JP5178081B2 - Curable composition for forming color filter, color filter using the same, method for producing the same, and solid-state imaging device - Google Patents

Abstract

The present invention provides a curable composition containing a resin, a compound containing an ethylenically unsaturated double bond and a photopolymerization initiator, wherein the resin is manufactured by polymerizing at least a monomer having a dipole moment of 2.0 or more as a copolymerization component, a color filter using the same and a manufacturing method therefor, and a solid image pickup element.

Description

  The present invention relates to a curable composition suitable for producing a color filter used for a liquid crystal display element (LCD), a solid-state imaging element (CCD, CMOS, etc.), and a color filter formed from the curable composition. And a manufacturing method thereof.

The color filter is an essential component for liquid crystal displays and solid-state image sensors.
Liquid crystal displays are more compact than CRTs that are widely used as display devices and have the same or better performance, so CRTs are being replaced as television screens, personal computer screens, and other display devices. Also, in recent years, the development trend of liquid crystal displays is moving from conventional monitor applications where the screen has a relatively small area to TV applications where a large screen and high image quality are required.

As for color filters for liquid crystal displays (LCDs), the substrate size is increasing due to the production of large TVs. A curable composition for use in color filter production using such a large substrate is desired to be cured with low energy in order to improve productivity.
In addition, liquid crystal displays for TV use are required to have higher image quality than those for conventional monitor use. That is, improvement in contrast and color purity.

With respect to the curable composition for use in color filter production, a finer particle size is required as the particle size of the colorant (organic pigment or the like) used for improving contrast (see, for example, Patent Document 1).
However, in order to improve dispersion stability when pigments with small particle sizes are incorporated into the curable composition, if the pigment adsorbability of the dispersant is improved, the dispersant bridges the pigment and promotes pigment aggregation. However, the stability over time such as dispersion stability is lowered, and the developability when a pattern is formed using the curable composition tends to be lowered.
Moreover, since the surface area increases when the pigment is refined, the use of the refined pigment tends to increase the amount of dispersant added for dispersing the pigment in the curable composition.
Furthermore, when the acid value of the resin added at the time of dispersion is improved in order to ensure developability, there is a tendency to promote pigment aggregation due to interactions such as hydrogen bonding between acid groups.
In order to obtain developability by adding a resin to the curable composition after dispersion of the pigment, it is necessary to add a large amount of the resin.

  In addition, a curable composition for use in color filter production is required to have a higher colorant (organic pigment) content in the solid content in order to improve color purity. 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 is decreased. While curability at low energy is desired, there is a problem that it is difficult to obtain curability at the exposed portion.

On the other hand, curing with low energy is also desired for curable compositions for use in the production of color filters for solid-state imaging devices. In addition, for color filters for solid-state imaging devices, the coloring pattern is becoming thinner, and accordingly, the pigment concentration in the composition is improved.
Furthermore, in the pigment-based color filter, the content of the pigment dispersant in the curable composition increases as the pigment is refined to reduce color unevenness due to the pigment being relatively coarse particles. There is a tendency. The increase in the content of the pigment dispersant in the curable composition is similar to the curable composition for LCD production, and the stability over time such as dispersion stability is reduced, or pattern formation is performed using the curable composition. When developing, there is a tendency that developability tends to decrease, and it is difficult to obtain curability.

  In order to cope with problems such as color unevenness in the formed coloring pattern, a technique using an organic solvent-soluble dye instead of a pigment as a colorant has been proposed (for example, see Patent Document 2). However, in dye-based color filters, with the increase in dye concentration, problems such as a polymerization-inhibiting effect derived from dyes and a decrease in stability over time, such as precipitation of dyes, have become prominent.

  As described above, in the case of a curable composition for use in manufacturing a color filter, in either case for a liquid crystal display or a solid-state imaging device, photopolymerization is an essential component for curing the curable composition. In addition to limiting the content of the colorant and the photopolymerizable monomer, the concentration of the colorant is high, so the sensitivity is low and sufficient curing cannot be obtained, the adhesion to the substrate is insufficient, unexposed The development rate is reduced and the generation of residues is observed. Desirable pattern formation is extremely difficult. Dispersion stability and developability are poor when the colorant is a pigment. Precipitation of dye when the colorant is a dye. Various problems such as low temporal stability have occurred.

In order to solve these problems, studies have been made on imparting polymerizability to a resin introduced mainly for imparting film-formability and developability and improving sensitivity (for example, Patent Document 3, 4). In addition, the latest color filter technology trends (published by Information Organization), paragraphs 85 to 87, state-of-the-art color filter process technologies and chemicals (CMC Publishing), paragraphs 129 to 150, and the like. However, even when these resins are used, satisfactory exposure sensitivity has not yet been obtained. Furthermore, since the exposure sensitivity is insufficient, there is a problem that curing is insufficient at a deep portion such as the vicinity of the substrate interface, and therefore, the substrate adhesion is poor.
JP 2006-30541 A JP-A-2-127602 JP 2000-321863 A JP 2003-029018 A

An object of the present invention is to provide a curable composition that cures with extremely high sensitivity and that has good storage stability.
Another object of the present invention is to provide a high sensitivity, formed with the above-mentioned curable composition, having little development residue in the uncured part, excellent adhesion to the substrate of the cured part, and having a desired cross section. An object of the present invention is to provide a color filter having a shape and a high-definition coloring pattern.
Furthermore, the objective of this invention is providing the solid-state image sensor provided with the said color filter manufactured by the manufacturing method excellent in the productivity of the said color filter, and this manufacturing method.

In view of the above circumstances, the present inventors have conducted extensive research and found that the above problems can be solved, thereby completing the present invention.
That is, the present invention is achieved by the following means.
<1>
Resin, triallylmethane, anthraquinone, azomethine, benzylidene, oxonol, cyanine, phenothiazine, pyrrolopyrazole azomethine, xanthene, phthalocyanine, benzopyran, indigo, pyrazole azo, anilinoazo, pyra A curable composition for forming a color filter, comprising at least one colorant selected from a zolotriazole azo series, a pyridone azo series, and an anthrapyridone series, a compound containing an ethylenically unsaturated double bond, and a photopolymerization initiator. there are, the resin has an ethylenically unsaturated double bond in a side chain, and the M- 8 a Table 1 below, M-9A, M-11A ~M-15A, M - 8 MA, M -9MA least one dipole modes selected from and M-11MA ~M-1 5 MA A color filter-forming curable composition characterized by a cement 2.5 or more monomers are polymerized resin as a copolymer component.

<2 >
1. the dipole moment 5 more monomers ether group, a cyano group, a phosphoric acid ester group, a lactone group, a urethane group, characterized in that it is a monomer having at least one group selected from carbonate group and acetal group according to <1> A curable composition for forming a color filter .
< 3 >
The curable composition for forming a color filter according to <1> or <2>, wherein the photopolymerization initiator is an oxime compound .

< 4 >
Furthermore, a sensitizer is contained , The curable composition for color filter formation as described in any one of <1>-< 3 > characterized by the above-mentioned.
<5>
The color according to any one of <1> to <4>, wherein the compound containing an ethylenically unsaturated double bond is a compound containing four or more (meth) acrylic acid ester structures. Curable composition for filter formation.
< 6 >
A color filter comprising a colored pattern formed from the curable composition for forming a color filter according to any one of < 1 > or < 5 > on a support.
< 7 >
The coloring which forms the colored layer which coats the curable composition for color filter formation as described in any one of < 1 > or < 5 > on a support body, and consists of this curable composition for color filter formation. A layer forming step, an exposure step of exposing the colored layer through a mask, an exposure step of exposing the colored layer after exposure through a mask, and developing to develop a colored pattern by developing the exposed colored layer And a process for producing a color filter.

< 8 >
A solid-state image sensor provided with the color filter manufactured by the manufacturing method of the color filter as described in < 7 >.

According to the present invention, even when a colorant is contained in a high concentration, the stability over time such as dispersion stability is good, the composition is cured with high sensitivity by exposure, and the adhesiveness to the substrate surface in the cured region. Therefore, it is possible to provide a curable composition that can form a good pattern with high removability of the uncured portion in the uncured region.
Furthermore, according to the present invention, a color filter that is formed using the curable composition of the present invention and has a colored pattern that is excellent in resolving power and adhesion between the support and the color filter with high productivity. A manufacturing method that can be manufactured can be provided.

Hereinafter, the color filter forming curable composition of the present invention (hereinafter referred to as “curable composition”) is a resin, triallylmethane, anthraquinone, azomethine, benzylidene, oxonol, cyanine, phenothiazine. At least one colorant selected from pyrrolopyrazole azomethine, xanthene, phthalocyanine, benzopyran, indigo, pyrazole azo, anilinoazo, pyrazolotriazole azo, pyridone azo, and anthrapyridone, ethylenic containing compound and a photopolymerization initiator containing an unsaturated double bond, has an ethylenically unsaturated double bond which the resin is in a side chain, and, in Table 1 below M- 8 a, M- 9A, M-11A ~M-15A , M - 8 MA, M-9MA, and M-11MA ~M-1 5 M Characterized in that at least one of the dipole moment 2.5 or more monomers selected a polymerized resin as a copolymer component a. Hereinafter, each component contained in the curable composition of this invention is demonstrated one by one.

<(A) Resin>
The resin in the present invention has at least a dipole moment of 2. It is a resin obtained by polymerizing five or more monomers as a copolymerization component. Resins of the present invention is that having a ethylenically unsaturated double bond in the side chain.
The resin is preferably a polymer compound having, as a side chain, groups represented by the following general formulas (1) to (3) as the ethylenically unsaturated double bond.

^Wherein, R l ^{to R ll} each independently represent a hydrogen atom, or a monovalent organic group. X and Y each independently represent an oxygen atom, a sulfur atom, or —N—R ¹² , and Z represents an oxygen atom, a sulfur atom, —N—R ^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 represents a monovalent organic group. As R ¹ , a hydrogen atom or an alkyl group, an alkoxyl group, an alkoxy group that may have a substituent may be used. A carbonyl group etc. are mentioned, Especially, a hydrogen atom, a methyl group, a methyl alkoxy group, and a methyl ester group are preferable. R ² and R ³ may each independently have 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, or a substituent. Alkyl group, aryl group which may have a substituent, alkoxy group which may have a substituent, aryloxy group which may have a substituent, alkylamino group which may have a substituent, substituted An arylamino group which may have a group, an alkylsulfonyl group which may have a substituent, an arylsulfonyl group which may have a substituent, and the like, among them, a hydrogen atom, a carboxyl group, alkoxycarbonyl A 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 that can be introduced include a methoxycarbonyl group, an ethoxycarbonyl group, an isopropyloxycarbonyl group, a methyl group, an ethyl group, and a phenyl group.
X represents an oxygen atom, a sulfur atom, or —N—R ^12, and examples of R ¹² include an alkyl group that may have a substituent.
In the general formula (1), examples of the alkyl group include a linear or cyclic alkyl group having 1 to 30 carbon atoms, preferably an alkyl group having 1 to 20 carbon atoms, and an alkyl group having 1 to 10 carbon atoms. Particularly preferred.
In the general formula (1), the aryl group includes 6 to 30 carbon atoms, preferably 6 to 20 carbon atoms, and particularly preferably 6 to 10 carbon atoms.

In the general formula (2), R ^{4 to} R ⁸ each independently represent a monovalent organic group, and R ^{4 to} R ⁸ are, for example, a hydrogen atom, a halogen atom, an amino group, a dialkylamino group, a carboxyl Group, alkoxycarbonyl group, sulfo group, nitro group, cyano group, alkyl group which may have a substituent, aryl group which may have a substituent, alkoxy group which may have a substituent, substituent An aryloxy group that may have a substituent, an alkylamino group that may have a substituent, an arylamino group that may have a substituent, an alkylsulfonyl group that may have a substituent, and a substituent. Arylsulfonyl groups that may be substituted, and the like. Among them, a hydrogen atom, a carboxyl group, an alkoxycarbonyl group, an alkyl group that may have a substituent, and an aryl group that may have a substituent are preferable. . Examples of the substituent that can be introduced include those listed in the general formula (1). Y represents an oxygen atom, a sulfur atom, or —N—R ¹² . Examples of R ¹² include the same as those in general formula (1). In the general formula (2), examples of the alkyl group and aryl group include the same as those in the general formula (1), and preferred examples are also the same.
In Formula (3), R ⁹ ~R ^ll may each independently represent a monovalent organic group, examples of the organic group, specifically, for example, a hydrogen atom, a halogen atom, an amino group, a dialkylamino Group, carboxyl group, alkoxycarbonyl group, sulfo group, nitro group, cyano group, alkyl group which may have a substituent, aryl group which may have a substituent, 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, a substituent An arylsulfonyl group that may have a group, and the like. Among them, a hydrogen atom, a carboxyl group, an alkoxycarbonyl group, an alkyl group that may have a substituent, and an aryl group that may have a substituent. Lumpur group.
Here, examples of the substituent that can be introduced include those exemplified in the general formula (1).
Z represents an oxygen atom, a sulfur atom, —N—R ¹² or a phenylene group. Examples of R ¹² include the same as those in general formula (1).
In the general formula (3), examples of the alkyl group and aryl group include the same as those in the general formula (1), and preferred examples are also the same.

  Among 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 synthesis methods 1) and 2) shown below.

Synthesis method 1)
After synthesizing a polymer compound by copolymerizing one or more radical polymerizable compounds represented by the following general formula (12) and a specific monomer described later, a proton is extracted using a base and Z is desorbed. To obtain a desired polymer compound.

In General Formula (12), R ^{1 to} R ³ and X have the same meanings as those in General Formula (1), and preferred examples thereof are also the same.
In 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). R ¹³ includes a hydrogen atom or an alkyl group which may have a substituent. Among them, a hydrogen atom, a methyl group, a methylalkoxy group, or a methyl ester group is preferable. A represents a divalent organic linking group. Although it does not specifically limit as a bivalent organic coupling group of A, A C1-C30 alkylene group (For example, a methylene, ethylene, cyclohexylene), A C6-C30 arylene group (For example, phenylene, Tolylene and naphthalylene), among which alkylene having 1 to 10 carbon atoms and arylene group having 6 to 15 carbon atoms are preferable.
In General Formula (13), R ^{1 to} R ³ have the same meanings as those in General Formula (1), and preferred examples are also the same.

Synthesis method 2)
After synthesizing a trunk polymer compound (a polymer compound constituting the main chain) by copolymerizing one or more radical polymerizable compounds having a functional group and a specific monomer described later, the side chain of the trunk polymer compound A method of obtaining a desired polymer compound by reacting a functional group with a compound having a structure represented by the general formula (13).

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

These radically polymerizable compounds 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.
These radical polymerizable compounds are polymerized by a normal radical polymerization method using at least one kind of radical polymerizable compound and a specific monomer described later and, if necessary, another radical polymerizable compound, and a desired amount of the polymer compound is synthesized. A group represented by the general formula (1) can be introduced by dropping and reacting a base in a polymer solution under cooling or heating conditions and performing a neutralization treatment with an acid as necessary. . A generally known suspension polymerization method or solution polymerization method can be applied to the production of the polymer compound.
As the base, either an inorganic compound or an organic compound may be used. Preferred inorganic bases include sodium hydroxide, potassium hydroxide, sodium carbonate, sodium hydrogen carbonate, potassium carbonate, potassium hydrogen carbonate and the like, and organic bases include sodium methoxide, sodium ethoxide, potassium t-butoxide. And metal amine alkoxides, triethylamine, pyridine, and organic amine compounds such as diisopropylethylamine.

