JP2008064963A - Curable composition, color filter and method for producing the same - Google Patents

Abstract

【選択図】なしA curable composition capable of curing with high sensitivity and obtaining a hardened portion even when a colorant is contained in a high concentration, and a colored pattern is formed using the curable composition Provided are a color filter excellent in resolving power and a manufacturing method capable of manufacturing the color filter with high productivity.
A curable composition comprising (A) a polymerizable compound represented by the following general formula (1), (B) a photopolymerization initiator, and (C) a colorant. . In General Formula (1), Ar ¹ represents an arylene group or a divalent heterocyclic group. R ¹ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. n represents an integer of 1 to 20. Z represents a hydrogen atom or a substituent that can be introduced into the benzene ring when n = 1, and represents an n-valent organic linking group when n is 2 or more.

[Selection figure] None

Description

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

The color filter is an essential component for liquid crystal displays and solid-state image sensors.
A liquid crystal display is more compact than a CRT, which is widely used as a display device, and is equivalent to or better in terms of performance. Therefore, the liquid crystal display is being replaced by a CRT as a television screen, a personal computer screen, 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.

With regard to color filters for liquid crystal displays, the substrate size is increasing for large TV production. 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. In order to improve the contrast, a curable composition used for producing a color filter is required to have a finer particle size of a colorant (organic pigment or the like) to be used (for example, see Patent Document 1). As a result, the amount of dispersant added to disperse the colorant tends to increase. In addition, in order to improve color purity, a higher content of colorants (organic pigments, etc.) in the solid content of the curable composition is required, and it accounts for the solid content in the curable composition. The contents of the photopolymerization initiator and polymerizable monomer tend to decrease.

  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. In order to form a thin film with the same color density as before, it is required to increase the content of the colorant in the curable composition used for producing the color filter. Furthermore, in the pigment-based color filter, the proportion of the pigment dispersant in the composition tends to increase as the pigment becomes finer.

  For curable compositions for color filter production, a technology that uses organic solvent-soluble dyes instead of pigments as colorants in order to deal with problems such as color unevenness that occur because pigments are relatively coarse particles. Has been proposed (see, for example, Patent Document 2). However, in the dye-based color filter, with the increase in the dye concentration, the problem of the polymerization-inhibiting effect derived from the dye has become more prominent.

Due to the above-mentioned factors, the photopolymerization initiator and the photopolymerizable monomer, which are components necessary for curing, are used for the curable composition applied to any color filter for liquid crystal displays and solid-state image sensors. In addition to being limited in amount, the concentration of the colorant in the composition is high, and also due to exposure and curing in the air, the sensitivity is low and sufficient curing cannot be obtained, and the color pattern formability The coloring pattern peeled off from the support during development.
JP 2006-30541 A JP-A-2-127602

The present invention has been made in view of the above-described problems, and an object thereof is to achieve the following objects.
That is, an object of the present invention is to provide a curable composition that can be cured with high sensitivity and a strong cured portion can be obtained even when the colorant is contained in a high concentration.
Furthermore, another object of the present invention is to provide a color filter excellent in resolving power formed by forming a colored pattern using the curable composition of the present invention, and a production method capable of producing the color filter with high productivity. It is to provide.

  As a result of intensive studies, the present inventor has found that the above problems can be solved by using a specific polymerizable compound, and has completed the present invention. That is, the means for solving the above problems are as follows.

  <1> (A) A curable composition comprising a polymerizable compound represented by the following general formula (1), (B) a photopolymerization initiator, and (C) a colorant.

In General Formula (1), Ar ¹ represents an arylene group or a divalent heterocyclic group. R ¹ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. Z represents a hydrogen atom or a substituent that can be introduced into the benzene ring when n = 1, and represents an n-valent organic linking group when n is 2 or more. .

<2> The curing according to <1>, wherein the content of the colorant (C) is in the range of 5 to 80% by mass in the total solid content in the curable composition. Sex composition.
<3> The curable composition according to <1> or <2>, further comprising (D) a compound having an adhesive group to a hard material in the molecule.
<4> The curable composition according to any one of <1> to <3>, wherein the curable composition is used for forming a colored pattern of a color filter.

<5> A color filter having a colored pattern formed on the support using the curable composition according to <4>.
<6> On a support, the process of apply | coating the curable composition of Claim 4, forming a curable composition layer, the process of exposing the said curable composition layer through a mask, and exposure Developing the subsequent curable composition layer to form a colored pattern, and a method for producing a color filter.

ADVANTAGE OF THE INVENTION According to this invention, even if it is a case where a coloring agent is contained in high concentration, it can harden | cure with high sensitivity and can provide the curable composition from which a firm hardening part is obtained.
Furthermore, according to the present invention, there are provided a color filter excellent in resolving power formed by forming a colored pattern using the curable composition of the present invention, and a production method capable of producing the color filter with high productivity. be able to.

  Hereinafter, the curable composition, the color filter, and the production method thereof of the present invention will be described in detail.

[Curable composition]
The curable composition of the present invention comprises (A) a polymerizable compound represented by the following general formula (1) (hereinafter, appropriately referred to as “specific polymerizable compound”), (B) a photopolymerization initiator, (C) a coloring agent.

In General Formula (1), Ar ¹ represents an arylene group or a divalent heterocyclic group. R ¹ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. n represents an integer of 1 to 20. Z represents a hydrogen atom or a substituent that can be introduced into the benzene ring when n = 1, and represents an n-valent organic linking group when n is 2 or more.

  Since the curable composition of the present invention has the above-described configuration, it can be cured with high sensitivity and a strong cured portion can be obtained even when the colorant is contained in a high concentration.

The curable composition of the present invention is a curable composition that is particularly suitably used for forming a colored pattern of a color filter.
When the curable composition of the present invention is applied to the formation of a color filter color pattern, it cures with high sensitivity even when the colorant, which is an essential component contained in the color filter color pattern, is contained in a high concentration. Therefore, a strong colored pattern having excellent pattern shape retention can be formed. Furthermore, the specific polymerizable compound that is a characteristic component of the present invention is capable of forming a highly hydrophobic cured portion by polymerization, and thus is formed on the support using the curable composition of the present invention. Since the colored pattern (cured portion) has improved hydrophobicity at the interface between the support and the colored pattern, when the uncured portion is developed and removed by the developer, the developer penetrates into the interface. It is considered that the peeling of the colored pattern from the support during development is effectively suppressed.

