KR101460571B1 - CURING COMPOSITION, COLOR FILTER USING THE SAME, METHOD FOR PRODUCING THE SAME, - Google Patents

Abstract

A curable composition containing a resin, a compound having an ethylenically unsaturated double bond and a photopolymerization initiator, wherein the resin is a resin obtained by polymerizing at least a monomer having a dipole moment of 2.0 or more as a copolymerization component, A manufacturing method thereof, and a solid-state imaging device.

Curable composition, color filter, solid-state image sensor

Description

TECHNICAL FIELD [0001] The present invention relates to a curable composition, a color filter using the curable composition, a method of manufacturing the same, and a solid-

TECHNICAL FIELD The present invention relates to a curable composition suitable for manufacturing a color filter used for a liquid crystal display (LCD), a solid-state image pickup device (CCD, CMOS, etc.), a color filter formed of the curable composition and a method for producing the same.

The color filter is a component essential to a liquid crystal display or a solid-state image pickup device.

The liquid crystal display is a CRT as a television screen, a personal computer screen, and other display devices in place of the CRT because it is dense and has equivalent or better performance than CRTs commonly used as display devices. In recent years, as a trend of development of a liquid crystal display, a screen has been changed to a television having a large screen and a high image quality in a conventional monitor application having a relatively narrow screen area.

Regarding color filters for liquid crystal displays (LCDs), the substrate size is expanding for the production of large television sets. The curable composition for use in manufacturing a color filter using such a large substrate is required to be cured at a low energy in order to improve productivity.

Further, as compared with those for a monitor application, a liquid crystal display for television applications is required to have high image quality, i.e., an improvement in contrast and color purity.

As to the curable composition for use in the production of a color filter, it is required to use a fine particle size colorant (organic pigment or the like) for the purpose of improving the contrast (for example, see JP-A 2006-30541) .

However, when pigments having a small particle size are contained in the curable composition and pigments adsorbability of the dispersant is improved for the purpose of improving dispersion stability, pigment aggregation is promoted by crosslinking of the pigment with the dispersant, and storage stability such as dispersion stability is improved There is a tendency that the developability is deteriorated when a pattern is formed using a curable composition.

In addition, the use of fine pigments tends to increase the addition amount of the dispersing agent for dispersing the pigments in the curable composition, since the surface area increases when fine pigments are used.

Further, when the acid value of the resin to be added during dispersion is improved in order to ensure developability, agglomeration of the pigment tends to be promoted by interaction of hydrogen bonds or the like between the acid groups.

In order to obtain the developability by adding the resin to the curable composition after dispersing the pigment, it is necessary to add a large amount of resin.

In addition, for the purpose of improving the color purity, the curable composition used for manufacturing the color filter is required to have a higher content of the colorant (organic pigment) in the solid content. However, when the colorant is contained at a high concentration in the curable composition, the content of the photopolymerization initiator and the photopolymerizable monomer in the curable composition decreases, so that the curable composition requires curability at low energy, but it is difficult to obtain curability at the exposed portion to be.

On the other hand, for the curable composition for use in the production of the color filter for a solid-state imaging device, curing at low energy is required. In addition, as for the color filter for use in the solid-state image pickup device, the development of the thin film of the colored pattern is promoted, and the pigment concentration in the composition is improved accordingly.

In addition, in the pigment-based color filter, the content of the pigment dispersant in the curable composition increases with the tendency of fine pigments to reduce the color unevenness caused by the fact that the pigment is relatively coarse particles. As in the case of the curable composition for the purpose of producing an LCD, the increase in the content of the pigment dispersant in the curable composition tends to lower the storage stability such as dispersion stability, and the developability in forming the pattern using the curable composition And it tends to be difficult to obtain hardenability, which is a problem.

Further, in order to cope with problems such as color unevenness in the formed coloring pattern, a technique of using an organic solvent-soluble dye instead of a pigment as a coloring agent has been proposed (for example, see JP-A-2-127602) . However, with respect to the dye-based color filter, with the increase of the dye concentration, the problem of deterioration of the storage stability such as polymerization inhibition effect derived from the dye and precipitation of the dye becomes remarkable.

As described above, according to the curable composition for use in the manufacture of color filters, in both cases of liquid crystal displays or solid-state image pickup devices, the content of the photopolymerization initiator and the photopolymerizable monomer as essential components for curing the curable composition And the concentration of the colorant is high. As a result, sufficient curability can not be obtained due to the low sensitivity, the adhesion to the substrate is insufficient, the developing speed is lowered at the unexposed portion, or residues are generated and it becomes very difficult to form a desired pattern And when the coloring agent is a pigment, dispersion stability and developability are deteriorated, and when the coloring agent is a dye, storage stability such as precipitation of the dye is lowered.

In order to cope with these problems, improvement of sensitivity by imparting polymerizability to a resin introduced in order to provide film-forming property, developability, and the like has been studied conventionally (see, for example, JP-A 2000-321763 And 2003-029018). In paragraphs 85 to 87 of "Color Filter Latest Technique Trend" (published by Johokiko Co., Ltd.), paragraphs 129 to 150 of "Process Technique and Chemicals for Latest Color Filter" (published by CMC Publishing Co., Ltd.) Technology is presented. However, even when these resins are used, satisfactory exposure sensitivity can not be obtained yet. In addition, due to insufficient exposure sensitivity, there is a problem that the hardness is insufficient at the deep portion such as the vicinity of the substrate interface and the substrate adhesion becomes poor.

An object of the present invention is to provide a curable composition which is cured very sensitively and has good storage stability.

Another object of the present invention is to provide a colored pattern having a high sensitivity formed by using the curable composition and having almost no developing residue of the uncured portion and having excellent adhesion to the substrate of the cured portion and having a high resolution and a desired cross- To provide a color filter.

It is still another object of the present invention to provide a method of manufacturing the color filter with excellent productivity and a solid-state image pickup device having the color filter manufactured by the manufacturing method.

As a result of intensive research in view of the above environment, the present inventors have found that the above problems can be solved and completed the present invention.

The present invention has been made in view of the above situation and provides a curable composition, a color filter using the same, a method of manufacturing the same, and a solid-state imaging device.

The first aspect of the present invention is

<1> A curable composition containing a resin, a compound having an ethylenically unsaturated double bond, and a photopolymerization initiator, wherein the resin is at least produced by polymerizing a monomer having a dipole moment of 2.0 or more as a copolymer component .

In a second aspect of the present invention,

&Lt; 2 > A color filter having a coloring pattern formed of a first type of curable composition containing a colorant or a sensitizer.

In a third aspect of the present invention,

&Lt; 3 > a step of forming a colored layer made of a curable composition by applying a first type of curable composition containing a colorant on a support; A step of exposing the colored layer through a mask, and a step of forming a colored pattern by developing the colored layer after exposure.

In a fourth aspect of the present invention,

<4> A solid-state image pickup device comprising a color filter manufactured by the method of manufacturing a color filter according to the third aspect.

INDUSTRIAL APPLICABILITY According to the present invention, even when a colorant is contained at a high concentration, even when the storage stability such as dispersion stability is satisfactory, the curable resin composition is cured with high sensitivity by exposure and has high adhesion to the substrate surface in the cured region, Can be formed by using the curable composition of the present invention.

Further, according to the present invention, it is possible to provide a color filter having a coloring pattern excellent in resolution and adhesion to a support formed using the curable composition of the present invention, and a manufacturing method of forming the color filter with high productivity.

Hereinafter, the curable composition of the present invention comprises a resin, a compound having an ethylenically unsaturated double bond, and a photopolymerization initiator, wherein the resin is produced by polymerizing at least a monomer having a dipole moment of 2.0 or more as a copolymer component.

It is also preferable that the resin has an ethylenically unsaturated double bond in the side chain.

Further, the curable compound of the present invention preferably further contains a coloring agent.

Hereinafter, each component contained in the curable composition of the present invention will be described in sequence.

&Lt; Resin (A) >

The resin of the present invention is a resin produced by polymerizing at least a monomer having a dipole moment of 2.0 or more as a copolymerization component. The resin of the present invention preferably has an ethylenically unsaturated double bond in the side chain.

The resin is preferably a polymer compound having a group represented by the following general formulas (1) to (3) as the ethylenically unsaturated double bond.

In the general formula, each of R ¹ to R ¹¹ independently represents a hydrogen atom or a monovalent organic group. X and Y each independently represent an oxygen atom, a sulfur atom or -NR ¹² , and Z represents an oxygen atom, a sulfur atom, -NR ¹² or a phenylene group. R ¹² represents a hydrogen atom or a monovalent organic group.

In the general formula (1), R ¹ to R ³ each independently represent a monovalent organic group. As R ¹ , a hydrogen atom or an alkyl, alkoxyl or alkoxycarbonyl group which may have a substituent can be exemplified. Particularly, a hydrogen atom, a methyl group, a methyl alkoxy group and a methyl ester group are preferable. Also, R &lt; ² & R ³ each independently represents a hydrogen atom, a halogen atom, an amino group, a dialkylamino group, a carboxyl group, an alkoxycarbonyl group, a sulfo group, a nitro group, a cyano group, an alkyl group which may have a substituent, Include an aryloxy group which may have a substituent, an alkylamino group which may have a substituent, an arylamino group which may have a substituent, an alkylsulfonyl group which may have a substituent, and an arylsulfonyl group which may have a substituent can do. Particularly, a hydrogen atom, a carboxyl group, an alkoxycarbonyl group, an alkyl group which may have a substituent, and an aryl group which may have a substituent are preferable.

Here, examples of the substituent to be introduced include a methoxycarbonyl group, an ethoxycarbonyl group, an isopropoxycarbonyl group, a methyl group, an ethyl group, and a phenyl group.

X represents an oxygen atom, a sulfur atom or -NR ¹² . Here, as R ¹² , an alkyl group which may have a substituent can be exemplified.

In the general formula (1), as the alkyl group, straight chain or cyclic alkyl groups having 1 to 30 carbon atoms can be exemplified. Alkyl groups having 1 to 20 carbon atoms are preferred, and alkyl groups having 1 to 10 carbon atoms are particularly preferred.

In the general formula (1), the aryl group may have 6 to 30 carbon atoms. It is particularly preferable that the carbon atom is 6 to 20 carbon atoms and the carbon atom is 6 to 10 carbon atoms.

In the general formula (2), R ⁴ to R ⁸ each independently represent a monovalent organic group. Examples of R ⁴ to R ⁸ include a hydrogen atom, a halogen atom, an amino group, a dialkylamino group, a carboxyl group, an alkoxycarbonyl group, a sulfo group, a nitro group, a cyano group, an alkyl group which may have a substituent, , An alkoxy group which may have a substituent, an aryloxy group which may have a substituent, an alkylamino group which may have a substituent, an arylamino group which may have a substituent, an alkylsulfonyl group which may have a substituent, Can be enumerated. Particularly, a hydrogen atom, a carboxyl group, an alkoxycarbonyl group, an alkyl group which may have a substituent, and an aryl group which may have a substituent are preferable. As the substituent to be introduced, those enumerated in the general formula (1) can be listed. Y represents an oxygen atom, a sulfur atom or -NR ¹² . As R ¹² , those listed in the general formula (1) can be listed. In the general formula (2), the alkyl groups and the aryl groups listed in the general formula (1) can be exemplified, and preferred examples are also applicable.

In the general formula (3), R ⁹ to R ¹¹ each independently represent a monovalent organic group. Specific examples of the organic group include a hydrogen atom, a halogen atom, an amino group, a dialkylamino group, a carboxyl group, an alkoxycarbonyl group, a sulfo group, a nitro group, a cyano group, an alkyl group which may have a substituent, An alkoxy group which may have a substituent, an aryloxy group which may have a substituent, an alkylamino group which may have a substituent, an arylamino group which may have a substituent, an alkylsulfonyl group which may have a substituent, Sulfonyl group, and the like. Particularly, a hydrogen atom, a carboxyl group, an alkoxycarbonyl group, an alkyl group which may have a substituent, and an aryl group which may have a substituent are preferable.

The introduced substituents can be enumerated in the same manner as those listed in the general formula (1).

Z represents an oxygen atom, a sulfur atom, -NR ¹² or a phenylene group. As R ¹² , those listed in the general formula (1) can be listed.

In the general formula (3), as the alkyl group and the aryl group, those listed in the general formula (1) can be listed and the same preferable examples can be applied.

Of the resins in the present invention, the polymer compound having a group represented by the general formula (1) can be produced by at least one of the following synthesis methods 1) and 2).

Synthesis method 1)

A method of synthesizing a polymer compound by copolymerizing at least one kind of a radical polymerizable compound represented by the following general formula (12) with a specific monomer described later and removing protons by using a base to thereby obtain a desired polymer compound .

In the general formula (12), R ¹ to R ³ And X are the same as those in the general formula (1), and the same preferable examples can be applied.

In the general formula (12), Z represents an anionic leaving group. Q represents an oxygen atom, -NH- or -NR ¹⁴ - (wherein R ¹⁴ represents an alkyl group which may have a substituent). As R ¹³ , a hydrogen atom, an alkyl group which may have a substituent, and the like can be exemplified. Particularly, a hydrogen atom, a methyl group, a methyl alkoxy group and a methyl ester group are preferable. A represents a divalent organic linking group. The divalent organic linking group A is not particularly limited and includes an alkylene group having 1 to 30 carbon atoms in total (e.g., methylene, ethylene, cyclohexylene) and an arylene group having 6 to 30 carbon atoms in total , Triphenylene, naphthalylene). Particularly preferred are alkylene having 1 to 10 carbon atoms and arylene having 6 to 15 carbon atoms in total.

In the general formula (13), R ¹ to R ³ are the same as those in the general formula (1), and the same preferred examples can be applied.

Synthesis method 2)

(A polymer compound containing a main chain) is synthesized by copolymerizing one or more kinds of radical polymerizing compounds having a functional group with a specific monomer described below to obtain a branched polymer compound having a side chain functional group of the above- To obtain a desired polymer compound.

Examples of the radically polymerizable compound represented by the general formula (12) include, but are not limited to, the following compounds.

The radically polymerizable compound represented by the general formula (12) can be easily obtained as a commercial product or by a synthesis method shown in Synthesis Examples described later.

One or more of these radical polymerizing compounds and specific monomers described below and, if necessary, other radical polymerizing compounds are polymerized by a conventional radical polymerization method to synthesize a polymer compound, cooling the desired amount of the base with a polymer solution Alternatively, the group represented by the general formula (1) may be introduced by dropwise addition under heating conditions, and if necessary, neutralization with an acid. For the production of the polymer compound, conventionally known suspension polymerization method or solution polymerization method and the like can be used.

As the base, either an inorganic compound or an organic compound can be used. Preferable examples of the inorganic base include sodium hydroxide, potassium hydroxide, sodium carbonate, sodium hydrogen chloride, potassium carbonate, potassium hydrogen carbonate, and the like. Examples of the organic base include metal alkoxides such as sodium methoxide, sodium ethoxide and potassium t-butoxide, organic amine compounds such as triethylamine, pyridine and diisopropylethylamine, and the like.

Examples of the functional groups of the radical polymerizing compound having a functional group used in the synthesis of the stem polymer compound in the synthesis method 2) include a hydroxyl group, a carboxyl group, a halogenated carboxylate group, a carboxylic anhydride group, an amino group, a halogenated alkyl group, An epoxy group, and the like. Examples of the radically polymerizable compound having such a functional group include 2-hydroxyethyl acrylate, 2-hydroxylethyl methacrylate, 4-hydroxybutyl acrylate, 4-hydroxybutyl methacrylate, acrylic acid, Methacrylic acid anhydride, N, N-dimethyl-2-aminoethyl methacrylate, 2-chloroethyl methacrylate, 2-ethyl isocyanate methacrylate, glycidyl acrylate, Glycidyl methacrylate, and the like.

A stem polymer compound is synthesized by polymerizing at least one of these radical polymerizing compounds with a specific monomer described below and optionally copolymerizing with another radical polymerizing compound to obtain a compound having a group represented by the general formula (13) To obtain the desired polymer compound.

Here, examples of the compound having a group represented by the general formula (13) include compounds listed as examples of the radically polymerizable compound having a functional group.

In the present invention, the polymer compound having a group represented by the general formula (2) can be produced by at least one of the following synthesis methods 3) and 4).

Synthesis method 3)

By polymerizing at least one unsaturated group represented by the general formula (2) and at least one radically polymerizable compound having an ethylenically unsaturated group having a higher degree of addition polymerization than the unsaturated group, a specific monomer described below and, if necessary, another radically polymerizable compound &Lt; / RTI &gt; This method uses a compound having a plurality of ethylenically unsaturated groups different in addition polymerization from one molecule such as allyl methacrylate.

Synthesis method 4)

A polymer compound is synthesized by copolymerizing at least one kind of radically polymerizable compound having a functional group with a specific monomer described below and reacting a compound having a side chain functional group with a compound represented by the following general formula (14) How to introduce a displayed group.

