JP2008009323A - Curable composition for color filter, color filter and method for manufacturing the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a curable composition for color filters having good pattern forming property and excellent adhesion to a hard surface as a substrate even when the composition contains a colorant at high concentration. <P>SOLUTION: The curable composition for color filters contains a compound represented by formula (1), a photopolymerization initiator, a polymerizable compound and a colorant. A color filter using the composition and a method for manufacturing the color filter are also provided. In the formula (1), A represents an aromatic ring or a heterocycle which may have a substituent; X represents an oxygen atom, a sulfur atom or -N(R<SP>3</SP>)-; Y represents an oxygen atom, a sulfur atom or -N(R<SP>3</SP>)-; and R<SP>1</SP>-R<SP>3</SP>each independently represent a hydrogen atom or a monovalent group of nonmetallic atoms. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

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

A color filter is an indispensable component for a liquid crystal display.
A liquid crystal display is more compact than a CRT as a display device and is equivalent or better in terms of performance, and is thus being replaced by a CRT as a television screen, a personal computer screen, or other display device. 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.

Liquid crystal displays for TV use are required to have higher image quality than those for conventional monitor applications. That is, improvement in contrast and color purity. In order to improve contrast, a curable composition for producing a color filter is required to have a finer particle size of a colorant (organic pigment or the like) to be used.
Further, in order to improve color purity, a higher content of the colorant (organic pigment) in the solid content of the curable composition for producing a color filter is required.

On the other hand, in the color filter for a solid-state image sensor, further higher definition is desired. However, in the curable composition to which the conventional pigment dispersion system is applied, there are problems such as color unevenness because the pigment is relatively coarse particles, and it is difficult to further improve the resolution. It was not suitable for applications requiring a fine pattern such as a solid-state imaging device. Therefore, a technique using an organic solvent-soluble dye instead of a pigment as a colorant has been proposed (for example, see Patent Document 1).
In addition, for color filters for solid-state imaging devices, there is a demand for thin color patterns, and in order to make thin films with the same color density as before, the use of colorants in curable compositions for color filter production It is required to increase the content rate.

As described above, in any case for a liquid crystal display or a solid-state imaging device, the curable composition for producing a color filter contains a colorant, and thus the components necessary for curing the curable composition. The content of the photopolymerization initiator and the photopolymerizable monomer is limited, resulting in insufficient strength, or sufficient curability and sufficient adhesion to a hard surface serving as a substrate. There was no problem.
Furthermore, in recent years, with an increase in substrate size, there is a demand for a highly sensitive curable composition that maintains a pattern shape for a long time even in a developing solution in a developing process and does not have any chipping or peeling in the pattern.

Regarding a curable composition for producing a color filter, when the composition is applied onto a substrate and exposed to curing, a photopolymerization initiator having a higher sensitivity that can sufficiently achieve a curing reaction even near the bottom of the coating film. Development is being attempted.
Conventionally, as a curable composition for producing a color filter, for example, a radiation-sensitive composition in which a binder polymer containing a carboxyl group, a polyfunctional acrylate such as pentaerythritol hexaacrylate, and a photopolymerization initiator are combined. 2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole as a highly sensitive photopolymerization initiator in such a radiation-sensitive composition, 2,2′-bis (2,3-dichlorophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole and the like have been proposed (for example, see Patent Documents 2 and 3).

  In addition, as a photopolymerization initiator applicable to the curable composition, 2,2′-bis (2-chlorophenyl) is used as a photopolymerization initiator applicable to a radiation-sensitive composition used for a printing plate or a photoresist. ) -4,4 ′, 5,5′-tetraphenylbiimidazole, 2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetra (alkoxyphenyl) biimidazole, 2,2 '-Bis (2-chlorophenyl) -4,4', 5,5'-tetra (dialkoxyphenyl) biimidazole, 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'- Tetra (trialkoxyphenyl) biimidazole has been proposed (see, for example, Patent Documents 4 and 5).

However, the sensitivity of any of the above curable compositions is not yet satisfactory, and it is necessary to irradiate with high energy radiation when curing. When a colored pattern of a color filter is formed using such a curable composition, if the irradiation amount is insufficient, problems such as missing or missing patterns, a remaining film rate or a decrease in pixel intensity are caused, and eventually In the coloring pattern of the obtained color filter, there arises a problem that the resolution and the adhesion between the support and the support are lowered.
As described above, even when the colorant is contained in a high concentration, the color filter curable composition that cures with high sensitivity and has good pattern formation properties, and the adhesion between the resolution and the support. Although a color filter having an excellent coloring pattern is desired, it has not been provided yet.
JP-A-2-127602 JP-A-6-75372 JP-A-6-75373, etc. Japanese Patent Publication No. 48-38403 JP-A-62-174204

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, the object of the present invention is to cure with high sensitivity, have good pattern forming properties, and excellent adhesion to a hard surface as a substrate even when the colorant is contained in a high concentration. An object of the present invention is to provide a color filter using a curable composition and having a color pattern excellent in resolving power and adhesion to a support, and a production method capable of producing the color filter with high productivity.

  As a result of intensive studies, the present inventor has found that the above-mentioned problems can be solved by a curable composition for a color filter because it contains a specific compound, and has completed the present invention. That is, the means for solving the above problems are as follows.

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

In the general formula (1), A represents an aromatic ring or a hetero ring which may have a substituent, X represents an oxygen atom, a sulfur atom or —N (R ³ ) —, Y represents an oxygen atom, sulfur It represents an atom or —N (R ³ ) —. R ¹ , R ² , and R ³ each independently represent a hydrogen atom or a monovalent nonmetallic atomic group, and A, R ¹ , R ² , and R ³ are bonded to each other to form an aliphatic group Or you may form an aromatic ring.

  <2> The curable composition for a color filter according to <1>, which contains a biimidazole compound as the photopolymerization initiator.

  <4> A color filter comprising a colored pattern formed using the curable composition for a color filter according to <1> or <2> on a support.

  <5> A step of applying a curable composition for a color filter according to <1> or <2> on a support to form a colored curable composition layer, and the colored curable composition layer. A method for producing a color filter, comprising: a step of exposing through a mask; and a step of developing the colored curable composition layer after exposure to form a colored pattern.

According to the present invention, even when the colorant is contained in a high concentration, the color filter is cured with high sensitivity, has a good pattern forming property, and has excellent adhesion to a hard surface as a substrate. A curable composition can be provided.
Furthermore, by using the curable composition for color filters of the present invention, a color filter having a colored pattern excellent in resolving power and adhesion to a support, and a production method capable of producing the color filter with high productivity Can be provided.