Examples of the functional group of the radical polymerizable compound having a functional group used for the synthesis of the trunk polymer compound in the synthesis method 2) include a hydroxyl group, a carboxyl group, a carboxylic acid halide group, a carboxylic acid anhydride group, an amino group, and a halogenated group. Examples thereof include an alkyl group, an isocyanate group, and an epoxy group. Examples of radically polymerizable compounds having these functional groups include 2-hydroxylethyl acrylate, 2-hydroxylethyl methacrylate, 4-hydroxybutyl acrylate, 4-hydroxybutyl methacrylate, acrylic acid, methacrylic acid, acrylic acid chloride, and methacrylic acid chloride. Methacrylic anhydride, N, N-dimethyl-2-aminoethyl methacrylate, 2-chloroethyl methacrylate, 2-isocyanate ethyl methacrylate, glycidyl acrylate, and grindyl methacrylate.
After synthesizing one or more kinds of such radically polymerizable compounds and a specific monomer described later and copolymerizing with other radically polymerizable compounds as necessary to synthesize a trunk polymer compound, the general formula (13) A desired polymer compound can be obtained by reacting a compound having a group represented by the formula:
Here, as an example of the compound having the group represented by the general formula (13), the compounds mentioned as examples of the radical polymerizable compound having the functional group described above can be given.

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

Synthesis method 3)
-One or more radically polymerizable compounds having an unsaturated group represented by the general formula (2) and an ethylenically unsaturated group having a higher addition polymerizability than the unsaturated group, and a specific monomer described later And a method of polymerizing another radical polymerizable compound as required to obtain a polymer compound. This method uses a compound having a plurality of ethylenically unsaturated groups having different addition polymerization properties in one molecule, for example, a compound such as allyl methacrylate.

Synthesis method 4)
A compound having a structure represented by a side chain functional group and the following general formula (14) after synthesizing a polymer compound by copolymerizing one or more radically polymerizable compounds having a functional group and a specific monomer described later. To introduce a group represented by the general formula (2).

R ^{4 to} R ⁸ in the general formula (14) are synonymous with those in the general formula (2), and preferred examples thereof are also the same.

Examples of the radically polymerizable compound having an unsaturated group represented by the general formula (2) and an ethylenically unsaturated group having a higher addition polymerizability than the unsaturated group include allyl acrylate, allyl methacrylate, 2- Examples include allyloxyethyl acrylate, 2-allyloxyethyl methacrylate, propargyl acrylate, propargyl methacrylate, allyl acrylate, allyl methacrylate, diallyl acrylate, diallyl methacrylate, N-allyl acrylamide, N-allyl methacrylamide, and the like.
Examples of the polymer compound obtained by polymerizing one or more radically polymerizable compounds 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)
-One or more radically polymerizable compounds having an unsaturated group represented by the general formula (3) and an ethylenically unsaturated group having a higher addition polymerizability than the unsaturated group, and a specific monomer described below. A method of obtaining a polymer compound by copolymerizing and, if necessary, copolymerizing with another radical polymerizable compound.

Synthesis method 6)
After synthesizing a polymer compound by copolymerizing one or more radically polymerizable compounds having a functional group and a specific monomer described later, a compound having a structure represented by the side chain functional group and the general formula (15) Method of introducing by reaction.

Examples of the radically polymerizable compound having an unsaturated group represented by the general formula (3) and an ethylenically unsaturated group having a higher addition polymerizability than the unsaturated group include vinyl acrylate, vinyl methacrylate, and 2-phenyl. Examples include vinyl acrylate, 2-phenylvinyl methacrylate, 1-propenyl acrylate, 1-propenyl methacrylate, vinyl acrylamide, vinyl methacrylamide and the like.
As the polymer compound obtained by copolymerization, the same compounds as those shown in the above synthesis method 2) can be obtained.
In General Formula (15), R ^{9 to} R ¹¹ have the same meanings as those in General Formula (3), and preferred examples are also the same.
Examples of the compound having the structure represented by the general formula (15) include 2-hydroxyethyl monovinyl ether, 4-hydroxybutyl monovinyl ether, diethylene glycol monovinyl ether, 4-chloromethylstyrene and the like.

  In the synthesis method 1), it is also preferable that the synthesis method uses at least one of the following general formula (4) or general formula (5) instead of the general formula (12) used in the synthesis method 1).

In General Formula (4) or (5), R ⁵ , R ⁶ , and R ⁷ represent hydrogen or a monovalent organic group, A ² represents an oxygen atom, a sulfur atom, or —NR ⁸ —, and G ¹ Represents an organic linking group, R ⁸ represents hydrogen or a monovalent organic group, and n represents an integer of 1 to 10. R ^{1 to} R ³ have the same meaning as in general formula (12), A ¹ has the same meaning as X in general formula (1), and X ¹ has the same meaning as Z in general formula (12).
R ^{9 to} R ¹³ represent hydrogen or a monovalent organic group, but at least one is a group represented by the following general formula (6). R ^{14 to} R ¹⁶ represent hydrogen or a monovalent organic group.
In the general formula (4) or (5), the monovalent organic group has the same meaning as the monovalent organic group in the general formula (1), and preferred examples are also the same.

In 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 have the same meanings as in general formula (4).
Preferable specific examples of the compound represented by the general formula (4) or (5) include those shown below (i-1 to i-60).

In the synthesis of a compound having a group represented by the general formula (1) obtained by using the general formula (4) or (5) (hereinafter also referred to as “polyvinyl polymer compound”), as described above. It is also a preferred embodiment to further copolymerize another general radical-polymerizable compound with a compound having a double bond using an elimination reaction.
In the synthesis methods 1) to 6), as described above, other general radical polymerizable compounds can be copolymerized as necessary. In the present invention, examples of the general radical polymerizable compound to be copolymerized include acrylic acid esters, methacrylic acid esters, N, N-2 substituted acrylamides, N, N-2 substituted methacrylamides, and styrenes. , Radically polymerizable compounds selected from acrylonitriles, methacrylonitriles and the like.
Specifically, for example, acrylic esters such as alkyl acrylate (the alkyl group preferably has 1 to 20 carbon atoms) (specifically, for example, methyl acrylate, ethyl acrylate, acrylic Propyl acrylate, butyl acrylate, amyl acrylate, ethyl hexyl acrylate, octyl acrylate, tert-octyl acrylate, chloroethyl acrylate, 2,2-dimethylhydroxypropyl acrylate, 5-hydroxypentyl acrylate, trimethylolpropane Monoacrylate, pentaerythritol monoacrylate, glycidyl acrylate, benzyl acrylate, methoxybenzyl acrylate, furfuryl acrylate, tetrahydrofurfuryl acrylate, etc.), aryl acrylate (for example, Such as E nil acrylate),

Methacrylic acid esters (eg, methyl methacrylate, ethyl methacrylate, propyl methacrylate, isopropyl methacrylate, amyl methacrylate, hexyl methacrylate, cyclohexyl methacrylate, benzyl methacrylate) such as alkyl methacrylate (the alkyl group preferably has 1 to 20 carbon atoms) , 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.) Aryl methacrylates (e.g., phenyl methacrylate, cresyl methacrylate, naphthyl methacrylate, etc.),

Styrenes such as styrene and alkyl styrene (for example, methyl styrene, dimethyl styrene, trimethyl styrene, ethyl styrene, diethyl styrene, isopropyl styrene, butyl styrene, hexyl styrene, cyclohexyl styrene, decyl styrene, benzyl styrene, chloromethyl styrene) , Trifluoromethyl styrene, ethoxymethyl styrene, acetoxymethyl styrene, etc.), alkoxy styrene (eg methoxy styrene, 4-methoxy-3-methyl styrene, dimethoxy styrene etc.), halogen styrene (eg chloro styrene, dichloro styrene, trichloro styrene) , Tetrachlorostyrene, pentachlorostyrene, bromostyrene, dibromostyrene, iodostyrene, fluorostyrene, trifluoro Styrene, 2-bromo-4-trifluoromethyl styrene, 4-fluoro-3-trifluoromethyl styrene etc.), acrylonitrile, methacrylonitrile, and the like.
Examples of the radical polymerizable compound containing a carboxylic acid include acrylic acid, methacrylic acid, itaconic acid, crotonic acid, incrotonic acid, maleic acid, p-carboxyl styrene, and the like.

Examples of the solvent used when synthesizing the polyvinyl polymer compound include ethylene dichloride, cyclohexanone, methyl ethyl ketone, acetone, methanol, ethanol, propanol, butanol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, 2 -Methoxyethyl acetate, 1-methoxy-2-propanol, 1-methoxy-2-propyl acetate, N, N-dimethylformamide, N, N-dimethylacetamide, dimethyl sulfoxide, toluene, ethyl acetate, methyl lactate, ethyl lactate, 1-methyl-2-pyrrolidone and the like can be mentioned.
These solvents may be used alone or in combination of two or more.

The resin in the present invention is a copolymer as described above, but is characterized by being a resin obtained 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. To do. The “specific monomer” here is a monomer other than the monomer containing an alkali-soluble group described later.
A numerical value calculated by the following calculation method was adopted as the dipole moment.
That is, the structure of the specific monomer obtained by the calculation method AM1 is optimized using CAChe6.1 (manufactured by Fujitsu Limited), and then the dipole moment is calculated using the optimum structure.
The specific monomer which is a copolymerization component of the resin in the present invention is not structurally limited as long as the dipole moment calculated by the above calculation method is 2.0 or more, but among them, from the viewpoint of sensitivity and storage stability from the value of the dipole moment is not less than 2.5, more preferably 2.5 to 15, still more preferably 3.0 to 10, is 3.5 to 9.0 Particularly preferred is 3.5 or more and 8.0 or less.
By setting the dipole moment of the specific monomer in the range of 2.5 or more and 15 or less, it is preferable from the viewpoint of ease of resin synthesis, sensitivity and developability of the curable composition containing the resin, and storage stability.

Among the above, the specific monomer preferably has at least one group selected from 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 linear, branched or cyclic ether group having 2 to 30 carbon atoms, particularly preferably a linear, branched or cyclic ether group having 2 to 15 carbon atoms. Examples of ether groups are 2-methoxyethyl, _{2-ethoxyethyl, MeOCH 2 CH 2 OCH 2 CH} 2 -, MeO (CH 2 CH 2 O) 2 CH 2 CH 2 -, oxetane-2-yl, oxetane - 3-yl, tetrahydrofuran-2-yl, tetrahydrofuran-3-yl, tetrahydro-2H-pyran-2-yl, octahydro-1H-isochromen-3-yl, oxirane-2-yl and the like can be mentioned.

  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. Examples of lactone groups include the following structures. In the following structure, R represents a hydrogen atom, an alkyl group, a cycloalkyl group, or an aryl group, and the alkyl group, the cycloalkyl group, or the aryl group independently has 1 to 20 carbon atoms.

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

The carbonic acid ester group contained in the specific monomer is preferably a linear or cyclic carbonic acid ester group having 1 to 30 carbon atoms, and is preferably a linear or cyclic carbonic acid ester group having 1 to 20 carbon atoms.
Examples of the carbonate group include, but are not limited to, the following structures.

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

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

As specific examples of the monomer, the following compounds are used.
That is, in the present invention, dipole moment 2.5 or more monomers, of the following Table 1, M- 8 A, M- 9A, M-11A ~M-15A, M - 8 MA, M-9MA, And M-11MA to M-1 5 MA.

The resin in the present invention is a resin obtained by polymerizing the specific monomer as a copolymerization component, and a component having a partial structure that can or may become an ethylenically unsaturated double bond in the side chain of the resin (hereinafter referred to as “resin double bond”). It is also a resin obtained by polymerizing the specific monomer.
As a combination of copolymerization components constituting the resin in the present invention, that is, a combination of “specific monomer” and “copolymerization component to be a double bond of resin”, M-1, M-8, i-1, i- 7, i-8, i-10, i-16, i-49 and M-9A, M-11A, M-12A, M-13A, M-14A, M-15A, M-9MA, M- A combination with any of 11MA, M-12MA, M-13MA, M-14MA, M-15MA is preferred, and any of M-1, i-1, i-10, i-16, i-49 and M- 11A, M-13A, M-14A, M-11MA, M-13MA, M-14MA, and a combination of Exemplified Compound i-1 and Exemplified Compound M-14MA, Exemplified Compound i-1 And Example Compound M-11MA A combination of exemplary compound i-1 and exemplary compound M-13MA, a combination of exemplary compound M-1 and exemplary compound M-14MA, a combination of exemplary compound M-1 and exemplary compound M-11MA, and exemplary compound M-1. The combination of exemplary compound M-13MA is particularly preferred.
The combination is preferable from the viewpoints of ease of resin synthesis, sensitivity and developability of the curable composition containing the resin, and storage stability.

  Although the resin in the present invention is a copolymer, the constitution of the copolymer may be any of a block copolymer, a random copolymer, a graft copolymer, etc. It is preferable in terms of ease of resin synthesis.

In the resin according to the present invention, the content of the copolymer component that forms the double bond of the resin is preferably 0.1 mol% to 95 mol%, more preferably 1 mol% to 85 mol%. It is particularly preferably 5 to 75 mol%.
Here, the “content of copolymerization component that becomes a double bond of the resin” specifically means the following.
That is, in the synthesis method 1), it means “content in the copolymer of the radically polymerizable compound represented by the general formula (12)”, and in the synthesis methods 2), 4) and 6), “ After copolymerizing a radically polymerizable compound having a functional group, in the copolymer as a copolymerization component in which the functional group reacts with any one of the general formula (13), the general formula (14), and the general formula (15). In the synthesis method 3) or 5), the unsaturated group represented by the general formula (2) or (3) and an ethylenic compound having a higher addition polymerizability than the unsaturated group It means “content in the copolymer of a radically polymerizable compound having an unsaturated group”.
By making content of the copolymerization component used as the double bond of the said resin into the said range, it is preferable from a viewpoint which a sensitivity improves and adhesiveness with a board | substrate is also favorable.

In the resin of the present invention, the content of the specific monomer as a copolymerization component is preferably 1 mol% to 90 mol%, more preferably 3 mol% to 70 mol%, and more preferably 5 mol% to Particularly preferred is 50 mol%.
By making content of the said specific monomer into the said range, it is preferable from a viewpoint which a sensitivity improves and adhesiveness with a board | substrate is also favorable.

In the resin, the molar ratio (component ratio) between the “content of the specific monomer” and the “content of the copolymer component that becomes a double bond of the resin” is 100: 1 to 1: 100. It is preferably 50: 1 to 1:50, more preferably 10: 1 to 1:10.
By making the component ratio of the copolymerization component which becomes a double bond of the specific monomer and the resin within the above range, it is preferable from the viewpoint of improving the sensitivity and improving the adhesion to the substrate.

  The resin in the present invention may be a resin obtained by polymerizing a monomer containing an alkali-soluble group as a copolymerization component. The “alkali-soluble group” as used herein refers to a functional group that is dissociated by a developer used at the time of pattern formation and improves the solubility in the developer (alkaline aqueous solution). The alkali-soluble group is preferably a functional group having a pKa in water at 25 ° C. of 11 or less. Examples of this functional group include a carboxyl group, a sulfo group, a sulfonamide group, a phosphoric acid group, a phenolic hydroxyl group, and the like, and a carboxyl group is most preferable.

In the resin of the present invention, the content of the monomer containing an alkali-soluble group as a copolymerization component is preferably 1 mol% to 90 mol%, more preferably 3 mol% to 70 mol%. It is particularly preferably 5 to 50 mol%.
By making content as a copolymerization component of the monomer containing the said alkali-soluble group into the said range, it is preferable from a viewpoint that a sensitivity improves and adhesiveness with a board | substrate is also favorable.

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

Specific examples of the resin in the present invention are listed below together with its weight average molecular weight , and among these, the present invention includes M-8A, M-9A, M-11A to M-15A, M-8MA, M in Table 1. It is a resin obtained by polymerizing at least one monomer having a dipole moment of 2.5 or more selected from -9MA and M-11MA to M-15MA as a copolymerization component .