In the general formula (14), R ⁴ to R ⁸ are the same as those in the general formula (2), and the same preferable examples can be applied.

Examples of the radically polymerizable compound having an unsaturated group represented by the general formula (2) and an ethylenically unsaturated group having a higher degree of addition polymerization than the unsaturated group include allyl acrylate, allyl methacrylate, 2-allyloxyethyl acrylate, 2- Allyl methacrylate, diallyl acrylate, diallyl methacrylate, N-allylacrylamide, N-allyl methacrylamide, N-allyl methacrylate, And the like can be enumerated as an example.

Further, examples of the polymer compound obtained by polymerizing at least one kind of radically polymerizable compound having a functional group include the examples shown in the above synthesis method 2).

Examples of the compound having the structure represented by the general formula (14) include allyl alcohol, allylamine, diallylamine, 2-allyloxyethyl alcohol, 2-chloro-1-butene and allyl isocyanate.

The polymer compound having a group represented by the general formula (3) according to the present invention can be produced by at least one of the synthesis methods 5) and 6) shown below.

Synthesis method 5)

, At least one unsaturated group represented by the general formula (3), at least one radically polymerizable compound having an ethylenically unsaturated group having a higher degree of addition polymerization than the unsaturated group, and a specific monomer described below, To obtain a polymer compound.

Synthesis method 6)

A method of synthesizing a polymer compound by copolymerizing at least one kind of radical polymerizable compound having a functional group with a specific monomer to be described later and introducing the compound by reacting a compound having a side chain functional group and a compound represented by the general formula (15).

As the radically polymerizable compound having an unsaturated group represented by the general formula (3) and an ethylenically unsaturated group having a higher degree of addition polymerization than the unsaturated group, vinyl acrylate, vinyl methacrylate, 2-phenylvinyl acrylate, 2- Vinyl methacrylate, 1-propenyl acrylate, 1-propenyl methacrylate, vinyl acrylamide, vinyl methacrylamide, and the like.

As the polymer compound obtained by copolymerization, those listed as examples in Synthesis Process 2) above can be obtained.

In the general formula (15), R ⁹ to R ¹¹ are the same as those in the general formula (3), and the same preferred examples can be applied.

Examples of the compound having a structure represented by the general formula (15) include 2-hydroxyethyl monovinyl ether, 4-hydroxybutyl monovinyl ether, diethylene glycol monovinyl ether, 4-chloromethyl styrene and the like .

A synthesis method using at least one of the following general formulas (4) and (5) instead of the general formula (12) used in the synthesis method 1) in the above synthesis method 1) is also preferable.

In the general formula (4) or (5), R ⁵ _, R ⁶ _, R ⁷ represents hydrogen or a monovalent organic group, A ² represents an oxygen atom, a sulfur atom or -NR ⁸ -, G ¹ represents an organic linking group, R ⁸ represents hydrogen or a monovalent organic group, 10 &lt; / RTI &gt; R ¹ to R ³ are the same as those in Formula (12), A ¹ is the same as X in Formula (1), and X ¹ is the same as Z in Formula (12).

R ⁹ to R ¹³ represent hydrogen or a monovalent organic group, and at least one of them is a group represented by the following general formula (6). R ¹⁴ ~ R ¹⁶ is hydrogen or 1 represents an organic group.

In the general formula (4) or (5), the monovalent organic group is the same as the monovalent organic group in the general formula (1), and the same preferred examples can be applied.

In the general formula (6), G ² represents an organic linking group, and m represents an integer of 1 to 10. R ¹ to R ³ _, A ¹ _{, and} X ¹ are the same as those in Formula (4).

Specific preferred examples of the compound represented by the general formula (4) or (5) include the following compounds (i-1 to i-60).

In the synthesis of a compound having a group represented by the general formula (1) (hereinafter also referred to as a "polyvinyl polymer compound") obtained by using the general formula (4) or (5), other general radical polymerizable compounds, The copolymerization of a compound having a double bond by the elimination reaction as described above is also an embodiment of the present invention.

In the above synthesis methods 1) to 6), other general radically polymerizable compounds may be copolymerized as required, as described above. Examples of the general radically polymerizable compound to be copolymerized in the present invention include acrylate, methacrylate, N, N-2 substituted acrylamide, N, N-2 substituted methacrylamide, styrene, acrylonitrile, methacryl Ronitril, and the like.

Specific examples include alkyl acrylates (the number of carbon atoms of the alkyl group is preferably from 1 to 20) (specifically, for example, methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, amyl acrylate, ethylhexyl Acrylate, octyl acrylate, t-octyl acrylate, chloroethyl acrylate, 2,2-dimethylhydroxylpropyl acrylate, 5-hydroxypentyl acrylate, trimethylolpropane monoacrylate, pentaerythritol monoacrylate, Acrylate such as glycidyl acrylate, benzyl acrylate, methoxybenzyl acrylate, furfuryl acrylate, tetrahydrofurfuryl acrylate and the like), aryl acrylate (for example, phenyl acrylate)

Alkyl methacrylate (the number of carbon atoms of the alkyl group is preferably from 1 to 20) (specifically, for example, methacrylate, ethyl methacrylate, propyl methacrylate, isopropyl methacrylate, Hexyl methacrylate, cyclohexyl methacrylate, benzyl methacrylate, chlorobenzyl methacrylate, octyl methacrylate, 4-hydroxybutyl methacrylate, 5-hydroxypentyl methacrylate, 2,2 -Dimethyl-3-hydroxypropyl methacrylate, trimethylolpropane monomethacrylate, pentaerythritol monomethacrylate, glycidyl methacrylate, furfuryl methacrylate, tetrahydrofurfuryl methacrylate, etc.) (Methacrylic acid esters) such as aryl methacrylate (e.g., phenyl methacrylate, cresyl methacrylate, naphthyl methacrylate, etc.) Methacrylate acids,

Styrene and alkylstyrene such as methylstyrene, dimethylstyrene, trimethylstyrene, ethylstyrene, diethylstyrene, isopropylstyrene, butylstyrene, hexylstyrene, cyclohexylstyrene, decylstyrene, benzylstyrene, chloromethylstyrene, trifluoromethylstyrene , Methoxystyrene, methoxystyrene, 4-methoxy-3-methylstyrene and dimethoxystyrene), halogen styrene (chlorostyrene, dichlorostyrene, trichlorostyrene, tetra But are not limited to, chlorostyrene, pentachlorostyrene, bromostyrene, dibromostyrene, iodostyrene, fluorostyrene, trifluorostyrene, 2-bromo-4-trifluoromethylstyrene and 4-fluoro- Styrene), acrylonitrile, methacrylonitrile, and the like.

Examples of the radically polymerizable compound containing a carboxylic acid include acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, p-carboxystyrene and the like.

Examples of the solvent used in the synthesis of the polyvinyl polymer compound include ethylene dichloride, cyclohexanone, methyl ethyl ketone, acetone, methanol, ethanol, propanol, butanol, ethylene glycol monomethyl ether, ethylene glycol Propyl acetate, N, N-dimethylformamide, N, N-dimethylacetoamide, dimethylsulfoxide, N, N-dimethylacetamide, Toluene, ethyl acetate, methyl lactate, ethyl lactate, 1-methyl-2-pyrrolidone, and the like.

These solvents may be used alone or as a mixture of two or more thereof.

As described above, the resin of the present invention as a copolymer is a resin prepared by polymerizing at least a monomer having a dipole moment of 2.0 or more (hereinafter, also referred to as "specific monomer") as a copolymerization component. Herein, "specific monomer" is a monomer other than the monomer having an alkali-soluble group described later.

As the above-mentioned dipole moment, the numerical value obtained by calculating by the following calculation method was used.

Namely, after the structure of the specific monomer obtained by the calculation method AM1 is optimized by using CAChe 6.1 (manufactured by Fujitsu Corp.), the dipole moment is calculated by the optimum structure.

In the present invention, the above structure is not limited as long as the dipole moment calculated by the above calculation method is 2.0 or more, depending on the specific monomer as the copolymerization component of the resin. From the viewpoints of sensitivity and storage stability, the value of the dipole moment is preferably 2.5 or more, more preferably 2.5 or more and 15 or less, still more preferably 3.0 or more and 10 or less, particularly preferably 3.5 or more and 9.0 or less, Most preferably 8.0 or less.

The dipole moment of the specific monomer is within the range of 2.5 to 15, and is preferable in view of ease of resin synthesis, sensitivity of the curable composition including the resin, developability and storage stability.

In the above examples, it is particularly preferable that the specific monomer has at least one group selected from the group consisting of an ether group, a cyano group, a phosphate ester group, a lactone group, a urethane group, a carbonate ester group and an acetal group.

The ether group contained in the specific monomer is preferably a straight chain, branched or cyclic ether group having 2 to 30 carbon atoms, and particularly preferably a straight chain, branched or cyclic ether group having 2 to 15 carbon atoms. Examples of ether groups include 2-methoxyethyl, 2-ethoxyethyl, MeOCH ₂ CH ₂ OCH ₂ CH ₂ -, MeO (CH ₂ CH ₂ O) ₂ CH ₂ CH ₂ -, oxetan- Tetrahydrofuran-2-yl, tetrahydro-2H-pyran-2-yl, octahydro-1H-isochromen-3-yl, Work, and so on.

The lactone group contained in the specific monomer is preferably a lactone group having 3 to 30 carbon atoms, and more preferably a lactone group having 5 to 20 carbon atoms. As examples of the lock tone group, the following structures can be listed. In the following structures, R represents a hydrogen atom, an alkyl group, a cycloalkyl group, or an aryl group, wherein each of the alkyl group, cycloalkyl group, and aryl group independently has 1 to 20 carbon atoms.

The urethane group contained in the specific monomer is preferably a straight chain or cyclic urethane group having 1 to 30 carbon atoms, and is preferably a straight chain or cyclic urethane group having 1 to 20 carbon atoms.

Examples of urethane groups include, but are not limited to, the following structures. In the following structures, R represents a hydrogen atom, an alkyl group, a cycloalkyl group, or an aryl group, wherein each of the alkyl group, cycloalkyl group, and aryl group independently has 1 to 20 carbon atoms.

The carbonate ester group contained in the specific monomer is preferably a straight chain or cyclic carbonate ester group having 1 to 30 carbon atoms, and is preferably a straight chain or cyclic carbonate ester group having 1 to 20 carbon atoms.

Examples of the carbonate ester group include, but are not limited to, the following structures.

The acetal group contained in the specific monomer is preferably a straight chain or cyclic acetal group having 1 to 30 carbon atoms, and is preferably a straight chain or cyclic acetal group having 1 to 20 carbon atoms. Examples of the acetal group include, but are not limited to, the following structures. In the following structures, R represents a hydrogen atom, an alkyl group, a cycloalkyl group, or an aryl group, wherein each of the alkyl group, cycloalkyl group, and aryl group independently has 1 to 20 carbon atoms.

The phosphate ester group contained in the specific monomer is preferably a straight chain or cyclic phosphate ester group having 1 to 30 carbon atoms and more preferably a straight chain or cyclic phosphate ester group having 1 to 20 carbon atoms. Examples of phosphate ester groups include, but are not limited to, the following structures.

As specific examples of the monomer, the following compounds can be preferably used, but the present invention is not limited thereto.

In the present invention, the resin is a resin prepared by polymerizing the above-mentioned specific monomer as a copolymer component, and a component having a partial structure that can be or becomes an ethylenically unsaturated double bond in the side chain of the resin (hereinafter referred to as " Copolymerizable component ") and a resin prepared by polymerizing the specific monomer.

M-1, M-8, i-1, i-7, and i-7 as a combination of the copolymerizable components providing the resin in the present invention, that is, a combination of "specific monomer" and " M-11A, M-12A, M-13A, M-14A, M-15A, M-9MA, M-11MA, The combination of any one of M-12MA, M-13MA, M-14MA, M-15MA and M-16MA is preferable and any combination of M-1, i-1, i-10, i- And combinations of any of M-11A, M-13A, M-14A, M-11MA, M-13MA and M-14MA are more preferable, and combinations of Exemplified Compound i-1 and Exemplified Compound M- a combination of Exemplified Compound M-1 and Exemplified Compound M-11MA, Exemplary Compound M-1 and Exemplified Compound M-13MA, Combination of Exemplified Compound M-1 and Exemplified Compound M-14MA, 11MA, and a combination of Exemplified Compound M-1 and Exemplified Compound M-13MA are particularly preferable.

The above combination is preferable from the viewpoints of ease of resin synthesis, sensitivity and developability of the curable composition containing the resin, and storage stability.

The constitution of the resin in the present invention may be a block copolymer, a random copolymer, a graft copolymer or the like as a copolymer. Particularly, a block copolymer is preferable from the viewpoint of ease of resin synthesis.

In the present invention, the content of the copolymer component providing the double bond of the resin is preferably from 0.1 mol% to 95 mol%, more preferably from 1 mol% to 85 mol%, still more preferably from 5 mol% to 75 mol% Is particularly preferable.

Here, the above "content of the copolymerizable component which provides the double bond of the resin" specifically means the following.

That is, in the synthesis method 1), "the content of the radical polymerizable compound represented by the general formula (12) in the copolymer" means that in the synthesis methods 2), 4) and 6) As a copolymerization component after the copolymerization of the compound and the reaction of the functional group with any one of the general formulas (13), (14) and (15) ". In the synthesis methods 3) or 5) Quot; means a content in the copolymer of the unsaturated group represented by the formula (2) or (3) and the radically polymerizable compound having an ethylenically unsaturated group having a higher degree of addition polymerization than the unsaturated group.

Since the content of the copolymerizable component providing the double bond of the resin is within the above range, the sensitivity is improved and the adhesion to the substrate is favorable.

In the resin of the present invention, the content of the specific monomer as the copolymerization component is preferably from 1 mol% to 90 mol%, more preferably from 3 mol% to 70 mol%, and from 5 mol% to 50 mol% Particularly preferred.

Since the content of the specific monomer is within the above range, the sensitivity is improved and the adhesion to the substrate is favorable.

In the resin, the molar ratio of the "content of the specific monomer" and "content of the copolymerizable component providing the double bond of the resin" in the resin is preferably 100: 1 to 1: 100, more preferably 50: More preferably from 10: 1 to 1:10, and particularly preferably from 10: 1 to 1:10.

The composition ratio of the specific monomer and the copolymerizable component that provides the double bond of the resin is within the above range, so that the sensitivity is improved and the adhesion to the substrate is favorable.

In the present invention, the resin may be a resin produced by polymerization with a monomer containing an alkali-soluble group as a copolymerization component. The term "alkali-soluble group" means a functional group which is decomposed by a developing solution used to form a pattern and has improved solubility in a developing solution (alkaline aqueous solution). The alkali-soluble group is preferably a functional group having a pKa of 11 or less in water at 25 ° C. As the functional group, for example, a carboxyl group, a sulfo group, a sulfonamide group, a phosphoric acid group, a phenol type hydroxyl group and the like can be exemplified. Particularly, a carboxyl group is most preferable.

The content of the alkali-soluble group-containing monomer as a copolymerizable component is preferably 1 mol% to 90 mol%, more preferably 3 mol% to 70 mol%, and particularly preferably 5 mol% to 50 mol% .

Since the content of the alkali-soluble group-containing monomer as the copolymer component is within the above range, the sensitivity is improved and the adhesion to the substrate is favorable.

The weight average molecular weight (in terms of polystyrene in the GPC measurement method) is preferably 500 to 100,000, more preferably 1,000 to 50,000, and particularly preferably 1,000 to 30,000. The molecular weight distribution (ratio of weight average molecular weight to number average molecular weight) is preferably 3.0 or less, and most preferably 2.0 or less.

Specific examples of the resin in the present invention are shown below together with their weight average molecular weight, but the present invention is not limited thereto.

According to the resin of the present invention, the total content (mol%) of the specific monomer and the copolymerizable component which provides the double bond of the resin is preferably 2 mol% to 98 mol%, more preferably 5 mol% to 90 mol% , And particularly preferably from 10 mol% to 80 mol%.

Since the total content is within the above range, the sensitivity is improved and the adhesion to the substrate is favorable.

The content of the resin is preferably from 0.1% by mass to 75% by mass, more preferably from 1% by mass to 50% by mass, and particularly preferably from 2% by mass to 40% by mass, based on the total solid content of the curable composition of the present invention . According to this range, good sensitivity and pattern formability can be obtained.

<(B) Photopolymerization initiator>

The curable composition of the present invention contains a photopolymerization initiator (B) for the purpose of improving sensitivity and pattern formation.

The photopolymerization initiator in the present invention is a compound which is decomposed by light and initiates and promotes polymerization of the polymerizable component in the present invention, and preferably has absorption in a wavelength region of 300 to 500 nm. The photopolymerization initiator may be used alone or in combination of two or more.