  The curable composition of the present invention can be applied to, for example, UV inks, adhesives and the like in addition to the use for forming a color filter color pattern.

  The components (A) to (C), which are essential components of the curable composition of the present invention, and optional components that can be used in combination with these components will be described in detail below.

<(A) Polymerizable compound represented by general formula (1)>
The curable composition of this invention contains the polymeric compound (specific polymeric compound) represented by following General formula (1).

In General Formula (1), Ar ¹ represents an arylene group or a divalent heterocyclic group. R ¹ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. n represents an integer of 1 to 20. Z represents a hydrogen atom or a substituent that can be introduced into the benzene ring when n = 1, and represents an n-valent organic linking group when n is 2 or more.

In general formula (1), the ring constituting the arylene group represented by Ar ¹ includes a benzene ring, a ring in which 2-3 benzene rings form a condensed ring, and a condensed benzene ring and a 5-membered unsaturated ring. The thing which formed the ring etc. are mentioned. Specific examples of the arylene group include carbocyclic divalent groups such as a benzene ring, naphthalene ring, anthracene ring, phenanthrene ring, indene ring, acenaphthylene ring and fluorene ring.
Examples of the divalent heterocyclic group represented by Ar ¹ include those having 3 to 20 carbon atoms and 1 to 5 heteroatoms. Specifically, heterocyclic rings such as quinoline ring, benzofuran ring, thioxanthone ring, carbazole ring, indole ring, benzofuran ring, imidazole ring such as pyridine ring, furan ring, and benzene ring condensed with a heterocyclic ring. A divalent group is mentioned.

Ar ¹ may have a substituent, and examples of the substituent include a monovalent nonmetallic atomic group excluding hydrogen. Examples of the substituent include a halogen atom (F, Cl, Br, I), a hydroxy group, a cyano group, a nitro group, a formyl group, a linear, branched, or cyclic alkyl group having 1 to 12 carbon atoms, Alkenyl group, alkynyl group, carbonyl group, alkoxy group, aryloxy group, carbonyl group, alkoxythio group, arylthio group, amino group, phenyl group, naphthyl group, sulfoxy group, sulfonyl group, carbamoyl group, sulfamoyl group, and substitution thereof Examples thereof include a substituent obtained by combining groups. Specific examples of these substituents include n-butyl group, s-butyl group, t-butyl group, dodecyl group, cyclohexyl group, trifluoromethyl group, chloromethyl group, bromophenyl group, mesityl group, vinyl group, Cinnamyl group, cyclopentene group, 1-propenyl group, ethynyl group, acetyl group, carboxyphenyl group, acetyloxy group, ethoxycarbonyl group, methoxy group, n-butoxy group, methylthiomethyl group, phenoxy group, diethylamino group, diphenylamino group Methylphenylamino group, methoxymethyl group, benzyloxy group, acetylamino group, acetylaminoethyl group, methoxysulfonyl group, ethylsulfoxy group, phenylsulfonyl group, carbamoylmethyl group, and the like. Among these substituents, more preferable substituents include alkyl groups, alkenyl groups, alkynyl groups, halogen atoms, hydroxy groups, and alkoxy groups.

When Ar ¹ represents a substituted arylene group or divalent heterocyclic group, Ar ¹ includes biphenyl, tolyl, xylyl, mesityl, cumenyl, chlorophenyl, bromophenyl, fluorophenyl, chloromethylphenyl, trifluoromethylphenyl Hydroxyphenyl, methoxyphenyl, methoxyethoxyphenyl, allyloxyphenyl, phenoxyphenyl, methylthiophenyl, tolylthiophenyl, ethylaminophenyl, diethylaminophenyl, morpholinophenyl, acetyloxyphenyl, benzoyloxyphenyl, N-cyclohexylcarbamoyloxyphenyl, N-phenylcarbamoyloxyphenyl, acetylaminophenyl, N-methylbenzoylaminophenyl, carboxyphenyl, methoxycarbo Nylphenyl, allyloxycarbonylphenyl, chlorophenoxycarbonylphenyl, carbamoylphenyl, N-methylcarbamoylphenyl, N, N-dipropylcarbamoylphenyl, N- (methoxyphenyl) carbamoylphenyl, N-methyl-N- (sulfophenyl) carbamoyl Phenyl, sulfophenyl, sulfonatophenyl, sulfamoylphenyl, N-ethylsulfamoylphenyl, N, N-dipropylsulfamoylphenyl, N-tolylsulfamoylphenyl, N-methyl-N- (phosphonophenyl) ) Sulfamoylphenyl, phosphonophenyl, phosphonatophenyl, diethylphosphonophenyl, diphenylphosphonophenyl, methylphosphonophenyl, methylphosphonatophenyl, Ruphosphonophenyl, tolylphosphonatophenyl, allylphenyl group, 1-propenylmethylphenyl group, 2-butenylphenyl group, 2-methylallylphenyl, 2-methylpropenylphenyl, 2-propynylphenyl, 2-butynylphenyl And divalent groups such as 3-butynylphenyl.

Ar ¹ is preferably an arylene group having no substituent, and particularly preferably a phenylene group having no substituent.

In General Formula (1), R ¹ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. The alkyl group may be linear or branched. Of these, a methyl group and an ethyl group are preferable.

  When the specific polymerizable compound is a polyfunctional type, the number of crosslinking points between the polymerizable compounds or the binder used as an optional component is increased, and the efficiency of the crosslinking reaction is dramatically improved. Since it can form, it is preferable.

  n represents an integer selected from 1 to 20. n is preferably 2 or more, and more preferably 3 or more.

