Ex . 4 10 0.10

K>

O

Comp . Ex . 5 10 0.10

Comp . Ex . 6 10 0.10

[Table 8]

Reactive Polymerization

Reactive urethane compound urethane initiator compound, g (Irgacure 184) , g

Comp . Ex . 7 10 0..10

κ>

O Ul

Comp . Ex . 8 10 0 ^" .10

Comp . Ex . 9 10 0.10

[Table 9]

Reactive Polymerization

Reactive urethane compound urethane initiator compound, g (Irgacure 184) , q

Comp. Ex. 10 10 0.10

κ>

Coiαp . Ex. 11 10 0.1Q O

Corαp. Ex. 12 10 0.10

Comp. Ex. 13 10 0.10

[Table 10 ]

Ex. 7 Ex. 8 Ex. 9 Ex. 10 Ex. 11 Ex. 12 Ex. 13 Ex. 14

Double bond

70 76 74 75 70 60 72 78 conversion, %

Viscosity change,

80 60 60 50 50 50 80 60 mj/cm ²

Adhesive strength,

0.70 0.80 0.80 0.70 0.80 1.00 0.75 0.80 N/mm ²

Decomposition temp., ⁰ C 355 350 350 355 350 360 355 360

Transmittance, % 98 97 98 97 98 99 99 98

Refractive index 1.418 1.49 1.45 1.52 1.5 1.58 1.52 1.49

κ>

O -4

[Table 11]

(T)Double bond conversion: A change in infrared absorption peak intensity of double bond (after exposure/before exposure * 100)

@ Viscosity change: Exposure necessary for an increase in viscosity of curable composition solution (33%) by exposure to light K>

O OC

O Adhesive strength: Adhesive strength on glass substrate

@ Transmittance: Transmittance at 550 nrα

©Decomposition temp.: Decomposition temp, as measured with differential scanning calorimeter

(B) Refractive index: Refractive index of cured film

[Table 12]

κ>

[Table 13] O

[Table 15]

Coirip. . Comp.

Ex. 23 Ex. 24 Ex. 25 Ex. 26 Ex. 27 Ex. 28 Ex. 14 Ex. 15

UB-I 28 0 0 0 0 0 0 0

UB-2 O 28 O O O 0 0 0

UB-3 O 0 28 0 0 0 0 0

UB-4 _. 0 0 0 28 0 0 0 0

(A)

UB-5 0 0 0 0 28 0 0 0

UB-6 0 0 0 0 0 28 0 0

UA-I 0 0 0 0 0 0 28 0

UA-2 0 0 0 0 0 0 0 28

(B) CB *1 42 42 42 42 42 42 42 ^• 42

HABI *2 3 3 3 3 3 3 3 3

(D)

EMK *3 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5

(F) TMPT *4 3 3 3 3 3 3 3 3

PMA *5 170 170 170 170 170 170 170 170

(G)

CH *6 80 80 80 ^• 80 80 80 80 80

(H) TPMB *7 2 2 2 2 2 2 2 2

Dispersant 4.2 4.2 4.2 4.2 4.2 4.2 4.2 4.2

*1: carbon black *2: 2, 2'-bis (o-chlorophenyl) -4, 4 ' , 5, 5'-tetraphenyl-l, 2 ' -bisimidazole

*3: 4, 4 ' -bis (diethylamino)benzophenone *4: trirαethylolpropane triacrylate

*5: propylene glycol monomethyl ether acetate

*6: cyclohexanone *7: trimethylolpropane tris-3-mercapto-butyrate

[Table 16]

κ> κ>

[ Table 17 ]

Table 17 (parts by weight)

Ex. 29 Ex. 30 Ex. 31 Ex. 32 Ex. 33 Ex. 34 Comp. Comp. Ex. 16 Ex. 17

UB-I 80 0 0 0 0 0 0 0

UB-2 0 80 0 0 0 0 0 0

UB-3 0 0 80 0 0 0 0 0

UB-4 0 0 0 80 0 0 0 0

(A)