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

  Hereinafter, the curable composition for color filters of the present invention, a color filter using the curable composition for color filters, and a method for producing the same will be described in detail.

[Curable composition for color filter]
The curable composition for a color filter of the present invention includes (A) a compound represented by the following general formula (1), (B) a polymerizable composition, (C) a polymerization initiator, and (D) a colorant. And containing.
Hereinafter, each component contained in the curable composition for color filters of the present invention (hereinafter sometimes simply referred to as “specific curable composition”) will be sequentially described.

<(A) Compound Represented by General Formula (1)>
The specific curable composition contains a compound represented by the following general formula (1) (hereinafter referred to as “specific sensitizer” as appropriate).

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

  The compound represented by the general formula (1) is a compound that can act as a sensitizer, and its mechanism of action is not yet clear, but it is irradiated by containing the compound in the curable composition of the present invention. The absorption efficiency of the active radiation is improved, and the curing sensitivity is improved. In addition, the compound represented by the general formula (1) can be excited to an energetic high state that absorbs active radiation, particularly ultraviolet rays, and thus initiates polymerization by efficiently transferring electrons or energy to the polymerization initiator. It is considered that the active polymerization initiating species of the agent can be generated to increase the sensitivity of the curing reaction of the curable composition.

  The compound represented by the general formula (1) will be described in detail. In the following, the compound represented by the general formula (1) may be appropriately referred to as “specific sensitizer”.

In the general formula (1), R ¹ , R ² and R ³ each independently represent a hydrogen atom or a monovalent nonmetallic atomic group. When R ¹ , R ² and R ³ represent a monovalent nonmetal atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted aromatic group It is preferably a heterocyclic residue, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted alkylthio group, a hydroxyl group, or a halogen atom.

Preferable examples of R ¹ , R ² and R ³ in the general formula (1) will be specifically described.
Preferable examples of the unsubstituted alkyl group represented by R ¹ , R ² and R ³ include linear, branched and cyclic alkyl groups having 1 to 20 carbon atoms, Specific examples thereof include methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group, tridecyl group, hexadecyl group, octadecyl group. , Eicosyl group, isopropyl group, isobutyl group, s-butyl group, t-butyl group, isopentyl group, neopentyl group, 1-methylbutyl group, isohexyl group, 2-ethylhexyl group, 2-methylhexyl group, cyclohexyl group, cyclopentyl group , 2-norbornyl group. Among these, linear alkyl groups having 1 to 12 carbon atoms, branched alkyl groups having 3 to 12 carbon atoms, and cyclic alkyl groups having 5 to 10 carbon atoms are more preferable.

As the alkylene group (alkyl moiety) in the substituted alkyl group represented by R ¹ , R ² and R ³ , any one of the above hydrogen atoms on the alkyl group having 1 to 20 carbon atoms is removed. Valent organic residues can be mentioned, preferably linear alkylene having 1 to 12 carbon atoms, branched alkylene having 3 to 12 carbon atoms and cyclic alkylene having 5 to 10 carbon atoms The group can be mentioned.

Examples of the substituent of the substituted alkyl group represented by R ¹ , R ² and R ³ include a monovalent nonmetallic atomic group excluding hydrogen, and preferred examples thereof include halogen atoms (—F, —Br). , -Cl, -I), hydroxyl group, alkoxy group, aryloxy group, mercapto group, alkylthio group, arylthio group, alkyldithio group, aryldithio group, amino group, N-alkylamino group, N, N-dialkylamino group N-arylamino group, N, N-diarylamino group, N-alkyl-N-arylamino group, acyloxy group, carbamoyloxy group, N-alkylcarbamoyloxy group, N-arylcarbamoyloxy group, N, N- Dialkylcarbamoyloxy group, N, N-diarylcarbamoyloxy group, N-alkyl-N-arylcal Vamoyloxy group, alkylsulfoxy group, arylsulfoxy group, acylthio group, acylamino group, N-alkylacylamino group, N-arylacylamino group, ureido group, N′-alkylureido group, N ′, N′-dialkyl Ureido group,

N′-arylureido group, N ′, N′-diarylureido group, N′-alkyl-N′-arylureido group, N-alkylureido group, N-arylureido group, N′-alkyl-N-alkylureido Group, N′-alkyl-N-arylureido group, N ′, N′-dialkyl-N-alkylureido group, N ′, N′-dialkyl-N-arylureido group, N′-aryl-N-alkylureido Group, N′-aryl-N-arylureido group, N ′, N′-diaryl-N-alkylureido group, N ′, N′-diaryl-N-arylureido group, N′-alkyl-N′-aryl -N-alkylureido group, N'-alkyl-N'-aryl-N-arylureido group, alkoxycarbonylamino group, aryloxycarbonyl Mino group, N-alkyl-N-alkoxycarbonylamino group, N-alkyl-N-aryloxycarbonylamino group, N-aryl-N-alkoxycarbonylamino group, N-aryl-N-aryloxycarbonylamino group, formyl Group, acyl group, carboxyl group,

Alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, N-alkylcarbamoyl group, N, N-dialkylcarbamoyl group, N-arylcarbamoyl group, N, N-diarylcarbamoyl group, N-alkyl-N-arylcarbamoyl group, Alkylsulfinyl group, arylsulfinyl group, alkylsulfonyl group, arylsulfonyl group, sulfo group (—SO ₃ H) and its conjugate base group (hereinafter referred to as sulfonate group), alkoxysulfonyl group, aryloxysulfonyl group, sulfinamoyl group N-alkylsulfinamoyl group, N, N-dialkylsulfinamoyl group, N-arylsulfinamoyl group, N, N-diarylsulfinamoyl group, N-alkyl-N-arylsulfinamoyl group, sulfamoy Group, N-alkylsulfamoyl group, N, N-dialkylsulfamoyl group, N-arylsulfamoyl group, N, N-diarylsulfamoyl group, N-alkyl-N-arylsulfamoyl group, A phosphono group (—PO ₃ H ₂ ) and its conjugate base group (hereinafter referred to as a phosphonate group),