In general formula (1), Z represents a hydrogen atom or a substituent that can be introduced into the benzene ring when n = 1, and represents an n-valent organic linking group when n is 2 or more.
Examples of the substituent that can be introduced into the benzene ring in the case of n = 1 include a carboxyl group, a hydroxyl group, an amino group, an alkoxy group, an alkylthio group, an arylthio group, a heterocycle, an alkoxycarbonyl group, an aryloxycarbonyl group, and a carbon number. Examples include 1-20 alkyl groups, alkenyl groups, alkynyl groups, aryl groups, and the like. These are carboxyl group, sulfonyl group, alkoxy group, hydroxyl group, alkylamino group, arylamino group, alkoxycarbonyl group, formyl group, phosphonic acid group, heterocycle, alkylthio group, arylthio group, amide group, urea group, sulfonamide You may have a substituent which has group etc.
In addition, the organic linking group is not particularly limited as long as it is an n-valent organic linking group, and can be configured to include the functional groups shown below. That is, the functional group is any group selected from the following divalent group, alkyl group, alkenyl group, alkynyl group, benzyl group, and the following divalent group 2 Examples thereof include a divalent group in which a group of at least species is combined.

  Z is more preferably an n-valent organic linking group containing the following groups.

The substitution position of Z- and CH ₂ = CR ¹ -substituted for Ar ¹ is not particularly limited, but from the viewpoint of ease of synthesis, CH ₂ = CR ^1- And preferably in the para position.

  Specific examples of the compound suitably used as the specific polymerizable compound are classified into groups I to VI for convenience from the structural features, and each group further has no heteroatom (a), and a heteroatom. It is classified into (b) group having However, the specific polymerizable compound used in the present invention is not limited to these.

  Specific examples of the compound suitably used as the specific polymerizable compound include the following exemplified compounds (VII-1) to (VII-4).

  Of the above-described exemplary compounds, the exemplary compounds of Groups II to VI and VII-1 to VII-4 having two or more styrene groups are preferable, and the compounds of Groups III to VI and VII-3 having three or more styrene groups are preferable. Illustrative compounds are more preferred. Among the exemplified compounds of groups I to IV, the exemplified compound of group (b) in which the linking group Z has a hetero atom is preferable in terms of solubility and developability of the uncured part.

  In the curable composition of the present invention, the specific polymerizable compound is contained in the range of 5 to 70% by mass in the total solid content contained in the curable composition from the viewpoint of the strength and sensitivity of the cured part. The content is preferably 10 to 65% by mass.

  A specific polymeric compound may be used independently and may use 2 or more types together. Moreover, only a specific polymeric compound may be used independently, and the other polymeric compound mentioned later may be used together in the range which does not impair the effect of this invention. As a content ratio in the case where the specific polymerizable compound and another polymerizable compound are used in combination, the other polymerizable compound is preferably 50% by mass or less based on the total polymerizable compound.

-Other polymerizable compounds that can be used in combination-
In the present invention, the other polymerizable compound that can be used in combination with the specific polymerizable compound is a polymerizable compound that is not included in the specific polymerizable compound, and has an ethylenically unsaturated double bond in the industrial field according to the present invention. A compound widely known as a compound having the above can be used without particular limitation. These include, for example, those having chemical forms such as monomers, prepolymers, that is, 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 hydroxyl group, amino group or mercapto group with a monofunctional or polyfunctional isocyanate or epoxy, and monofunctional or polyfunctional 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, etc. . Moreover, the EO modified body of these compounds, or PO modified body is also mentioned.

  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, and their EO-modified product, PO-modified products thereof.

  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. A vinyl urethane containing two or more polymerizable vinyl groups in one molecule obtained by adding a vinyl monomer containing a hydroxyl group represented by the following general formula (2) to a polyisocyanate compound having two or more isocyanate groups. Compounds and the like.

_{CH 2 = C (R 4)} COOCH 2 CH (R 5) OH (2)
(However, R ₄ and R ₅ 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 curable composition having a very high 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.

  In the present invention, when another polymerizable compound is added, from the viewpoint of curing sensitivity, it preferably contains two or more ethylenically unsaturated bonds, and more preferably contains three or more. Especially, it is preferable to contain 2 or more (meth) acrylic acid ester structures, it is more preferable to contain 3 or more, and it is most preferable to contain 4 or more. Furthermore, it is preferable to contain an EO modified body from the viewpoint of curing sensitivity and developability of the unexposed area. Moreover, it is preferable to contain a urethane bond from a viewpoint of hardening sensitivity and exposure part intensity | strength.

  From the above viewpoints, bisphenol A diacrylate, modified bisphenol A diacrylate EO, 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.) Made), DPHA-40H (made by Nippon Kayaku Co., Ltd.), UA-306H, UA-306T, UA-306I, AH-600, T-600, AI-600 (made by Kyoeisha).

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

<(B) Photopolymerization initiator>
The curable composition of the present invention contains (B) a photopolymerization initiator.
The photopolymerization initiator in the present invention is a compound that is decomposed by light and starts and accelerates the polymerization of the specific polymerizable compound, and preferably has 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, hexaaryes. Examples include rubiimidazole compounds, organic boric acid compounds, disulfonic acid compounds, oxime ester compounds, onium salt compounds, and acylphosphine (oxide) compounds.

  Specific examples of the organic halogenated compound include Wakabayashi et al., “Bull Chem. Soc Japan” 42, 2924 (1969), US Pat. No. 3,905,815, Japanese Patent Publication No. 46-4605, JP 48-36281, JP 55-3070, JP 60-239736, JP 61-169835, JP 61-169837, JP 62-58241, JP 62 -212401, JP-A-63-70243, JP-A-63-298339, M.S. P. Hutt “Journal of Heterocyclic Chemistry” 1 (No 3), (1970) ”, and the oxazole compound and s-triazine compound substituted with a trihalomethyl group.

  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, and Kunz, Martin “Rad Tech'98. Proceeding April 19-22, 1998, Chicago”. The organic borate described in JP-A-6-157623, JP-A-6-175564, JP-A-6-175561, or organic boron oxosulfonium complex, JP-A-6-175554 No. 6, JP-A-6-175553 Organoboron iodonium complexes described in JP-A-9-188710, organoboron phosphonium complexes described in JP-A-9-348710, 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. . In addition, as another preferable form of the sulfonium salt, an iodonium salt in which one substituent of the triarylsulfonium salt has a coumarin or an anthraquinone structure and absorption at 300 nm or more is preferable.

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.A. 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.