In the resin of the present invention, the total content (mol%) of the specific monomer and the copolymer component that forms a double bond of the resin is preferably 2 mol% to 98 mol%, and preferably 5 mol% to 90 mol. It is more preferably mol%, and particularly preferably 10 mol% to 80 mol%. ,
By making the total content within the above range, it is preferable from the viewpoint of improving the sensitivity and improving the adhesion to the substrate.

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

<(B) Photopolymerization initiator>
The curable composition of this invention contains (B) photoinitiator for a sensitivity and pattern formation improvement.
The photopolymerization initiator in the present invention is a compound that is decomposed by light and initiates and accelerates polymerization of a polymerizable component in the present invention, and preferably has an absorption in a wavelength region of 300 to 500 nm. Moreover, a photoinitiator can be used individually or in combination of 2 or more types.

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, hexaaryls. Examples thereof include a rubiimidazole compound, an organic boric acid compound, a disulfonic acid compound, an oxime ester compound, an onium salt compound, an acylphosphine (oxide) compound, and an alkylamino compound.
Hereinafter, each of these compounds will be described in detail.

Specific examples of organic halogenated compounds include Wakabayashi et al., “Bull Chem. Soc.
Japan 42, 2924 (1969), U.S. Pat. No. 3,905,815, JP-B 46-4605, JP-A 48-36281, JP-A 55-32070, JP-A 60-239736 JP, 61-169835, JP 61-169437, JP 62-58241, JP 62-212401, JP 63-70243, JP 63-298339, M.M. P. Hut "Journal of Heterocyclic Chemistry" 1 (No3), (1970) "The compound described in a brush is mentioned, Especially, the oxazole compound substituted by the trihalomethyl group and s-triazine compound are mentioned.

  As the s-triazine compound, more preferably, an s-triazine derivative in which at least one mono-, di-, or trihalogen-substituted methyl group is bonded to the s-triazine ring, specifically, for example, 2,4,6- Tris (monochloromethyl) -s-triazine, 2,4,6-tris (dichloromethyl) -s-triazine, 2,4,6-tris (trichloromethyl) -s-triazine, 2-methyl-4,6- Bis (trichloromethyl) -s-triazine, 2-n-propyl-4,6-bis (trichloromethyl) -s-triazine, 2- (α, α, β-trichloroethyl) -4,6-bis (trichloro Methyl) -s-triazine, 2-phenyl-4,6-bis (trichloromethyl) -s-triazine, 2- (p-methoxyphenyl) -4,6-bis (trichloro) Methyl) -s-triazine, 2- (3,4-epoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (p-chlorophenyl) -4,6-bis (trichloromethyl)- s-triazine, 2- [1- (p-methoxyphenyl) -2,4-butadienyl] -4,6-bis (trichloromethyl) -s-triazine, 2-styryl-4,6-bis (trichloromethyl) -S-triazine, 2- (p-methoxystyryl) -4,6-bis (trichloromethyl) -s-triazine, 2- (pi-propyloxystyryl) -4,6-bis (trichloromethyl)- s-triazine, 2- (p-tolyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4-natoxynaphthyl) -4,6-bis (trichloromethyl) s-triazine, 2-phenylthio-4,6-bis (trichloromethyl) -s-triazine, 2-benzylthio-4,6-bis (trichloromethyl) -s-triazine, 2,4,6-tris (dibromomethyl) ) -S-triazine, 2,4,6-tris (tribromomethyl) -s-triazine, 2-methyl-4,6-bis (tribromomethyl) -s-triazine, 2-methoxy-4,6- Bis (tribromomethyl) -s-triazine and the like can be mentioned.

  Examples of the oxydiazole compound include 2-trichloromethyl-5-styryl-1,3,4-oxodiazole, 2-trichloromethyl-5- (cyanostyryl) -1,3,4-oxodiazole, 2- Examples include trichloromethyl-5- (naphth-1-yl) -1,3,4-oxodiazole, 2-trichloromethyl-5- (4-styryl) styryl-1,3,4-oxodiazole, and the like. .

  Examples of the carbonyl compound include benzophenone, Michler ketone, 2-methylbenzophenone, 3-methylbenzophenone, 4-methylbenzophenone, 2-chlorobenzophenone, 4-bromobenzophenone, 2-carboxybenzophenone and other benzophenone derivatives, 2,2-dimethoxy-2 -Phenylacetophenone, 2,2-diethoxyacetophenone, 1-hydroxycyclohexyl phenylketone, α-hydroxy-2-methylphenylpropanone, 1-hydroxy-1-methylethyl- (p-isopropylphenyl) ketone, 1-hydroxy -1- (p-dodecylphenyl) ketone, 2-methyl- (4 ′-(methylthio) phenyl) -2-morpholino-1-propanone, 1,1,1-trichloromethyl- (p-butylphenyl) , Acetophenone derivatives such as 2-benzyl-2-dimethylamino-4-morpholinobutyrophenone, thioxanthone, 2-ethylthioxanthone, 2-isopropylthioxanthone, 2-chlorothioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone Thioxanthone derivatives such as 2,4-diisopropylthioxanthone, and benzoic acid ester derivatives such as ethyl p-dimethylaminobenzoate and ethyl p-diethylaminobenzoate.

  Examples of the ketal compound include benzyl methyl ketal and benzyl-β-methoxyethyl ethyl acetal.

  Examples of the benzoin compound include mbenzoin isopropyl ether, benzoin isobutyl ether, benzoin methyl ether, methyl o-benzoylbenzoate, and the like.

  Examples of the acridine compound include 9-phenylacridine, 1,7-bis (9-acridinyl) heptane, and the like.

  Examples of the organic peroxide compound include trimethylcyclohexanone peroxide, acetylacetone peroxide, 1,1-bis (tert-butylperoxy) -3,3,5-trimethylcyclohexane, 1,1-bis (tert-butylperoxide). Oxy) cyclohexane, 2,2-bis (tert-butylperoxy) butane, tert-butyl hydroperoxide, cumene hydroperoxide, diisopropylbenzene hydroperoxide, 2,5-dimethylhexane-2,5-dihydroper Oxide, 1,1,3,3-tetramethylbutyl hydroperoxide, tert-butylcumyl peroxide, dicumyl peroxide, 2,5-dimethyl-2,5-di (tert-butylperoxy) hexane, 2 , -Oxanoyl peroxide, succinic peroxide, benzoyl peroxide, 2,4-dichlorobenzoyl peroxide, diisopropyl peroxydicarbonate, di-2-ethylhexyl peroxydicarbonate, di-2-ethoxyethyl peroxydicarbonate , Dimethoxyisopropyl peroxycarbonate, di (3-methyl-3-methoxybutyl) peroxydicarbonate, tert-butyl peroxyacetate, tert-butyl peroxypivalate, tert-butyl peroxyneodecanoate, tert- Butyl peroxyoctanoate, tert-butyl peroxylaurate, tersyl carbonate, 3,3 ′, 4,4′-tetra- (t-butylperoxycarbonyl) benzophenone, 3,3 ′, 4 '-Tetra- (t-hexylperoxycarbonyl) benzophenone, 3,3', 4,4'-tetra- (p-isopropylcumylperoxycarbonyl) benzophenone, carbonyldi (t-butylperoxydihydrogen diphthalate) , Carbonyldi (t-hexylperoxydihydrogen diphthalate) and the like.

  Examples of the azo compound include azo compounds described in JP-A-8-108621.

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

  Examples of the azide compound include organic azide compounds described in U.S. Pat. No. 2,848,328, U.S. Pat. No. 2,852,379 and U.S. Pat. No. 2,940,553, 2,6-bis (4-azidobenzylidene) -4-ethyl. And cyclohexanone (BAC-E).

  Examples of the metallocene compound include JP-A-59-152396, JP-A-61-151197, JP-A-63-41484, JP-A-2-249, JP-A-2-4705, Various titanocene compounds described in JP-A-5-83588, such as di-cyclopentadienyl-Ti-bis-phenyl, di-cyclopentadienyl-Ti-bis-2,6-difluorophen-1-yl, di -Cyclopentadienyl-Ti-bis-2,4-di-fluorophen-1-yl, di-cyclopentadienyl-Ti-bis-2,4,6-trifluorophen-1-yl, di- Cyclopentadienyl-Ti-bis-2,3,5,6-tetrafluorophen-1-yl, di-cyclopentadienyl-Ti-bis-2,3,4,5,6-pentaful Lophen-1-yl, di-methylcyclopentadienyl-Ti-bis-2,6-difluorophen-1-yl, di-methylcyclopentadienyl-Ti-bis-2,4,6-trifluoropheny -1-yl, di-methylcyclopentadienyl-Ti-bis-2,3,5,6-tetrafluorophen-1-yl, di-methylcyclopentadienyl-Ti-bis-2,3,4 , 5,6-pentafluorophen-1-yl, iron-arene complexes described in JP-A-1-304453 and JP-A-1-152109, and the like.

  As the hexaarylbiimidazole compound, for example, JP-B-6-29285, US Pat. Nos. 3,479,185, 4,311,783, 4,622,286, etc. And, 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, p-dichlorophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole, 2,2 ′ -Bis (o-chlorophenyl) -4,4 ', 5,5'-tetra (m-methoxyphenyl) biidazole, 2,2'-bis (o, o'-dichlorophenyl) -4,4', 5,5 '-Tetraphenylbi Dazole, 2,2′-bis (o-nitrophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole, 2,2′-bis (o-methylphenyl) -4,4 ′, 5 Examples include 5′-tetraphenylbiimidazole, 2,2′-bis (o-trifluorophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole, and the like.

  Examples of the organic borate compound include JP-A-62-143044, JP-A-62-1050242, JP-A-9-188585, JP-A-9-188686, JP-A-9-188710, JP-A-2000. -131837, Japanese Patent Application Laid-Open No. 2002-107916, Japanese Patent No. 2764769, Japanese Patent Application No. 2000-310808, etc., and Kunz, Martin “Rad Tech '98. Proceeding April 19-22, 1998, Chicago”. Organoboron salts described in JP-A-6-157623, JP-A-6-175564, JP-A-6-175561, JP-A-6-175554 In Japanese Patent Laid-Open No. 6-175553 Organoboron iodonium complexes, organoboron phosphonium complexes described in JP-A-9-188710, JP-A-6-348011, JP-A-7-128785, JP-A-7-140589, JP-A-7- Specific examples include organoboron transition metal coordination complexes such as those described in Japanese Patent No. 306527 and Japanese Patent Laid-Open No. 7-292014.

  Examples of the disulfone compound include compounds described in JP-A No. 61-166544 and Japanese Patent Application No. 2001-132318.

  Examples of oxime ester compounds include J.M. C. S. Perkin II (1979) 1653-1660), J. MoI. C. S. Perkin II (1979) 156-162, Journal of Photopolymer Science and Technology (1995) 202-232, JP-A 2000-66385, compounds described in JP-A 2000-80068, JP-T 2004-534797 Compounds and the like.

  Examples of onium salt compounds include S.I. I. Schlesinger, Photogr. Sci. Eng. , 18, 387 (1974), T.A. S. Bal et al, Polymer, 21, 423 (1980), diazonium salts described in U.S. Pat. No. 4,069,055, ammonium salts described in JP-A-4-365049, U.S. Pat. No. 4,069, No. 055, No. 4,069,056, phosphonium salts described in European Patent Nos. 104 and 143, U.S. Pat. Nos. 339,049 and 410,201, JP Examples include iodonium salts described in JP-A No. -150848 and JP-A-2-296514.

  The iodonium salt that can be suitably used in the present invention is a diaryl iodonium salt, and is preferably substituted with two or more electron donating groups such as an alkyl group, an alkoxy group, and an aryloxy group from the viewpoint of stability. .

Examples of the sulfonium salt that can be suitably used in the present invention include European Patent Nos. 370,693, 390,214, 233,567, 297,443, 297,442, and U.S. Pat. 933,377, 161,811, 410,201, 339,049, 4,760,013, 4,734,444, 2,833,827, Germany Examples thereof include sulfonium salts described in the specifications of Patent Nos. 2,904,626, 3,604,580, and 3,604,581, and are preferably electron withdrawing groups from the viewpoint of stability. It is preferably substituted. The electron withdrawing group preferably has a Hammett value greater than zero. Preferred electron-withdrawing groups include halogen atoms and carboxylic acids.
Other preferable sulfonium salts include sulfonium salts in which one substituent of the triarylsulfonium salt has a coumarin or anthraquinone structure and absorbs at 300 nm or more. As another preferable sulfonium salt, a sulfonium salt in which the triarylsulfonium salt has an allyloxy group or an arylthio group as a substituent and has absorption at 300 nm or more can be mentioned.

Moreover, as an onium salt compound, J.M. V. Crivello et al, Macromolecules, 10 (6), 1307 (1977), J. MoI. V. Crivello
et al, J. et al. Polymer Sci. , Polymer Chem. Ed. , 17, 1047 (1979), a selenonium salt described in C.I. S. Wen et al, Teh, Proc. Conf. Rad. Curing ASIA, p478 Tokyo, Oct (1988), and onium salts such as arsonium salts.

  Examples of the acylphosphine (oxide) compound include Irgacure 819, Darocur 4265, Darocur TPO and the like manufactured by Ciba Specialty Chemicals.

  Examples of the alkylamino compound include compounds having a dialkylaminophenyl group described in paragraph No. [0047] of JP-A-9-281698, JP-A-6-19240, JP-A-6-19249, and the like. An amine compound is mentioned. Specifically, compounds having a dialkylaminophenyl group include compounds such as ethyl p-dimethylaminobenzoate, and dialkylaminophenyl carbaldehydes such as p-diethylaminobenzcarbaldehyde and 9-julolidylcarbaldehyde. Examples of the amine compound include triethanolamine, diethanolamine, and triethylamine.

<(B) Photopolymerization initiator>
As the photopolymerization initiator (B) used in the present invention, from the viewpoint of exposure sensitivity, a triazine compound, an alkylamino compound, a benzyldimethyl ketal compound, an α-hydroxyketone compound, an α-aminoketone compound, an acylphosphine compound, Phosphine oxide compounds, metallocene compounds, oxime compounds, biimidazole compounds, onium compounds, benzothiazole compounds, benzophenone compounds, acetophenone compounds and derivatives thereof, cyclopentadiene-benzene-iron complexes and salts thereof, halo A compound selected from the group consisting of a methyloxadiazole compound and a 3-aryl-substituted coumarin compound is preferred.

  More preferably, they are triazine compounds, alkylamino compounds, α-aminoketone compounds, acylphosphine compounds, phosphine oxide compounds, oxime compounds, biimidazole compounds, onium compounds, benzophenone compounds, acetophenone compounds. More preferably, at least one compound selected from the group consisting of triazine compounds, alkylamino compounds, oxime compounds, and biimidazole compounds.

  (B) It is preferable that content of a photoinitiator is 0.1 mass%-50 mass% with respect to the total solid of the curable composition of this invention, More preferably, 0.5 mass%-30 % By mass, particularly preferably 1% by mass to 20% by mass. Within this range, good sensitivity and pattern formability can be obtained.

<(C) Compound containing ethylenically unsaturated double bond>
The curable composition of the present invention contains a compound containing an ethylenically unsaturated double bond other than the resin (hereinafter, sometimes simply referred to as “compound containing an ethylenically unsaturated double bond”). can do.