Dialkyl phosphono group (—PO ₃ (alkyl) ₂ ), diaryl phosphono group (—PO ₃ (aryl) ₂ ), alkylaryl phosphono group (—PO ₃ (alkyl) (aryl)), monoalkyl phosphono group (—PO ₃ H (alkyl)) and its conjugate base group (hereinafter referred to as alkyl phosphonate group), monoaryl phosphono group (—PO ₃ H (ary)) and its conjugate base group (hereinafter referred to as aryl phosphonate) ), Phosphonooxy group (—OPO ₃ H ₂ ) and its conjugate base group (hereinafter referred to as phosphonatooxy group), dialkylphosphonooxy group (—OPO ₃ (alkyl) ₂ ), diarylphosphine Phonoxy group (—OPO ₃ (aryl) ₂ ), alkylaryl phosphonooxy group (—OPO ₃ (Alkyl) (aryl)), monoalkylphosphonooxy group (—OPO ₃ H (alkyl)) and its conjugate base group (hereinafter referred to as alkylphosphonatooxy group), monoarylphosphonooxy group (—OPO). ₃ H (aryl)) and its conjugate base group (hereinafter referred to as arylphosphonatooxy group), cyano group, nitro group, aryl group, heteroaryl group, alkenyl group, and alkynyl group.

Specific examples of the alkyl group in these substituents include the alkyl groups described above as unsubstituted alkyl groups represented by R ¹ , R ² and R ³ .
Specific examples of the aryl group include phenyl, biphenyl, naphthyl, tolyl, xylyl, mesityl, cumenyl, chlorophenyl, bromophenyl, chloromethylphenyl, hydroxyphenyl, methoxyphenyl, ethoxy Phenyl group, phenoxyphenyl group, acetoxyphenyl group, benzoyloxyphenyl group, methylthiophenyl group, phenylthiophenyl group, methylaminophenyl group, dimethylaminophenyl group, acetylaminophenyl group, carboxyphenyl group, methoxycarbonylphenyl group, Ethoxyphenylcarbonyl group, phenoxycarbonylphenyl group, N-phenylcarbamoylphenyl group, phenyl group, cyanophenyl group, sulfophenyl group, sulfonatophenyl group, phosphonophenyl group It can be exemplified phosphonophenyl phenyl group.

  Examples of the heteroaryl group include a monocyclic or polycyclic aromatic ring containing at least one of a nitrogen atom, an oxygen atom and a sulfur atom. Particularly preferred examples of the heteroaryl ring in the heteroaryl group include, for example, thiophene, thiathrene, furan, pyran, isobenzofuran, chromene, xanthene, phenoxazine, pyrrole, pyrazole, isothiazole, isoxazole, pyrazine, pyrimidine, pyridazine, Indolizine, isoindolizine, indoir, indazole, purine, quinolidine, isoquinoline, phthalazine, naphthyridine, quinazoline, cinolin, pteridine, carbazole, carboline, phenanthrine, acridine, perimidine, phenanthroline, phthalazine, phenalazine, phenoxazine, furan And phenoxazine and the like, and these may be further benzo-fused or may have a substituent.

Examples of the alkenyl group include vinyl group, 1-propenyl group, 1-butenyl group, cinnamyl group, 2-chloro-1-ethenyl group, and the like.
Examples of the alkynyl group include ethynyl group, 1-propynyl group, 1-butynyl group, trimethylsilylethynyl group and the like.
Examples of G ₁ in the acyl group (G ₁ CO—) include a hydrogen atom, and the above alkyl group and aryl group.

  Among these substituents, more preferred are a halogen atom (—F, —Br, —Cl, —I), an alkoxy group, an aryloxy group, an alkylthio group, an arylthio group, an N-alkylamino group, N, N-dialkylamino group, acyloxy group, N-alkylcarbamoyloxy group, N-arylcarbamoyloxy group, acylamino group, formyl group, acyl group, carboxyl group, alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, N-alkyl Carbamoyl group, N, N-dialkylcarbamoyl group, N-arylcarbamoyl group, N-alkyl-N-arylcarbamoyl group, sulfo group, sulfonate group, sulfamoyl group, N-alkylsulfamoyl group, N, N-dialkylsulfuric group Famoyl group, N-aryls Famoyl group, N-alkyl-N-arylsulfamoyl group, phosphono group, phosphonate group, dialkyl phosphono group, diaryl phosphono group, monoalkyl phosphono group, alkyl phosphonate group, monoaryl phosphono group, aryl phosphine group Examples include an onato group, a phosphonooxy group, a phosphonateoxy group, an aryl group, and an alkenyl group.

Preferred examples of the substituted alkyl group as R ¹ , R ² and R ³ include combinations of the above-described substituent and an alkylene group (alkyl moiety). Specific examples include a chloromethyl group, a bromomethyl group, 2- Chloroethyl, trifluoromethyl, methoxymethyl, methoxyethoxyethyl, allyloxymethyl, phenoxymethyl, methylthiomethyl, tolylthiomethyl, ethylaminoethyl, diethylaminopropyl, morpholinopropyl, acetyloxy Methyl group, benzoyloxymethyl group, N-cyclohexylcarbamoyloxyethyl group, N-phenylcarbamoyloxyethyl group, acetylaminoethyl group, N-methylbenzoylaminopropyl group, 2-oxoethyl group, 2-oxopropyl group, carbo Xylpropyl group, methoxycarbonylethyl group, allyloxycarbonylbutyl group, chlorophenoxycarbonylmethyl group, carbamoylmethyl group, N-methylcarbamoylethyl group, N, N-dipropylcarbamoylmethyl group, N- (methoxyphenyl) carbamoylethyl group N-methyl-N- (sulfophenyl) carbamoylmethyl group,

Sulfobutyl group, sulfonatobutyl group, sulfamoylbutyl group, N-ethylsulfamoylmethyl group, N, N-dipropylsulfamoylpropyl group, N-tolylsulfamoylpropyl group, N-methyl-N- (phosphono Phenyl) sulfamoyloctyl group, phosphonobutyl group, phosphonatohexyl group, diethylphosphonobutyl group, diphenylphosphonopropyl group, methylphosphonobutyl group, methylphosphonatobutyl group, tolylphosphonohexyl group, tolylphosphine group Onatohexyl group, phosphonooxypropyl group, phosphonatoxybutyl group, benzyl group, phenethyl group, α-methylbenzyl group, 1-methyl-1-phenylethyl group, p-methylbenzyl group, cinnamyl group, allyl group, 1-propenylmethyl group, 2- Thenyl group, 2-methylallyl group, 2-methyl propenyl methyl group, 2-propynyl group, 2-butynyl, 3-butynyl, and the like.