Examples of the photopolymerization initiator include organic halogenated compounds, oxydiazole compounds, carbonyl compounds, ketal compounds, benzoin compounds, acridine compounds, organic peroxide compounds, azo compounds, coumarin compounds, azide compounds, metallocene compounds , Hexaarylbimidazole compounds, organic boric acid compounds, disulfonic acid compounds, oxime ester compounds, onium salt compounds, acylphosphine (oxide) compounds, alkylamino compounds and the like.

Hereinafter, each compound will be described in detail.

Specific examples of the organic halogenated compound include Wakabayashi et al. Bull Chem. Soc Japan 42, 2924 (1969), U.S. Patent No. 3,905,815, JP-B-46-4605, JP-B-48-36281, JP-A-55-32070, -239736, 61-169835, 61-169837, 62-58241, 62-212401, 63-70243, 63-298339, MP Hutt, Journal of Heterocyclic Chemistry "1 (No 3), (1970)", etc. In particular, oxazole compounds and s-triazine compounds substituted with a trihalomethyl group can be exemplified.

The s-triazine compound is more preferably a s-triazine derivative in which at least one mono-, di-, or trihalogen-substituted methyl group is bonded to a s-triazine ring, more specifically, Tris (dichloromethyl) -s-triazine, 2,4,6-tris (dichloromethyl) -s-triazine, 2,4,6-tris (trichloromethyl) (Trichloromethyl) -s-triazine, 2-n-propyl-4,6-bis (trichloromethyl) (trichloromethyl) -s-triazine, 2- (p-methoxyphenyl) -4,6-bis (trichloromethyl) Phenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (3,4-epoxyphenyl) (Trichloromethyl) -s-triazine and 2- [1- (p-methoxyphenyl) -2,4-butadienyl] -4,6-bis Methyl) -s-triazine, 2- (Trichloromethyl) -s-triazine, 2- (p-methoxystyryl) -4,6-bis (trichloromethyl) Bis (trichloromethyl) -s-triazine, 2- (p-tolyl) -4,6-bis (Trichloromethyl) -s-triazine, 2-phenylthio-4,6-bis (trichloromethyl) -s-triazine, 2-benzylthio- -S-triazine, 2,4,6-tris (dibromomethyl) -s-triazine, 2,4,6-tris (tribromomethyl) -s- (Tribromomethyl) -s-triazine, 2-methoxy-4,6-bis (tribromomethyl) -s-triazine and the like can be exemplified. have.

As the oxadiazole compound, there may be mentioned 2-trichloromethyl-5-styryl-1,3,4-oxodiazole, 2-trichloromethyl-5- (cyanostyryl) -1,3,4- Sol, 2-trichloromethyl-5- (naphtho-1-yl) -1,3,4-oxodiazole, 2-trichloromethyl- 4-oxodiazole, and the like.

Examples of the carbonyl compound include benzophenone, Michler's ketone, 2-methylbenzophenone, 3-methylbenzophenone, 4-methylbenzophenone, 2-chlorobenzophenone, 4-bromobenzophenone, Hydroxyphenyl acetophenone, 1-hydroxycyclohexyl phenyl ketone,? -Hydroxy-2-methylphenyl propanone, 1- (P-dodecylphenyl) ketone, 1-hydroxy-1- (p-dodecylphenyl) Acetophenone derivatives such as polyno-1-propanone, 1,1,1-trichloromethyl- (p-butylphenyl) ketone and 2-benzyl-2- 2-isopropylthioxanthone, 2-chlorothioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, and 2,4- Thioxanthone derivatives such as diisopropylthioxanthone, p-dimethyl Mino ethyl benzoate, p- can be listed diethyl aminoethyl and the like, such as benzoin benzoin benzoate benzoate derivative.

As the ketal compound, benzyl methyl ketal, benzyl- beta -methoxyethyl ethyl acetal and the like can be exemplified.

Examples of the benzoin compound include m benzoin isopropyl ether, benzoin isobutyl ether, benzoin methyl ether, methyl o-benzoyl benzoate, and the like.

As the acridine compound, 9-phenylacridine, 1,7-bis (9-acridinyl) heptane and the like can be exemplified.

Examples of the organic peroxide compound include trimethylcyclohexanone peroxide, acetylacetone peroxide, 1,1-bis (tert-butylperoxy) -3,3,5-trimethylcyclohexane, 1,1-bis Butylperoxy) cyclohexane, 2,2-bis (tert-butylperoxy) butane, tert-butyl hydroperoxide, cumene hydroperoxide, diisopropylbenzene hydroperoxide, 2,5- Dihydroperoxide, 1,1,3,3-tetramethylbutyl hydroperoxide, tert-butylcumyl peroxide, dicumyl peroxide, 2,5-dimethyl-2,5-di (tert- butyl Peroxy) hexane, 2,5-oxanooyl peroxide, succinic peroxide, benzoyl peroxide, 2,4-dichlorobenzoyl peroxide, diisopropyl peroxydicarbonate, di-2-ethylhexyl peroxydicarbo- Di-2-ethoxyethyl peroxydicarbonate, dimethoxyisopropyl peroxycar Butyl peroxyacetate, tert-butyl peroxypivalate, tert-butyl peroxyneodecanoate, tert-butyl peroxypivalate, di (3-methyl-3-methoxybutyl) peroxydicarbonate, 3,3 ', 4,4'-tetra- (t-butylperoxycarbonyl) benzophenone, 3,3', 4,4'-tetramethylbenzoyl peroxide, (T-butylperoxycarbonyl) benzophenone, 3,3 ', 4,4'-tetra- (p-isopropylcumylperoxycarbonyl) benzophenone, carbonyldi Oxy diphthalate dihydrogen), carbonyl di- (t-hexyl peroxy diphthalate dihydrogen), and the like.

As the azo compound, for example, azo compounds described in JP-A-8-108621 can be exemplified.

Examples of the coumarin compound include 3-methyl-5-amino- ((s-triazin-2-yl) amino) 2-yl) amino) -3-phenylcoumarin, 3-butyl-5-dimethylamino- ((s-triazin-2-yl) amino) -3-phenyl coumarin and the like.

Examples of the diazide compound include organic azide compounds described in U.S. Patent Nos. 2,848,328, 2,852,379 and 2,940,853, 2,6-bis (4-azidobenzylidene) -4-ethylcyclohexanone (BAC- And so on.

Examples of the metallocene compound include di-cyclopentadienyl-Ti-bisphenyl, dicyclopentadienyl-Ti-bis-2,6-difluorophenyl-1-yl, di-cyclopentadienyl-Ti Di-cyclopentadienyl-Ti-bis-2,4,6-trifluorophenyl-1-yl, di-cyclopentadienyl- Bis-2,3,5,6-tetrafluorophenyl-1-yl, di-cyclopentadienyl-Ti-bis-2,3,4,5,6-pentafluorophenyl- Di-methylcyclopentadienyl-Ti-bis-2,6-difluorophenyl-1-yl, di-methylcyclopentadienyl-Ti-bis-2,4,6-trifluorophenyl- Di-methylcyclopentadienyl-Ti-bis-2,3,5,6-tetrafluorophenyl-1-yl, di-methylcyclopentadienyl-Ti-bis- 5,6-pentafluorophenyl-1-yl, iron-arene complexes described in JP-A-1-304453 and 1-152109, etc., JP-A-59-152396, JP-A-61-151197 No. 63-41484, No. 2-249, No. 2-4705, and It can be exemplified by various titanocene compounds described in JP-5-83588 call.

Examples of the hexaaryl biimidazole compound include various compounds described in JP-A-6-29285, U.S. Patent Nos. 3,479,185, 4,311,783 and 4,622,286, specifically 2,2'-bis (o -Chlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis (o-bromophenyl)) 4,4', 5,5'-tetraphenylbiimidazole , 2,2'-bis (o-chlorophenyl) -4,4 ', 5,5'-tetraphenylbimidazole, 2,2'-bis Bis (o, o'-dichlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis (O-nitrophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis (o-methylphenyl) -4,4', 5,5'- Tetraphenylbiimidazole, 2,2'-bis (o-trifluorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, and the like.

Examples of the organic borate compound include compounds described in JP-A Nos. 62-143044, 62-150242, 9-188685, 9-188686, 9-188710, 2000-131837 and 2002-107916 Organoborates described in Japanese Patent No. 2,764,769, Japanese Patent Application Laid-Open No. 2002-116539 and Kunz, Martin, "Rad Tech '98. Proceeding April 19-22, 1998, Chicago", Japanese Patent Application Laid- Organosulfonium borate complex or organic oxosulfonium borate complex described in JP-A No. 6-175564 and JP-A No. 6-175561, Organic iodonium complex disclosed in JP-A Nos. 6-175554 and 6-175553, Borate complexes, organic phosphonium borate complexes disclosed in Japanese Patent Application Laid-Open No. 9-188710, Japanese Patent Application Laid-Open Nos. 6-348011, 7-128785, 7-140589, 7-306527, Organo boron transition metal coordination complexes such as those described in JP-A-292014 can be cited as specific examples.

Examples of the disulfonic acid compound include compounds described in JP-A-61-166544 and JP-A-2002-328465.

(1979) 1653-1660), J.C.S. Perkin II (1979) 156-162, Journal of Photopolymer Science and Technology (1995) 202-232, and Compounds described in Japanese Patent Application Laid-Open No. 2000-66385, Japanese Patent Application Laid-Open No. 2000-80068, and Japanese Patent Application Laid-Open No. 2004-534797.

As the onium salt compounds, there may be mentioned, for example, those described in SI Schlesinger, Photogr. Sci. Eng., 18, 387 (1974) and T. Bal et al, Polymer, 21, 423 (1980), U.S. Patent No. 4,069,055 and Japanese Patent Application Laid- Ammonium salts, phosphonium salts disclosed in U.S. Patent Nos. 4,069,055 and 4,069,056, European Patent No. 104,143, U.S. Patent Nos. 339,049 and 410,201, and Japanese Patent Laid-Open Nos. 2-150848 and 2-296514 And iodonium described therein.

The iodonium salt preferably used in the present invention is a diaryliodonium salt. From the viewpoint of stability, it is preferable that two or more groups are substituted with an electron-donating group such as an alkyl group, an alkoxy group and an aryloxy group.

Examples of sulfonium salts that are preferably used in the present invention include those described in European Patent Nos. 370,693, 390,214, 233,567, 297,443 and 297,442, US Patent Nos. 4,933,377, 161,811, 410,201, 339,049 , 4,760,013, 4,734,444 and 2,833,827, and the sulfonium salts disclosed in German Patent Nos. 2,904,626, 3,604,580 and 3,604,581. It is preferably substituted with an electron-withdrawing group in terms of stability. It is preferable that the Hammett value of the electron attractive group exceeds 0. Preferred examples of the electron-withdrawing group include a halogen atom and a carboxylic acid.

As other preferable sulfonium salts, sulfonium salts having one substituent group of a triarylsulfonium salt having a coumarin and anthraquinone structure and having absorption at 300 nm or more can be enumerated. Other preferred sulfonium salts include sulfonium salts in which the triarylsulfonium salt has an allyloxy group or an arylthio group as a substituent and has absorption at 300 nm or more.

As the onium salt compounds, there may be mentioned, for example, those described in J. V. Crivello et al, Macromolecules, 10 (6), 1307 (1977, J.V. Crivello et al., J. Polymer Sci., Polymer Chem. 1979) and onium salts such as arsonium salts described in C.S. Wen et al, Tech, Proc. Conf., Curing ASIA, p478 Tokyo, Oct (1988).

As the acylphosphine (oxide) compound, there may be mentioned Chiba Specialty Chemicals Corp. Products IRUGACURE 819, DAROCURE 4265, DAROCURE TPO are listed.

Examples of the alkylamino compound include compounds having a dialkylaminophenyl group such as those disclosed in Japanese Patent Application Laid-Open No. 9-281698, Paragraph [0047], Japanese Patent Application Laid-Open Nos. 6-19240 and 6-19249, Amine compounds can be listed. Specifically, examples of the compound having a dialkylaminophenyl group include compounds such as p-dimethylaminobenzoate and dialkylaminophenylcarbamates such as p-diethylaminobenzcarbaldehyde and 9-julolydylcarbaldehyde And examples of the alkylamine compound include triethanolamine, diethanolamine, triethylamine, and the like.

&Lt; Photopolymerization initiator (B) >

From the viewpoint of exposure sensitivity, the photopolymerization initiator (B) used in the present invention is preferably at least one compound selected from the group consisting of triazine-based compounds, alkylamino compounds, benzyldimethylketal compounds,? -Hydroxyketone compounds,? -Amino ketone compounds, acylphosphine- Based compound, a benzophenone-based compound, an acetophenone-based compound and a derivative thereof, a cyclopentadiene-benzene-iron complex and a cyclopentadiene- A salt thereof, a halomethyloxadiazole compound and a 3-aryl-substituted coumarin compound are preferable.

A triazine compound, an alkylamino compound, an? -Amino ketone compound, an acylphosphine compound, a phosphine oxide compound, an oxime compound, a nonimidazole compound, an onium compound, a benzophenone compound or an acetophenone compound desirable. At least one compound selected from the group consisting of triazine compounds, alkylamino compounds, oxime compounds and nonimidazole compounds is more preferable.

The content of the photopolymerization initiator (B) is preferably 0.1% by mass to 50% by mass, more preferably 0.5% by mass to 30% by mass, and particularly preferably 1% by mass to 1% by mass, relative to the total solid content of the curable composition of the present invention. 20% by mass. According to the above range, good sensitivity and pattern formability can be obtained.

&Lt; Compound having an ethylenically unsaturated double bond (C) >

The curable composition of the present invention may contain a compound having an ethylenically unsaturated double bond other than the above-mentioned resin (hereinafter also referred to as "compound having an ethylenically unsaturated double bond").

The compound having an ethylenically unsaturated double bond used in the present invention is an addition-polymerizable compound having at least one ethylenically unsaturated double bond in addition to the above-mentioned resin, and contains at least one terminal ethylenic unsaturated bond, preferably two or more &Lt; / RTI &gt; Such groups of compounds are well known in the art and thus can be used without limitation in the present invention. They have, for example, monomers, prepolymers, i.e. oligomers with dimers or trimer, mixtures thereof and the chemical form of the copolymer. Examples of the monomer and the copolymer thereof include unsaturated carboxylic acids (such as acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid and maleic acid), esters and amides thereof. Preferably, an ester of an unsaturated carboxylic acid and an aliphatic polyhydric alcohol compound and an amide of an unsaturated carboxylic acid and an aliphatic polyvalent amine compound can be used. Further, an addition reaction product of an unsaturated carboxylic acid ester or amide having a polynuclear substituent group such as a hydroxyl group, an amino group and a mercapto group with a monofunctional or polyfunctional isocyanate or epoxy, or a dehydration with a monofunctional or polyfunctional carboxylic acid Condensation reaction products and the like can be preferably used. Further, an addition reaction product of an unsaturated carboxylic acid ester or amide having an electrophilic substituent such as an isocyanate group and an epoxy group with a monofunctional or polyfunctional alcohol, amine or thiol, and a leaving group such as a halogen group or a tosyloxy group Substitution reaction of an unsaturated carboxylic acid ester or amide having a monofunctional or polyfunctional alcohol, amine or thiol is also preferable. As another example, a group of compounds in which the above unsaturated carboxylic acid is substituted with an unsaturated phosphonic acid, styrene, vinyl ether, or the like may be used.

Specific examples of the monomer of the ester of the aliphatic polyhydric alcohol compound and the unsaturated carboxylic acid include ethylene glycol diacrylate, triethylene glycol diacrylate, 1,3-butanediol diacrylate, tetramethylene glycol diacrylate, propylene glycol diacryl Trimethylol propane triacrylate, trimethylol propane tri (acryloyloxypropyl) ether, trimethylol ethane triacrylate, hexane diol diacrylate, 1,4-cyclohexanediol di Acrylate, tetraethylene glycol diacrylate, pentaerythritol diacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol diacrylate, dipentaerythritol hexaacrylate, sorbitol triacrylate, sorbitol Tra has acrylate, sorbitol pentaacrylate, sorbitol hexaacrylate, tri (acryloyloxyethyl) isocyanurate, polyester acrylate oligomer and isocyanuric acid EO- acrylic acid esters such as modified triacrylate.

Tetramethylene glycol dimethacrylate, triethylene glycol dimethacrylate, neopentyl glycol dimethacrylate, trimethylolpropane trimethacrylate, trimethylol ethane trimethacrylate, ethylene glycol dimethacrylate, 1,3 -Butanediol dimethacrylate, hexanediol dimethacrylate, pentaerythritol dimethacrylate, pentaerythritol trimethacrylate, pentaerythritol tetramethacrylate, dipentaerythritol dimethacrylate, dipentaerythritol hexamethacrylate (3-methacryloxy-2-hydroxypropoxy) phenyl] dimethylmethane and bis- [p- (methacryloxyethoxy) phenyl] thiomorpholinecarboxylate, And methacrylic acid esters such as dimethyl methane.