  The compound containing an ethylenically unsaturated double bond that can be used in the present invention is an addition-polymerizable compound having at least one ethylenically unsaturated double bond other than the above-mentioned resin, and has terminal ethylene. Selected from compounds having at least one, preferably two or more, unsaturated unsaturated bonds. Such a compound group is widely known in the industrial field, and can be used without any particular limitation in the present invention. These have chemical forms such as monomers, prepolymers, i.e. dimers, trimers and oligomers, or mixtures thereof and copolymers thereof. Examples of monomers and copolymers thereof include unsaturated carboxylic acids (for example, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.), and esters and amides thereof. In this case, an ester of an unsaturated carboxylic acid and an aliphatic polyhydric alcohol compound, or an amide of an unsaturated carboxylic acid and an aliphatic polyvalent amine compound is used. In addition, an addition reaction product of an unsaturated carboxylic acid ester or amide having a nucleophilic substituent such as a hydroxy group, an amino group or a mercapto group with a monofunctional or polyfunctional isocyanate or epoxy, and a monofunctional or polyfunctional compound. A dehydration condensation reaction product with a functional carboxylic acid is also preferably used. Further, an addition reaction product of an unsaturated carboxylic acid ester or amide having an electrophilic substituent such as an epoxy group or an epoxy group with a monofunctional or polyfunctional alcohol, amine or thiol, a halogen group or In addition, a substitution reaction product of an unsaturated carboxylic acid ester or amide having a leaving substituent such as a tosyloxy group and a monofunctional or polyfunctional alcohol, amine or thiol is also suitable. As another example, it is also possible to use a group of compounds substituted with unsaturated phosphonic acid, styrene, vinyl ether or the like instead of the unsaturated carboxylic acid.

  Specific examples of the monomer of an ester of an aliphatic polyhydric alcohol compound and an unsaturated carboxylic acid include acrylic acid esters such as ethylene glycol diacrylate, triethylene glycol diacrylate, 1,3-butanediol diacrylate, and tetramethylene glycol. Diacrylate, propylene glycol diacrylate, neopentyl glycol diacrylate, trimethylolpropane triacrylate, trimethylolpropane tri (acryloyloxypropyl) ether, trimethylolethane triacrylate, hexanediol diacrylate, 1,4-cyclohexanediol diacrylate , Tetraethylene glycol diacrylate, pentaerythritol diacrylate, pentaerythritol triacrylate , Pentaerythritol tetraacrylate, dipentaerythritol diacrylate, dipentaerythritol hexaacrylate, sorbitol triacrylate, sorbitol tetraacrylate, sorbitol pentaacrylate, sorbitol hexaacrylate, tri (acryloyloxyethyl) isocyanurate, polyester acrylate oligomer, isocyanuric acid There are EO-modified triacrylate and the like.

  Methacrylic acid esters include tetramethylene glycol dimethacrylate, triethylene glycol dimethacrylate, neopentyl glycol dimethacrylate, trimethylolpropane trimethacrylate, trimethylolethane trimethacrylate, ethylene glycol dimethacrylate, 1,3-butanediol dimethacrylate, Hexanediol dimethacrylate, pentaerythritol dimethacrylate, pentaerythritol trimethacrylate, pentaerythritol tetramethacrylate, dipentaerythritol dimethacrylate, dipentaerythritol hexamethacrylate, sorbitol trimethacrylate, sorbitol tetramethacrylate, bis [p- (3-methacryloxy- 2-hydroxypro ) Phenyl] dimethyl methane, bis - [p- (methacryloxyethoxy) phenyl] dimethyl methane.

  Itaconic acid esters include ethylene glycol diitaconate, propylene glycol diitaconate, 1,3-butanediol diitaconate, 1,4-butanediol diitaconate, tetramethylene glycol diitaconate, pentaerythritol diitaconate And sorbitol tetritaconate. Examples of crotonic acid esters include ethylene glycol dicrotonate, tetramethylene glycol dicrotonate, pentaerythritol dicrotonate, and sorbitol tetradicrotonate. Examples of isocrotonic acid esters include ethylene glycol diisocrotonate, pentaerythritol diisocrotonate, and sorbitol tetraisocrotonate. Examples of maleic acid esters include ethylene glycol dimaleate, triethylene glycol dimaleate, pentaerythritol dimaleate, and sorbitol tetramaleate.

  Examples of other esters include aliphatic alcohol esters described in JP-B-51-47334 and JP-A-57-196231, JP-A-59-5240, JP-A-59-5241, and JP-A-2-226149. Those having the aromatic skeleton described above and those having an amino group described in JP-A-1-165613 are also preferably used. Furthermore, the ester monomers described above can also be used as a mixture.

  Specific examples of amide monomers of aliphatic polyvalent amine compounds and unsaturated carboxylic acids include methylene bis-acrylamide, methylene bis-methacrylamide, 1,6-hexamethylene bis-acrylamide, 1,6-hexamethylene bis. -Methacrylamide, diethylenetriamine trisacrylamide, xylylene bisacrylamide, xylylene bismethacrylamide and the like. Examples of other preferable amide monomers include those having a cyclohexylene structure described in JP-B-54-21726.

  In addition, urethane-based addition polymerizable compounds produced by using an addition reaction of isocyanate and hydroxyl group are also suitable, and specific examples thereof include, for example, one molecule described in JP-B-48-41708. Containing two or more polymerizable vinyl groups in one molecule obtained by adding a vinyl monomer containing a hydroxyl group in the compound represented by the following general formula (A) to a polyisocyanate compound having two or more isocyanate groups Vinyl urethane compounds to be used.

^{_{CH 2 = C (R 10)}} COOCH 2 CH (R 11) OH formula (A)
(However, R ¹⁰ and R ¹¹ represent H or CH _3. )

  Also, urethane acrylates such as those described in JP-A-51-37193, JP-B-2-32293, and JP-B-2-16765, JP-B-58-49860, JP-B-56-17654, Urethane compounds having an ethylene oxide skeleton described in JP-B-62-39417 and JP-B-62-39418 are also suitable. Further, by using addition polymerizable compounds having an amino structure or a sulfide structure in the molecule described in JP-A-63-277653, JP-A-63-260909, and JP-A-1-105238, It is possible to obtain a photopolymerizable composition excellent in the photosensitive speed.

  Other examples include polyester acrylates, epoxy resins and (meth) acrylic acid as described in JP-A-48-64183, JP-B-49-43191, JP-B-52-30490, and JP-A-52-30490. Mention may be made of polyfunctional acrylates and methacrylates such as reacted epoxy acrylates. Further, specific unsaturated compounds described in JP-B-46-43946, JP-B-1-40337 and JP-B-1-40336, vinylphosphonic acid compounds described in JP-A-2-25493, and the like can also be mentioned. . In some cases, a structure containing a perfluoroalkyl group described in JP-A-61-22048 is preferably used. Furthermore, Journal of Japan Adhesion Association vol. 20, no. 7, pages 300 to 308 (1984), which are introduced as photocurable monomers and oligomers, can also be used.

About these addition polymerizable compounds, the details of usage methods such as the structure, single use or combined use, addition amount and the like can be arbitrarily set according to the performance design of the curable composition. For example, it is selected from the following viewpoints.
From the viewpoint of sensitivity, a structure having a large unsaturated group content per molecule is preferable, and in many cases, a bifunctional or higher functionality is preferable. Further, in order to increase the strength of the image area, that is, the cured film, those having three or more functionalities are preferable. Further, different functional numbers and different polymerizable groups (for example, acrylic acid ester, methacrylic acid ester, styrenic compound, vinyl ether type). A method of adjusting both sensitivity and strength by using a 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 a compound containing three or more, and most preferably a compound containing four or more. preferable. Moreover, it is preferable to contain an EO modified body from a viewpoint of hardening sensitivity and the developability of an unexposed part. Moreover, it is preferable to contain a urethane bond from a viewpoint of hardening sensitivity and exposure part intensity | strength.
In addition, the selection and use method of the addition polymerization compound is an important factor for the compatibility and dispersibility with other components (for example, resin, photopolymerization initiator, pigment) in the curable composition, For example, the compatibility may be improved by using a low-purity compound or using two or more kinds in combination. In addition, a specific structure may be selected for the purpose of improving the adhesion with a substrate or the like.

  From the above viewpoint, bisphenol A diacrylate, bisphenol A diacrylate EO modified product, trimethylolpropane triacrylate, trimethylolpropane tri (acryloyloxypropyl) ether, trimethylolethane triacrylate, tetraethylene glycol diacrylate, pentaerythritol diacrylate Acrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, sorbitol triacrylate, sorbitol tetraacrylate, sorbitol pentaacrylate, sorbitol hexaacrylate, tri (acryloyloxy D (I) Isocyanurate, pentaerythritol tetraacrylate EO modified product, dipentaerythritol hexaacrylate EO modified product, etc. are mentioned as preferable ones. Also, as commercially available products, urethane oligomer UAS-10, UAB-140 (Sanyo Kokusaku Pulp Co., Ltd.) Manufactured), DPHA-40H (manufactured by Nippon Kayaku Co., Ltd.), UA-306H, UA-306T, UA-306I, AH-600, T-600, AI-600 (manufactured by Kyoei), UA-7200 (Shin Nakamura Chemical Co., Ltd.) Product).

  Among them, bisphenol A diacrylate EO modified, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, tri (acryloyloxyethyl) isocyanurate, pentaerythritol tetraacrylate EO modified, di Examples of commercially available modified products such as pentaerythritol hexaacrylate EO include DPHA-40H (manufactured by Nippon Kayaku Co., Ltd.), UA-306H, UA-306T, UA-306I, AH-600, T-600, AI-600 ( Kyoeisha) is more preferable.

The content of the compound containing an ethylenically unsaturated double bond other than the resin (C) other than the resin (A) in the present invention is 1% by mass to 90% in the solid content of the curable composition of the present invention. The mass is preferably 5% by mass, more preferably 5% by mass to 80% by mass, and still more preferably 10% by mass to 70% by mass.
In particular, when the curable composition of the present invention is used for forming a colored pattern of a color filter, the content of the compound containing an ethylenically unsaturated double bond other than the resin (C) is 5% by mass in the above range. It is preferably -50% by mass, more preferably 7% by mass to 40% by mass, and still more preferably 10% by mass to 35% by mass.

  The content ratio (mass ratio) between the (A) resin and the compound containing an ethylenically unsaturated double bond other than the (C) (A) resin is sensitivity and removability of unexposed areas (developability). ), (A) / (C) is preferably 0.001 to 100, more preferably 0.005 to 50, and still more preferably 0.01 to 10.

<(D) Colorant>
The curable composition of the present invention, it contains (D) colorant.
The colorant contained in the curable composition of the present invention can be used by mixing one or more dyes and pigments described later . The colorant is preferably a pigment from the viewpoint of durability such as heat resistance and light resistance.

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

  Examples of inorganic pigments include metal compounds represented by metal oxides, metal complex salts, and the like. Specifically, iron, cobalt, aluminum, cadmium, lead, copper, titanium, magnesium, chromium, zinc, antimony, etc. And metal oxides of the above metals.

As an organic pigment, for example,
C. I. 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;
C. I. 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;
Examples thereof include carbon black.

  In the present invention, those having a basic N atom in the structural formula of the pigment can be preferably used. These pigments having a basic N atom exhibit good dispersibility in the composition of the present invention. Although the cause is not fully elucidated, it is presumed that the good affinity between the photosensitive polymerization component and the pigment has an influence.

  Examples of the pigment that can be preferably used in the present invention include the following. However, the present invention is not limited to these.

C. I. Pigment Yellow 11, 24, 108, 109, 110, 138, 139, 150, 151, 154, 167, 180, 185
C. I. Pigment orange 36, 71,
C. I. 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 can be used alone or in various combinations in order to increase color purity. Specific examples of the above combinations are shown below. For example, as a red pigment, an anthraquinone pigment, a perylene pigment, a diketopyrrolopyrrole pigment alone or at least one of them, a disazo yellow pigment, an isoindoline yellow pigment, a quinophthalone yellow pigment or a perylene red pigment , Etc. can be used. For example, as an anthraquinone pigment, C.I. I. Pigment red 177, and perylene pigments include C.I. I. Pigment red 155, C.I. I. Pigment Red 224, and diketopyrrolopyrrole pigments include C.I. I. Pigment red 254, and C.I. I. Mixing with Pigment Yellow 139 is preferred. The mass ratio of the red pigment to the yellow pigment is preferably 100: 5 to 100: 50. If it is 100: 4 or less, it may be difficult to suppress the light transmittance from 400 nm to 500 nm, and the color purity may not be improved. When the ratio is 100: 51 or more, the dominant wavelength is shorter than the short wavelength, and the deviation from the NTSC target hue may be large. In particular, the mass ratio is optimally in the range of 100: 10 to 100: 30. In the case of a combination of red pigments, it can be adjusted in accordance with the chromaticity.

  As the green pigment, a halogenated phthalocyanine pigment can be used alone, or a mixture thereof with a disazo yellow pigment, a quinophthalone yellow pigment, an azomethine yellow pigment or an isoindoline yellow pigment can be used. For example, C.I. I. Pigment Green 7, 36, 37 and C.I. I. Pigment yellow 83, C.I. I. Pigment yellow 138, C.I. I. Pigment yellow 139, C.I. I. Pigment yellow 150, C.I. I. Pigment yellow 180 or C.I. I. Mixing with Pigment Yellow 185 is preferred. The mass ratio of the green pigment to the yellow pigment is preferably 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 can be used alone, or a mixture thereof with a dioxazine purple pigment can be used. For example, C.I. I. Pigment blue 15: 6 and C.I. I. Mixing with pigment violet 23 is preferred. The mass ratio of the blue pigment to the violet pigment is preferably 100: 0 to 100: 30, more preferably 100: 10 or less.

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

When used for a color filter, the average particle diameter of the pigment is preferably 100 nm or less from the viewpoint of color unevenness and contrast, and is preferably 5 nm or more from the viewpoint of dispersion stability. More preferably, it is 5-75 nm as an average particle diameter of a pigment, More preferably, it is 5-55 nm, Most preferably, it is 5-35 nm.
The average particle diameter of the pigment can be measured by a known method such as an electron microscope.

  Among these, the pigment is preferably a pigment selected from anthraquinone, azomethine, benzylidene, cyanine, diketopyrrolopyrrole, and phthalocyanine.

Moreover, when using the composition of this invention for color filters, it is preferable to use the dye which melt | dissolves uniformly in a composition from a viewpoint of uneven color and contrast.
The dye that can be 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 No. 64-90403, Japanese Patent Application Laid-Open No. 64-91102, Japanese Patent Application Laid-Open No. 1-94301, Japanese Patent Application Laid-Open No. 6-11614, No. 2592207, US Pat. No. 4,808,501. Specification, US Pat. No. 5,667,920, US Pat. No. 5,059,500, JP-A-5-333207, JP-A-6-35183, JP-A-6-51115 JP-A-6-194828, JP-A-8-21599, JP-A-4-249549, JP-A-10-123316, JP-A-11-302283, JP-A-7-286107, JP 2001-4823, JP-A-8-15522, JP-A-8-29771, JP-A-8-146215, JP-A-11-3434. 7, JP-A-8-62416, JP-A-2002-14220, JP-A-2002-14221, JP-A-2002-14222, JP-A-2002-14223, JP-A-8-302224 The dyes disclosed in JP-A-8-73758, JP-A-8-179120, JP-A-8-151531, and the like can be used.

  The chemical structure includes pyrazole azo, anilino azo, triphenyl methane, anthraquinone, anthrapyridone, benzylidene, oxonol, pyrazolotriazole azo, pyridone azo, cyanine, phenothiazine, pyrrolopyrazole azomethine, Xanthene-based, phthalocyanine-based, benzopyran-based and indigo-based dyes can be used.

In addition, after pattern exposure of the curable composition and curing of the exposed portion, unexposed portions are removed by water or alkali development to form a pattern, for example, when a colored pattern of a resist or a color filter is formed. From the viewpoint of completely removing the binder, dye, and the like in the non-light-irradiated part due to the acid dye, an acid dye and / or a derivative thereof may be suitably used.
In addition, a direct dye, a basic dye, a mordant dye, an acid mordant dye, an azoic dye, a disperse dye, an oil-soluble dye, a food dye, and / or a derivative thereof can be usefully used.