  As the photopolymerization initiator (B) used in the present invention, from the viewpoint of exposure sensitivity, a trihalomethyltriazine compound, a benzyldimethyl ketal compound, an α-hydroxyketone compound, an α-aminoketone compound, an acylphosphine compound, phosphine Oxide compounds, metallocene compounds, oxime compounds, triallylimidazole dimers, onium compounds, benzothiazole compounds, benzophenone compounds, acetophenone compounds and derivatives thereof, cyclopentadiene-benzene-iron complexes and salts thereof, halomethyl oxa Compounds selected from the group consisting of diazole compounds and 3-aryl substituted coumarin compounds are preferred.

  More preferred are trihalomethyltriazine compounds, α-aminoketone compounds, acylphosphine compounds, phosphine oxide compounds, oxime compounds, triallylimidazole dimers, onium compounds, benzophenone compounds, acetophenone compounds, and trihalo compounds. Most preferred is at least one compound selected from the group consisting of a methyltriazine compound, an α-aminoketone compound, an oxime compound, a triallylimidazole dimer, and a benzophenone compound.

  It is preferable that content of the photoinitiator contained in the curable composition of this invention is 0.1-50 mass% with respect to the total solid contained in a curable composition, More preferably, it is 0. 0.5 to 30% by mass, particularly preferably 1 to 20% by mass. Within this range, better sensitivity and a hardened part can be formed.

<(C) Colorant>
The curable composition of the present invention contains a colorant. By containing a colorant, a colored cured body composed of a curable composition can be formed, and the curable composition of the present invention is applied, for example, to the formation of a colored pattern of an image forming material or a color filter. Can do.

  There is no restriction | limiting in particular in the coloring agent contained in the curable composition of this invention, A conventionally well-known various dye and pigment can be used 1 type or in mixture of 2 or more types. The colorant is preferably a pigment from the viewpoint of durability such as heat resistance and light resistance in the cured part.

  As the pigment that can be used in the curable composition of the present invention, conventionally known various inorganic pigments or organic pigments can be used. Further, considering that it is preferable to have a high transmittance, whether it is an inorganic pigment or an organic pigment, it is preferable to use a fine one as much as possible, and considering the handling properties, the average particle diameter of the pigment is 0.01 μm to 0.1 μm is preferable, and 0.01 μm to 0.05 μm is more preferable. Examples of the inorganic pigment include metal compounds represented by metal oxides, metal complex salts, and the like. Specifically, iron, cobalt, aluminum, cadmium, lead, copper, titanium, magnesium, chromium, zinc And metal oxides such as antimony, and composite oxides of the above metals.

As the organic pigment, for example,
CI Pigment Yellow 11, 24, 31, 53, 83, 93, 99, 108, 109, 110, 138, 139, 147, 150, 151, 154, 155, 167, 180, 185, 199,;
CI Pigment Orange 36, 38, 43, 71;
CI Pigment Red 81, 105, 122, 149, 150, 155, 171, 175, 176, 177,209, 220, 224, 242, 254, 255, 264, 270;
CI pigment violet 19, 23, 32, 39;
CI Pigment Blue 1, 2, 15, 15: 1, 15: 3, 15: 6, 16, 22, 60, 66;
CI Pigment Green 7, 36, 37;
CI Pigment Brown 25, 28;
CI 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 pigments that can be preferably used in the present invention include the following. However, the present invention is not limited to these.

CI Pigment Yellow 11, 24, 108, 109, 110, 138, 139, 150, 151, 154, 167, 180, 185,
CI Pigment Orange 36, 71,
CI Pigment Red 122, 150, 171, 175, 177, 209, 224, 242, 254, 255, 264,
CI Pigment Violet 19, 23, 32,
CI Pigment Blue 15: 1, 15: 3, 15: 6, 16, 22, 60, 66,
CI 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 the curable composition of the present invention is used for a color filter, the primary particle diameter of the pigment is preferably 10 to 100 nm, more preferably 10 to 70 nm, and even more preferably 10 to 50 nm from the viewpoint of color unevenness and contrast. Preferably, 10 to 40 nm is most preferable.

  Moreover, when using the curable 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.

  There is no restriction | limiting in particular in the curable composition of this invention, The dye which can be used as a coloring agent does not have a restriction | limiting, According to the application aspect of a curable composition, dye well-known in the said field | area can be used. When the composition of the present invention is used as a curable composition for a color filter, for example, JP-A 64-90403, JP-A 64-91102, JP-A-1-94301, Japanese Patent Laid-Open No. 6-11614, No. 2592207, U.S. Pat. No. 4,808,501, U.S. Pat. No. 5,667,920, U.S. Pat. No. 5,059,500, JP-A-5-333207, JP-A-6-35183, JP-A-6-51115, JP-A-6-194828, JP-A-8-2111599, JP-A-4-249549, JP-A-10 -123316, JP-A-11-302283, JP-A-7-286107, JP-A 2001-4823, JP-A-8-15522, JP JP-A-8-29771, JP-A-8-146215, JP-A-11-343437, JP-A-8-62416, JP2002-14220, JP2002-14221, JP2002-2002. 14222, JP 2002-14223, JP 8-302224, JP 8-73758, JP 8-179120, JP 8-151431, 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 the case of a resist system that performs water or alkali development, an acid dye and / or a derivative thereof may be suitably used from the viewpoint of completely removing the binder and / or dye in the light non-irradiated part by development.
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, other in the composition. It is selected in consideration of all the required performances such as interaction with the components, light resistance and heat resistance.

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.

  Among these, as the colorant (C), triallylmethane, anthraquinone, azomethine, benzylidene, oxonol, cyanine, phenothiazine, pyrrolopyrazole azomethine, xanthene, phthalocyanine, benzopyran, indigo A colorant selected from pyrazole azo, anilino azo, pyrazolotriazole azo, pyridone azo, and anthrapyridone is preferable.

  As content of the coloring agent in the curable composition of this invention, it is preferable that it is 5-80 mass% in the total solid contained in a curable composition, 10-70 mass% is more preferable, 20 -70 mass% is still more preferable.

  In particular, when the curable composition of the present invention is used for forming a color pattern of a color filter, the content of the colorant is the above-mentioned from the viewpoint of chromaticity, strength of the cured part, and development latitude during alkali development. In the range of content, it is preferable that it is 20 mass% or more, More preferably, it is 30 mass% or more.

  The curable composition of this invention may further contain the arbitrary component explained in full detail below as needed with the (A) thru | or (C) component demonstrated above. Hereinafter, optional components that can be contained in the curable composition of the present invention will be described.