Ethylene glycol diacetonate, propylene glycol diacetonate, 1,3-butanediol diacetonate, 1,4-butanediol diacetonate, tetramethylene glycol diacetonate, pentaerythritol diacetonate, and sorbitol tetra taconate Of itaconic acid ester. Crotonic acid esters such as ethylene glycol dichlortonate, tetramethylene glycol dichlonate, pentaerythritol dichlonate and sorbitol tetradecrhotonate. And isocrotonic acid esters such as ethylene glycol diisocrotonate and pentaerythritol diisocrotonate. Maleic acid esters such as ethylene glycol dimaleate, triethylene glycol dimaleate, pentaerythritol dimaleate and sorbitol tetramaleate.

Examples of other esters include aliphatic alcohol esters described in, for example, Japanese Patent Application Laid-Open Nos. 51-47334 and 57-196231, Japanese Laid-Open Patent Application Nos. 59-5240, 59-5241, An ester having an aromatic skeleton described in JP-A No. 2-226149 and an ester having an amino group described in JP-A No. 1-165613 are also preferably used. The above-mentioned ester monomer can also be used as a mixture.

Specific examples of the monomer of the amide of the aliphatic polyvalent amine compound and the unsaturated carboxylic acid include methylene bis-acrylamide, methylenebis-methacrylamide, 1,6-hexamethylenebis-acrylamide, 1,6-hexamethylenebis - methacrylamide, diethylenetriamintris acrylamide, xylene bisacrylamide and xylene bismethacrylamide. Examples of other preferable amide-based monomers include monomers having a cyclohexylene structure described in Japanese Patent Publication No. 54-21726.

Also, urethane-based addition polymerizable compounds prepared by the addition reaction of an isocyanate and a hydroxyl group are also preferable. Specific examples thereof include a polyisocyanate compound having two or more isocyanate groups in one molecule, as described in, for example, Japanese Patent Publication No. 48-41708, and a compound represented by the following general formula (A) And vinyl urethane compounds having two or more polymerizable vinyl groups in the molecule to which the vinyl monomer having been added is added.

???????? CH ₂ = C (R ¹⁰ ) COOCH ₂ CH (R ¹¹ ) OH ????? (A)

(Wherein R ¹⁰ and R ¹¹ represent H or CH ₃ ).

Further, urethane acrylates described in JP-A-51-37193, JP-A-2-32293 and JP-A-2-16765, and JP-A-58-49860, JP-A-56-17654, 62-39417 and 62-39418 are also preferable. The urethane compound having an ethylene oxide skeleton is also preferable. Further, by using an addition-polymerizable compound having an amino structure or sulfide structure in the molecule described in Japanese Patent Application Laid-Open Nos. 63-277653, 63-260909 and 1-105238, a photopolymerizable composition Can be obtained.

Other examples include polyester acrylates and epoxy resins described in each specification of Japanese Patent Application Laid-Open No. 48-64183, Japanese Patent Publication Nos. 49-43191 and 52-30490, and epoxy resins by reaction of (meth) acrylic acid And polyfunctional acrylates and methacrylates such as epoxy acrylates obtained. Specific examples of the unsaturated compounds described in JP-B-46-43946, JP-A-1-40337 and 1-40336 and vinylphosphonic acid compounds described in JP-A-2-25493 are listed. A structure having a perfluoroalkyl group described in JP-A-61-22048 may be preferably used. Adhesion Society of Japan, vol. 20, No. 7, p. Compounds introduced as photocurable monomers and oligomers in the Journal of &lt; RTI ID = 0.0 &gt; 300-308 &lt; / RTI &gt; (1984) can also be used.

The structure of the addition compound, the structure of the addition compound, the use thereof alone, or the combination thereof and the amount thereof to be added can be arbitrarily set according to the performance design of the curable composition. For example, it can be selected from the following viewpoints.

From the viewpoint of sensitivity, a structure having a large amount of unsaturated groups per molecule is preferable. In most cases, a bifunctionality or more is preferable. Further, in order to improve the strength of the image portion, that is, the cured film, it is preferable to have a trifunctional or more functionality. A method of adjusting both the sensitivity and the strength by using a combination of other functional water and other polymerizable groups (for example, acrylate ester, methacrylate ester, styrene compound, vinyl ether compound) is also effective. From the viewpoint of curing sensitivity, it is preferable to use a compound containing two or more (meth) acrylic acid ester structures, more preferably to use a compound containing three or more, and to use a compound containing four or more Most preferred. In addition, from the viewpoints of curing sensitivity and developability of the unexposed portion, it is preferable to contain an EO-modified substance. In addition, from the viewpoints of curing sensitivity and exposure part strength, it is preferable to contain a urethane bond.

Also, regarding the compatibility and dispersibility with other components (resin, photopolymerization initiator, pigment) and the like in the curable composition, selection and use of the addition-polymerizable compound is an important factor. For example, the use of a low purity compound or the use of a combination of two or more may improve compatibility. In addition, a specific structure may be selected for the purpose of improving adhesion with a substrate or the like.

In view of the above, it is preferable that bisphenol A diacrylate, bisphenol A diacrylate EO-modified material, trimethylolpropane triacrylate, trimethylolpropane tri (acryloyloxypropyl) ether, trimethylol ethane triacrylate, tetraethylene glycol But are not limited to, diacrylate, diacrylate, pentaerythritol diacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, sorbitol triacrylate, sorbitol tetra Acrylate, sorbitol pentaacrylate, sorbitol hexaacrylate, tri (acryloyloxyethyl) isocyanurate, pentaerythritol tetraacrylate EO-modified material, dipentaerythritol hexaacrylate EO-modified material As the preferred examples can be exemplified. UH-140 (manufactured by Sanyo Kokusaku Pulp Corp.), DPHA-40H (manufactured by Nippon Kayaku Co., Ltd.), UA-306H, UA-306T, UA- 600, T-600, AI-600 (manufactured by Kyoeisha Chemical CO., Ltd.) and UA-7200 (manufactured by Shin-Nakamura Chemical.

Of these, preferred are EO-modified bisphenol A diacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, tri (acryloyloxyethyl) isocyanurate , EO-modified pentaerythritol tetraacrylate and EO-modified dipentaerythritol hexaacrylate are more preferable. UH-600, UH-600, T-600 and AI-600 (products of Kyoeisha Chemical CO., LTD.) Are commercially available as DPHA-40H (product of Nippon Kayaku Co., Ltd.) Is more preferable.

In the present invention, the content of the compound having an ethylenically unsaturated double bond other than the resin (C) The content of the resin (A) in the solid content of the curable composition of the present invention is preferably 1% by mass to 90% by mass, more preferably 5% by mass to 80% by mass, still more preferably 10% by mass to 70% Do.

In particular, when the curable composition of the present invention is used for forming a coloring pattern of a color filter, the content of the compound having an ethylenically unsaturated double bond other than the (C) resin is preferably 5% by mass to 50% by mass in the above range By mass, more preferably 7% by mass to 40% by mass, and still more preferably 10% by mass to 35% by mass.

From the viewpoints of the sensitivity and the removability (developability) of the unexposed portion, the content ratio (mass ratio) of the resins (A) and (C); The compound having an ethylenically unsaturated double bond other than the resin (A) is preferably (A) / (C) of 0.001 to 100, more preferably 0.005 to 50, further preferably 0.01 to 10.

&Lt; Colorant (D) >

The curable composition of the present invention preferably contains a colorant (D).

The colorant to be contained in the curable composition of the present invention is not particularly limited, and various conventionally known dyes and pigments may be used singly or as a mixture of two or more kinds. From the viewpoint of durability such as heat resistance and light resistance, the colorant is preferably a pigment.

As the pigment contained in the curable composition of the present invention, conventionally known various inorganic pigments or organic pigments can be used, and a high transmittance is preferable.

As the inorganic pigment, metal compounds represented by metal oxides, metal complex salts and the like can be exemplified. Specifically, metal oxides such as iron, cobalt, aluminum, cadmium, lead, copper, titanium, magnesium, chromium, zinc and antimony, and complex oxides of the above metals can be exemplified.

As the organic pigment, for example,

CI Pigment Yellow 11, 24, 31, 53, 83, 93, 99, 108, 109, 110, 138, 139, 147, 150, 151, 154, 155, 167, 180, 185, 199;

C. I. Pigment Orange 36, 38, 43, 71;

CI Pigment Red 81, 105, 122, 149, 150, 155, 171, 175, 176, 177, 209, 220, 224, 242, 254, 255, 264, 270;

C.I. Pigment Violet 19, 23, 32, 39;

C. I. Pigment Blue 1, 2, 15, 15: 1, 15: 3, 15: 6, 16, 22, 60, 66;

C.I. Pigment Green 7, 36, 37;

C.I. Pigment Brown 25, 28;

C. I. Pigment Black 1, 7;

Carbon black, and the like.

In the present invention, those having a basic N atom in the structural formula of the pigment can be particularly preferably used. These basic N atom-bearing pigments exhibit advantageous dispersibility in the composition of the present invention. Although the cause thereof is not sufficiently clarified, it is presumed that the good affinity between the photosensitive polymer component and the pigment affects it.

As the pigment preferably used in the present invention, the following can be listed. However, the present invention is not limited thereto:

CI Pigment Yellow 11, 24, 108, 109, 110, 138, 139, 150, 151, 154, 167, 180, 185;

C.I. Pigment Orange 36, 71;

CI Pigment Red 122, 150, 171, 175, 177, 209, 224, 242, 254, 255, 264;

C.I. Pigment Violet 19, 23, 32;

C.I. Pigment Blue 15: 1, 15: 3, 15: 6, 16, 22, 60, 66;

C.I. Pigment Black 1.

These organic pigments may be used singly or in various combinations thereof in order to improve color purity. Specific examples of the combination are shown below. For example, as the red pigment, an anthraquinone pigment, a perylene pigment or a diketopyrrolopyrrole pigment alone, or an azo yellow pigment, an isoindoline yellow pigment, a quinophthalone yellow pigment, A mixture of perylene-based red pigments may be used. For example, CI Pigment Red 177 is listed as an anthraquinone pigment, CI Pigment Red 155 and CI Pigment Red 224 are listed as perylene pigments, and diketopyrrolopyr As the roll type pigment, CI Pigment Red 254 is listed. From the viewpoint of color reproducibility, a mixture with CI Pigment Yellow 139 is preferable. The mass ratio of the red pigment to the yellow pigment is preferably from 100: 5 to 100: 50. When the ratio is 100: 4 or less, it is difficult to suppress the light transmittance of 400 nm to 500 nm, and the color purity may not be improved. If the ratio is 100: 51 or more, the dominant wavelength becomes closer to a short wavelength, and the deviation from the NTSC target color may increase. Particularly, it is most preferable that the mass ratio is in the range of 100: 10 to 100: 30. In the case of a combination of red pigments, the ratio can be adjusted according to the chromaticity.

As the green pigment, a halogenated phthalocyanine pigment may be used singly or in combination with an azo yellow pigment, a quinophthalone yellow pigment, an azomethine yellow pigment or an isoindoline yellow pigment. Examples thereof include C. I. Pigment Green 7, 36, 37 and C.I. Pigment Yellow 83, C.I. Pigment Yellow 138, C.I. Pigment Yellow 139, C.I. Pigment Yellow 150, C.I. Pigment Yellow 180 or C.I. Pigment Yellow 185 is preferred. The mass ratio of the green pigment to the yellow pigment is preferably from 100: 5 to 100: 150. The mass ratio is particularly preferably in the range of 100: 30 to 100: 120.

As the blue pigment, a phthalocyanine pigment may be used singly or a mixture of the phthalocyanine pigment and a dioxazine-based purple pigment may be used. For example, a mixture of C. I. Pigment Blue 15: 6 and C. I. Pigment Violet 23 is preferred. The mass ratio of the blue pigment to the purple pigment is preferably 100: 0 to 100: 30, more preferably 100: 10 or less.

As the black matrix pigment, carbon, titanium carbon, iron oxide, and titanium oxide are used alone or in a mixture thereof. The combination of carbon and titanium carbon is preferred. The mass ratio of carbon to titanium carbon is preferably in the range of 100: 0 to 100: 60.

When the pigment is used for a color filter, the average particle size of the pigment is preferably 100 nm or less from the viewpoint of color heterogeneity and contrast, and is preferably 5 nm or more from the viewpoint of dispersion stability. The average particle size of the pigment is more preferably 5 to 75 nm, still more preferably 5 to 55 nm, and particularly preferably 5 to 35 nm.

The average particle size of the pigment can be measured by a known method such as an electron microscope.

In particular, the pigment is preferably a pigment selected from anthraquinone-based, azomethine-based, benzylidene-based, cyanine-based, diketopyrrolopyrrole-based and phthalocyanine-based pigments.

When the composition of the present invention is used for a color filter, it is preferable to use a dye that is uniformly dissolved in the composition from the viewpoint of color irregularity and contrast.

The dye used as the colorant contained in the curable composition of the present invention is not particularly limited and conventionally known dyes for color filters can be used. For example, Japanese Patent Application Laid-Open Nos. 64-90403, 64-91102, 1-94301 and 6-11614, 2,592,207, 4,808,501, 5,667,920, No. 5,059,500, Japanese Patent Application Laid-Open Nos. 5-333207, 6-35183, 6-51115, 6-194828, 8-211599, 4-249549, 10-123316, 11-302283, 7-286107, 2001-4823, 8-15522, 8-29771, 8-146215, 11-343437, 8-62416, 2002-14220 , 2002-14221, 2002-14222, 2002-14223, 8-302224, 8-73758, 8-179120, and 8-151531 can be used.

Examples of the chemical structure include a pyrazolone group, anilino group, triphenylmethane group, anthraquinone group, anthrapyridone group, benzilidene group, oxolin group, pyrazolotriazole group, pyridazo group, cyanine group, phenothiazine group, A dicyclopentadiene-based dye, a dicyclopentadiene-based dye, a dicyclopentadiene-based dye,

In addition, in the case of forming a pattern by removing the unexposed portion with water or an alkali development after the pattern exposure of the curable composition and the curing of the exposed portion and forming a colored pattern of, for example, a resist or a color filter, From the viewpoint of completely removing the binder and the dye, the acid dye and / or the derivative thereof may be suitably used.

Also suitable are direct dyes, basic dyes, mordant dyes, acid mordant dyes, azoic dyes, disperse dyes, oil soluble dyes, food dyes and / or derivatives thereof.

The acidic dye is not particularly limited as long as it has an acidic group such as a sulfonic acid and a carboxylic acid. The acidic dye is soluble in an organic solvent or a developing solution, salt-forming property with a basic compound, absorbance, interaction with other components in the composition, Can be selected in consideration of the required performance.