  The acidic dye is not particularly limited as long as it has an acidic group such as sulfonic acid or carboxylic acid, but is soluble in an organic solvent or a developer, salt-forming with a basic compound, absorbance, and other components in the composition. It is selected in consideration of all required performance such as interaction with components, light resistance, heat resistance and the like.

Hereinafter, although the specific example of an acidic dye is given, in this invention, it is not limited to these. For example,
acid alizarin violet N;
acid black 1, 2, 24, 48;
acid blue 1,7,9,15,18,23,25,27,29,40,42,45,51,62,70,74,80,83,86,87,90,92,96,103, 112, 113, 120, 129, 138, 147, 150, 158, 171, 182, 192, 210, 242, 243, 256, 259, 267, 278, 280, 285, 290, 296, 315, 324: 1, 335, 340;
acid chroma violet K;
acid Fuchsin;
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, 95107, 108, 169, 173;

acid red 1,4,8,14,17,18,26,27,29,31,34,35,37,42,44,50,51,52,57,66,73,80,87,88, 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, 227,228,249,252,257,258,260,261,266,268,270,274,277,280,281,195,308,312,315,316,339,341,345,346,349, 382, 383, 394, 401, 412, 417, 418, 422, 426;
acid violet 6B, 7, 9, 17, 19;
acid yellow 1,3,7,9,11,17,23,25,29,34,36,38,40,42,54,65,72,73,76,79,98,99,111,112, 113, 114, 116, 119, 123, 128, 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 2,33,34,35,38,39,43,47,50,54,58,68,69,70,71,86,93,94,95,98,102,108,109,129, 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, 207, 211, 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, 115, 117, 119,137,149,150,153,155,156,158,159,160,161,162,164,166,167,170,171,172,173,188,189,190,192,193 194,196,198,199,200,207,209,210,212,213,214,222,228,229,237,238,242,243,244,245,247,248,250,251,252, 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;
Modern Yellow 5, 8, 10, 16, 20, 26, 30, 31, 33, 42, 43, 45, 56, 50, 61, 62, 65;
Modern Orange 3, 4, 5, 8, 12, 13, 14, 20, 21, 23, 24, 28, 29, 32, 34, 35, 36, 37, 42, 43, 47, 48;

Modern Red 1, 2, 3, 4, 9, 11, 12, 14, 17, 18, 19, 22, 23, 24, 25, 26, 30, 32, 33, 36, 37, 38, 39, 41, 43, 45, 46, 48, 53, 56, 63, 71, 74, 85, 86, 88, 90, 94, 95;
Modern Violet 2, 4, 5, 7, 14, 22, 24, 30, 31, 32, 37, 40, 41, 44, 45, 47, 48, 53, 58;
Modern Blue 2, 3, 7, 8, 9, 12, 13, 15, 16, 19, 20, 21, 22, 23, 24, 26, 30, 31, 32, 39, 40, 41, 43, 44, 48, 49, 53, 61, 74, 77, 83, 84;
Modern 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 mentioned above, 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 preferred.
Other than the above, azo, xanthene and phthalocyanine acid dyes are also preferred. I. Solvent Blue 44, 38; C.I. I. Acid dyes such as Solvent orange 45; Rhodamine B, Rhodamine 110, and derivatives of these dyes are also preferably used.

In the present invention, (D) as the colorant, triallylmethane, anthraquinone, azomethine, benzylidene, oxonol, cyanine, phenothiazine, pyrrolopyrazole azomethine, xanthene, phthalocyanine, benzopyran, indigo, pyrazole azo, anilino azo series, pyrazolotriazole azo series, pyridone azo, Ru colorants der selected from anthrapyridone series.

  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, including the case where it is used for forming a color filter color pattern, and is 40% by mass or more and 80% by mass or less. More preferably, it is more preferable that it is 50 mass% or less and 75 mass% or less.

<(E) Binder polymer>
The curable composition of the present invention may contain (E) a binder polymer as long as the effects of the present invention are not impaired for the purpose of improving film properties.
It is preferable to use a linear organic polymer as the binder polymer. As such a “linear organic polymer”, a known one 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 selected and used not only as a film forming agent but also according to the use as water, weak alkaline water or an organic solvent developer. For example, when a water-soluble organic polymer is used, water development becomes possible. Examples of such linear organic polymers include radical polymers having a carboxylic acid group in the side chain, such as JP-A-59-44615, JP-B-54-34327, JP-B-58-12777, and JP-B-54-25957. , JP-A-54-92723, JP-A-59-53836, JP-A-59-71048, that is, a resin obtained by homopolymerizing or copolymerizing a monomer having a carboxyl group, acid anhydride Resins in which acid anhydride units are hydrolyzed, half-esterified or half-amidated, or epoxy acrylate modified with unsaturated monocarboxylic acid and acid anhydride, etc. It is done. Examples of the monomer having a carboxyl group include acrylic acid, methacrylic acid, itaconic acid, crotonic acid, maleic acid, fumaric acid, 4-carboxylstyrene, and the monomer having an acid anhydride includes maleic anhydride. It is done.
Similarly, there is an acidic cellulose derivative having a carboxylic acid group in the side chain. In addition, those obtained by adding a cyclic acid anhydride to a polymer having a hydroxyl group are useful.

  When the binder polymer is used as an alkali-soluble copolymer, a monomer other than the monomers listed above can be used as the compound to be copolymerized. Examples of other monomers include the following compounds (1) to (12).

(1) 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 3-hydroxypropyl acrylate, 4-hydroxybutyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, 3-hydroxypropyl methacrylate, 4-hydroxybutyl methacrylate Acrylic acid esters and methacrylic acid esters having an aliphatic hydroxyl group such as
(2) Methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, isobutyl acrylate, amyl acrylate, hexyl acrylate, 2-ethylhexyl acrylate, octyl acrylate, benzyl acrylate, acrylic acid-2- Alkyl acrylates such as chloroethyl, glycidyl acrylate, 3,4-epoxycyclohexylmethyl acrylate, vinyl acrylate, 2-phenylvinyl acrylate, 1-propenyl acrylate, allyl acrylate, 2-allyloxyethyl acrylate, propargyl acrylate;

(3) Methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, isobutyl methacrylate, amyl methacrylate, hexyl methacrylate, 2-ethylhexyl methacrylate, cyclohexyl methacrylate, benzyl methacrylate, methacrylic acid-2- Alkyl methacrylates such as chloroethyl, glycidyl methacrylate, 3,4-epoxycyclohexylmethyl methacrylate, vinyl methacrylate, 2-phenylvinyl methacrylate, 1-propenyl methacrylate, allyl methacrylate, 2-allyloxyethyl methacrylate, and propargyl methacrylate.
(4) Acrylamide, methacrylamide, N-methylolacrylamide, N-ethylacrylamide, N-hexylmethacrylamide, N-cyclohexylacrylamide, N-hydroxyethylacrylamide, N-phenylacrylamide, N-nitrophenylacrylamide, N-ethyl- Acrylamide or methacrylamide such as N-phenylacrylamide, vinylacrylamide, vinylmethacrylamide, N, N-diallylacrylamide, N, N-diallylmethacrylamide, allylacrylamide, allylmethacrylamide.

(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, α-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-acryloylacrylamide, N-acetylmethacrylamide, N-propionylmethacrylamide, N- (p-chlorobenzoyl) methacrylamide.
(12) A methacrylic acid monomer having a hetero atom bonded to the α-position. For example, compounds described in Japanese Patent Application No. 2001-115595, Japanese Patent Application No. 2001-115598, and the like can be mentioned.

  Among these, a (meth) acrylic resin having an allyl group, a vinyl ester group, and a carboxyl group in the side chain and a side chain described in JP-A Nos. 2000-187322 and 2002-62698 are doubled. An alkali-soluble resin having a bond and an alkali-soluble resin having an amide group in the side chain described in JP-A No. 2001-242612 are preferable because of excellent balance of film strength, sensitivity, and developability.

In addition, Japanese Patent Publication No. 7-2004, Japanese Patent Publication No. 7-120041, Japanese Patent Publication No. 7-120042, Japanese Patent Publication No. 8-12424, Japanese Patent Laid-Open No. 63-287944, Japanese Patent Laid-Open No. 63-287947, Japanese Patent Laid-Open No. Urethane binder polymers containing acid groups described in No. 271741 and Japanese Patent Application No. 10-116232, and urethane binder polymers having acid groups and double bonds in side chains as described in JP-A No. 2002-107918 Is very excellent in strength, and is advantageous in terms of suitability for low exposure.
In addition, the acetal-modified polyvinyl alcohol-based binder polymer having an acid group described in European Patent 993966, European Patent 1204000, Japanese Patent Application Laid-Open No. 2001-318463, and the like is preferable because of its excellent balance of film strength and developability.
In addition, polyvinyl pyrrolidone, polyethylene oxide, and the like are useful as the water-soluble linear organic polymer. In order to increase the strength of the cured film, alcohol-soluble nylon, polyether of 2,2-bis- (4-hydroxyphenyl) -propane and epichlorohydrin, and the like are also useful.

(E) The weight average molecular weight of the binder polymer is preferably 3000 or more, more preferably 5000 to 300,000, and the number average molecular weight is preferably 1,000 or more, more preferably 2, The range is from 000 to 250,000. The polydispersity (weight average molecular weight / number average molecular weight) is preferably 1 or more, and more preferably 1.1 to 10.
These binder polymers may be any of random polymers, block polymers, graft polymers and the like.

(E) The binder polymer can be synthesized by a conventionally known method. Solvents used in the synthesis include, for example, tetrahydrofuran, ethylene dichloride, cyclohexanone, methyl ethyl ketone, acetone, methanol, ethanol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, 2-methoxyethyl acetate, diethylene glycol dimethyl ether, 1-methoxy. Examples include 2-propanol, 1-methoxy-2-propyl acetate, N, N-dimethylformamide, N, N-dimethylacetamide, toluene, ethyl acetate, methyl lactate, ethyl lactate, dimethyl sulfoxide, and water. These solvents are used alone or in combination of two or more.
Examples of the radical polymerization initiator used in synthesizing the binder polymer that can be used in the present invention include known compounds such as an azo initiator and a peroxide initiator.

  (E) When the curable composition of the present invention is used for forming a colored pattern of a color filter, the content of the binder polymer is that of the present invention from the viewpoint of the balance between pigment dispersion stability over time and developability. It is preferably 5% by mass or more and 60% by mass or less, more preferably 7% by mass or more and 50% by mass or less, and more preferably 10% by mass or less and 40% by mass or less with respect to the total solid content of the curable composition. Most preferred.

  The curable composition of this invention may further contain the component explained in full detail as needed.

<(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.

Dispersants (pigment dispersants) that can be used in the present invention include polymer dispersants [for example, polyamidoamines and salts thereof, polycarboxylic acids and salts thereof, high molecular weight unsaturated acid esters, modified polyurethanes, modified polyesters, modified polymers. (Meth) acrylate, (meth) acrylic copolymer, naphthalene sulfonic acid formalin condensate], polyoxyethylene alkyl phosphate ester, polyoxyethylene alkyl amine, alkanol amine, pigment derivative and the like.
The polymer dispersant can be further classified into a linear polymer, a terminal-modified polymer, a graft polymer, and a block polymer according to the structure.

  The polymer dispersant is adsorbed on the surface of the pigment and acts to prevent reaggregation. Therefore, a terminal-modified polymer, a graft polymer and a block polymer having an anchor site to the pigment surface can be mentioned as preferred structures. On the other hand, the pigment derivative has an effect of promoting the adsorption of the polymer dispersant by modifying the pigment surface.

  Specific examples of the pigment dispersant that can be used in the present invention include “Disperbyk-101 (polyamidoamine phosphate), 107 (carboxylic acid ester), 110 (copolymer containing an acid group), 130 (polyamide) manufactured by BYK Chemie. ), 161, 162, 163, 164, 165, 166, 170 (polymer copolymer) ”,“ BYK-P104, P105 (high molecular weight unsaturated polycarboxylic acid) ”,“ EFKA 4047, 4050, 4010, manufactured by EFKA, 4165 (polyurethane series), EFKA4330, 4340 (block copolymer), 4400, 4402 (modified polyacrylate), 5010 (polyesteramide), 5765 (high molecular weight polycarboxylate), 6220 (fatty acid polyester), 6745 (phthalocyanine) Derivatives), 6750 (azo) "Adisper PB821, PB822" manufactured by Ajinomoto Fan Techno Co., "Floren TG-710 (urethane oligomer)" manufactured by Kyoeisha Chemical Co., "Polyflow No. 50E, No. 300 (acrylic copolymer)", “Disparon KS-860, 873SN, 874, # 2150 (aliphatic polycarboxylic acid), # 7004 (polyetherester), DA-703-50, DA-705, DA-725” manufactured by Enomoto Kasei Co., Ltd., Kao “Demol RN, N (Naphthalenesulfonic acid formalin polycondensate), MS, C, SN-B (aromatic sulfonic acid formalin polycondensate)”, “Homogenol L-18 (polymer polycarboxylic acid)”, “ Emulgen 920, 930, 935, 985 (polyoxyethylene nonylphenyl ether) ”,“ acetamine 86 (stearylamine acetate) ", Lubrizol" Solsperse 5000 (phthalocyanine derivative), 22000 (azo pigment derivative), 13240 (polyesteramine), 3000, 17000, 27000 (polymer having a functional part at the end), 24000, 28000, 32000, 38500 (graft type polymer) ”,“ Nikkor T106 (polyoxyethylene sorbitan monooleate), MYS-IEX (polyoxyethylene monostearate) ”manufactured by Nikko Chemicals, and the like.

  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 a pigment derivative and a polymer dispersant.

As content of the dispersing agent in this invention, it is preferable that it is 1 mass%-100 mass% with respect to a pigment, 3 mass%-100 mass% are more preferable, 5 mass%-80 mass% are still more preferable. .
Specifically, when a polymer dispersant is used, the amount used is preferably in the range of 5% by mass to 100% by mass and more preferably in the range of 10% by mass to 80% by mass with respect to the pigment. preferable. In the case of using a pigment derivative, the amount used is preferably in the range of 1% by mass to 30% by mass with respect to the pigment, and more preferably in the range of 3% by mass to 20% by mass. It is preferably in the range of 5% by mass to 15% by mass.

  In the present invention, when a pigment and a dispersant are used, the total content of the pigment and the dispersant is 35% by mass or more based on the total solid content constituting the curable composition from the viewpoint of curing sensitivity and color density. It is preferably 90% by mass or less, more preferably 45% by mass or more and 85% by mass or less, and further preferably 50% by mass or more and 80% by mass or less.

<(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 photosensitive wavelength. As the sensitizer that can be used in the present invention, those that sensitize the above-mentioned photopolymerization initiator by an electron transfer mechanism or an energy transfer mechanism are preferable.

Examples of the sensitizer that can be used in the present invention include those belonging to the compounds listed below and having an absorption wavelength in a wavelength region of 300 nm to 450 nm.
Examples of preferred sensitizers include those belonging to the following compounds and having an absorption wavelength in the range of 330 nm to 450 nm.
For example, polynuclear aromatics (for example, phenanthrene, anthracene, pyrene, perylene, triphenylene, 9,10-dialkoxyanthracene), xanthenes (for example, fluorescein, eosin, erythrosine, rhodamine B, rose bengal), thioxanthones (Isopropylthioxanthone, diethylthioxanthone, chlorothioxanthone), cyanines (eg thiacarbocyanine, oxacarbocyanine), merocyanines (eg merocyanine, carbomerocyanine), phthalocyanines, thiazines (eg thionine, methylene blue, toluidine blue) , Acridines (eg, acridine orange, chloroflavin, acriflavine), anthraquinones (eg, anthraquinone), squariums (eg Squalium), acridine orange, coumarins (eg 7-diethylamino-4-methylcoumarin), ketocoumarin, phenothiazines, phenazines, styrylbenzenes, azo compounds, diphenylmethane, triphenylmethane, distyrylbenzenes, carbazole , Porphyrins, spiro compounds, quinacridone, indigo, styryl, pyrylium compounds, pyromethene compounds, pyrazolotriazole compounds, benzothiazole compounds, barbituric acid derivatives, thiobarbituric acid derivatives, acetophenone, benzophenone, thioxanthone, Michler's ketone and other aromatics Examples include ketone compounds and heterocyclic compounds such as N-aryloxazolidinones. Further, European Patent No. 568,993, US Patent No. 4,508,811, No. 5,227,227, JP-A-2001-125255, JP-A-11- And the compounds described in Japanese Patent No. 271969.