UB-5 0 0 0 0 80 0 0 0 U(

UB-6 0 0 0 0 0 80 . 0 • 0

UA-I 0 0 0 0 0 0 80 0

UA-2 0 0 0 0 0 0 0 80

(C) EPICON 860 14 14 14 14 14 14 14 14

TPO 2 2 2 2 2 2 2 2

(D)

EMK 2 ^• 2 2 2 2 2 2 2

(E) PC-I 2 2 2 2 2 2 2 2

Plating resistance O O O O O O Δ Δ

As shown in Tables 1 to 9, Examples 7 to 22 have the same structure as Comparative Examples 1 to 7 and 9 to 13, except for the presence of an "ethylenically unsaturated group-containing urethane bond, thiourethane bond, or urea bond. Further, in Tables 10 to 13, the polymerization initiator is incorporated in an amount of 0.1% by weight. Since, however, the number of ethylenically unsaturated groups in the compounds of Examples 7 to 22 is large and, thus, as compared with the Comparative Examples, the amount of the polymerization initiator based on one ethylenically unsaturated group is so small that this influence is considered to be negligible.

Accordingly, Examples 7 to 22 will be compared with Comparative Examples 1 to 7 and 9 to 13. For the conversion of the ethylenically unsaturated group, the

Examples are lower than the Comparative Examples, whereas, for the exposure necessary for an increase in viscosity, an increase in viscosity was observed at a lower exposure for the Examples. ^" The reason for this is believed to reside in that the presence of ethylenically unsaturated groups adjacent to each other in the reactive monomer used in the Examples causes an accelerated curing speed and increased viscosity which suppress radical mobility and inhibits the conversion of the ethylenically unsaturated

group .

For the adhesive strength, Examples 7 to 22 had higher adhesive strength than ^• Comparative Examples 1 to 7 and 9 to 13 . Further, for the deposition temperature as measured with a differential scanning calorimeter, due to different structures of the compounds of the Examples and Comparative Examples , the Examples had somewhat higher values . As with the above case, this is also considered attributable to the effect of the adj acent ethylenically unsaturated group in the reactive monomer .

In the X-ray analysis , as a result of a comparison of the compound prepared in Example 7 with the compound prepared in Comparative Example 8 , it was found that, for the compound prepared in Comparative Example 8 , a crystalline region was observed for the cured sample, whereas, for the compound prepared in Example 7 , a crystalline region was not observed, indicating that, for Example 7 , curing proceeds in an amorphous manner .

For the transmittance, Examples 7 to 22 were higher than Comparative Examples 1 to 7 and 9 to 13 . The reason for this is believed to reside in that, as is apparent from the results of X-ray analysis of Example 7 and Comparative Example 8 , the crystallization is suppressed in Examples 7 to 22 .

It is apparent that the refractive index depends upon the structure of the fluorourethane compound used in Examples 1 to 14 and Comparative Example 1 to 7 and further depends upon, the fluorine content. As is apparent from the above Examples, the reactive monomer obtained by reacting the isocyanate compound containing two adjacent ethylenically unsaturated groups in its molecule with, a compound containing a hydroxyl, mercapto, or amino group is excellent in curability, adhesive strength to the substrate, heat resistance, and transparency and carx be used as the reactive monomer useful in the curab3_e composition.

Further, as a result of a comparison of Examples 23 to 28 with Comparat-Lve Examples 14 and 15, it was found that the incorporation of the reactive (meth)acrylate polymer produced from the ethylenically unsaturated group- containing isocyanate compound according to the present invention can increase the sensitivity and pencil hardness and can lower the reflectance. Furthermore, a comparison of Examples 29 to 34 with Comparative Examples 16 and 17 shows that the incorrporation of the reactive (meth) acrylate can improve chemical resistance.