The following are examples of acid dyes, but the present invention is not limited thereto. Examples include:

Acid Alizarin Violet N;

Acid Black 1, 2, 24, 48;

Acid blue 1, 7, 9, 15, 18, 23, 25, 27, 29, 40, 42, 45, 51, 62, 70, 74, 80, 83, 86, 87, 90, 1, 112, 113, 120, 129, 138, 147, 150, 158, 171, 182, 192, 210, 242, 243, 256, 259, 267, 278, 280, 285, 290, 296, 315, 335, 340;

Acid chromium violet K;

Acidic fluff;

Acid green 1, 3, 5, 9, 16, 25, 27, 50, 58, 63, 65, 80, 104, 105, 106, 109;

Acid Orange 6, 7, 8, 10, 12, 26, 50, 51, 52, 56, 62, 63, 64, 74, 75, 94, 95, 107, 108, 169, 173;

Acid Red 1, 4, 8, 14, 17, 18, 26, 27, 29, 31, 34, 35, 37, 42, 44, 50, 51, 52, 57, 66, 73, 91, 92, 94, 97, 103, 111, 114, 129, 133, 134, 138, 143, 145, 150, 151, 158, 176, 182, 183, 198, 206, 211, 215, 216, 217, 277, 280, 281, 195, 308, 312, 315, 316, 339, 341, 345, 346, 349, 266, 268, 382, 383, 394, 401, 412, 417, 418, 422, 426;

Acidic violet 6B, 7, 9, 17, 19;

Acid yellow 1, 3, 7, 9, 11, 17, 23, 25, 29, 34, 36, 38, 40, 42, 54, 65, 72, 73, 76, 79, 98, 99, 112, 134, 135, 138, 139, 140, 144, 150, 155, 157, 160, 161, 163, 168, 169, 172, 177, 178, 179, 184, 190, 193, 196, 197, 199, 202, 203, 204, 205, 207, 212, 214, 220, 221, 228, 230, 232, 235, 238, 240, 242, 243, 251;

Direct Yellow 2, 33, 34, 35, 38, 39, 43, 47, 50, 54, 58, 68, 69, 70, 71, 86, 93, 94, 95, 98, 136, 138, 141;

Direct Orange 34, 39, 41, 46, 50, 52, 56, 57, 61, 64, 65, 68, 70, 96, 97, 106, 107;

Direct Red 79, 82, 83, 84, 91, 92, 96, 97, 98, 99, 105, 106, 107, 172, 173, 176, 177, 179, 181, 182, 184, 204, 213, 218, 220, 221, 222, 232, 233, 234, 241, 243, 246, 250;

Direct Violet 47, 52, 54, 59, 60, 65, 66, 79, 80, 81, 82, 84, 89, 90, 93, 95, 96, 103, 104;

Direct Blue 57, 77, 80, 81, 84, 85, 86, 90, 93, 94, 95, 97, 98, 99, 100, 101, 106, 107, 108, 109, 113, 114, 173, 181, 172, 173, 188, 189, 190, 192, 193, 163, 164, 166, 167, 170, 171, 242, 243, 244, 245, 247, 248, 250, 251, 252, 256, 257, 259, 260, 268, 274, 275, 293;

Direct Green 25, 27, 31, 32, 34, 37, 63, 65, 66, 67, 68, 69, 72, 77, 79, 82;

Mordant yellow 5, 8, 10, 16, 20, 26, 30, 31, 33, 42, 43, 45, 56, 50, 61, 62, 65;

Mordant orange 3, 4, 5, 8, 12, 13, 14, 20, 21, 23, 24, 28, 29, 32, 34, 35, 36, 37, 42, 43, 47, 48;

37, 38, 39, 41, 41, 42, 41, 42, 43, 42, 43, 45, 46, 48, 53, 56, 63, 71, 74, 85, 86, 88, 90, 94, 95;

Mordant violet 2, 4, 5, 7, 14, 22, 24, 30, 31, 32, 37, 40, 41, 44, 45, 47, 48, 53, 58;

36, 30, 31, 32, 39, 40, 41, 43, 44, 48, 49, 53, 61, 74, 77, 83, 84;

Mushrooms green 1,3,4,5,10,15,19,26,29,33,34,35,41,43, 53;

Food Yellow 3;

And derivatives of these dyes.

Among the acid dyes, acid black 24;

Acid Blue 23, 25, 29, 62, 80, 86, 87, 92, 138, 158, 182, 243, 324: 1;

Acid Orange 8, 51, 56, 74, 63;

Acid Red 1, 4, 8, 34, 37, 42, 52, 57, 80, 97, 114, 143, 145, 151, 183, 217, 249;

Acid violet 7;

Acid yellow 17, 25, 29, 34, 42, 72, 76, 99, 111, 112, 114, 116, 134, 155, 169, 172, 184, 220, 228, 230, 232, 243;

Dyes such as Acid Green 25 and derivatives of these dyes are preferable.

In addition to the above-mentioned dyes, azo dyes, xanthane dyes and phthalocyanine dyes are also preferable, and C.I. Solvent Blue 44, 38; C.I.Solvent Orange 45; Acid dyes such as Rhodamine B and Phodamine 110 and derivatives of these dyes are preferably used.

Among them, the colorant (D) is preferably at least one selected from the group consisting of triallyl methane, anthraquinone, azomethine, benzylidene, oxolin, cyanine, phenothiazine, pyrrolopyrazolamomethine, xanthene, phthalocyanine, A colorant selected from pyran, indigo, pyrazoloazo, anilinoazo, pyrazolotriazo, pyridazo, and anthrapyridone is preferable.

The content of the colorant in the curable composition of the present invention is preferably 30% by mass or more and 85% by mass or less, more preferably 40% by mass or more and 80% by mass or less, more preferably 50% And most preferably not less than 75% by mass.

&Lt; Binder polymer (E) >

The curable composition of the present invention may contain the binder polymer (E) within the range not impairing the effect of the present invention for the purpose of improving the coating film.

As the binder polymer, it is preferable to use a linear organic polymer. As such "linear organic polymer ", conventionally known ones can be arbitrarily used. Preferably, a linear organic polymer that is soluble or swellable in water or weak alkaline water is selected to enable water development or weak alkaline water development. The linear organic polymer is used not only as a coating film forming agent, but also according to its use as water, weak alkaline water or an organic solvent developer. For example, the use of a water-soluble organic polymer enables water development. Examples of such linear organic polymers include those disclosed in Japanese Patent Application Laid-open No. 59-44615, Japanese Patent Publication Nos. 54-34327, 58-12577, 54-25957, 54-92723, 59- 53836 and 59-71048, which is obtained by polymerizing or copolymerizing a monomer having a carboxyl group or a polymer obtained by polymerizing or copolymerizing a monomer having an acid anhydride, And a radical polymer having a carboxylic acid group in the side chain such as epoxy acrylate obtained by modifying an epoxy resin with an unsaturated monocarboxylic acid and an acid anhydride. Examples of the monomer having a carboxylic acid group include acrylic acid, methacrylic acid, itaconic acid, crotonic acid, maleic acid, fumaric acid, and 4-carboxystyrene. As the monomer having an acid anhydride, maleic anhydride and the like can be exemplified.

Likewise, there is an acidic cellulose derivative having a carboxylic acid group in its side chain. It is also useful to add a cyclic acid anhydride to the polymer having a hydroxyl group.

When the binder polymer is used as an alkali-soluble copolymer, monomers other than those described above may also be used as the copolymerized compound. Examples of other monomers include the following compounds (1) to (12):

(1) a polyfunctional monomer selected from the group consisting of 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 3-hydroxypropyl acrylate, 4-hydroxybutyl acrylate, 2-hydroxyethyl methacrylate, Acrylate esters and methacrylate esters having aliphatic hydroxyl groups such as acrylate, 3-hydroxypropyl methacrylate and 4-hydroxybutyl methacrylate.

(2) a polyfunctional acrylate such as methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, isobutyl acrylate, amyl acrylate, hexyl acrylate, 2-ethylhexyl acrylate, octyl acrylate, Acrylate, glycidyl acrylate, 3,4-epoxycyclohexylmethyl acrylate, vinyl acrylate, 2-phenylvinyl acrylate, 1-propenyl acrylate, allyl acrylate, 2-allyloxyethyl acrylate and Alkyl acrylates such as propargyl acrylate.

(3) a polyfunctional monomer selected from the group consisting of methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, isobutyl methacrylate, amyl methacrylate, hexyl methacrylate, 2-ethylhexyl methacrylate, cyclohexyl methacrylate Acrylates such as methyl acrylate, ethyl acrylate, butyl acrylate, ethyl acrylate, butyl acrylate, 2-ethylhexyl methacrylate, 2-ethylhexyl methacrylate, Alkyl methacrylates such as propenyl methacrylate, allyl methacrylate, 2-allyloxyethyl methacrylate and propargyl methacrylate.

(4) A method for producing a polymer comprising the steps of: (1) polymerizing an acrylamide, a methacrylamide, N-methylol acrylamide, N-ethyl acrylamide, N-hexylmethacrylamide, N-cyclohexyl acrylamide, N- , N-nitrophenyl acrylamide, N-ethyl-N-phenyl acrylamide, vinyl acrylamide, vinyl methacrylamide, N, N-diallylacrylamide, N, N-diallylmethacrylamide, Acrylamides such as allyl methacrylamide, and methacrylamides.

(5) Vinyl ethers such as ethyl vinyl ether, 2-chloroethyl vinyl ether, hydroxyethyl vinyl ether, propyl vinyl ether, butyl vinyl ether, octyl vinyl ether and phenyl vinyl ether.

(6) Vinyl esters such as vinyl acetate, vinyl chloroacetate, vinyl butyrate and vinyl benzoate.

(7) styrenes such as styrene,? -Methylstyrene, methylstyrene, chloromethylstyrene and p-acetoxystyrene.

(8) Vinyl ketones such as methyl vinyl ketone, ethyl vinyl ketone, propyl vinyl ketone and phenyl vinyl ketone.

(9) Olefins such as ethylene, propylene, isobutylene, butadiene and isoprene.

(10) N-vinylpyrrolidone, acrylonitrile, methacrylonitrile and the like;

(11) Unsaturated imides such as maleimide, N-acryloyl acrylamide, N-acetyl methacrylamide, N-propionyl methacrylamide and N- (p-chlorobenzoyl) methacrylamide.

(12) A methacrylic acid-based monomer having a hetero atom bonded to the? -Position of a compound described in JP-A-2002-309057 and 2002-311569.

Of these examples, (meth) acrylic resins having an allyl group or a vinyl ester group and a carboxyl group in the side chain, alkali-soluble resins having a double bond in the side chain described in JP-A Nos. 2000-187322 and 2002-62698, The alkali-soluble resin having an amide group in the side chain described in JP-A-2001-242612 is preferable for balance of these excellent film strength, sensitivity and developability.

Japanese Patent Publication Nos. 7-12004, 7-120041, 7-120042, 8-12424, 63-287944, 63-287947, 1-271741 And Urethane Binder Polymers Having Acidic Groups and Double Bonds on the Side Chain as described in Japanese Patent Application Laid-Open No. 10-116232 and Urethane Binder Polymers Having Acidic Groups as described in JP-A No. 2002-107918, It is advantageous in terms of low light exposure suitability.

The acetal-modified polyvinyl alcohol-based binder polymer having an acidic group described in European Patent No. 993966, European Patent No. 1204000 and Japanese Patent Laid-Open No. 2001-318463 is suitable because it has a good balance between strength and developability.

Further, as the water-soluble linear organic polymer, polyvinylpyrrolidone and polyethylene oxide are useful. In addition, alcohol-soluble nylons and polyethers of 2,2-bis- (4-hydroxyphenyl) -propane and epichlorohydrin are also useful in order to improve the strength of the cured film.

The weight average molecular weight of the binder polymer (E) is preferably 3,000 or more, more preferably 5,000 to 300,000. The number average molecular weight is preferably 1,000 or more, more preferably 2,000 to 250,000. The polydispersity (weight average molecular weight / number average molecular weight) is preferably 1 or more, more preferably 1.1 to 10.

These binder polymers may be random polymers, block polymers, graft polymers or the like.

The binder polymer (E) can be synthesized by a conventionally known method. Examples of the solvent to be used for the synthesis include tetrahydrofuran, ethylene dichloride, cyclohexanone, methyl ethyl ketone, acetone, methanol, ethanol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, Methoxy-2-propyl acetate, N, N-dimethylformamide, N, N-dimethylacetoamide, toluene, ethyl acetate, methyl lactate Tartrate, ethyl lactate, dimethylsulfoxide, water, and the like. These solvents may be used alone or as a mixture of two or more thereof.

As the radical polymerization initiator used in synthesizing the binder polymer used in the present invention, known compounds such as an azo-based initiator and a peroxide initiator can be exemplified.

When the curable composition of the present invention is used for forming a coloring pattern of a color filter from the viewpoints of stability of pigment dispersion stability over time and developability over time, the content of the binder polymer (E) is preferably 5% by mass or less based on the total solid content of the curable composition of the present invention. By mass to 60% by mass, more preferably 7% by mass to 50% by mass, and most preferably 10% by mass to 40% by mass.

The curable composition of the present invention further contains the following components described in detail as necessary.

<(F) Dispersant>

When the curable composition of the present invention contains a pigment as the colorant (D), it is preferable to add the dispersant (F) from the viewpoint of improving the dispersibility of the pigment.

Examples of the dispersant (pigment dispersant) used in the present invention include a polymer dispersant [a polyamideamine and its salt, a polycarboxylic acid and its salt, a high molecular weight unsaturated acid ester, a modified polyurethane, a modified polyester, a modified poly (Meth) acrylic copolymer and naphthalenesulfonic acid formalin condensate], and polyoxyethylene alkylphosphoric acid ester, polyoxyethylene alkylamine, alkanolamine, pigment derivative, and the like.

From the viewpoint of the structure, the polymer dispersant can be further classified into a linear polymer, a terminal modified polymer, and a graft polymer.

The polymer dispersant adsorbs on the surface of the pigment to prevent re-aggregation. Therefore, a terminal modified polymer having a pigment surface, an anchor portion, a grafted polymer and a block polymer can be listed as preferred structures. On the other hand, the pigment derivative provides an effect of promoting the adsorption of the polymer dispersant by improving the pigment surface.

Specific examples of the pigment dispersant used in the present invention include BYK Chemie Corp. (Copolymer containing an acid group), 130 (polyamide), 161, 162, 163, 164, 165, 166, 170 (polyamide amine phosphate) EFKA 4047, 4050, 4010, 4165 (polyurethane system), EFKA4330, 4340 (block copolymer), 4400, and EFKA Corp. manufactured by EFKA Corp., "BYK-P104, P105 (high molecular weight unsaturated polycarboxylic acid) 4802 (modified polyacrylate), 5010 (polyester amide), 5765 (high molecular weight polycarboxylate), 6220 (fatty acid polyester, 6745 (phthalocyanine derivative), 6750 (azo pigment derivative), Ajinomoto Fan Techno Corp. "FRONT TG-710 (urethane oligomer)", "POLYFLOW No. 50E, No. 300 (acrylic copolymer)" manufactured by Kyoeisha Chemical Co., Ltd., "DISPERON (Aliphatic polyvaleric carboxylic acid), # 7004 (polyether ester), DA-703-50, DA-705, DA-725 ", KA-860, 873N, 874, # 2150 (aromatic polycarboxylic acid), "EMARGEN 920, 930 ", " DEMOL RN, N (naphthalenesulfonic acid formalin polycondensate), MS, C, SN-B (aromatic sulfonic acid formalin polycondensate) SOLEX 5000 (phthalocyanine derivative), 22000 (azo pigment derivative), 13240 (polyester amine) manufactured by RUBERESOL Corp., , 3000, 17000, 27000 (polymer having a functional group at the terminal), 24000, 28000, 32000, 38500 (graft polymer) ", NIKKO CHEMICAL Corp. NIKKOL T106 (polyoxyethylene sorbitan monooleate), and MYS-IEX (polyoxyethylene monostearate).

These dispersants may be used alone or in combination of two or more. In the present invention, it is particularly preferable to use a combination of the pigment derivative and the polymer derivative.

The content of the dispersing agent in the present invention is preferably 1% by mass to 100% by mass, more preferably 3% by mass to 100% by mass, and still more preferably 5% by mass to 80% by mass with respect to the pigment.

Specifically, when a polymer dispersant is used, its amount to be used is preferably in the range of 5 mass% to 100 mass% with respect to the pigment, and more preferably in the range of 10 mass% to 80 mass%. When the pigment derivative is used, the amount of the pigment derivative is preferably in the range of 1% by mass to 30% by mass, more preferably in the range of 3% by mass to 20% by mass, more preferably in the range of 5% % Of the total weight of the composition.

In the present invention, when the pigment and the dispersant are used, the total amount of the pigment and the dispersant is preferably from 35% by mass to 90% by mass, more preferably from 45% by mass to 90% by mass with respect to the total solid content of the curable composition, By mass to 85% by mass, and more preferably 50% by mass to 80% by mass.

<(G) sensitizer>

The curable composition of the present invention preferably contains (G) a sensitizer for the purpose of improving the radical generation efficiency of the polymerization initiator and increasing the wavelength of the photosensitive wavelength. As the sensitizer used in the present invention, it is preferable that the photopolymerization initiator can be increased or decreased by an electron transfer mechanism or an energy transfer mechanism.

As the sensitizer used in the present invention, those having the absorption wavelength in the wavelength region of 300 nm to 450 nm belong to the compounds listed below.

As a preferable sensitizer, those belonging to the following compounds and having an absorption wavelength in the wavelength region of 330 nm to 450 nm can be exemplified.

Examples of the aromatic ring include polynuclear aromatic groups (such as phenanthrene, anthracene, pyrene, perylene, triphenylene, and 9,10-dialkoxyanthracene), xanthenes (fluorene, eosin, erythrosine, rhodamine B, Bismuth, etc.), thioxanthones (isopropylthioxanthone, diethylthioxanthone, chlorothioxanthone, etc.), cyanines (thiacarbocyanine and oxacarbocyanine etc.), merocyanines (Such as acridine orange, chloroflavin, and acriflavine), anthraquinones (such as anthraquinones), anthraquinones (such as anthraquinones), phthalocyanines, thiazines (such as thionine, methylene blue, and toluidine blue) Quinone and the like), squaluminium (such as squalium), acridine orange, coumarins (such as 7-diethylamino-4-methylcoumarin), ketocoumarin, phenothiazine, phenazine, styrylbenzenes, Azo compounds, diphenylmethane, triphenylmethane, distyrylbenzene, carbazoles, porphyrin, spiro Wherein the compound is selected from the group consisting of a quinacridone compound, a quinacridone, an indigo, a styryl, a pyrylium compound, a pyromethene compound, a pyrazolo thiazole compound, a benzothiazole compound, a barbituric acid derivative, a thiobarbitic acid derivative, acetophenone, Aromatic ketone compounds such as helix ketone, and heterocyclic compounds such as N-aryloxazolidinone. Further, compounds described in European Patent No. 568,993, US Pat. Nos. 4,508,811 and 5,227,227, Japanese Patent Laid-Open Nos. 2001-125255 and 11-271969, and the like can be exemplified.