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

In general formula (i), A ¹ represents a sulfur atom or NR ⁵⁰ , R ⁵⁰ represents an alkyl group or an aryl group, and L ² represents the basic nucleus of the dye in combination with adjacent A ¹ and the adjacent carbon atom. Represents a non-metallic atomic group to be formed, R ⁵¹ and R ⁵² each independently represent a hydrogen atom or a monovalent non-metallic atomic group, and R ⁵¹ and R ⁵² are bonded to each other to form an acidic nucleus of the dye. Also good. W represents an oxygen atom or a sulfur atom. Examples of the alkyl group of R ⁵⁰ include an alkyl group having 1 to 30 carbon atoms, preferably an alkyl group having 1 to 20 carbon atoms, and most preferably an alkyl group having 1 to 10 carbon atoms. Examples of the aryl group of R ⁵⁰ include 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.

In General Formula (ii), Ar ¹ and Ar ² each independently represent an aryl group, and are linked via a bond with —L ³ —. Here, L ³ represents —O— or —S—. W is synonymous with that shown in the general formula (i). The aryl group of Ar ^{1 includes} 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. The aryl group of Ar ^{2 includes} 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.

In the general formula (iii), A ² represents a sulfur atom or NR ⁵⁹ , L ⁴ represents a nonmetallic atomic group that forms a basic nucleus of a dye in combination with an adjacent A ² and a carbon atom, R ⁵³ , R ⁵⁴ , R ⁵⁵ , R ⁵⁶ , R ⁵⁷ and R ⁵⁸ each independently represent a monovalent nonmetallic atomic group, and R ⁵⁹ represents an alkyl group or an aryl group. The alkyl group of R ^59, there may be mentioned alkyl groups having 1 to 30 carbon atoms, preferably an alkyl group having 1 to 20 carbon atoms, most preferably an alkyl group having 1 to 10 carbon atoms. The aryl group of R ^59, there may be mentioned aryl groups having 6 to 30 carbon atoms, preferably an aryl group having 6 to 20 carbon atoms, most preferably an aryl group having 6 to 10 carbon atoms.

In general formula (iv), A ³ and A ⁴ each independently represent —S— or —NR ⁶² — or —NR ⁶³ —, wherein R ⁶² and R ⁶³ each independently represent a substituted or unsubstituted alkyl group, substituted Or an unsubstituted aryl group, and L ⁵ and L ⁶ each independently represent a nonmetallic atomic group that forms a basic nucleus of a dye together with adjacent A ³ , A ⁴ and an adjacent carbon atom; ⁶⁰ and R ⁶¹ are each independently a monovalent non-metallic atomic group, or may be bonded to each other to form an aliphatic or aromatic ring. Examples of the alkyl group for R ⁶² and R ⁶³ include an alkyl group having 1 to 30 carbon atoms, preferably an alkyl group having 1 to 20 carbon atoms, and most preferably an alkyl group having 1 to 10 carbon atoms. Examples of the aryl group of R ⁶² and R ⁶³ include 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 a substituent in the case of substitution with these, an alkyl group, a halogen atom (a fluorine atom, a chlorine atom, a bromine atom, an iodine atom), an alkoxyl group, an alkoxycarbonyl group, an acyl group, a hydroxyl group, and an amino group are preferable. 1-30 are preferable, as for carbon number which comprises these substituents, 1-20 are more preferable, and 1-10 are the most preferable.

  Moreover, as a preferable sensitizer which can be contained in the curable composition of this invention, at least 1 type selected from the compound represented by the following general formula (IV)-(VI) other than the above thing is mentioned. These may be used individually by 1 type, and may use 2 or more types together.

In general formula (IV) or general formula (V), R ¹ and R ² each independently represent a monovalent substituent, and R ³ , R ⁴ , R ⁵ and R ⁶ each independently represent a hydrogen atom or Represents a monovalent substituent. n represents an integer of 0 to 5, n ′ represents an integer of 0 to 5, and n and n ′ are not both 0. When n is 2 or more, a plurality of R ¹ may be the same or different. When n ′ is 2 or more, a plurality of R ² may be the same or different. The monovalent substituent is preferably an alkyl group, a halogen atom (a fluorine atom, a chlorine atom, a bromine atom, an iodine atom), an alkoxyl group, an alkoxycarbonyl group, an acyl group, a hydroxyl group, or an amino group. 1-30 are preferable, as for carbon number which comprises these substituents, 1-20 are more preferable, and 1-10 are the most preferable.

  The compound represented by the general formula (IV) is preferably a compound represented by the following general formula (IV-1) from the viewpoint of colorability and sensitivity when a colorant is contained.

In general formula (IV-1), R ¹ and R ² each independently represents a monovalent substituent. n represents an integer of 0 to 5, and n ′ represents an integer of 1 to 5. When n is 2 or more, a plurality of R ¹ may be the same or different, and when n ′ is 2 or more, a plurality of R ² are the same or different. Also good.

In the general formula (IV-1), the monovalent substituent represented by ^{R 1} and ^{R 2} are synonymous with the monovalent substituent represented by ^{R 1} and ^{R 2} in the general formula (IV) The preferable range is also the same.

The general formula (IV) or general formula (V) compounds represented by is preferably a molar extinction coefficient epsilon at a wavelength of 365nm is ^{500mol -1} · L · ^cm -1 or more, epsilon at a wavelength of 365nm is 3000 mol ^- more preferably ¹ · L · ^{cm -1} or more, and most preferably ε at a wavelength of 365nm is 20000mol ^-1 · L · ^{cm -1} or more. It is preferable that the value of the molar extinction coefficient ε at each wavelength is in the above range because the sensitivity improvement effect is high from the viewpoint of light absorption efficiency.
Here, the molar extinction coefficient ε is determined by measuring a transmission spectrum of a sample at 365 nm using a dye solution adjusted to a concentration of 0.01 g / l in a 1-methoxy-2-propanol solution, and UV-visible absorption of the sample. It is obtained by determining the absorbance from the spectrum. The measurement apparatus used was a Varian UV-Vis-MR Spectrophotometer Cary 5G type spectral altimeter.

Although the preferable specific example of a compound represented by general formula (IV) or general formula (V) is illustrated below, this invention is not limited to these.
Note that in this specification, a chemical formula may be described by a simplified structural formula, and a solid line or the like that does not clearly indicate an element or a substituent particularly 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 general formula (VI), A represents an aromatic ring or a hetero ring which may have a substituent, X represents an oxygen atom, a sulfur atom, or —N (R ³ ) —, Y represents an oxygen atom, A sulfur atom or -N (R < ³ >)-is represented. R ¹ , R ² , and R ³ each independently represent a hydrogen atom or a monovalent nonmetallic atomic group, and A, R ¹ , R ² , and R ³ are each bonded to each other to form an aliphatic group Or you may form an aromatic ring.

In the general formula (VI), when R ¹ , R ² and R ³ represent a monovalent nonmetallic atomic group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted alkenyl group A substituted or unsubstituted aromatic heterocyclic residue, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted alkylthio group, a hydroxy group, or a halogen atom.
The alkyl group is preferably a linear, branched or cyclic alkyl group having 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, and particularly preferably 1 to 15 carbon atoms. For example, methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, iso-butyl group, tert-butyl group, n-octyl group, n-dodecyl group, cyclopentyl group, cyclopentyl group, benzyl group, 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, etc. are mentioned.
The alkenyl group is preferably a linear, branched or cyclic alkenyl group having 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, and particularly preferably 1 to 15 carbon atoms. For example, vinyl, allyl, cyclohexenyl, geranyl and the like can be mentioned.
The aromatic heterocyclic residue is preferably a 5- to 7-membered substituted or unsubstituted, saturated or unsaturated, aromatic or non-aromatic, monocyclic or condensed aromatic heterocyclic residue, and more Preferably, it is an aromatic heterocyclic residue in which the ring constituent atom is selected from a carbon atom, a nitrogen atom and a sulfur atom, and has at least one heteroatom of any 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 can be mentioned.
As said alkoxyl group, a linear, branched or cyclic C1-C30 alkoxyl group is preferable, C1-C20 is more preferable, C1-C10 is especially preferable. For example, methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, tert-butoxy and the like can be mentioned.
The alkylthio group is preferably a linear, 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, a methylthio, ethylthio, n-decylthio group, etc. are mentioned.
The monovalent non-metallic atomic group may be substituted as described above, and 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, and an alkoxycarbonyl group. , Acyl group, hydroxy group, alkylthio group, arylthio group and the like. When these substituents have carbon, the total carbon number is preferably 1-30, more preferably 1-20, and most preferably 1-10.

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

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

The compound represented by the general formula (VI) according to the present invention can be further subjected to various chemical modifications for improving the properties of the curable composition.
For example, the sensitizer (hereinafter referred to as “sensitizing dye”) and an addition polymerizable compound structure (for example, acryloyl group or methacryloyl group) are bonded by a method such as a covalent bond, an ionic bond, or a hydrogen bond. Thus, it is possible to increase the strength of the exposed film and to suppress unnecessary precipitation of the sensitizing dye from the exposed film.
In addition, partial structures having radical generating ability in the sensitizing dye and the above-described photopolymerization initiator (for example, reductive decomposable sites such as alkyl halide, onium, peroxide, biimidazole, borate, amine, trimethylsilylmethyl) , An oxidatively cleavable site such as carboxymethyl, carbonyl, imine, etc.), the photosensitivity can be remarkably enhanced particularly in a state where the concentration of the starting system is low.

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

  The compounds represented by the above general formulas (IV) to (VI) have a very high concentration of the colorant (for example, pigment) in the curable composition, and light of the formed color pattern (photosensitive layer) is transmitted. When the rate is extremely low, specifically, it is added when the 365 nm light transmittance of the photosensitive layer when formed without adding a sensitizing dye is 10% or less. The effect of enhancing the properties is remarkably exhibited. In particular, among the above general formulas (IV) to (VI), the compound represented by the general formula (VI) is most preferable, and specifically, the compounds of (VI56) to (VI122) are most preferable.

A sensitizer may be used individually by 1 type and may use 2 or more types together.
The content of the sensitizer in the curable composition of the present invention is 0.1% by mass to 20% with respect to the total solid content of the curable composition from the viewpoint of light absorption efficiency into the deep part and initiation decomposition efficiency. It is preferable that it is mass%, and 0.5 mass%-15 mass% are more preferable. By setting it as the said range, the light absorption efficiency to the deep part of a curable composition becomes high, and it is preferable at the point from which initial decomposition efficiency becomes favorable.

<(H) Co-sensitizer>
The curable composition of the present invention can also contain a co-sensitizer. In the present invention, the co-sensitizer has functions such as further improving the sensitivity of the sensitizing dye and the photopolymerization initiator to actinic radiation or suppressing the inhibition of polymerization of the polymerizable compound by oxygen.
Examples of such cosensitizers include amines such as M.I. R. Sander et al., “Journal of Polymer Society”, Vol. 10, 3173 (1972), Japanese Patent Publication No. 44-20189, Japanese Patent Publication No. 51-82102, Japanese Patent Publication No. 52-134692, Japanese Patent Publication No. 59-138205. No. 60-84305, JP-A 62-18537, JP-A 64-33104, Research Disclosure 33825, and the like. Specific examples include triethanolamine. P-dimethylaminobenzoic acid ethyl ester, p-formyldimethylaniline, p-methylthiodimethylaniline and the like.

  Other examples of co-sensitizers include thiols and sulfides such as thiol compounds described in JP-A-53-702, JP-B-55-500806, JP-A-5-142772, No. 56-75643, such as 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, 2-mercaptobenzimidazole, 2-mercapto-4 (3H) -quinazoline, β-mercapto. And naphthalene.

  Other examples of the co-sensitizer include amino acid compounds (eg, N-phenylglycine), organometallic compounds described in JP-B-48-42965 (eg, tributyltin acetate), JP-B 55- Examples include a hydrogen donor described in Japanese Patent No. 34414, a sulfur compound (eg, trithiane) described in Japanese Patent Laid-Open No. 6-308727, and the like.

  The content of the co-sensitizer is in the range of 0.1% by mass to 30% by mass with respect to the mass of the total solid content of the curable composition from the viewpoint of improving the curing rate due to the balance between the polymerization growth rate and the chain transfer. Is preferable, the range of 0.5 mass% to 25 mass% is more preferable, and the range of 1.0 mass% to 20 mass% is still more preferable.

<(I) Polymerization inhibitor>
In the present invention, a small amount of a thermal polymerization inhibitor may be added in order to prevent unnecessary thermal polymerization of a compound having an ethylenically unsaturated double bond that can be polymerized during the production or storage of the curable composition. desirable.
Examples of the thermal polymerization inhibitor that can be used in the present invention include hydroquinone, p-methoxyphenol, di-t-butyl-p-cresol, pyrogallol, t-butylcatechol, benzoquinone, 4,4′-thiobis (3-methyl-6). -T-butylphenol), 2,2'-methylenebis (4-methyl-6-t-butylphenol), N-nitrosophenylhydroxyamine primary cerium salt and the like.

  (H) 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 entire composition. If necessary, a higher fatty acid derivative such as behenic acid or behenic acid amide may be added to prevent polymerization inhibition due to oxygen, and it may be unevenly distributed on the surface of the photosensitive layer in the course of drying 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>
Furthermore, in the present invention, in order to improve the physical properties of the cured film, known additives such as inorganic fillers, plasticizers, and sensitizers that can improve the ink inking property on the surface of the photosensitive layer, substrate adhesion You may add the board | substrate adhesion agent which can improve this.
Examples of plasticizers include dioctyl phthalate, didodecyl phthalate, triethylene glycol dicaprylate, dimethyl glycol phthalate, tricresyl phosphate, dioctyl adipate, dibutyl sebacate, and triacetyl glycerin. 10 mass% or less can be added with respect to the total mass of the compound which has an ionic unsaturated double bond, and a binder.

When the curable composition of the present invention is applied to the surface of a hard material such as a substrate, an additive for improving the adhesion to the surface of the hard material (hereinafter referred to as “substrate adhesion agent”) is added. May be.
As the substrate adhesion agent, known materials can be used, but it is particularly preferable to use a silane coupling agent, a titanate coupling agent, or an aluminum coupling agent.
Examples of the silane coupling agent include γ- (2-aminoethyl) aminopropyltrimethoxysilane, γ- (2-aminoethyl) aminopropyldimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxy. Silane, γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropyltriethoxysilane, γ-acryloxypropyltrimethoxysilane, γ-acryloxypropyl Triethoxysilane, γ-isocyanatopropyltrimethoxysilane, γ-isocyanatopropyltriethoxysilane, N-β- (N-vinylbenzylaminoethyl) -γ-aminopropyltrimethoxysilane / hydrochloride, γ-glycidoxypro Pyrtrimethoxysilane, γ-glycidoxypropyltriethoxysilane, aminosilane, γ-mercaptopropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, vinyltriacetoxysilane, γ- Chloropropyltrimethoxysilane, hexamethyldisilazane, γ-anilinopropyltrimethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (β-methoxyethoxy) silane, octadecyldimethyl [3- (trimethoxysilyl) propyl ] Ammonium chloride, γ-chloropropylmethyldimethoxysilane, γ-mercaptopropylmethyldimethoxysilane, methyltrichlorosilane, dimethyldichlorosilane, trimethyl Chlorosilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, bisallyltrimethoxysilane, tetraethoxysilane, bis (trimethoxysilyl) hexane, phenyltrimethoxysilane, N- (3-acryloxy-2-hydroxy Propyl) -3-aminopropyltriethoxysilane, N- (3-methacryloxy-2-hydroxypropyl) -3-aminopropyltriethoxysilane, (methacryloxymethyl) methyldiethoxysilane, (acryloxymethyl) methyldimethoxysilane , Etc.
Among them, γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropyltriethoxysilane, γ-acryloxypropyltrimethoxysilane, γ-acryloxypropyltriethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-aminopropyltri Ethoxysilane and phenyltrimethoxysilane are preferred, and γ-methacryloxypropyltrimethoxysilane is most preferred.