Specific examples of the unsubstituted aryl group preferable as R ¹ , R ² and R ³ include those in which 1 to 3 benzene rings form a condensed ring, and a benzene ring and a 5-membered unsaturated ring form a condensed ring. Specific examples include phenyl group, naphthyl group, anthryl group, phenanthryl group, indenyl group, acenaphthenyl group, fluorenyl group, and among these, phenyl group, naphthyl group Is more preferable.

Specific examples of the preferred substituted aryl group as R ¹ , R ² and R ³ include those having a monovalent nonmetallic atomic group as a substituent on the ring-forming carbon atom of the above-mentioned unsubstituted aryl group. . Examples of preferred substituents include the alkyl groups and substituted alkyl groups described above, and those previously shown as substituents in the substituted alkyl group. Preferable specific examples of the substituted aryl group represented by R ¹ , R ² and R ³ include a biphenyl group, a tolyl group, a xylyl group, a mesityl group, a cumenyl group, a chlorophenyl group, a bromophenyl group, a fluorophenyl group, and a chloromethyl group. Phenyl group, trifluoromethylphenyl group, hydroxyphenyl group, methoxyphenyl group, methoxyethoxyphenyl group, allyloxyphenyl group, phenoxyphenyl group, methylthiophenyl group, tolylthiophenyl group, ethylaminophenyl group, diethylaminophenyl group, morpholino Phenyl group, acetyloxyphenyl group, benzoyloxyphenyl group, N-cyclohexylcarbamoyloxyphenyl group, N-phenylcarbamoyloxyphenyl group,

Acetylaminophenyl group, N-methylbenzoylaminophenyl group, carboxyphenyl group, methoxycarbonylphenyl group, allyloxycarbonylphenyl group, chlorophenoxycarbonylphenyl group, carbamoylphenyl group, N-methylcarbamoylphenyl group, N, N-di Propylcarbamoylphenyl group, N- (methoxyphenyl) carbamoylphenyl group, N-methyl-N- (sulfophenyl) carbamoylphenyl group, sulfophenyl group, sulfonatophenyl group, sulfamoylphenyl group, N-ethylsulfamoyl Phenyl group, N, N-dipropylsulfamoylphenyl group, N-tolylsulfamoylphenyl group, N-methyl-N- (phosphonophenyl) sulfamoylphenyl group, phosphonophenyl group, phos Onatophenyl group, diethylphosphonophenyl group, diphenylphosphonophenyl group, methylphosphonophenyl group, methylphosphonatophenyl group, tolylphosphonophenyl group, tolylphosphonatophenyl group, allyl group, 1-propenylmethyl group, 2 -Butenyl group, 2-methylallylphenyl group, 2-methylpropenylphenyl group, 2-propynylphenyl group, 2-butynylphenyl group, 3-butynylphenyl group and the like can be mentioned.

Specific examples of preferred unsubstituted alkenyl groups as R ¹ , R ² and R ³ include a vinyl group and a 1-propenyl group.
Specific examples of preferred substituted alkenyl groups as R ¹ , R ² and R ³ include those having a monovalent non-metallic atomic group excluding a hydrogen atom as a substituent on the above-described unsubstituted alkenyl group.

Specific examples of preferable unsubstituted aromatic heterocyclic residues as R ¹ , R ² and R ³ include thiophene, furan, pyrrole, pyrazole, thiazole, oxazole, pyrimidine, pyridazine, imidazole, quinoline, triazole, indole, And carbazole.
Specific examples of preferred substituted aromatic heterocyclic residues as R ¹ , R ² and R ³ include a monovalent nonmetallic atom excluding a hydrogen atom as a substituent on the above-mentioned unsubstituted aromatic heterocyclic residue. The thing which has a group is mentioned.
.

Specific examples of preferably unsubstituted alkoxy groups as R ¹ , R ² and R ³ include methoxy group, ethoxy group, propoxy group, butoxy group, hexyloxy group, octyloxy group, dodecyloxy group, 2-ethylhexyloxy group and the like. Is mentioned.
Specific examples of preferred substituted alkoxy groups as R ¹ , R ² and R ³ include those having a monovalent non-metallic atomic group excluding a hydrogen atom as a substituent on the above-mentioned unsubstituted alkoxy group.
.

Specific examples of preferably unsubstituted alkylthio groups as R ¹ , R ² and R ³ include methylthioxy group, ethylthioxy group, propylthioxy group, butylthioxy group, hexylthioxy group, octylthioxy group, dodecylthioxy group. Groups and the like.
Specific examples of preferred substituted alkylthio groups as R ¹ , R ² and R ³ include those having a monovalent nonmetallic atomic group excluding a hydrogen atom as a substituent on the above-mentioned unsubstituted alkylthio group.

Next, A in the general formula (1) will be described. A represents an aromatic ring or a hetero ring which may have a substituent. Specific examples of the aromatic ring or hetero ring which may have a substituent include R ¹ and R in the general formula (1). It includes the same as those described for ² and R ^3.
Specific examples of the aromatic ring preferable as A include benzene, methoxybenzene, dimethoxybenzene, trimethoxybenzene, diethylaminobenzene, diphenylaminobenzene, methylthiobenzene, anthracene, phenylthiobenzene, thianthrene, phenothiazine, julolidine, dibenzothiophene, dibenzofuran. , Carbazole, bismethoxyphenylbenzene, and the like.
Specific examples of the heterocyclic ring preferable as A include pyridine, benzthiazole, benzoxazole, and benzthiazole.

X in the general formula (1) represents an oxygen atom, a sulfur atom, or —N (R ³ ) —, and is preferably an oxygen atom.
Y in the general formula (1) represents an oxygen atom, a sulfur atom, or —N (R ³ ) —, and is preferably —N (R ³ ) —.

  One preferred embodiment of the compound represented by the general formula (1) is a compound represented by the following general formula (2) from the viewpoint of improving the decomposition efficiency of the photopolymerization initiator.

In General Formula (2), A represents an aromatic ring or a hetero ring which may have a substituent, and Y represents an oxygen atom, a sulfur atom, or —N (R ³ ) —. R ¹ , R ² , and R ³ each independently represent a hydrogen atom or a monovalent nonmetallic atomic group, and A, R ¹ , R ² , and R ³ are each bonded to each other to form an aliphatic group Or you may form an aromatic ring.

Details ^A, of R 1, ^{R 2,} and ^{R 3} in the general formula (2), wherein ^A in the general formula (1) ^is the same as R 1, ^{R 2,} and ^{R 3.}

  As a compound represented by General formula (2), it is preferable that they are the compounds (2-1)-(2-35) shown below, for example.