Examples of the more preferable sensitizer include compounds represented by the following general formulas (i) to (iv).

In general formula (i), A ¹ is a sulfur atom or NR ⁵⁰ , R ⁵⁰ is an alkyl group or an aryl group, L ² is a non-metallic atomic group forming a basic nucleus of the pigment in association with the adjacent A ¹ and adjacent carbon atoms, R ⁵¹ and R ⁵² each independently represent a hydrogen atom or a monovalent nonmetal atomic group and may bond to each other to form an acidic nucleus of the pigment. W is an oxygen atom or a sulfur atom. As the alkyl group for R ^50, an alkyl group having 1 to 30 carbon atoms may be listed, but an alkyl group having 1 to 20 carbon atoms is preferable, and an alkyl group having 1 to 10 carbon atoms is most preferable. As the aryl group for R ^50, an aryl group having 6 to 30 carbon atoms can be exemplified, but an aryl group having 6 to 20 carbon atoms is preferable, and an aryl group having 6 to 10 carbon atoms is most preferable.

In the general formula (ii), Ar ¹ and Ar ² are each independently an aryl group and are connected through a bond by -L ³ -. Wherein L &lt; ³ &gt; is -O- or -S-. W is the same as that shown in the general formula (i). The aryl group of Ar ^{1 may be} an aryl group having 6 to 30 carbon atoms, preferably an aryl group having 6 to 20 carbon atoms, and most preferably an aryl group having 6 to 10 carbon atoms. As the aryl group of Ar ^2, an aryl group having 6 to 30 carbon atoms can be exemplified, but an aryl group having 6 to 20 carbon atoms is preferable, and an aryl group having 6 to 10 carbon atoms is most preferable.

In formula (iii), A ² is a sulfur atom or NR ⁵⁹ , L ⁴ is a non-metallic atomic group which forms a basic nucleus of a dye jointly with adjacent A ² and carbon atoms, and R ⁵³ , R ⁵⁴ , R ⁵⁵ , R ⁵⁶ , R ⁵⁷ and R ⁵⁸ are each independently a monovalent nonmetal atomic group, and R ⁵⁹ is an alkyl group or an aryl group. As the alkyl group for R ^59, an alkyl group having 1 to 30 carbon atoms can be exemplified, but an alkyl group having 1 to 20 carbon atoms is preferable, and an alkyl group having 1 to 10 carbon atoms is most preferable. As the aryl group for R ^59, an aryl group having 6 to 30 carbon atoms can be exemplified, but an aryl group having 6 to 20 carbon atoms is preferable, and an aryl group having 6 to 10 carbon atoms is most preferable.

In formula (iv), A ³ and A ⁴ are each independently -S-, -NR ⁶² - or -NR ⁶³ -, and R ⁶² and R ⁶³ each independently represent a substituted or unsubstituted alkyl group, a substituted aryl group, L ^5, L ⁶ are each independently adjacent to a ^3, a non-metallic atomic group forming a basic nucleus of the pigment in ^four or adjacent carbon atoms and co, R ^60, R ⁶¹ each independently represent a monovalent non-metallic Or they may be bonded to each other to form an aliphatic or aromatic ring. As the alkyl group for R ⁶² and R ^63, an alkyl group having 1 to 30 carbon atoms can be exemplified, but an alkyl group having 1 to 20 carbon atoms is preferable, and an alkyl group having 1 to 10 carbon atoms is most preferable. As the aryl group for R ⁶² and R ^63, an aryl group having 6 to 30 carbon atoms can be exemplified, but an aryl group having 6 to 20 carbon atoms is preferable, and an aryl group having 6 to 10 carbon atoms is most preferable. As the substituent in the case of substitution, an alkyl group, a halogen atom (fluorine atom, chlorine atom, bromine atom, iodine atom), an alkoxyl group, an alkoxycarbonyl group, an acyl group, a hydroxyl group and an amino group are preferable. The number of carbon atoms of these substituents is preferably 1 to 30, more preferably 1 to 20, and most preferably 1 to 10.

As the preferable sensitizer contained in the curable composition of the present invention, at least one selected from the group consisting of the compounds represented by the following general formulas (IV) to (VI) can be exemplified in addition to the above-mentioned sensitizers. These may be used singly or in combination of two or more.

In the general formula (IV) or (V), R ¹ and R ² are each independently a monovalent substituent, and R ³ , R ⁴ , R ⁵ and R ⁶ are each independently a hydrogen atom or a monovalent substituent. n is an integer of 0 to 5, and n 'is an integer of 0 to 5, wherein n and n' are not simultaneously 0. When n is 2 or more, a plurality of R ^{1 s} may be the same or different. If more than n 'is 2, a plurality of present R ² may be the same or different, respectively. As the monovalent substituent, an alkyl group, a halogen atom (fluorine atom, chlorine atom, bromine atom, iodine atom), an alkoxyl group, an alkoxycarbonyl group, an acyl group, a hydroxyl group and an amino group are preferable. The number of carbon atoms of these substituents is preferably 1 to 30, more preferably 1 to 20, and most preferably 1 to 10.

The compound represented by the general formula (IV) is preferably a compound represented by the following general formula (IV-1) from the viewpoint of coloring property and sensitivity in the case of containing a coloring agent.

In the general formula (IV-1), R ¹ and R ² are each independently a monovalent substituent. n is an integer of 0 to 5, and n 'is an integer of 1 to 5. When n is 2 or more, plural R ^{1 s} may be the same or different. When n 'is 2 or more, a plurality of R ² present may be the same or different.

In the general formula (Ⅳ-1), R 1 is a substituent represented by ¹ and R ² are monovalent substituents represented by R ¹ and R ² in the general formula (Ⅳ), to apply the same preferred range.

As the compound represented by the general formula (IV) or the general formula (V), the molar extinction coefficient? At 365 nm is preferably 500 mol ^-1 L · cm ^-1 or more, and the ε at a wavelength of 365 nm is 3,000 mol ^-1 · L · cm ^-1 or more, and most preferably, ε at a wavelength of 365 nm is 20,000 mol ^-1 · L · cm ^-1 or more. Since the value of the molar extinction coefficient? At each wavelength falls within the above range, the sensitivity improving effect is high, which is preferable from the viewpoint of light absorption efficiency.

Here, the molar extinction coefficient? Is determined by measuring the transmission spectrum of a sample at 365 nm using a sample of a dye solution adjusted to a concentration of 0.01 g / l in a 1-methoxy-2-propanol solution Can be obtained by calculating the absorbance. As a measuring device, Varian Corp. UV-Vis-MR spectrophotometer Cary5G type spectrophotometer was used.

Specific preferred examples of the compound represented by the general formula (IV) or (V) are shown below, but the present invention is not limited thereto.

Here, the general formula can be represented by a simple structural formula, and a solid line or the like in which the element or the substituent is not indicated represents a hydrocarbon group. In the following specific examples, Me represents a methyl group, Et represents an ethyl group, Bu represents a butyl group, n-Bu represents an n-butyl group, and Ph represents a phenyl group.

In the general formula (Ⅵ), A is an aromatic ring which may have a substituent or a hetero ring, X is an oxygen atom, a sulfur atom or -N (R ³⁾ -, and, Y is an oxygen atom, a sulfur atom or -N (R ³⁾ -to be. R ¹ , R ² and R ³ are each independently a hydrogen atom or a monovalent nonmetal atomic group. A, R ¹ , R ² and R ³ may be bonded to each other to form an aliphatic or aromatic ring.

In the general formula (VI), when R ¹ , R ² and R ³ are a monovalent nonmetal atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted aromatic heterocycle A substituted or unsubstituted alkoxy group, a substituted or unsubstituted alkylthio group, a hydroxyl group or a halogen atom.

The alkyl group is preferably an alkyl group of 1 to 30 carbon atoms in the linear, branched or cyclic form, more preferably 1 to 20 carbon atoms, particularly preferably 1 to 15 carbon atoms. For example, a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an iso-butyl group, a tert- , Bicyclo [2,2,1] -heptan-2-yl, and the like.

The aryl group is preferably an aryl group having 6 to 30 carbon atoms, more preferably 6 to 20 carbon atoms, and particularly preferably 6 to 15 carbon atoms. For example, a phenyl group, a naphthyl group, and the like.

The alkenyl group is preferably an alkenyl group having 1 to 30 carbon atoms in a straight chain, branched or cyclic form, more preferably 1 to 20 carbon atoms, and particularly preferably 1 to 15 carbon atoms. For example, vinyl, allyl, cyclohexenyl, geranyl, and the like.

The aromatic heterocyclic residue is preferably a 5- to 7-membered substituted or unsubstituted, saturated or unsaturated, aromatic or non-aromatic, monocyclic or condensed ring aromatic fused residue. More preferably an aromatic heterocyclic residue having a ring atom selected from the group consisting of a carbon atom, a nitrogen atom and a sulfur atom, and having a hetero atom of at least any one of a nitrogen atom, an oxygen atom and a sulfur atom. More preferably a 5- or 6-membered aromatic heterocyclic residue having 3 to 30 carbon atoms. For example, 2-pyridyl, 4-pyridyl, 2-pyrimidinyl, 2-benzothiazolyl, imidazol-2-yl and the like.

The alkoxyl group is preferably a straight chain, branched or cyclic alkoxyl group having 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, and particularly preferably 1 to 10 carbon atoms. For example, methoxy, ethoxy, n-propoxy, isobutoxy, n-butoxy, isobutoxy, tert-butoxy and the like.

The alkylthio group is preferably a straight chain, branched or cyclic alkylthio group having 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, and particularly preferably 1 to 10 carbon atoms. For example, methylthio, ethylthio, n-decylthio and the like.

The monovalent non-metallic atomic group may be substituted as described above. Examples of the substituent include an alkyl group, an alkenyl group, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, an alkoxy group, an alkoxycarbonyl group, an acyl group, a hydroxyl group, an alkylthio group and an arylthio group. When these substituents have carbon atoms, the total number of carbon atoms is preferably from 1 to 30, more preferably from 1 to 20, and most preferably from 1 to 10.

In the compound represented by the general formula (VI), from the viewpoint of improving the decomposition efficiency of the photopolymerization initiator, Y is preferably an oxygen atom or -N (R ³ ) -, most preferably -N (R ³ ) -. R ³ are each independently a hydrogen atom or a monovalent nonmetal atomic group.

Hereinafter, preferable specific examples (VI1) to (VI124) of the compound represented by the general formula (VI) are shown, but the present invention is not limited thereto. In addition, it is not clear about the isomer of a double bond connecting an acidic nucleus and a basic nucleus, and the present invention is not limited to any one isomer.

The compound represented by the general formula (VI) according to the present invention may further be subjected to various chemical modifications to improve the properties of the curable composition.

For example, by bonding a sensitizer (hereinafter also referred to as a "sensitizing dye") and an addition-modifying compound structure (such as acryloyl group and methacryloyl group) by covalent bonding, ionic bonding, hydrogen bonding or the like, And unnecessary precipitation of the sensitizing dye from the exposed film can be suppressed.

Further, it is also possible to use a combination of a sensitizing dye and a partial structure having a radical generating ability in the above-mentioned photopolymerization initiator (a reducing decomposition site such as alkyl halide, onium, peroxide and biimidazole, and a borate, amine, trimethylsilylmethyl, carboxymethyl, carbonyl and amine The oxidative cleavage site of the photocatalyst) remarkably improves the photosensitivity especially in the low concentration of the exposure clock.

In the curable composition of the present invention, the compounds represented by the general formulas (IV) to (VI) may be used singly or in combination of two or more kinds.

When the light transmittance of the colored pattern (photosensitive layer) formed is very low due to the concentration of the coloring agent (pigment or the like) in the curable composition, specifically, when the light transmittance of 365 nm of the photosensitive layer formed without adding the sensitizing dye is 10 %, The effect of improving the photosensitivity can be remarkably exhibited by adding the compound represented by the above general formulas (IV) to (VI). Among the above-mentioned general formulas (IV) to (VI), the compound represented by the general formula (VI) is most preferable. Specifically, the compounds (VI56) to (VI122) are most preferable.

The sensitizers may be used alone or in combination of two or more.

The content of the sensitizer in the curable composition of the present invention is preferably 0.1% by mass to 20% by mass, more preferably 0.5% by mass to 15% by mass, based on the total solid content of the curable composition, % Is more preferable. The above range is preferable because the light absorbing efficiency at the core portion of the curable composition is increased and the initial decomposition efficiency is improved.

<(H) Notarization>

The curable composition of the present invention may contain a notarization agent. In the present invention, the notarization sensitizer further acts to enhance the sensitivity of the sensitizing dye or photopolymerization initiator to the active radiation, or to inhibit polymerization inhibition of the polymerizable compound by oxygen.

Examples of such notarization include M. R. Sander et al. Quot; Journal of Polymer Society "vol. 10, page 3, 173 (1972), Japanese Patent Publication Nos. 44-20189, 51-82102, 52-134692, 59-138205, 60-84305, 62-18537, Amines such as those described in Research Disclosure No. 33825, and the like. Specifically, triethanolamine, p-dimethylaminoethyl ester benzoate, p-formyldimethylaniline, p-methylthiodymethyl aniline and the like can be exemplified.

Other examples of the notarization agent include thiol and sulfide, for example, the thiol compounds described in JP 53-702 A, JP 55-500806 A and JP 5-142772 A, Disulfide compounds disclosed in JP-B-56-75643, specifically, 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, 2-mercaptobenzimidazole, 2-mercapto-4 (3H) Zolene and? -Mercaptonaphthalene.

Other examples of the notarization agent include amino acid compounds (e.g., N-phenylglycine), organometallic compounds described in Japanese Patent Publication No. 48-42965 (such as tributyltin acetate, etc.) A hydrogen donor compound disclosed in JP-A-55-34414, and a sulfur compound (e.g., trithian) disclosed in JP-A-6-308727.

From the viewpoint of the improvement of the curing rate in accordance with the polymerization growth rate and the balance of the chain transfer, the content of the notarization agent relative to the mass of the total solid content of the curable composition is preferably in the range of 0.1 to 30 mass%, more preferably 0.5 to 25 By mass, more preferably in the range of 1.0% by mass to 20% by mass,

&Lt; (I) Polymerization inhibitor >

In the present invention, it is preferable to add a small amount of a thermal polymerization inhibitor in order to inhibit unnecessary thermal polymerization of a compound having a polymerizable ethylenically unsaturated double bond during the production or preservation of the curable composition.

Examples of the thermal polymerization inhibitor used in the present invention include hydroquinone, p-methoxyphenol, di-t-butyl-p-cresol, pyrogallol, t-butylcatechol, benzoquinone, 4,4'-thiobis Methyl-6-t-butylphenol), 2,2'-methylenebis (4-methyl-6-t-butylphenol) and N-nitrosophenylhydroxyamine trinitrate.

The addition amount of the polymerization inhibitor is preferably about 0.01% by mass to about 5% by mass with respect to the mass of the total composition. If necessary, a higher fatty acid derivative such as behenic acid or behenic acid amide may be added in order to prevent the polymerization inhibition by oxygen, and may be dispersed non-uniformly on the surface of the photosensitive layer during the drying step after coating. The amount of the higher fatty acid derivative added is preferably about 0.5% by mass to about 10% by mass of the total composition.

<Other additives>

In the present invention, known additives such as an inorganic filler for improving the physical properties of the cured coating film, a plasticizer and a sensitizer for improving the ink property of the surface of the photosensitive layer, and a substrate adhesion agent for improving substrate adhesion may be added good.

As the plasticizer, for example, dioctyl phthalate, didodecyl phthalate, triethylene glycol dicaprylate, dimethyl glycol phthalate, tricresyl phosphate, dioctyl adipate, dibutyl sebacate, triacetyl glycerol and the like can be exemplified. When a coupling agent is used, it may be added in an amount of 10 mass% or less based on the total mass of the compound having an ethylenically unsaturated double bond and the coupling agent.

When the curable composition of the present invention is used on the surface of a hard material such as a substrate, an additive for improving the adhesion to the surface of the hard material (hereinafter also referred to as "substrate adhesion agent") may be added.

As the substrate adhering agent, known materials can be used. In particular, it is preferable to use a silane-based coupling agent, a titanate-based coupling agent or an aluminum-based coupling agent.