<(D) Compound having adhesive group to hard material in molecule>
In the case where the curable composition of the present invention is applied to a hard material and cured, the compound having an adhesive group to the hard material in the molecule (hereinafter referred to as the following) from the viewpoint of further improving the adhesion. It is preferable to appropriately contain “adhesive group-containing compound”.

  The curable composition of the present invention contains a compound having an adhesive group to a hard material in the molecule, for example, when the curable composition of the present invention is applied to the formation of a colored pattern of a color filter. For example, the colored pattern and the support can be more firmly adhered to each other, and the suppression of peeling of the colored pattern when the uncured portion is removed by development can be further improved.

  In the present invention, the adhesive group is a group capable of forming an interaction selected from the group consisting of a covalent bond, an ionic bond, a hydrogen bond, a polar interaction, and a van der Waals interaction with the surface of a hard material. Specifically, an acid group, an ester group of an acid, an acid onium salt, an acid metal salt, a substituent that generates a silanol group by hydrolysis, an onium group, a phenolic hydroxyl group, a zwitterionic group, a chelating group And groups having at least one partial structure selected from the group consisting of:

Adhesive groups include acid groups such as sulfonic acid groups, phosphonic acid groups and carboxyl groups; ester groups of these acids; metal salts of these acids; onium salts of these metals; onium groups such as ammonium groups and pyridinium groups; alkoxy It is preferably a group selected from a substituent that generates a silanol group by hydrolysis such as a silyl group; a zwitterionic group such as a phenolic hydroxyl group and an N-oxide group; and a chelating group such as iminodiacetic acid.
Among these adhesive groups, an alkoxysilyl group and / or a hydrolyzed group thereof is preferable from the viewpoint of adhesion to a hard material.

The hard material is a material that becomes a support substrate to which the curable composition of the present invention can be applied, and is, for example, an inorganic material such as a glass substrate or a silicon substrate, or cellulose diacetate, cellulose triacetate, or propion. Examples thereof include organic resin materials such as acid cellulose, cellulose butyrate, cellulose acetate butyrate, cellulose nitrate, polyethylene terephthalate, polyethylene, polystyrene, polypropylene, polycarbonate, and polyvinyl acetal.
When the curable composition of the present invention is used for forming a colored pattern of a color filter, among these hard materials, those selected from transparent hard materials and silicon substrates can be mentioned, among which glass substrates and silicon A substrate is preferred.

  In addition, the adhesive group-containing compound may further have a group for improving developability and a group for improving sensitivity in the molecule as necessary.

  The group for improving developability is preferably a functional group having a hetero atom, such as an alkoxy group, alkoxycarbonyl group, carboxyl group, hydroxyl group, amino group, urethane group, amide group, thiol group, sulfo group, urea group, Etc.

  Examples of the group for improving the sensitivity include a continuous mobility group such as a carbon-carbon double bond group and a thiol group, and a group capable of reacting with an alkali-soluble group in the photosensitive layer. Group, acrylic group, styryl group, vinyl ether group, allyl group, cyclic alkenyl group, cyclic alkoxy group, furyl group, oxetane group, epoxy group, tetrahydrofuran group are preferable, and from the viewpoint of sensitivity, methacryl group, acrylic group, styryl group Is more preferable.

  (D) As a preferable form of the compound component having an adhesive group, it preferably has an alkoxysilyl group, and may be a low molecule or a polymer. From the viewpoint of developability, the molecular weight is particularly preferably 500 or less. From the viewpoint of sensitivity, it is preferable to have a thiol group and / or a carbon-carbon double bond group.

  Hereinafter, although the specific example of the adhesive group containing compound which can be used for this invention is illustrated, the adhesive group containing compound in this invention is not limited to these.

  Only 1 type may be used for an adhesive group containing compound, and 2 or more types may be used together.

  When the adhesive group-containing compound is contained in the curable composition of the present invention, the content is preferably 0.05 to 20% by mass in the total solid content contained in the curable composition. 0.1-15 mass% is more preferable, and 0.5-10 mass% is still more preferable.

<(E) Dispersant>
When the curable composition of this invention contains a pigment as (C) a coloring agent, it is preferable to add (D) a dispersing agent from a viewpoint of improving the dispersibility of this 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 1-150 mass% with respect to a pigment, 3-100 mass% is more preferable, and 5-80 mass% is still more preferable.
Specifically, if a polymer dispersant is used, the amount of use thereof is preferably in the range of 5 to 100% by mass, more preferably in the range of 10 to 80% by mass with respect to the pigment. In the case of using a pigment derivative, the amount used is preferably in the range of 1 to 30% by mass, more preferably in the range of 3 to 20% by mass, based on the pigment, A range of 15% by mass is particularly preferable.

  In the present invention, when using a pigment and a dispersant as a colorant, the total content of the colorant and the dispersant is based on the total solid content constituting the curable composition from the viewpoint of curing sensitivity and color density. It is preferably 30% by mass or more and 90% by mass or less, more preferably 40% by mass or more and 85% by mass or less, and further preferably 50% by mass or more and 80% by mass or less.

<(F) Sensitizer>
The curable composition of the present invention may contain a sensitizer for the purpose of improving the radical generation efficiency of the radical 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 (V).

(In 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 a basic nucleus of the dye in combination with the adjacent A ² and the adjacent carbon atom. Represents a nonmetallic atomic group to be formed, R ⁵¹ and R ⁵² each independently represent a hydrogen atom or a monovalent nonmetallic atomic group, and R ⁵¹ and R ⁵² are bonded to each other to form an acidic nucleus of the dye. W represents an oxygen atom or a sulfur atom.)