  Examples of titanate coupling agents include isopropyl triisostearoyl titanate, isopropyl tridecylbenzenesulfonyl titanate, isopropyl tris (dioctyl pyrophosphate) titanate, tetraisopropyl bis (dioctyl phosphite) titanate, tetraoctyl bis (ditridecyl phosphite). ) Titanate, tetra (2,2-diallyloxymethyl) bis (di-tridecyl) phosphite titanate, bis (dioctylpyrophosphate) oxyacetate titanate, bis (dioctylpyrophosphate) ethylene titanate, isopropyltrioctanoyl titanate, isopropyldi Methacrylic isostearoyl titanate, isopropyl isostearoyl diacryl titanate, Li isopropyl tri (dioctyl phosphate) titanate, isopropyl tricumylphenyl titanate, isopropyl tri (N- amidoethyl-aminoethyl) titanate, dicumyl phenyloxy acetate titanate, diisostearoyl ethylene titanate.

  Examples of the aluminum coupling agent include acetoalkoxyaluminum diisopropylate.

  The content of the substrate adhesive is 0.1 mass with respect to the total solid content of the curable composition of the present invention, from the viewpoint of leaving no residue in the unexposed area when the curable composition is exposed. % To 30% by mass, more preferably 0.5% to 20% by mass, and particularly preferably 1% to 10% by mass.

  The curable composition of the present invention can be cured with high sensitivity and storage stability can be improved by adopting the above-described configuration. Moreover, the curable composition of this invention shows the high adhesiveness to the surface (for example, hard materials, such as a board | substrate) to apply. Accordingly, the curable composition of the present invention can be preferably used in the fields of image forming materials such as three-dimensional stereolithography, holography, and color filters, inks, paints, adhesives, and coating agents.

[Color filter and manufacturing method thereof]
Next, the color filter of the present invention and the manufacturing method thereof will be described.
The color filter of the present invention is characterized by having a colored pattern formed using the curable composition of the present invention on a support.
Hereinafter, the color filter of the present invention will be described in detail through its manufacturing method (color filter manufacturing method of the present invention).

The method for producing a color filter of the present invention comprises a colored layer forming step of forming a colored layer comprising the curable composition by applying the curable composition of the present invention on a support, and using the colored layer as a mask. And a developing step of developing the colored layer after exposure to form a colored pattern.
Hereafter, each process in the manufacturing method of this invention is demonstrated.

<Colored layer forming step>
In the colored layer forming step, the curable composition of the present invention is applied on the support to form a colored layer comprising the curable composition.

As the support that can be used in this step, for example, soda glass, Pyrex (registered trademark) glass, quartz glass, and the like obtained by attaching a transparent conductive film to these, an image sensor, etc. Examples of the photoelectric conversion element substrate include a silicon substrate and a complementary metal oxide semiconductor (CMOS). These substrates may have black stripes that separate pixels.
Further, an undercoat layer may be provided on these supports, if necessary, in order to improve adhesion to the upper layer, prevent diffusion of substances, or flatten the substrate surface.

As a coating method of the curable composition of the present invention on the support, various coating methods such as slit coating, ink jet method, spin coating, cast coating, roll coating, screen printing method and the like can be applied.
The film thickness immediately after application of the curable composition is preferably 0.1 to 10 μm, more preferably 0.2 to 5 μm, from the viewpoint of film thickness uniformity of the coating film and ease of drying of the coating solvent. 0.2-3 micrometers is more preferable.

  The colored layer (curable composition layer) applied on the substrate can be dried (prebaked) at a temperature of 50 ° C. to 140 ° C. for 10 to 300 seconds using a hot plate, oven, or the like.

The coating film thickness after drying of the curable composition (hereinafter referred to as “dry film thickness” as appropriate) can be used for LCD color filters and can be used for LCD thinning, from the viewpoint of securing color density. 0.1 μm or more and less than 2.0 μm is preferable, 0.2 μm or more and 1.8 μm or less is more preferable, and 0.3 μm or more and 1.75 μm or less is particularly preferable.
In addition, in order to use it as an IS color filter, the light in the oblique direction does not reach the light receiving unit from the viewpoint of securing the color density, and the difference in the light collection rate between the end and the center of the device becomes remarkable. From the viewpoint of reducing defects, it is preferably 0.05 μm or more and less than 1.0 μm, more preferably 0.1 μm or more and 0.8 μm or less, and particularly preferably 0.2 μm or more and 0.7 μm or less.

<Exposure process>
In the exposure step, the colored layer (curable composition layer) formed in the colored layer forming step is exposed through a mask having a predetermined mask pattern.
In the exposure in this step, the pattern exposure of the coating film can be performed by exposing through a predetermined mask pattern and curing only the part of the coating film irradiated with light. As radiation that can be used for exposure, ultraviolet rays such as g-line and i-line are particularly preferably used. Irradiation dose is more preferably preferably ^{10~1000mJ / cm 2 5~1500mJ / cm 2} , and most preferably 10 to 500 mJ / cm ^2.
If the color filter of the present invention is a liquid crystal display device, it is more preferably preferably 10~150mJ / cm ² 5~200mJ / cm ² within the above range, and most preferably 10 to 100 mJ / cm ^2. Further, when the color filter of the present invention is for a solid-state imaging device, more preferably 30~1500mJ / cm ² is preferably 50~1000mJ / cm ² within the above range, and most preferably 80~500mJ / cm ^2.

<Development process>
Subsequently, by performing an alkali development process (development process), the light non-irradiated part is eluted in the alkaline aqueous solution by the exposure, and only the photocured part remains. It can be carried out by developing with a developing solution to form a patterned film composed of pixels of each color (3 colors or 4 colors). As the developer, an organic alkali developer that does not damage the underlying circuit or the like is desirable. The development temperature is usually 20 ° C. to 30 ° C., and the development time is 20 to 90 seconds.

Examples of the alkaline agent used in the developer include ammonia water, ethylamine, diethylamine, dimethylethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, choline, pyrrole, piperidine, 1,8-diazabicyclo- [5, 4, 0] -7-undecene and the like, and inorganic compounds such as sodium hydroxide, potassium hydroxide, sodium hydrogen carbonate, potassium hydrogen carbonate, and the like. The concentration of these alkali agents is 0.001% by mass to 10%. An alkaline aqueous solution diluted with pure water so as to have a mass%, preferably 0.01 mass% to 1 mass%, is preferably used as the developer. In the case where a developer composed of such an alkaline aqueous solution is used, it is generally washed (rinsed) with pure water after development.
Next, excess developer is washed away and dried.

  In the production method of the present invention, the colored pattern formed is cured by heating (post-baking) and / or exposure as necessary after performing the above-described colored layer forming step, exposure step, and development step. A curing step may be included.

The post-baking is a heat treatment after development for complete curing, and usually a heat curing treatment at 100 ° C. to 240 ° C. is performed. When the substrate is a glass substrate or a silicon substrate, 200 ° C. to 240 ° C. is preferable in the above temperature range.
This post-bake treatment is performed continuously or batchwise using a heating means such as a hot plate, a convection oven (hot air circulation dryer), a high-frequency heater, or the like so that the coating film after development is in the above-described condition. be able to.

  By repeating the colored layer forming step, the exposure step, and the developing step (and, if necessary, the curing step) described above for the desired number of hues, a color filter having a desired hue is produced.

  The application of the curable composition of the present invention has been described mainly with respect to the application to the pixels of the color filter, but it goes without saying that it can also be applied to a black matrix provided between the pixels of the color filter. The black matrix is subjected to pattern exposure and alkali development in the same manner as in the above pixel production method except that a black pigment such as carbon black or titanium black is added to the curable composition of the present invention as a colorant. Further, after that, post-baking can be performed to promote the curing of the film.

Since the color filter of the present invention is produced using the curable composition of the present invention having excellent exposure sensitivity, the cured composition in the exposed area is excellent in adhesion to the substrate and development resistance, and formed coloration The adhesion between the pattern and the support substrate is high, and the pattern giving a desired cross-sectional shape has high resolution.
Moreover, the solid-state image sensor of this invention is equipped with the color filter of this invention manufactured by the manufacturing method of the color filter of the said invention.
Therefore, specifically, the color filter of the present invention can be suitably used for a solid-state imaging device such as a liquid crystal display device or a CCD, and is particularly suitable for a high-resolution CCD device or CMOS that exceeds 1 million pixels. is there. The color filter of the present invention can be used as, for example, a color filter disposed between a light receiving portion of each pixel constituting a CCD element and a microlens for condensing light.

  EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, this invention is not limited by these.

[Synthesis Example 1]
<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 and stirred. After adding 39.2 g of pyridine and 0.1 g of p-methoxyphenol, the mixture was cooled in an ice bath containing ice water. After the temperature of the mixture became 5 ° C. or lower, 114.9 g of 2-bromoisobutanoic acid bromide was added dropwise using a dropping funnel over 3 hours. After completion of dropping, the ice bath was removed and the mixture was further stirred for 3 hours. The reaction mixture was poured into 750 ml of water and stirred for 1 hour. The aqueous 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 1M hydrochloric acid, 500 ml of saturated aqueous sodium hydrogen carbonate solution and 500 ml of saturated brine. 100 g of magnesium sulfate was added to the organic layer, dehydrated and dried, and then filtered. The solvent was distilled off under reduced pressure to obtain 120.3 g of residue.
The obtained residue was confirmed to be compound (i-1) from ¹ H-NMR, IR, and mass spectrometry spectrum. Moreover, the purity was 95% from HPLC.

(1) Synthesis of Resin (I) 86 g of 1-methyl-2-pyrrolidone was placed in a 1000 ml three-necked flask and heated to 90 ° C. under a nitrogen stream. 1 of 55 g of compound (i-1), 47 g of exemplary compound M-14MA, 13 g of methacrylic acid, dimethyl 2,2′-azobis (2-methylpropionate) (V-601, manufactured by Wako Pure Chemical Industries, Ltd.) -A solution of 86 g of methyl-2-pyrrolidone was added dropwise over 2 hours. After completion of dropping, the mixture was further stirred for 2 hours. The reaction solution was cooled to room temperature and then poured into 7 L of water to precipitate a polymer compound. The precipitated polymer compound was collected by filtration, washed with water and dried to obtain 110 g of a polymer compound.
It was 13100 as a result of measuring a mass mean molecular weight by the gel permeation chromatography method (GPC) which used the obtained high molecular compound as a standard substance. Moreover, when the acid value was calculated | required by titration, it was 1.25 meq / g (calculated value 1.30 meq / g), and it was confirmed that superposition | polymerization was performed normally.

The polymer compound 110g and p-methoxyphenol 0.1g which were obtained in a 1000 ml three necked flask were put, and it cooled in the ice bath containing 1-methyl-2-pyrrolidone 470g ice water. After the temperature of the mixture became 5 ° C. or lower, 100 g of 1,8-diazabicyclo [5.4.0] -7-undecene (DBU) was added dropwise over 1 hour using a dropping funnel. After completion of dropping, the ice bath was removed and the mixture was further stirred for 8 hours. The reaction solution was adjusted to pH 7 by adding concentrated hydrochloric acid and then poured into 7 L of water to precipitate a polymer compound resin (I). The precipitated polymer compound was collected by filtration, washed with water and dried to obtain 95 g of a polymer compound.
When ¹ H-NMR of the obtained polymer compound was measured, it was confirmed that 100% of the side chain groups derived from the compound (i-1) were converted to ethylene methacrylate groups. Moreover, it was 12100 as a result of measuring a mass mean molecular weight by the gel permeation chromatography method (GPC) used as the polystyrene standard substance. Furthermore, when the acid value was determined by titration, it was 1.45 meq / g (calculated value 1.51 meq / g).

[Example 1]
[A1. Preparation of curable composition]
Here, an example in which a curable composition containing a pigment is prepared for forming a color filter for use in a liquid crystal display element will be described.

A1-1. Preparation of pigment dispersion Preparation of pigment dispersion
As a pigment, C.I. I. Pigment Green 36 and C.I. I. 40 parts by mass (average particle diameter 61 nm) of 30/70 (mass ratio) mixture with CI Pigment Yellow 219, and 50 parts by mass of BYK2001 (Disperbyk: BYK Corporation (solid content concentration 45.1% by mass)) as a dispersant. (22.6 parts by mass in terms of solid content), 5 parts by mass of the resin (I) in the present invention, and 110 parts by mass of ethyl 3-ethoxypropionate as a solvent were mixed and dispersed by a bead mill for 15 hours. A pigment dispersion (P1) was prepared.
With respect to the pigment dispersion (P1), the average particle size of the pigment was measured by a dynamic light scattering method (measured using a Microtrac Nanotrac UPA-EX150 (manufactured by Nikkiso Co., Ltd. without further dilution of P1)). Met.

A1-2. Preparation of curable composition (coating liquid) A curable composition solution was prepared by stirring and mixing the pigment dispersion liquid P1 subjected to the dispersion treatment so as to have the following composition ratio.
(D) Colorant (Pigment dispersion (P1)) 600 parts by mass (B) Photopolymerization initiator (2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetra (Phenyl-1,2'-biimidazole) 30 parts by mass. (C) Pentaerythritol tetraacrylate 50 parts by mass. (E) Alkali-soluble resin (benzyl methacrylate / methacrylic acid / hydroxyethyl methacrylate copolymer, molar ratio: 80 / 10/10, Mw: 10000) 5 parts by mass. Solvent: 900 parts by mass of PGMEA. Substrate adhesion agent (3-methacryloxypropyltrimethoxysilane) 1 part by mass. (F) Sensitizer (compound α below) 15 parts by mass.・ (G) Co-sensitizer (2-mercaptobenzimidazole) 15 parts by mass

[A2. (Production of color filter)
A2-1. Formation of the curable composition layer The curable composition containing the pigment as a resist solution was slit-coated on a 550 mm × 650 mm glass substrate under the following conditions, and then allowed to stand for 10 minutes, followed by vacuum drying and pre-baking ( prebake) (100 ° C., 80 seconds) to form a curable composition coating film (curable composition layer).

(Slit application conditions)
・ Gap of the opening at the tip of the coating head: 50 μm
・ Application speed: 100 mm / second ・ Clearance between substrate and application head: 150 μm
・ Dry film thickness 1.75μm
・ Application temperature: 23 ℃

A2-2. Exposure and development Thereafter, the coating film of the curable composition is exposed in a pattern using a test photomask having a line width of 20 μm using a 2.5 kW ultra-high pressure mercury lamp. After the exposure, the entire surface of the coating film is organic-based. The sample was covered with a 10% aqueous solution of a developer (trade name: CD, manufactured by FUJIFILM Electronics Materials Co., Ltd.) and allowed to stand for 60 seconds.

A2-3. Heat treatment After standing still, pure water was sprayed in the form of a shower to wash away the developer, and the coating film subjected to such exposure (photocuring) treatment and development treatment was heated in an oven at 220 ° C. for 1 hour (post-baking). Thereby, the color filter formed by forming a curable composition coating film (colored layer) on the glass substrate was obtained.