  One preferred embodiment of the compound represented by the general formula (1) is a compound represented by the following general formula (3) from the viewpoint of improving the decomposition efficiency of the photopolymerization initiator.

In General Formula (3), A represents an aromatic ring or a hetero ring which may have a substituent, and X represents an oxygen atom, a sulfur atom, or —N (R ³ ) —. R ³ , R ⁴ , and R ⁵ each independently represent a hydrogen atom or a monovalent nonmetallic atomic group, and A, R ³ , R ⁴ , and R ⁵ are each bonded to each other to form an aliphatic group Alternatively, they may be bonded to form an aromatic ring. Ar represents an aromatic ring or a heterocyclic ring having a substituent. However, the Ar skeleton has a substituent having a sum of Hammett values greater than zero.

A, R ³ , R ⁴ , and R ⁵ in the general formula (3) have the same meanings as the corresponding A, R ³ , R ² , and R ¹ in the general formula (1), respectively.

Ar represents an aromatic ring or a hetero ring having a substituent, and specific examples thereof include an aromatic ring or a hetero ring having a substituent among those previously described in the description of A in the general formula (1). Specific examples are given as well.
However, as a substituent that can be introduced into Ar in the general formula (3), it is essential that the sum of Hammett values is 0 or more. Examples of such a substituent include a trifluoromethyl group, a carbonyl group, and the like. , Ester groups, halogen atoms, nitro groups, cyano groups, sulfoxide groups, amide groups, carboxyl groups and the like. The Hammett values of these substituents are shown below. Trifluoromethyl group (—CF ₃ , m: 0.43, p: 0.54), carbonyl group (eg, —COHm: 0.36, p: 0.43), ester group (—COOCH ₃ , m: 0 .37, p: 0.45), halogen atom (eg, Cl, m: 0.37, p: 0.23), cyano group (—CN, m: 0.56, p: 0.66), sulfoxide group (For example, —SOCH ₃ , m: 0.52, p: 0.45), an amide group (for example, —NHCOCH ₃ , m: 0.21, p: 0.00), a carboxyl group (—COOH, m: 0. 37, p: 0.45). The parenthesis represents the introduction position of the substituent in the aryl skeleton and the Hammett value, and (m: 0.50) is the Hammett value of 0.50 when the substituent is introduced at the meta position. Indicates that there is.
Among these, preferable examples of Ar include a phenyl group having a substituent, and preferable substituents on the Ar skeleton include an ester group and a cyano group. The substitution position is particularly preferably located at the ortho position on the Ar skeleton.

  As a compound represented by General formula (3), it is preferable that they are the compounds (3-1)-(3-32) shown below, for example.

  Furthermore, one of the suitable embodiments of the compound represented by the general formula (1) is a compound represented by the following general formula (4) from the viewpoint of improving the decomposition efficiency of the photopolymerization initiator. The specific sensitizer according to the present invention is more preferably a compound represented by the following general formula (4).

In General Formula (4), A represents an aromatic ring or a hetero ring which may have a substituent, and X represents an oxygen atom, a sulfur atom, or —NR ²¹ —. R ²¹ , R ²² , R ²³ , and R ²⁶ each independently represent a hydrogen atom or a monovalent nonmetallic atomic group. R ²⁴ and R ²⁵ each independently represent a monovalent nonmetallic atomic group. A, R ²³ , R ²⁴ , R ²⁵ and R ²⁶ may be bonded to each other to form an aliphatic or aromatic ring.

Here, when R ²¹ , R ²² , R ²³ , R ²⁴ , R ²⁵ , and R ²⁶ represent a monovalent nonmetallic atomic group, a substituted or unsubstituted alkyl group or a substituted or unsubstituted aryl is preferable. Represents a group.

Next, preferable examples of R ²¹ , R ²² , R ²³ , R ²⁴ , R ²⁵ and R ²⁶ in the general formula (4) will be described.
Preferred examples of the unsubstituted alkyl group represented by R ²¹ , R ²² , R ²³ , R ²⁴ , R ²⁵ , and R ²⁶ are linear, branched, and Examples of the cyclic alkyl group include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, and dodecyl. Group, tridecyl group, hexadecyl group, octadecyl group, eicosyl group, isopropyl group, isobutyl group, s-butyl group, t-butyl group, isopentyl group, neopentyl group, 1-methylbutyl group, isohexyl group, 2-ethylhexyl group, 2 -A methylhexyl group, a cyclohexyl group, a cyclopentyl group, and a 2-norbornyl group can be mentioned. Among these, linear alkyl groups having 1 to 12 carbon atoms, branched alkyl groups having 3 to 12 carbon atoms, and cyclic alkyl groups having 5 to 10 carbon atoms are more preferable.

The alkylene group (alkyl moiety) in the substituted alkyl group represented by R ²¹ , R ²² , R ²³ , R ²⁴ , R ²⁵ , and R ²⁶ is the hydrogen atom on the alkyl group having 1 to 20 carbon atoms described above. Any one of them can be used as a divalent organic residue, preferably a straight chain having 1 to 12 carbon atoms, a branched chain having 3 to 12 carbon atoms, and carbon. Mention may be made of cyclic alkylene groups having 5 to 10 atoms.

As a substituent in the substituted alkyl group represented by R ²¹ , R ²² , R ²³ , R ²⁴ , R ²⁵ , and R ²⁶ , a monovalent non-metallic atomic group other than hydrogen is used, and a preferred example is Is a halogen atom (-F, -Br, -Cl, -I), hydroxyl group, alkoxy group, aryloxy group, mercapto group, alkylthio group, arylthio group, alkyldithio group, aryldithio group, amino group, N-alkyl Amino group, N, N-dialkylamino group, N-arylamino group, N, N-diarylamino group, N-alkyl-N-arylamino group, acyloxy group, carbamoyloxy group, N-alkylcarbamoyloxy group, N -Arylcarbamoyloxy group, N, N-dialkylcarbamoyloxy group, N, N-diarylcarbamoyl group Si group, N-alkyl-N-arylcarbamoyloxy group, alkylsulfoxy group, arylsulfoxy group, acyloxy group, acylthio group, acylamino group, N-alkylacylamino group, N-arylacylamino group, ureido group, N′-alkylureido group, N ′, N′-dialkylureido group,