(In the formula (II), Ar ¹ and Ar ² each independently represent an aryl group and are linked via a bond with —L ³ —, where L ³ represents —O— or —S—. W is a general formula (X
It is synonymous with that shown in IV). )

(In the 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 adjacent A ² and a carbon atom, R ⁵³ , R ⁵⁴ , R ⁵⁵ , R ⁵⁶ , R ⁵⁷
And R ⁵⁸ each independently represents a monovalent non-metallic atomic group, and R ⁵⁹ represents an alkyl group or an aryl group. )

(In Formula (IV), A ³ and A ⁴ each independently represent —S— or —NR ⁶² — or —NR ⁶³ —, and R ⁶³ and R ⁶⁴ each independently represents a substituted or unsubstituted alkyl group, substituted Or an unsubstituted aryl group, L ⁵ and L ⁶ each independently represent a nonmetallic atomic group that forms a basic nucleus of a dye in cooperation with adjacent A ³ , A ^4, and adjacent carbon atoms; ⁶⁰ and R ⁶¹ are each independently a monovalent non-metallic atomic group or can be bonded to each other to form an aliphatic or aromatic ring.

(In the formula (V), R ⁶⁶ represents an aromatic ring or a hetero ring which may have a substituent, and A ⁵ represents an oxygen atom, a sulfur atom or —NR ⁶⁷ —. R ⁶⁴ , R ⁶⁵ and R ⁶⁷ each independently represents a hydrogen atom or a monovalent non-metallic atomic group, and R ⁶⁷ and R ⁶⁴ , and R ⁶⁵ and R ⁶⁷ may be bonded to each other to form an aliphatic or aromatic ring. it can.)

  Preferable specific examples of the compounds represented by the general formulas (I) to (V) include those shown below.

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 preferably 0.1 to 20% by mass in terms of solid content from the viewpoint of light absorption efficiency to the deep part and initiation decomposition efficiency, and is 0. More preferably, the content is 5 to 15% by mass.

<(G) Binder polymer>
In the curable composition of the present invention, a binder polymer can be further used as necessary for the purpose of improving the film properties. It is preferable to use a linear organic polymer as the binder. 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 an alkali-soluble resin is used as a copolymer, a monomer other than the above-mentioned monomers can also be used as the compound to be copolymerized. Examples of other monomers include the following compounds (1) to (13).

(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 as described in JP 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 excellent in strength, and is advantageous in terms of printing durability and 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.

The weight average molecular weight of the binder polymer that can be used in the present invention is preferably 5,000 or more, more preferably 10,000 to 300,000, and the number average molecular weight is preferably 1,000 or more. More preferably, it is the range of 2,000-250,000. 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.

The binder polymer that can be used in the present invention 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.

<(H) Co-sensitizer>
The curable composition of the present invention preferably contains a co-sensitizer. In the present invention, the co-sensitizer has functions such as further improving the sensitivity of the sensitizing dye and 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 these co-sensitizers is in the range of 0.1 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 polymerization growth rate and chain transfer. Preferably, the range of 1-25 mass% is more preferable, and the range of 0.5-20 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.

  The addition amount of the thermal 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, a known additive such as an inorganic filler, a plasticizer, or a sensitizer capable of improving the ink inking property on the surface of the photosensitive layer may be added to improve the physical properties of the cured film. Good.
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 binder.

  The curable composition of the present invention is cured with high sensitivity and has good storage stability. Moreover, the high adhesiveness to hard material surfaces, such as a board | substrate which applies a curable composition, is shown. 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).

A step of applying the curable composition of the present invention on a support to form a curable composition layer (hereinafter abbreviated as “curable composition layer forming step” as appropriate), and the curable composition. A step of exposing the layer through a mask (hereinafter abbreviated as “exposure step” as appropriate), and a step of developing the curable composition layer after exposure to form a colored pattern (hereinafter referred to as “development step” as appropriate). Abbreviated as “.”).
Hereafter, each process in the manufacturing method of this invention is demonstrated.

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

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.

  As a coating film thickness of a curable composition, 0.1-10 micrometers is preferable, 0.2-5 micrometers is more preferable, 0.2-3 micrometers is further more preferable.

  Drying (prebaking) of the photocurable composition layer applied on the substrate can be performed at a temperature of 50 ° C. to 140 ° C. for 10 to 300 seconds using a hot plate, an oven, or the like.

<Exposure process>
In the exposure step, the curable composition layer formed in the curable composition layer forming step is exposed through a mask having a predetermined mask pattern.
In this step, the pattern of the coating film is exposed through a predetermined mask pattern, only the coating film portion irradiated with light is cured, developed with a developer, and each color (three colors or four colors). This can be done by forming a pattern-like film consisting of these pixels. 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>
Next, by performing an alkali development treatment, the light-irradiated portion is eluted in the alkaline aqueous solution by the exposure, and only the photocured portion remains. 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 an alkaline aqueous solution obtained by diluting these alkaline agents with pure water so as to have a concentration of 0.001 to 10% by mass, preferably 0.01 to 1% by mass. Is preferably used as a 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, followed by heat treatment (post-bake). Thus, the said process can be repeated sequentially for every color, and a cured film can be manufactured.
Thereby, a color filter is obtained.
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.

  In the production method of the present invention, after performing the above-described curable composition layer forming step, exposure step, and development step, if necessary, the formed colored pattern is cured by heating and / or exposure. A process may be included.

  By repeating the curable composition 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 patterned exposure and alkaline development in the same manner as the above pixel manufacturing method except that a black colorant 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 uses the curable composition of the present invention, the formed colored pattern exhibits high adhesion to the support substrate, and the cured composition is excellent in development resistance. It is possible to form a high-resolution pattern that is excellent in exposure sensitivity, has good adhesion to the substrate of the exposed portion, and gives a desired cross-sectional shape. Therefore, it 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 a CMOS that exceeds 1 million pixels. 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 and a microlens for condensing light.

EXAMPLES Hereinafter, although an Example demonstrates this invention further more concretely, it is not limited to a following example.

  Examples The curable composition of the present invention will be described more specifically with reference to examples. However, the present invention is not limited to the following examples as long as the gist thereof is not exceeded.

[Examples 1 to 10]
[A-1. Preparation of curable composition]
Here, an example in which a curable composition containing a colorant (pigment) is prepared for forming a color filter for use in a liquid crystal display element will be described.