Examples of silane coupling agents include γ- (2-aminoethyl) aminopropyltrimethoxysilane, γ- (2-aminoethyl) aminopropyldimethoxysilane, β- (3,4-epoxycyclohexyl) Aminopropyltrimethoxysilane,? -Aminopropyltrimethoxysilane,? -Methacryloxypropyltrimethoxysilane,? -Methacryloxypropyltriethoxysilane,? -Acryloxypropyltrimethoxysilane,? -Methacryloxypropyltrimethoxysilane, -Isocyanate propyltrimethoxysilane,? -Isocyanate propyltriethoxysilane, N -? - (N-vinylbenzylaminoethyl) -? - aminopropyltrimethoxysilane, Γ-mercaptopropyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylethoxysilane, aminosilane, γ-mercaptopropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane, methyl The Vinyltriethoxysilane,? -Chloropropyltrimethoxysilane, hexamethyldisilazane,? -Anilinopropyltrimethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltriethoxysilane, vinyltriethoxysilane, Octadecyldimethyl [3- (trimethoxysilyl) propyl] ammonium chloride,? -Chloropropylmethyldimethoxysilane,? -Mercaptopropylmethyldimethoxysilane,? -Mercaptopropylmethyldimethoxysilane , Trimethylchlorosilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, bisallyltrimethoxysilane, tetraethoxysilane, bis (trimethoxysilyl) Hydroxypropyl) -3-aminopropyltriethoxysilane, N- (3-methacryloxy-2-hydroxypropyl) Aminopropyltriethoxysilane, (meta Reel yloxymethyl) can be enumerated, methyl diethoxy silane, and (acryloxypropyl) methyl dimethoxysilane.

In particular, it is preferable to use at least one member selected from the group consisting of? -Methacryloxypropyltrimethoxysilane,? -Methacryloxypropyltriethoxysilane,? -Acryloxypropyltrimethoxysilane,? -Acryloxypropyltriethoxysilane,? -Mercaptopropyltri Methoxysilane,? -Aminopropyltriethoxysilane and phenyltrimethoxysilane are preferable, and? -Methacryloxypropyltrimethoxysilane is most preferable.

Examples of titanate-based coupling agents include isopropyltriisostearoyl titanate, isopropyltridecylbenzenesulfonyl titanate, isopropyl tris (dioctyl pyrophosphate) titanate, tetraisopropyl bis (dioctylphosphite) (Di-tridecyl) phosphite titanate, bis (dioctyl pyrophosphate) oxyacetate titanate (di-tridecylphosphate) titanate, tetra , Bis (dioctyl pyrophosphate) ethylene titanate, isopropyl trioctanoyl titanate, isopropyl dimethacryl isostearoyl titanate, isopropyl isostearoyl diacrylate titanate, triisopropyl tri (dioctyl Phosphate) titanate, isopropyl tricumyl phenyl titanate, isopropyl tri (N-amide ethyl amino Nonethyl) titanate, dicumylphenyloxyacetate titanate, and diisostearoylethylene titanate.

Examples of the aluminum-based coupling agent include acetoalkoxyaluminum diisopropylate.

The content of the substrate adhesion agent with respect to the total solid content of the curable composition of the present invention is preferably from 0.1% by mass to 30% by mass, more preferably from 0.5% by mass to 30% by mass, from the viewpoint of preventing remnants remaining in the unexposed portion upon exposure to the curable composition. By mass to 20% by mass, and particularly preferably 1% by mass to 10% by mass.

According to the above configuration, the curable composition of the present invention can be cured with high sensitivity, and storage stability is also preferable. Further, the curable composition of the present invention exhibits high adhesiveness to the surface of a material (a hard material such as a substrate) to be used. Therefore, the curable composition of the present invention can be advantageously used in the fields of image forming materials such as three-dimensional photo molding, holography and color filters, or inks, paints, adhesives, coatings and the like.

[Color filter and manufacturing method thereof]

Next, the color filter of the present invention and the manufacturing process thereof will be described.

The color filter of the present invention is characterized by having a coloring pattern using the curable composition of the present invention on a support.

Next, the color filter of the present invention will be described in detail with reference to the production process thereof (the process for producing the color filter of the present invention).

The method for producing a color filter of the present invention comprises the steps of: forming a colored layer comprising a curable composition by applying the curable composition of the present invention on a supporting member; an exposure step of exposing the colored layer through a mask; And developing the layer to form a colored pattern.

Hereinafter, each step in the production method of the present invention will be described.

&Lt; Coloring layer forming step &

In the colored layer formation step, the colored layer made of the curable composition is formed by applying the curable composition of the present invention on the supporting member.

Examples of the support that can be used in this step include soda glass, Pyrex (registered trademark) glass, quartz glass, a glass having a transparent conductive film adhered thereon, and a photoelectric conversion element substrate used in an imaging device, A silicon substrate and a complementary metal oxide semiconductor (CMOS). On these substrates, a black stripe for separating each pixel may be formed.

If necessary, a lower coating layer may be formed on these supports for improving the adhesion with the upper layer, preventing diffusion of substances, and planarizing the surface of the substrate.

As a method of applying the curable composition of the present invention to the support member, various coating methods such as slit coating, ink jet coating, spin coating, cast coating, roll coating and screen coating can be used.

The film thickness of the curable composition is preferably 0.1 to 10 占 퐉, more preferably 0.2 to 5 占 퐉, and even more preferably 0.2 to 3 占 퐉, from the viewpoints of uniformity of the coating film of the coating film and ease of drying of the coating solvent.

The colored layer (curable composition layer) coated on the substrate may be dried (pre-baked) at 50 to 140 DEG C for 10 to 300 seconds in a hot plate, an oven or the like.

The coating film thickness (hereinafter also referred to as "dried film thickness") of the curable composition after drying is preferably from 0.1 μm or more to less than 2.0 μm from the viewpoint of compatibility for LCD and color density for use as a color filter for LCD, More preferably 0.2 μm or more and 1.8 μm or less, and particularly preferably 0.3 μm or more and 1.75 μm or less.

Further, in order to use as a color filter for IS, the thickness is preferably 0.05 mu m or more and less than 1.0 mu m from the viewpoint of securing the color density and reducing the problems such as a remarkable difference in the light collection ratio between the distal end portion and the central portion of the device , More preferably from 0.1 탆 to 0.8 탆, and particularly preferably from 0.2 탆 to 0.7 탆.

<Exposure Step>

In the exposure step, the colored layer (curable composition layer) formed in the colored layer formation step is exposed through a mask having a predetermined mask pattern.

According to the exposure in this step, the pattern exposure of the coated film can be performed by exposing it through a predetermined mask pattern by light irradiation so as to cure only the coated film portion. As the radiation used for exposure, ultraviolet rays such as g-line and i-line can be preferably used. Dose is 5 ~ 1,500mJ / cm ² is preferable, and 10 ~ 1,000mJ / cm ^2, and more preferred, most preferred 10 ~ 500mJ / cm ^2.

If the color filter is a liquid crystal display device of the present invention tolerate, the 5 ~ 200mJ / cm ² in the above range is preferable, more preferably ^{10 ~ 150mJ / cm 2, 10} ~ 100mJ / cm 2 is most preferred. Further, when the color filter the solid-state image sensor of the present invention tolerate, is 30 ~ 1,500mJ / cm ² from the above-mentioned range is preferable, and, and is 50 ~ 1,000mJ / cm ² and more preferably 80 ~ 500mJ / cm ² is most preferably .

<Development step>

Then, by performing the alkali developing step (developing step), only the portion having the light irradiation portion eluted with the alkali aqueous solution against the photo-curing by the above exposure remains. And developing with a developing solution to form a pattern coating film having each color (3 or 4 colors). As the developing solution, an organic alkali developing solution free from the risk of damage to the basic circuit is preferable. The development temperature is usually 20 to 30 ° C, and the development time is 20 to 90 seconds.

Examples of the alkali agent to be used as the developer include aqueous ammonia, ethylamine, diethylamine, dimethylethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, choline, pyrrole, piperidine and 1,8-diazabicyclo - [5,4,0] -7-undecene, inorganic compounds such as sodium hydroxide, potassium hydroxide, sodium hydrogen chloride and potassium hydrogencarbonate. An alkaline aqueous solution obtained by diluting these alkali agents with pure water to a concentration of 0.001 mass% to 10 mass%, preferably 0.01 mass% to 1 mass% can be preferably used. When a developer composed of such an aqueous alkaline solution is used, it is generally rinsed with pure water after development.

Then, after the cleaning to remove the surplus developer, it is dried.

The production method of the present invention includes a curing step of curing by heating (post-baking) and / or exposure after the coloring layer forming step, the exposure step and the developing step as described above, and then, if necessary,

Post-baking is a post-development heat treatment for completing curing, and heat curing treatment is usually performed at 100 to 240 캜. When the substrate is a glass substrate or a silicon substrate, the temperature is preferably 200 to 240 DEG C within the above temperature range.

This post-baking treatment can be carried out continuously or batchwise using a heating means such as a hot plate, a convection oven (hot-air circulation type drier) and a high-frequency heater so that the coating film becomes the above-mentioned condition after development.

By repeating the above-mentioned coloring layer forming step, the exposure step and the developing step (and further, if necessary, the curing step) only the desired number of hues, a color filter having a desired color can be produced.

While the use of the curable composition of the present invention has been mainly described as a pixel of a color filter, It goes without saying that the present invention is also applicable to a black matrix provided between pixels of a color filter. The black matrix is preferably used as the curable composition of the present invention, except that a coloring agent having a black pigment such as carbon black or titanium black is used as the curable composition of the present invention, Can be formed in the same manner.

Since the color filter of the present invention is produced by using the curable composition of the present invention having excellent exposure sensitivity, the composition cured in the exposure part is excellent in adhesion to the substrate and developing resistance, and the formed color pattern is high The pattern having adhesion and providing a desired cross-sectional shape has a high resolution.

Further, the solid-state image pickup device of the present invention includes the color filter of the present invention manufactured by the above-described method of manufacturing a color filter of the present invention.

Therefore, specifically, the color filter of the present invention can be preferably used for a liquid crystal display element and a solid-state image pickup element such as a CCD, and can be suitably used for a high-resolution CCD element or CMOS exceeding 1,000,000 pixels in particular. The color filter of the present invention can be used as a color filter disposed between a light receiving portion of each pixel including a CCD element and a microlens for condensing.

Example

Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited thereto.

[Synthesis Example 1]

&Lt; Synthesis of Compound (i-1) >

In a 500 ml three-necked flask, 58.6 g of 2-hydroxyethyl methacrylate was added, 250 ml of acetone was added thereto, and the mixture was stirred. 39.2 g of pyridine and 0.1 g of p-methoxyphenol were added thereto and then cooled in an iced ice bath. After the temperature of the liquid mixture became 5 占 폚 or less, 114.9 g of 2-bromoisobutanoic acid bromide was added dropwise thereto in a dropping funnel over 3 hours. After completion of the dropping operation, the ice bath was removed and stirring was further continued for 3 hours. The reaction mixture was poured into 750 ml of water and stirred for 1 hour. Water mixture was extracted three times with 500 ml of ethyl acetate using a separatory funnel. The organic layer was washed successively with 500 ml of 1 M hydrochloric acid, 500 ml of a saturated aqueous sodium hydrogencarbonate solution and 500 ml of saturated brine. 100 g of magnesium sulfate was added to the organic layer, followed by dehydration and drying, followed by filtration. Vacuum removal of the solvent gave 120.3 g of a residue.

It was confirmed from the ¹ H-NMR, IR and mass spectrometry spectra that the obtained residue was the compound (i-1). In addition, the purity from HPLC was 95%.

(1) Synthesis of resin (I)

86 g of 1-methyl-2-pyrrolidone in a 1,000 ml three-necked flask was heated to 90 DEG C in a nitrogen stream. 55 g of the compound (i-1), 47 g of the exemplified compound M-14MA, 13 g of methacrylic acid and 8.2 g of 2,2'-azobis (2-methylpropionate) (V-601, produced by Wako Pure Chemical Industries, Ltd.) g and 86 g of 1-methyl-2-pyrrolidone was added dropwise over 2 hours. After completion of the dropping operation, this was further stirred for 2 hours. After the reaction solution was cooled to room temperature, it was poured into 7 L of water to precipitate a polymer compound. The precipitated polymer compound was filtered, washed with water and dried to obtain 110 g of a polymer compound.

The weight average molecular weight of the polymer compound obtained by gel permeation chromatography (GPC) using polystyrene as a standard substance was measured and found to be 13,100. Further, the acid value was measured by titration to find that it was 1.25 meq / g (calculated value: 1.30 meq / g), and thus it was confirmed that the polymerization was carried out normally.

110 g of the obtained polymer compound, 0.1 g of p-methoxyphenol and 470 g of 1-methyl-2-pyrrolidone were placed in a 1,000-mL three-necked flask and cooled in an ice bath containing ice water. After the temperature of the liquid mixture became 5 占 폚 or less, 100 g of 1,8-diazabicyclo [5.4.0] -7-undecene (DBU) was added dropwise thereto over a period of 1 hour using a dropping funnel. After completion of the dropping operation, the ice bath was removed and the mixture was further stirred for 8 hours. Concentrated hydrochloric acid was added to the reaction solution to adjust the pH to 7, and this was added to 7 L of water to precipitate the resin (I) of the polymer compound. The precipitated polymer compound was filtered, washed with water and dried to obtain 95 g of a polymer compound.

According to ¹ H-NMR measurement of the obtained polymer compound, it was confirmed that 100% of the side chain groups derived from the compound (i-1) were converted into ethylene methacrylate groups. Further, the mass average molecular weight was measured by gel permeation chromatography (GPC) using polystyrene as a standard substance, and the result was 12,100. The acid value was measured by titration to find that it was 1.45 meq / g (calculated value: 1.51 meq / g).

[Example 1]

[A1. Preparation of curable composition]

Here, a production example of a curable composition containing a pigment for forming a color filter for use in a liquid crystal display element is described and described.

A1-1. Preparation of pigment dispersion

Preparation of pigment dispersion

40 parts by mass (average particle size: 61 nm) of a 30/70 (mass ratio) mixture of C.I. Pigment Green 36 and C.I. Pigment Yellow 219 as a pigment (Disperbyk: Bic Chemie (BYK) Corp., 50 parts by mass of BYK2001 (about 22.6 parts by mass based on solid content) of a solid content concentration of 45.1% by mass, 5 parts by mass of the resin (I) of the present invention and 110 parts by mass of 3-ethoxyethyl propionate as a solvent Was mixed and dispersed in a beads mill for 15 hours to prepare a pigment dispersion (P1).

The average particle size of the pigment was measured by dynamic light scattering method using Microtrac Nanotrac UPA = EX150 (manufactured by Nikkisou Co., Ltd.) without further dilution of P1 with respect to the pigment dispersion (P1), which was 32 nm.

A1-2. Preparation of Curable Composition (Coating Liquid)

Using the dispersion-treated pigment dispersion P1, the curable composition solution was prepared by stirring and mixing in the following composition ratio.

Colorant (D) (Pigment dispersion (P1)) 600 parts by mass

Photopolymerization initiator (B)

(30 parts by weight) of 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole

(C) 50 parts by mass of pentaerythritol tetraacrylate

5 parts by mass of (E) an alkali-soluble resin (benzyl methacrylate / methacrylic acid / hydroxylethyl methacrylate copolymer, molar ratio: 80/10/10, Mw: 10,000)

Solvent: PGMEA 900 parts by weight

· 1 part by mass of substrate adhesion agent (3-methacryloxypropyltrimethoxysilane)

(F) 15 parts by mass of a sensitizer (the following compound?)

(G) 15 parts by weight of notarized sensitizer (2-mercaptobenzoimidazole)

                The general formula?

[A2. Manufacture of Color Filter]

A2-1. Formation of Curable Composition Layer

The curable composition containing the pigment was applied to a glass substrate of 550 mm x 650 mm as a resist solution by slit coating under the following conditions, left as it was for 10 minutes, vacuum dried and prebaked (at 100 캜 for 80 seconds) To form a curable composition coating film (curable composition layer).

(Slit application condition)

Distance between openings at the tip of the application head: 50 탆

· Coating speed: 100mm / sec

Clearance between the substrate and the coating head: 150 mu m

Dry film thickness: 1.75 탆

· Application temperature: 23 ℃

A2-2. Exposure, development

Thereafter, the curable composition coating film was exposed in a pattern using a 20 mu m line-width photomask using a 2.5 kW extra-high pressure mercury lamp. After exposure, the entire surface of the coated film was covered with a 10% aqueous solution of an organic developing solution (trade name: CD, manufactured by Fuji Film Electronics Materials Corp.), and left for 60 seconds.

A2-3. Heat treatment

After the solution was left standing, pure water was sprayed onto the shower surface to clean the developer, and the exposed (photocuring) treatment and the developed coating film were heated in an oven at 220 ° C for 1 hour (post baking). Thus, a color filter having a curable composition coating film (colored layer) formed on a glass substrate was obtained.