N′-arylureido group, N ′, N′-diarylureido group, N′-alkyl-N′-arylureido group, N-alkylureido group, N-arylureido group, N′-alkyl-N-alkylureido Group, N′-alkyl-N-arylureido group, N ′, N′-dialkyl-N-alkylureido group, N ′, N′-dialkyl-N-arylureido group, N′-aryl-N-alkylureido Group, N′-aryl-N-arylureido group, N ′, N′-diaryl-N-alkylureido group, N ′, N′-diaryl-N-arylureido group, N′-alkyl-N′-aryl -N-alkylureido group, N'-alkyl-N'-aryl-N-arylureido group, alkoxycarbonylamino group, aryloxycarbonylamino group, N-alkyl-N- Alkoxycarbonyl amino group, N- alkyl -N- aryloxycarbonylamino group, N- aryl -N- alkoxycarbonylamino group, N- aryl -N- aryloxycarbonylamino group, a formyl group, an acyl group, a carboxyl group,

Alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, N-alkylcarbamoyl group, N, N-dialkylcarbamoyl group, N-arylcarbamoyl group, N, N-diarylcarbamoyl group, N-alkyl-N-arylcarbamoyl group, Alkylsulfinyl group, arylsulfinyl group, alkylsulfonyl group, arylsulfonyl group, sulfo group (—SO ₃ H) and its conjugate base group (hereinafter referred to as sulfonate group), alkoxysulfonyl group, aryloxysulfonyl group, sulfinamoyl group N-alkylsulfinamoyl group, N, N-dialkylsulfinamoyl group, N-arylsulfinamoyl group, N, N-diarylsulfinamoyl group, N-alkyl-N-arylsulfinamoyl group, sulfamoy Group, N-alkylsulfamoyl group, N, N-dialkylsulfamoyl group, N-arylsulfamoyl group, N, N-diarylsulfamoyl group, N-alkyl-N-arylsulfamoyl group, A phosphono group (—PO ₃ H ₂ ) and its conjugated base group (hereinafter referred to as a phosphonato group),

Dialkylphosphono group (—PO ₃ (alkyl) ₂ ), diarylphosphono group (—PO ₃ (aryl) ₂ ), alkylarylphosphono group (—PO ₃ (alkyl) (aryl)), monoalkylphosphono group (—PO ₃ H (alkyl)) and its conjugated base group (hereinafter referred to as alkylphosphonate group), monoarylphosphono group (—PO ₃ H (aryl)) and its conjugated base group (hereinafter referred to as arylphosphonate) Group), a phosphonooxy group (—OPO ₃ H ₂ ) and its conjugate base group (hereinafter referred to as phosphonatoxy group), a dialkylphosphonooxy group (—OPO ₃ (alkyl) ₂ ), a diarylphosphonooxy group ( -OPO ₃ (aryl) _2), alkylaryl phosphono group _{(-OPO 3 (alkyl) (aryl} )), monoalkyl Suhonookishi group (-OPO ₃ H (alkyl)) and its conjugated base group (hereinafter, referred to as alkylphosphonato group.), Monoarylphosphono group (-OPO ₃ H (aryl)) and its conjugated base group ( Hereinafter, it is referred to as an arylphosphonatoxy group.), A cyano group, a nitro group, an aryl group, a heteroaryl group, an alkenyl group, an alkynyl group, and a silyl group.

Specific examples of the alkyl group in these substituents include the alkyl groups described above as unsubstituted alkyl groups represented by R ²¹ , R ²² , R ²³ , R ²⁴ , R ²⁵ , and R ²⁶ , These may further have a substituent.
Specific examples of the aryl group include phenyl, biphenyl, naphthyl, tolyl, xylyl, mesityl, cumenyl, chlorophenyl, bromophenyl, chloromethylphenyl, hydroxyphenyl, methoxyphenyl, ethoxy Phenyl group, phenoxyphenyl group, acetoxyphenyl group, benzoyloxyphenyl group, methylthiophenyl group, phenylthiophenyl group, methylaminophenyl group, dimethylaminophenyl group, acetylaminophenyl group, carboxyphenyl group, methoxycarbonylphenyl group, Ethoxyphenylcarbonyl group, phenoxycarbonylphenyl group, N-phenylcarbamoylphenyl group, phenyl group, cyanophenyl group, sulfophenyl group, sulfonatophenyl group, phosphonophenyl group It can be exemplified phosphonophenyl phenyl group.

  The heteroaryl group includes a group derived from a monocyclic or polycyclic aromatic ring containing at least one of nitrogen, oxygen and sulfur atoms. Particularly preferred examples of the heteroaryl ring in the heteroaryl group include, for example, thiophene, thiathrene, furan, pyran, isobenzofuran, chromene, xanthene, phenoxazine, pyrrole, pyrazole, isothiazole, isoxazole, pyrazine, pyrimidine, pyridazine, Indolizine, isoindolizine, indoir, indazole, purine, quinolidine, isoquinoline, phthalazine, naphthyridine, quinazoline, cinolin, pteridine, carbazole, carboline, phenanthrine, acridine, perimidine, phenanthroline, phthalazine, phenalazine, phenoxazine, furan , Phenoxazine, and the like, and these may be further benzo-fused or may have a substituent.

Examples of the alkenyl group include vinyl group, 1-propenyl group, 1-butenyl group, cinnamyl group, 2-chloro-1-ethenyl group, and the like.
Examples of the alkynyl group include ethynyl group, 1-propynyl group, 1-butynyl group, trimethylsilylethynyl group and the like.
Examples of G ₁ in the acyl group (G ₁ CO—) include hydrogen and the above alkyl groups and aryl groups.

  Among these substituents, even more preferable are halogen atoms (—F, —Br, —Cl, —I), alkoxy groups, aryloxy groups, alkylthio groups, arylthio groups, N-alkylamino groups, N, N -Dialkylamino group, acyloxy group, N-alkylcarbamoyloxy group, N-arylcarbamoyloxy group, acylamino group, formyl group, acyl group, carboxyl group, alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, N-alkylcarbamoyl group Group, N, N-dialkylcarbamoyl group, N-arylcarbamoyl group, N-alkyl-N-arylcarbamoyl group, sulfo group, sulfonate group, sulfamoyl group, N-alkylsulfamoyl group, N, N-dialkylsulfa group Moyl group, N-arylsulfur Amoyl group, N-alkyl-N-arylsulfamoyl group, phosphono group, phosphonate group, dialkyl phosphono group, diaryl phosphono group, monoalkyl phosphono group, alkyl phosphonate group, monoaryl phosphono group, aryl phosphino group Examples include an onato group, a phosphonooxy group, a phosphonateoxy group, an aryl group, an alkenyl group, and an alkylidene group (such as a methylene group).