A-1-1. First, the following components were kneaded and dispersed with two rolls.
(C) Colorant:
C. I. Pigment Red 254 22 parts by mass C.I. I. Pigment Yellow 139 8 parts by mass Resin solution (benzyl methacrylate / methacrylic acid / hydroxyethyl methacrylate copolymer, molar ratio: 80/10/10,
Mw: 10000, solvent: propylene glycol methyl ether acetate 60%, resin solid content concentration: 40%) 40 parts by mass; solvent: propylene glycol methyl ether acetate 20 parts by mass; dispersant: (trade name: BY-161, BYK) 2 parts by mass

Furthermore, the following components were added to the dispersion obtained above and finely dispersed in a sand mill for a whole day and night.
・ Solvent: Propylene glycol methyl ether acetate (PGMEA)
200 parts by mass

・界面活性剤（商品名：テトラニック１５０Ｒ１、ＢＡＳＦ社） ０．２質量部
・溶剤：ＰＧＭＥＡ １００質量部
（実施例４については、溶剤をＰＧＭＥＡ／１−メトキシー２−プロパノール
＝８０質量部／２０質量部に変更） A-1-2. Preparation of curable composition (coating liquid) The following components were further added to the dispersion-treated pigment, followed by stirring and mixing to prepare a curable composition.
-(A) Specific polymerizable compound (types listed in Table 1) 6 parts by mass-DPHA (manufactured by Nippon Kayaku Co., Ltd.) 6 parts by mass-(B) Photopolymerization initiator (types described in Table 1) 0.5 Parts by mass (• (F) sensitizer (type described in Table 1) 0.25 parts by mass)
(・ Additives (types listed in Table 1) 0.35 parts by mass)
-(D) Compound having an adhesive group (the following compound (D-1)) 0.1 part by mass

-Surfactant (trade name: Tetranic 150R1, BASF) 0.2 parts by mass-Solvent: 100 parts by mass of PGMEA (For Example 4, the solvent is PGMEA / 1-methoxy-2-propanol = 80 parts by mass / 20 Change to mass part)

[A-2. (Production of color filter)
A-2-1. 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 at the opening at the tip of the coating head: 50 μm
Coating speed: 100 mm / second Clearance between substrate and coating head: 150 μm
Application thickness (dry thickness): 2 μm
Application temperature: 23 ° C

A-2-2. Exposure and development Thereafter, the photocurable coating film is exposed in a pattern using a test mask with a line width of 20 μm using a 2.5 kW ultra-high pressure mercury lamp. After exposure, the entire surface of the coating film is exposed to an alkaline developer. It was covered with a 1% aqueous solution of (CDK-1, manufactured by FUJIFILM Electronics Materials Co., Ltd.) and allowed to stand for 40 seconds.

A-2-3. Heat treatment After standing still, pure water was sprayed in a shower to wash away the developer, and the coating film subjected to the photocuring treatment and the development treatment was heated in an oven at 220 ° C. for 1 hour (post-baking). This obtained the color filter which has a colored layer (colored pattern) on a glass substrate.

[A-3. (Performance evaluation)
Exposure sensitivity of a curable composition coating film (colored layer) formed on a glass substrate using the curable composition (coating liquid) prepared above, and development of a colored pattern formed by the coating liquid Liquid resistance was evaluated as follows. The results are shown in Table 1.

A-3-1. Exposure sensitivity of coating film (colored layer),
The exposure dose was changed to various exposure doses of 10 to 100 mJ / cm ² to perform exposure and development, 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.

A-3-2. Exposure at developer resistance of 75 mJ / cm ² and immersion in a 2% aqueous solution of an alkaline developer (CDK-1, manufactured by Fuji Film Electronics Materials Co., Ltd.) until the colored pattern peels off and elutes from the glass substrate The time (seconds) was measured. The longer the time (seconds) is, the better the developer resistance is.

[Comparative Example 1]
In the curable composition prepared in Example 1, the specific polymerizable compound and the polymerization initiator were replaced with those shown in Table 1, respectively, except that no sensitizer and additive were used. While preparing the curable composition of the comparative example 1, the coloring pattern was formed and the color filter was obtained. Furthermore, the same evaluation as in Example 1 was performed. The results are shown in Table 1.

[Comparative Example 2]
In the curable composition prepared in Example 1, the specific polymerizable compound and the polymerization initiator were respectively replaced with those shown in Table 1, and the glass substrate used in Example 1 was used as the polyethylene terephthalate substrate having the same size. The curable composition of Comparative Example 2 was prepared in the same manner as Example 1 except that the post-baking process was changed to an irradiation process of 10,000 mJ / cm ² with a high-pressure mercury lamp, and the coloring pattern was changed. Formed to obtain a color filter. Furthermore, the same evaluation as in Example 1 was performed. The results are shown in Table 1.

  From the results shown in Table 1, the curable compositions of Examples containing specific polymerizable compounds have high sensitivity, and are excellent in developer resistance without peeling of the colored pattern formed by this curable composition. It turns out that the strong hardening part was formed with the curable composition.

  The specific polymerizable compounds (polymerizable compounds (A) to (H)), comparative polymerizable compounds (H-1, H-2), and photopolymerization initiators (B-1 to B) shown in Table 1 below. -4), sensitizers (Z-1 to Z-3), and additives (T-1, T-2) are shown in detail.

  Hereinafter, an example in which a curable composition containing a colorant (dye) is prepared for forming a color filter for use in a solid-state imaging device will be described.

[Example 11]
[B-1. Preparation of resist solution
Components of the following composition were mixed and dissolved to prepare a resist solution.
<composition>
Propylene glycol monomethyl ether acetate 19.20 parts by mass (PGMEA: solvent)
・ Ethyl lactate 36.67 parts by mass ・ Binder polymer 30.51 parts by mass
[Benzyl methacrylate / methacrylic acid / methacrylic acid-2-
40% PGMEA solution of hydroxyethyl copolymer (molar ratio = 60/22/18)]
・ Dipentaerythritol hexaacrylate 12.20 parts by mass
(Photopolymerizable compound)
・ Polymerization inhibitor (p-methoxyphenol) 0.0061 parts by mass
・ 0.83 parts by mass of fluorosurfactant
(F-475, manufactured by Dainippon Ink & Chemicals, Inc.)
-Photopolymerization initiator 0.586 parts by mass
(TAZ-107 (trihalomethyltriazine-based photopolymerization initiator),
(Midori Chemical Co., Ltd.)

[B-2. 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 as to have a dry film thickness of 2 μm, and further heated and dried in an oven at 220 ° C. for 1 hour to form an undercoat layer, thereby obtaining a silicon wafer substrate with an undercoat layer. It was.