[A3. (Performance evaluation)
Storage stability of the coating solution comprising the curable composition prepared above, exposure sensitivity of the curable composition coating film (colored layer) formed on the glass substrate using the curable composition, substrate adhesion The developability and the pattern cross-sectional shape were evaluated as follows. The results are shown in Table 1.

A3-1. Stability over time of curable composition After the curable composition (coating solution) prepared above was stored at room temperature for 1 month, the viscosity of the solution was measured and evaluated according to the following criteria.
-Evaluation criteria-
○: No increase in viscosity was observed.
Δ: An increase in viscosity of 5% or more and less than 10% was observed.
X: An increase in viscosity of 10% or more was observed.

A3-2. Exposure sensitivity of curable composition coating film (colored layer),
The curable composition coating film was exposed by changing the exposure dose to various exposure doses of 10 to 100 mJ / cm ² , and the exposure dose at which the pattern line width after post-baking was 20 μm was evaluated as exposure sensitivity. A smaller exposure sensitivity value indicates higher sensitivity.

A3-3. Developability, pattern cross-sectional shape, and substrate adhesion The developability, pattern cross-sectional shape, and substrate adhesion were evaluated by confirming the substrate surface and cross-sectional shape after post-baking with an optical microscope and SEM photograph observation. Details of the evaluation method and evaluation criteria are as follows.

<Developability>
In the exposure step, the presence or absence of residue in the area not irradiated with light (unexposed portion) was observed to evaluate developability.
-Evaluation criteria-
A: No residue was observed at all in the unexposed area.
Δ: A slight residue was confirmed in the unexposed area, but it was practically unproblematic.
X: Residue was remarkably confirmed in the unexposed part.

<Pattern cross-sectional shape>
The cross-sectional shape of the formed pattern was observed. The pattern cross-sectional shape is most preferably a forward taper, and a rectangular shape is next preferred. Reverse taper is not preferred.

<Board adhesion>
The evaluation of the substrate adhesion was performed by observing whether or not a pattern defect occurred. The evaluation criteria are as follows.
-Evaluation criteria-
○: No pattern defect was observed.
(Triangle | delta): Although the pattern defect | defect was hardly observed, the defect | deletion was partially observed.
X: A pattern defect was remarkably observed.

[Comparative Example 1]
A color filter was produced 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 performed. The results are shown in Table 2.

[Example 2, Comparative Example 1-2～1-5, Example 7, Comparative Example 1-6 to 1 -8
In the curable composition prepared in Example 1, a color filter was prepared in the same manner as in Example 1 except that the resin described in Table 2 was used instead of the resin (I). Similar evaluations were made. The results are shown in Table 2.

[ Comparative Example 1-1 , Comparative Example 2]
In the curable composition prepared in Example 1, all the examples except that the following resin (II) and resin (III) synthesized by the same method as the resin (I) were used instead of the resin (I). A color filter was prepared in the same manner as in Example 1 and evaluated in the same manner as in Example 1. The dipole moment of the monomer a used for the resin (II) was calculated to be 2.48. Moreover, the dipole moment of n-butyl acrylate used for resin (III) was calculated to be 1.58. The results are shown in Table 2.

  From the results of Table 2, it can be seen that the curable compositions of Examples containing the resin in the present invention are excellent in storage stability in the solution state. In addition, when a colored pattern is formed on the support using this curable composition, the exposure sensitivity is high for each comparative example not using the resin in the present invention, and the developability is excellent. It can be seen that a color filter excellent in both substrate adhesion and pattern cross-sectional shape is obtained.

[Example 12]
Hereinafter, an example of preparing a curable composition containing a colorant (pigment) for forming a color filter for use in a solid-state imaging device will be described.

[B1. Preparation of resist solution
Components of the following composition were mixed and dissolved to prepare a resist solution.
<Composition of resist solution>
Propylene glycol monomethyl ether acetate 19.20 parts by mass (PGMEA: solvent)
-36.67 parts by mass of ethyl lactate-(E) resin (40% PGMEA solution of benzyl methacrylate / methacrylic acid / methacrylic acid-2-hydroxyethyl copolymer (molar ratio = 60/22/18)) 30.51 Mass parts. (C) Ethylenically unsaturated double bond-containing compound (dipentaerythritol hexaacrylate) 12.20 parts by mass Polymerization inhibitor (p-methoxyphenol) 0.0061 parts by mass Fluorosurfactant (F -475, manufactured by Dainippon Ink & Chemicals, Inc.) 0.83 parts by mass (B) Photopolymerization initiator (trihalomethyltriazine-based photopolymerization initiator) 0.586 parts by mass (TAZ-107, Midori Chemical Co., Ltd.) Made)

[B2. Production of silicon substrate with undercoat layer]
A 6 inch silicon wafer was heat-treated in an oven at 200 ° C. for 30 minutes. Next, the resist solution is applied onto the silicon wafer so that the dry film thickness is 1.5 μm, and further heated and dried in an oven at 220 ° C. for 1 hour to form an undercoat layer. A silicon wafer substrate with an undercoat layer Got.

[B3. Preparation of pigment dispersion
As a pigment, C.I. I. Pigment Green 36 and C.I. I. 40 parts by mass (average particle diameter 65 nm) of 30/70 (mass ratio) mixture with CI Pigment Yellow 150, and 50 parts by mass of BYK2001 (Disperbyk: BYK Corporation (BYK), solid concentration 45.1% by mass) as a dispersant. (22.6 parts by mass in terms of solid content), 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 are mixed and dispersed by a bead mill for 15 hours to obtain a pigment dispersion (P2) was prepared.
With respect to the pigment dispersion (P2), the average particle diameter of the pigment was measured by a dynamic light scattering method in the same manner as in Example 1. As a result, it was 32 nm.

[B4. Preparation of curable composition (coating liquid)]
A curable composition solution was prepared by stirring and mixing the pigment dispersion P2 subjected to the dispersion treatment so as to have the following composition ratio.
-(D) Colorant (pigment dispersion (P2)) 600 parts by mass-(B) Photopolymerization initiator (oxime photopolymerization initiator)
(CGI-124, manufactured by Ciba Specialty Chemicals) 30 parts by mass. (C-1) TO-1382 (manufactured by Toagosei Co., Ltd.) 25 parts by mass. (C-1) 30 parts by mass of dipentaerythritol hexaacrylate. -Solvent (PGMEA) 900 parts by mass-Substrate adhesion agent (3-methacryloxypropyltrimethoxysilane) 1 part by mass

[B5. Preparation and evaluation of color filter with curable composition]
<Evaluation of pattern formation and sensitivity>
The curable composition prepared as described above was prepared using the B2. The colored layer (coating film) was formed by coating on the undercoat layer of the silicon wafer with the undercoat layer obtained in (1). Then, heat treatment (pre-baking) was performed for 120 seconds using a hot plate at 100 ° C. so that the dry film thickness of the coating film became 0.7 μm.
Next, using an i-line stepper exposure apparatus FPA-3000i5 + (manufactured by Canon Inc.), exposure was performed at various exposure doses of 50 to 1200 mJ / cm ² through an Island pattern mask having a pattern of 2 μm square at a wavelength of 365 nm.
Thereafter, the silicon wafer substrate on which the irradiated coating film is formed is placed on a horizontal rotary table of a spin shower developing machine (DW-30 type, manufactured by Chemitronics Co., Ltd.), and CD-2000 (FUJIFILM Corporation). Paddle development was performed at 23 ° C. for 60 seconds using Electronics Materials Co., Ltd. to form a colored pattern on the silicon wafer substrate.

The silicon wafer on which the colored pattern is formed is fixed to the horizontal rotary table by a vacuum chuck method, and the silicon wafer substrate is rotated at a rotational speed of 50 r. p. m. While being rotated, pure water was supplied from the upper part of the rotation center in the form of a shower through a spray nozzle, followed by rinsing treatment, and then spray drying.
Thereafter, the size of the colored pattern was measured using a length measuring SEM “S-9260A” (manufactured by Hitachi High-Technologies Corporation). The exposure dose at which the pattern line width was 2 μm was evaluated as the exposure sensitivity. A smaller exposure sensitivity value indicates higher sensitivity. The measurement results are shown in Table 2 below.

<Developability>
In the exposure step, the presence or absence of residue in the area not irradiated with light (unexposed portion) was observed to evaluate developability.
-Evaluation criteria-
A: No residue was observed at all in the unexposed area.
Δ: A slight residue was confirmed in the unexposed area, but it was practically unproblematic.
X: Residue was remarkably confirmed in the unexposed part.

<Pattern formability>
The cross-sectional shape of the formed pattern was observed. The pattern cross-sectional shape is preferably rectangular, and reverse taper is not preferable.

<Board adhesion>
As an evaluation of substrate adhesion, it was observed whether or not a pattern defect occurred. These evaluation items were evaluated based on the following criteria: -Evaluation criteria-
○: No pattern defect was observed.
(Triangle | delta): Although the pattern defect | defect was hardly observed, the defect | deletion was partially observed.
X: A pattern defect was remarkably observed.

<Stability over time of curable composition>
B4. After the curable composition (coating solution) prepared in 1 was stored at room temperature for 1 month, the viscosity of the solution was measured and evaluated according to the following criteria.
-Evaluation criteria-
○: No increase in viscosity was observed.
Δ: An increase in viscosity of 5% or more and less than 10% was observed.
X: An increase in viscosity of 10% or more was observed.
<Color unevenness>
The color unevenness was evaluated by analyzing the luminance distribution by the following method and based on the ratio of the pixels whose deviation from the average is within ± 5% to the total number of pixels. The evaluation criteria are as follows.
A method for measuring the luminance distribution will be described. First, the curable composition is mixed with the B2. It applied on the undercoat layer of the glass plate with an undercoat layer obtained by the same method, and the colored layer (coating film) was formed. Heat treatment (pre-baking) was performed for 120 seconds using a hot plate at 100 ° C. so that the dry film thickness of the coating film became 0.7 μm. The luminance distribution of this coated glass plate was analyzed using an image taken with a microscope MX-50 (Olympus).
-Evaluation criteria-
○: Pixels whose deviation from the average is within ± 5% is 99% or more of the total number of pixels Δ: Pixels whose deviation from the average is within ± 5% is 95% or more and less than 99% of the total number of pixels × : Pixels whose deviation from the average is within ± 5% is less than 95% of the total number of pixels

[Comparative Example 3]
In the curable composition prepared in Example 12, except that the resin (I) was not used, a color filter in which a colored pattern was formed in the same manner as in Example 12 was obtained. Evaluation was performed. The results are shown in Table 3.

[Examples 13 to 14, Comparative Examples 3-2 to 3-4, Example 18, Comparative Examples 3-5 to 3-7 , Comparative Examples 3-1 and 4]
In the curable composition prepared in Example 12, a color filter was prepared in the same manner as in Example 12 except that the resin described in Table 3 was used instead of the resin (I). Similar evaluations were made. The results are shown in Table 3.

From the results of Table 3, the curable compositions (pigment-based) of the examples containing the resin in the present invention used for forming a color filter for solid-state imaging device were excellent in storage stability in the solution state. It turns out that it is. In addition, when a colored pattern is formed on a support using this curable composition, the exposure sensitivity is high and the developability is superior to the comparative example not using the resin in the present invention. It can be seen that a color filter excellent in all of adhesion, pattern cross-sectional shape, and color unevenness is obtained.
From these results, the curable compositions of the examples achieved excellent pattern formability even when producing color filters for solid-state imaging devices, as in the case of producing color filters for liquid crystal display devices. I found out that

[Example 23]
Hereinafter, an example of preparing a curable composition containing a colorant (dye) for forming a color filter for use in a solid-state imaging device will be described.

[C1. Preparation of resist solution and production of silicon substrate with undercoat layer]
[B1. Preparation of resist solution] and [B2. A silicon substrate with an undercoat layer was produced in the same manner as in [Preparation of silicon substrate with undercoat layer].

[C2. Preparation of curable composition (coating liquid)]
The compound of the following composition was mixed and melt | dissolved and the colored photosensitive resin composition was prepared.
-Cyclohexanone (solvent) 80 parts by mass-(D) Varifast Yellow 1101 (dye) 6.0 parts by mass-(D) Acid Red 57 (dye) 6.0 parts by mass-(C) Dipentaerythritol hexaacrylate 2.5 Part by mass. (B) Oxime-based photopolymerization initiator 2.0 parts by mass (CGI-124, manufactured by Ciba Specialty Chemicals)
-Resin (I) in the present invention 1.5 parts by mass

[C3. Preparation and evaluation of color filter with curable composition]
[B5. Preparation and evaluation of a color filter were carried out in the same manner as in [Preparation and evaluation of color filter by colored photosensitive resin composition]. The results are shown in Table 4.

[Comparative Example 5]
In the curable composition prepared in Example 23, except that the resin (I) was changed to pentaerythritol triacrylate, a color filter having a colored pattern formed in the same manner as in Example 23 was obtained. Similar evaluations were made. The results are shown in Table 4.

[ Comparative Example 5-2, Example 25, Comparative Examples 5-3 to 5-5, Example 29, Comparative Examples 5-6 to 5-8 , Comparative Examples 5-1 and 6]
In the curable composition prepared in Example 23, a color filter was prepared in the same manner as in Example 23 except that the resin described in Table 4 was used instead of the resin (I). Similar evaluations were made. The results are shown in Table 4.

From the result of Table 4, the curable composition (dye system) of the Example containing the resin in this invention used for color filter formation for solid-state image sensor use is excellent in the storage stability in the solution state. I understand that.
Further, from the results of Examples in which a colored pattern was formed on a support using this curable composition, the Examples had higher exposure sensitivity and excellent developability than those of Comparative Examples, and also had substrate adhesion and patterns. It can be seen that an excellent color filter is obtained in any of the cross-sectional shapes.
In addition, from these results, the curable compositions of the examples achieved excellent pattern formation when producing color filters for solid-state imaging devices as well as when producing color filters for liquid crystal display devices. It turns out that is possible.

Claims (8)

Resin, triallylmethane, anthraquinone, azomethine, benzylidene, oxonol, cyanine, phenothiazine, pyrrolopyrazole azomethine, xanthene, phthalocyanine, benzopyran, indigo, pyrazole azo, anilinoazo, pyra A curable composition for forming a color filter, comprising at least one colorant selected from a zolotriazole azo series, a pyridone azo series, and an anthrapyridone series, a compound containing an ethylenically unsaturated double bond, and a photopolymerization initiator. there are, the resin has an ethylenically unsaturated double bond in a side chain, and the M- 8 a table 1, M-9A, M- 11A ~M-15A, M - 8 MA, M- 9 mA, and M-11MA ~M-1 5 at least one dipole Mome selected from MA A color filter-forming curable composition characterized by a preparative 2.5 or more monomers are polymerized resin as a copolymer component.

The monomer having a dipole moment of 2.5 or more is a monomer having at least one group selected from 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 curable composition for forming a color filter according to claim 1. The curable composition for forming a color filter according to claim 1 or 2, wherein the photopolymerization initiator is an oxime compound. Furthermore, a sensitizer is contained, The curable composition for color filter formation as described in any one of Claims 1-3 characterized by the above-mentioned. The color according to any one of claims 1 to 4, wherein the compound containing an ethylenically unsaturated double bond is a compound containing four or more (meth) acrylic acid ester structures. Curable composition for filter formation. A color filter comprising a colored pattern formed on the support by the curable composition for forming a color filter according to any one of claims 1 to 5. The colored layer which forms the colored layer which coats the curable composition for color filter formation as described in any one of Claims 1-5 on a support body, and consists of this curable composition for color filter formation. A forming step, an exposing step of exposing the colored layer through a mask, an exposing step of exposing the exposed colored layer through a mask, and a developing step of developing the exposed colored layer to form a colored pattern And a method for producing a color filter. A solid-state imaging device comprising a color filter manufactured by the method for manufacturing a color filter according to claim 7.