Examples of the substituted alkyl group represented by R ²¹ , R ²² , R ²³ , R ²⁴ , R ²⁵ , and R ²⁶ include a combination of the above-described substituent and an alkylene group (alkyl moiety). Specific examples As chloromethyl, bromomethyl, 2-chloroethyl, trifluoromethyl, methoxymethyl, methoxyethoxyethyl, allyloxymethyl, phenoxymethyl, methylthiomethyl, tolylthiomethyl, ethylaminoethyl Group, diethylaminopropyl group, morpholinopropyl group, acetyloxymethyl group, benzoyloxymethyl group, N-cyclohexylcarbamoyloxyethyl group, N-phenylcarbamoyloxyethyl group, acetylaminoethyl group, N-methylbenzoylaminopropyl group, 2 -Oxoeth Group, 2-oxopropyl group, carboxypropyl group, methoxycarbonylethyl group, allyloxycarbonylbutyl group, chlorophenoxycarbonylmethyl group, carbamoylmethyl group, N-methylcarbamoylethyl group, N, N-dipropylcarbamoylmethyl group, N- (methoxyphenyl) carbamoylethyl group, N-methyl-N- (sulfophenyl) carbamoylmethyl group,

Sulfobutyl group, sulfonatopropyl group, sulfonatobutyl group, sulfamoylbutyl group, N-ethylsulfamoylmethyl group, N, N-dipropylsulfamoylpropyl group, N-tolylsulfamoylpropyl group, N-methyl- N- (phosphonophenyl) sulfamoyloctyl group, phosphonobutyl group, phosphonatohexyl group, diethylphosphonobutyl group, diphenylphosphonopropyl group, methylphosphonobutyl group, methylphosphonatobutyl group, tolylphosphono Hexyl group, tolylphosphonatohexyl group, phosphonooxypropyl group, phosphonatooxybutyl group, benzyl group, phenethyl group, α-methylbenzyl group, 1-methyl-1-phenylethyl group, p-methylbenzyl group, cinnamyl Group, allyl group, 1-propyl Penirumechiru, 2-butenyl, 2-methylallyl group, 2-methyl propenyl methyl group, 2-propynyl group, 2-butynyl, 3-butynyl, and the like.

Specific examples of the unsubstituted aryl group represented by R ²¹ , R ²² , R ²³ , R ²⁴ , R ²⁵ , and R ²⁶ include those in which 1 to 3 benzene rings form a condensed ring, benzene A ring and a 5-membered unsaturated ring form a condensed ring. Specific examples include a phenyl group, a naphthyl group, an anthryl group, a phenanthryl group, an indenyl group, an acenaphthenyl group, and a fluorenyl group. Among these, a phenyl group and a naphthyl group are more preferable.

Specific examples of the preferred substituted aryl group as R ²¹ , R ²² , R ²³ , R ²⁴ , R ²⁵ , and R ²⁶ include a monovalent group as a substituent on the ring-forming carbon atom of the aforementioned unsubstituted aryl group. Those having nonmetallic atomic groups are used. Examples of preferred substituents include the alkyl groups, substituted alkyl groups, and those previously shown as substituents in the substituted alkyl group. Preferred examples of such a substituted aryl group include biphenyl group, tolyl group, xylyl group, mesityl group, cumenyl group, chlorophenyl group, bromophenyl group, fluorophenyl group, chloromethylphenyl group, trifluoromethylphenyl group. Hydroxyphenyl group, methoxyphenyl group, methoxyethoxyphenyl group, allyloxyphenyl group, phenoxyphenyl group, methylthiophenyl group, tolylthiophenyl group, ethylaminophenyl group, diethylaminophenyl group, morpholinophenyl group, acetyloxyphenyl group, Benzoyloxyphenyl group, N-cyclohexylcarbamoyloxyphenyl group, N-phenylcarbamoyloxyphenyl group,

Acetylaminophenyl group, N-methylbenzoylaminophenyl group, carboxyphenyl group, methoxycarbonylphenyl group, allyloxycarbonylphenyl group, chlorophenoxycarbonylphenyl group, carbamoylphenyl group, N-methylcarbamoylphenyl group, N, N-di Propylcarbamoylphenyl group, N- (methoxyphenyl) carbamoylphenyl group, N-methyl-N- (sulfophenyl) carbamoylphenyl group, sulfophenyl group, sulfonatophenyl group, sulfamoylphenyl group, N-ethylsulfamoyl Phenyl group, N, N-dipropylsulfamoylphenyl group, N-tolylsulfamoylphenyl group, N-methyl-N- (phosphonophenyl) sulfamoylphenyl group, phosphonophenyl group, phos Onatophenyl group, diethylphosphonophenyl group, diphenylphosphonophenyl group, methylphosphonophenyl group, methylphosphonatophenyl group, tolylphosphonophenyl group, tolylphosphonatophenyl group, allylphenyl group, 1-propenylmethylphenyl group 2-butenylphenyl group, 2-methylallylphenyl group, 2-methylpropenylphenyl group, 2-propynylphenyl group, 2-butynylphenyl group, 3-butynylphenyl group, and the like.

A more preferred example of R ²¹ is a substituted or unsubstituted aryl group, and a more preferred example of R ²² and R ²⁶ is a substituted or unsubstituted alkyl group. Particularly preferred examples of R ²² include an alicyclic alkyl group, and specific examples include a cyclohexyl group, a cycloheptyl group, and a cyclooctyl group. Preferred examples of R ²³ , R ²⁴ , and R ²⁵ include a substituted or unsubstituted aryl group or a substituted or unsubstituted alkyl group. Particularly preferred examples include R ²³ and R ²⁴ , or R ^24. And R ²⁵ , or R ²³ and R ²⁵ are bonded by a divalent linking group. Specifically, a cycloalkyl structure is formed between R ²³ , R ²⁴ , and R ²⁵ . It is preferable. Preferable cycloalkyl structures include a cyclohexyl structure, a cycloheptyl structure, a cyclooctyl structure, and an adamantane structure.
The reason why these substituents are suitable is not clear, but by having such substituents, the interaction between the electronically excited state caused by light absorption and the initiator compound becomes particularly large, and the radical of the initiator compound The efficiency of generating an acid or base is improved (sensitivity improving effect), and a bulky structure is introduced adjacent to the imine structure, so that hydrolysis, oxidative decomposition, etc. from the photosensitive film due to decomposition of the imine structure It is conceivable that disappearance is suppressed (storage stability improving effect).