[B-3. Preparation of curable composition (dye system)]
A compound having the following composition was mixed and dissolved to prepare a curable composition.
<composition>
-Cyclohexanone (solvent) 80 parts by mass-Valifast Yellow 1101 ((C) Colorant: Dye) 5.0 parts by mass-Acid Red 57 ((C) Colorant: Dye) 5.0 parts by mass-Dipentaerythritol hexaacrylate (Other polymerizable compound) 3.5 parts by mass-(A) Specific polymerizable compound (the polymerizable compound (A)) 2.5 parts by mass-(B) Photopolymerization initiator (type described in Table 2) 2.0 parts by mass (CGI-124, manufactured by Ciba Specialty Chemicals;
Oxime-based photopolymerization initiator)
Glycerol propoxylate 0.5 part by mass (number average molecular weight Mn: 1500, molar extinction coefficient ε = 0)

[B-5. Preparation and evaluation of color filter with curable composition]
<Formation of colored pattern and evaluation of sensitivity>
B-3. The curable composition prepared in step B-2. The curable composition layer (coating film) was formed by coating on the undercoat layer of the silicon wafer substrate with the undercoat layer obtained in (1). Then, a 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 0.9 μm.
Next, using an i-line stepper exposure apparatus FPA-3000i5 + (manufactured by Canon, Inc.), exposure was performed at various exposure doses of 100 to 1600 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). Using paddle development for 30 seconds at 23 ° C. using Electronics Materials Co., Ltd., a colored pattern was formed on the silicon wafer substrate.

A silicon wafer substrate on which a 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 results of measurement evaluation are shown in Table 2 below.

<Evaluation of developer resistance>
A curable composition coating film (colored layer) formed by coating the curable composition A-1 (coating liquid) on the undercoat layer of the silicon wafer substrate with the undercoat layer was exposed at 900 mJ / cm ² ; The sample was immersed in an alkaline developer (CD-2000, manufactured by Fuji Film Electronics Materials Co., Ltd.), and the time (seconds) until the image was peeled off and eluted from the glass substrate was measured.
It shows that it is so favorable that time (second) is long.

[Examples 12 to 14]
Except for replacing the polymerizable compound (A), which is a specific polymerizable compound, used in “B-3. Preparation of curable composition” in Example 11 with the polymerizable compound shown in Table 2 below, A curable composition was prepared in the same manner as in Example 11, and a color pattern was formed together to obtain a color filter. Furthermore, the same evaluation as in Example 11 was performed. The results are shown in Table 2.
. The results are shown in Table 2.

[Comparative Example 3]
Except that the polymerizable compound (A), which is a specific polymerizable compound, used in “B-3. Preparation of curable composition” in Example 11 was replaced with the comparative polymerizable compound (H-1), A curable composition was prepared in the same manner as in Example 11, and a color pattern was formed together to obtain a color filter. Furthermore, the same evaluation as in Example 11 was performed. The results are shown in Table 2.

[Example 15]
Preparation of curable composition (pigment type) for color filter for solid-state imaging device C-1. First, the following components were kneaded and dispersed with two rolls.
・ C. I. Pigment Red 254 22 parts by mass I. Pigment Yellow 139 8 parts by mass Resin solution (benzyl methacrylate / methacrylic acid / hydroxyethyl methacrylate copolymer, molar ratio: 80/10/10,
Mw: 10000, solvent: propylene glycol methyl ether-teracetate 60%, resin solid content concentration: 40% 40 parts by mass Solvent: propylene glycol methyl ether acetate 20 parts by mass Dispersant: (trade name: BY-161, BYK) 2 parts by mass

Furthermore, the following components were added to the dispersion obtained above and finely dispersed in a sand mill for a whole day and night.
・ Solvent: Propylene glycol methyl ether acetate (PGMEA)
200 parts by mass

C-2. Preparation of curable composition (coating liquid) The following components were further added to the dispersion-treated pigment, followed by stirring and mixing to prepare a curable composition solution.
<Composition>
-The polymerizable compound (A) [(A) specific polymerizable compound] 10 parts by mass-4-Benzoxolane-2,6-di (trichloromethyl)-
s-Triazine [(B) photopolymerization initiator] 0.5 parts by mass Surfactant (trade name: Tetranic 150R1, BASF) 0.2 parts by mass Solvent: PGMEA 100 parts by mass

  Using the curable composition solution (coating solution) prepared above, the curable composition described in the section “B-3. Preparation of curable composition for color filter (dye system) for use in solid-state imaging device” is used. The coating / exposure / development and performance evaluation performed in Example 11 were performed. The results are shown in Table 2.

[Comparative Example 4]
The polymerizable compound (A) used in “C-2. Preparation of curable composition (coating liquid)” in Example 15 was changed to the comparative polymerizable compound (H-2) shown in Table 2 below. Except for this, the same procedure as in Example 16 was performed. The results are summarized in Table 2.

  From the results shown in Table 2, the curable compositions of Examples containing the specific polymerizable compound have high sensitivity, and are excellent in developer resistance without peeling of the colored pattern formed by this curable composition. It turns out that the hardened | cured part was formed with the curable composition.

Claims (6)

(A) A curable composition comprising a polymerizable compound represented by the following general formula (1), (B) a photopolymerization initiator, and (C) a colorant.

(In General Formula (1), Ar ¹ represents an arylene group or a divalent heterocyclic group. R ¹ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. N represents an integer of 1 to 20. Z represents a hydrogen atom or a substituent that can be introduced into the benzene ring when n = 1, and represents an n-valent organic linking group when n is 2 or more.)   2. The curable composition according to claim 1, wherein the content of the colorant (C) is in a range of 5 to 80% by mass in the total solid content contained in the curable composition.   Furthermore, (D) The curable composition of Claim 1 or Claim 2 containing the compound which has an adhesive group to a hard material in a molecule | numerator.   The curable composition according to any one of claims 1 to 3, wherein the curable composition is used for forming a colored pattern of a color filter.   A color filter comprising a colored pattern formed using the curable composition according to claim 4 on a support.   The process of apply | coating the curable composition of Claim 4 on a support body, forming the curable composition layer, the process of exposing the said curable composition layer through a mask, and the said after exposure And developing the curable composition layer to form a colored pattern.