[A3. Performance evaluation]

The storage stability of the coating liquid composed of the curable composition prepared above and the curability of the curable composition film (colored layer) formed on the glass substrate using the curable composition were evaluated as follows: exposure sensitivity, substrate adhesion, developability and cross- did. The results are shown in Table 1.

A3-1. Storage stability of the curable composition

After the prepared curable composition (coating liquid) was stored at room temperature for one month, the viscosity of the solution was measured and evaluated according to the following criteria.

-Evaluation standard-

A: No viscosity increase

B: Viscosity increase from 5% to less than 10%

C: Viscosity increase of 10% or more

A3-2. Exposure sensitivity of the curable composition coating film (colored layer)

The curable composition coating film was exposed at various exposure amounts varying from 10 to 100 mJ / cm &lt; ² &gt; to evaluate the exposure sensitivity at which the pattern line width after post-baking became 20 mu m. The smaller the exposure sensitivity value, the higher the sensitivity.

A3-3. Developability, pattern cross-sectional shape, substrate adhesion

The post-baked substrate surface and its cross-sectional shape were observed by an optical microscope and an SEM photograph to evaluate developability, cross-sectional shape of the pattern, and substrate adhesion. Details of the evaluation method and evaluation criteria are as follows.

<Developability>

The developing property was evaluated by observing the presence of a residue in a light-unexposed region (unexposed portion) in the exposure step.

-Evaluation standard-

A: Residue is not confirmed in minerals

B: A little confirmation that the residue in the unexposed area does not cause practical problems

C: Remnant is remarkably confirmed in the unexposed area

&Lt; Pattern cross-sectional shape &

Sectional shape of the formed pattern was observed. The pattern cross-sectional shape is most preferably a regular taper, and then a rectangle is preferable. Reverse tapering is undesirable.

&Lt; Substrate adhesion property &

The substrate adhesion was evaluated according to observation of whether or not the pattern was defective. The evaluation criteria are as follows.

-Evaluation standard-

A: No pattern defect was observed.

B: The pattern defect was hardly observed, but some defect was observed.

C: Pattern defects were remarkably observed.

[Comparative Example 1]

A color filter was prepared in the same manner as in Example 1 except that the resin (I) was not used in the curable composition prepared in Example 1, and the same evaluation as in Example 1 was carried out. The results are shown in Table 2.

[Examples 2 to 10]

A color filter was prepared in the same manner as in Example 1 except that the resin shown in Table 2 was used in place of the resin (I) in the curable composition prepared in Example 1, and the same evaluation as in Example 1 was carried out. The results are shown in Table 2.

[Example 11, Comparative Example 2]

Except that Resin (II) and Resin (III) synthesized in the same manner as Resin (I) were used in place of Resin (I) in the curable composition prepared in Example 1, And the same evaluation as in Example 1 was carried out. The dipole moment of the monomer used for Resin (II) was calculated to be 2.48. The dipole moment of n-butyl acrylate used in Resin (III) was calculated to be 1.58. The results are shown in Table 2.

From the results in Table 2, it can be seen that the curable composition of the example containing the resin of the present invention has stable storage stability in the solution state. In the case where the curable composition is used to form a colored pattern on the supporting member, the comparative example using no resin of the present invention is excellent in exposure sensitivity and developing property, It can be seen that this excellent color filter is obtained.

[Example 12]

Hereinafter, an example of producing a curable composition containing a coloring agent (pigment) for forming a color filter for a solid-state image sensor will be described.

[B1. Preparation of Resist Solution]

A resist solution was prepared by mixing and dissolving the following composition components.

&Lt; Composition of Resist Solution >

Propylene glycol monomethyl ether acetate 19.20 parts by mass

(PGMEA: solvent)

Ethyl lactate 36.67 parts by mass

(E) resin (40% PGMEA solution of benzyl methacrylate / methacrylic acid / 2-hydroxyethyl methacrylate copolymer (molar ratio = 60/22/18)) 30.51 parts by mass

(C) Ethylenically unsaturated double bond-containing compound (dipentaerythritol hexaacrylate) 12.20 parts by mass

Polymerization inhibitor (p-methoxyphenol) 0.0061 parts by mass

Fluorine-based surfactant (F-475, manufactured by Dainippon Ink Chemical Industry, Corp.)

                                                                   0.83 parts by mass

Photopolymerization initiator (B) (trihalomethyltriazine-based photopolymerization initiator) 0.586 parts by mass

(TAZ-107, manufactured by Midori Kagaku Co., Ltd.)

[B2. Preparation of silicon substrate having base coating layer]

A 6 inch silicon wafer was heat treated in an oven at 200 占 폚 for 30 minutes. Then, the resist solution was coated on the silicon wafer so that the dry film thickness became 1.5 占 퐉, and the base coating layer was formed by heating and drying in an oven at 220 占 폚 for 1 hour to form a silicon wafer substrate having the base coating layer .

[B3. Preparation of pigment dispersion]

40 parts by mass (average particle size 65 nm) of a mixture of C.I. Pigment Green 36 and C.I. Pigment Yellow 150, 30/70 by mass (mass ratio) as a pigment, and dispersant (Disperbyk: BYK Chemi (BYK) Corp.). , 10 parts by mass of the resin (I) in the present invention, and 110 parts by mass of propylene glycol monomethyl ether as a solvent) were dispersed in a bead mill The pigment dispersion (P2) was prepared by mixing and dispersing for 15 hours.

The average particle size of the pigment for the pigment dispersion (P2) was measured by the dynamic light scattering method in the same manner as in Example 1, which was 32 nm.

[B4. Preparation of curable composition (coating liquid)

Using the dispersion-treated pigment dispersion P2, the curable composition solution was prepared by stirring and mixing in the following composition ratio.

Colorant (D) (Pigment dispersion (P2)) 600 parts by mass

Photopolymerization initiator (B) (Oxime photopolymerization initiator) 30 parts by mass

(CGI-124, available from Chiba Specialty Chemicals, Corp.)

(C-1) 25 parts by mass of TO-1382 (manufactured by Toa Gosei Corp.)

(C-1) 30 parts by mass of dipentaerythritol hexaacrylate

Solvent (PGMEA) 900 parts by mass

· 1 part by mass of substrate adhesion agent (3-methacryloxypropyltrimethoxysilane)

[B5. Preparation and Evaluation of Color Filter by Curable Composition]

&Lt; Pattern formation and sensitivity evaluation >

The curable composition prepared as described above was applied to the base coating layer of the silicon wafer having the base coating layer obtained in the step B2 to form a colored layer (coating film). Next, heat treatment (prebaking) was carried out for 120 seconds using a hot plate at 100 캜 so that the dried film thickness of the coated film became 0.7 탆.

Then, using an i-line stepper exposure apparatus FPA-3000i5 + (manufactured by Canon Inc.), exposure was carried out at various exposure amounts of 50 to 1,200 mJ / cm ² through an Island pattern mask having a pattern of 2 탆 square at a wavelength of 365 nm.

Thereafter, the silicon wafer substrate on which the coated film was irradiated was placed on a horizontal rotary table of a spin-shower developing machine (DW-30 type, manufactured by Chemitronics Corp.), and CD-2000 (manufactured by Fuji Film Electronics Materials, And puddle development at 23 DEG C for 60 seconds to form a colored pattern on the silicon wafer substrate.

Pure water is supplied from the injection nozzle to the showerhead while rotating the silicon wafer substrate at a rotation speed of 50 rpm by a rotary device fixed to the horizontal rotary table by a chuck system in a vacuum chucking manner Followed by rinsing, followed by spray drying.

Thereafter, the size of the colored pattern was measured using the length measurement SEM "S-9260A" (manufactured by Hitachi High Technologies Corp.). The exposure amount at which the pattern line width became 2 탆 was evaluated as the exposure sensitivity. The smaller the exposure sensitivity value, the higher the sensitivity. The measurement results are shown in Table 2 below.

<Developability>

The developing property was evaluated by observing the presence of a residue in a light-unexposed region (unexposed portion) in the exposure step.

-Evaluation standard-

A: Residue is not confirmed in minerals

B: A little confirmation that the residue in the unexposed area does not cause practical problems

C: Remnant is remarkably confirmed in the unexposed area

&Lt; Pattern Formability >

Sectional shape of the formed pattern was observed. The pattern cross-sectional shape is most preferably a regular taper, then a rectangle is preferred, and a reverse taper is not preferred.

&Lt; Substrate adhesion property &

As to the substrate adhesion, it was observed whether or not the pattern was defective. These evaluation items were evaluated according to the following evaluation criteria.

-Evaluation standard-

A: No pattern defect was observed.

B: The pattern defect was hardly observed, but some defect was observed.

C: Pattern defects were remarkably observed.

<Storage Stability of Curable Composition>

After the curable composition (coating liquid) prepared in the step B4 was stored at room temperature for one month, the viscosity of the solution was measured and evaluated according to the following criteria.

-Evaluation standard-

A: No viscosity increase

B: Viscosity increase from 5% to less than 10%

C: Viscosity increase of 10% or more

<Uneven color>

The color unevenness was evaluated by calculating the ratio of the pixels whose deviations from the average are within ± 5% to the total number of pixels by analyzing the luminance distribution by the following method. The evaluation criteria are as follows.

A method of measuring the luminance distribution will be described. First, a curable composition was applied on a base coating layer of a glass plate having a base coating layer obtained in the same manner as in Step B2 above to form a colored layer (coating film). Heat treatment (pre-baking) was performed for 120 seconds using a hot plate at 100 占 폚 so that the dried film thickness of the coated film became 0.7 占 퐉. An image photographed with a microscope MX-50 (manufactured by Olympus Corp.) was analyzed for the luminance distribution of the coated glass plate.

-Evaluation standard-

A: Pixels whose deviation from the average is within ± 5% occupy more than 99% of the total number of pixels.

B: Pixels within ± 5% deviation from the average occupy 95% or more and less than 99% of the total number of pixels

C: Pixels within ± 5% deviation from the average occupy less than 95% of the total number of pixels

[Comparative Example 3]

A color filter in which a colored pattern was formed in the same manner as in Example 12 except that the resin (I) was not used in the curable composition prepared in Example 12 was obtained and evaluated in the same manner as in Example 12. The results are shown in Table 3.

[Examples 13 to 22, Comparative Example 4]

A color filter was produced in the same manner as in Example 12 except that the resin shown in Table 3 was used in place of the resin (I) in the curable composition prepared in Example 12, and the same evaluations as in Example 12 were carried out. The results are shown in Table 3.

From the results shown in Table 3, it can be seen that the curable composition (pigment system) of the example containing the resin in the present invention used for forming a color filter for use in a solid-state image sensor is excellent in storage stability in a solution state. In addition, when the curable composition is used to form a colored pattern on the support member, the exposure sensitivity is high and the developability is excellent, and the substrate adhesion, the cross-sectional shape of the pattern and the cross- It can be seen that a color filter excellent in color unevenness is obtained.

From these results, it can be seen that the curable composition of the examples realizes excellent pattern formability both in the case of producing a color filter for use in a solid-state imaging device and in the case of producing a color filter for use in a liquid crystal display element.

[Example 23]

Hereinafter, an embodiment for producing a curable composition containing a colorant (dye) for forming a color filter for a solid-state image sensor will be described.

[C1. Preparation of Resist Solution and Production of Silicon Substrate with Base Coating Layer]

The results of [B1. Preparation of resist solution] and [B2. Production of a silicon substrate having a base coating layer] A silicon substrate having a base coating layer was produced in the same manner as in the above.

[C2. Preparation of curable composition (coating liquid)

The following composition was mixed and dissolved to prepare a colored photosensitive resin composition.

Cyclohexanone (solvent) 80 parts by mass

(D) Valifast Yellow 1101 (dye) 6.0 parts by mass

(D) Acid Red 57 (dye) 6.0 parts by mass

(C) 2.5 parts by mass of dipentaerythritol hexaacrylate

· 2.0 parts by mass of the oxime-based photopolymerization initiator (B)

(CGI-124, a product of Ciba Specialty Chemicals Corp.)

- 1.5 parts by mass of the resin (I)

[C3. Preparation and Evaluation of Color Filter by Curable Composition]

[B5. Production and Evaluation of Color Filter by Curable Composition] A color filter was produced and evaluated in the same manner as described above. The results are shown in Table 4.

[Comparative Example 5]

A color filter having a colored pattern formed in the same manner as in Example 23 except that the resin (I) was changed to pentaerythritol triacrylate in the curable composition prepared in Example 23 was evaluated and evaluated in the same manner as in Example 23. The results are shown in Table 4.

[Examples 24 to 33, Comparative Example 6]

A color filter was produced in the same manner as in Example 23 except that the resin shown in Table 4 was used in place of the resin (I) in the curable composition prepared in Example 23, and the same evaluations as in Example 23 were carried out. The results are shown in Table 4.

From the results shown in Table 4, it can be seen that the curable composition (dye system) of the embodiment containing the resin of the present invention used for the formation of the color filter for the solid-state image sensor has excellent storage stability in the solution state.

From the results of Examples in which a colored pattern was formed on the supporting member using this curable composition, a color filter having a high exposure sensitivity, excellent developing property, and excellent substrate adhesion and pattern cross-sectional shape was obtained as compared with Comparative Example .

From these results, it can be understood that, even when a color filter for use in a solid-state imaging device is manufactured, the curable composition of the embodiment realizes excellent pattern formation as in the case of producing a color filter for use in a liquid crystal display element.

Embodiments of the present invention are described below.

<1> A curable composition containing a resin, a compound having an ethylenically unsaturated double bond, and a photopolymerization initiator, wherein the resin is produced by polymerizing at least a monomer having a dipole moment of 2.0 or more as a copolymer component.

&Lt; 2 > The curable composition of < 1 >, wherein the monomer is a monomer having a dipole moment of 2.5 or more.

&Lt; 3 > The curable composition according to < 1 >, wherein the resin has an ethylenically unsaturated double bond in its side chain obtained by polymerizing at least a monomer having a dipole moment of 2.5 or more as a copolymerization component.

<4> A curable composition according to any one of <1> to <3>, wherein the monomer having a dipole moment of 2.0 or more is an ether group Wherein the curable composition has at least one selected from the group consisting of

<5> The curable composition according to any one of <1> to <4>, further comprising a colorant.

<6> The curable composition according to any one of <1> to <5>, further comprising a sensitizer.

<7> A color filter having a coloring pattern formed of the curable composition of <5> or <6>

<8> A process for producing a colored pattern, comprising the steps of: forming a colored layer made of a curable composition by applying the curable composition of <5> or <6>; exposing the colored layer through a mask; Wherein the step of forming the color filter comprises the steps of:

&Lt; 9 > A solid-state imaging device comprising the color filter manufactured by the manufacturing method of the color filter of < 8 >.

Claims (13)

1. A curable composition comprising a resin, a compound having an ethylenically unsaturated double bond and a photopolymerization initiator, wherein the resin is prepared by polymerizing at least a monomer having a dipole moment of 2.0 or more as a copolymerization component, wherein the monomer having a dipole moment of 2.0 or more is a phosphate ester group , A lactone group, a urethane group, a carbonate ester group, and an acetal group. The curable composition of claim 1, wherein the monomer has a dipole moment of at least 2.5. The curable composition according to claim 1, wherein the resin is obtained by polymerizing a monomer having an ethylenically unsaturated double bond in a side chain and at least a dipole moment of 2.5 or more as a copolymerization component. delete The curable composition according to claim 1, further comprising a colorant. The curable composition according to claim 1, further comprising a sensitizer. A color filter having a coloring pattern formed of the curable composition according to claim 5. A step of forming a colored layer made of a curable composition by applying the curable composition according to claim 5 on a support, a step of exposing the colored layer through a mask, and a step of forming a colored pattern by developing the colored layer after exposure Wherein the color filter comprises a plurality of color filters. A solid-state imaging device comprising a color filter manufactured by the method for manufacturing a color filter according to claim 8. The curable composition according to claim 1, wherein the monomer has a dipole moment of not less than 3.5 and not more than 9.0. The curable composition according to claim 1, wherein the resin further contains, as a copolymerization component, a monomer containing an alkali-soluble group selected from a carboxyl group, a sulfo group, a sulfonamide group, a phosphoric acid group and a phenolic hydroxyl group. The curable composition according to claim 1, wherein the resin has a side chain represented by any one of the following general formulas (1) to (3).

In the above general formulas (1) to (3) R ¹ to R ¹¹ each independently represent a hydrogen atom or a monovalent organic group, X and Y each independently represent an oxygen atom, a sulfur atom or -NR ¹² , Z represents an oxygen atom, a sulfur atom, -NR ¹² or a phenylene group, R ¹² represents a hydrogen atom or a monovalent organic group. 11. The curable composition according to claim 10, wherein the monomer is selected from the group consisting of the following compounds.

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