Next, A in the general formula (4) will be described. A represents an aromatic ring or a hetero ring which may have a substituent, and specific examples of the aromatic ring or hetero ring which may have a substituent include R ²¹ , R ²² , R ²³ and R ^24. , R ²⁵ , and R ²⁶ are the same as those exemplified in the description.
Among them, preferable A includes an alkoxy group, a thioalkyl group, and an aryl group having an amino group, and more preferable A includes an aryl group having an amino group. Particularly preferred aryl groups having an amino group include a dialkylaminoaryl group and a diarylaminoaryl group. Specific examples include a dimethylaminophenyl group, a diethylaminophenyl group, a piperidinophenyl group, a morpholinophenyl group, and a julolidine group. Group and diphenylaminophenyl group.

  Hereinafter, preferred specific examples (D1) to (D121) of the compound represented by the general formula (1) (specific sensitizer) are shown, but the present invention is not limited thereto. Further, the isomer by the double bond connecting the acidic nucleus and the basic nucleus is not clear, and the present invention is not limited to either isomer.

A method for synthesizing the compound represented by the general formula (1) will be described.
The compound represented by the general formula (1) is usually obtained by a condensation reaction between an acidic nucleus having an active methylene group and a substituted or unsubstituted aromatic ring or heterocyclic ring. For example, Japanese Patent Publication No. 59-28329 It can be synthesized with reference to the description in the publication.
For example, as shown in the following reaction formula (1), a synthesis method using a condensation reaction of an acidic nucleus compound and a basic nucleus raw material having an aldehyde group or a carbonyl group on the heterocycle can be mentioned. The condensation reaction is carried out in the presence of a base, if necessary. As the base, generally used ones such as amines, pyridines (trialkylamine, dimethylaminopyridine, diazabicycloundecene DBU, etc.), metal amides (lithium diisopropylamide, etc.), metal alkoxides ( Sodium methoxide, potassium-t-butoxide, etc.) and metal hydrides (sodium hydride, potassium hydride, etc.) can be used without limitation.

Further, as another desirable synthesis method of the compound represented by the general formula (1), a method according to the following reaction formula (2) may be mentioned. That is, as an acidic nucleus compound in the reaction formula (1), an acid nucleus compound in which Y is a sulfur atom is used as a starting material, and a dye precursor is obtained by a condensation reaction of a basic nucleus material having an aldehyde group or a carbonyl group on the heterocycle. The process up to the step of synthesizing the body is carried out in the same manner as in the above reaction formula (1), and then the dye precursor is further reacted with a sulfur atom to form a metal sulfide and a metal salt and water or 1 This is a reaction in which a secondary amine compound (R—NH _2, where R represents a monovalent nonmetallic atomic group) is allowed to act.
Among these, the reaction represented by the reaction formula (2) has a high yield of each reaction and is particularly preferable in terms of synthesis efficiency. In particular, this reaction is used when the compound represented by the general formula (4) is synthesized. The reaction represented by formula (2) is useful.

In the reaction formula (2), M ^{n +} X _n represents a metal salt that can chemically interact with a sulfur atom of a thiocarbonyl group to form a metal sulfide. As specific compounds, for example, M is Al, Au, Ag, Hg, Cu, Zn, Fe, Cd, Cr, Co, Ce, Bi, Mn, Mo, Ga, Ni, Pd, Pt, Ru, Rh. , Sc, Sb, Sr, Mg, Ti, etc., and X is F, Cl, Br, I, NO ₃ , SO ₄ , NO ₂ , PO ₄ , CH ₃ CO _2, etc., AgBr, AgI, AgF, AgO, AgCl, Ag ₂ O, Ag (NO ₃ ), AgSO ₄ , AgNO ₂ , Ag ₂ CrO ₄ , Ag ₃ PO ₄ , Hg ₂ (NO ₃ ) ₂ , HgBr ₂ , Hg ₂ Br ₂ , HgO, HgI ₂ , Hg (NO ₃ ) ₂ , Hg (NO ₂ ) ₂ , HgBr ₂ , HgSO ₄ , Hg ₂ I ₂ , Hg ₂ SO ₄ , Hg (CH ₃ CO ₂ ) ₂ , AuBr, AuBr ₃ , AuI, AuI ₃ , _{auF 3, Au 2 O 3,} AuCl, AuC1 3, CuCl, C _{I, CuI 2, CuF 2,} CuO, CuO 2, Cu (NO 3) 2, CuSO 4, Cu 3 (PO 4) 2 of such compounds. Among these, a silver salt can be used as the most preferable metal salt in that it easily interacts with a sulfur atom.

In the case of synthesizing the compound represented by the general formula (4), R ¹ , R ² and Y in the reaction formulas (1) and (2) are respectively represented by the general formula (4). Corresponds to R ²⁶ , R ²² , and N—C (R ²³ ) (R ²⁴ ) (R ²⁵ ).

With respect to the compound (specific sensitizer) represented by the general formula (1) according to the present invention, various chemical modifications for improving the properties of the curable composition can be further performed.
For example, by combining a specific sensitizer and an addition polymerizable compound structure (for example, an acryloyl group or a methacryloyl group) by a method such as a covalent bond, an ionic bond, a hydrogen bond, etc., It is possible to suppress unnecessary precipitation of the specific sensitizer from the exposed film.
Further, a partial structure having a radical generating ability in a specific sensitizer and a photopolymerization initiator described later (for example, reductive decomposable sites such as alkyl halide, onium, peroxide, biimidazole, onium, biimidazole, borate, etc. , Amine, trimethylsilylmethyl, carboxymethyl, carbonyl, imine and other oxidatively cleavable sites) can significantly increase the photosensitivity particularly in a low concentration of the starting system.

  In the curable composition of the present invention, the compound represented by the general formula (1) (specific sensitizer) may be used alone or in combination of two or more.

The content of the specific sensitizer in the curable composition of the present invention is preferably 0.1% by mass to 20% by mass and more preferably 0.2% by mass to 20% by mass in the total solid content of the curable composition. preferable.
When the specific sensitizer according to the present invention has a very high concentration of the colorant in the curable composition and the light transmittance of the formed color pattern (photosensitive layer) becomes extremely low, specifically, By adding it when the transmittance of 365 nm light of the photosensitive layer when it is formed without adding a specific sensitizer is 10% or less, the effect is remarkably exhibited.

<(B) Photopolymerization initiator>
The curable composition of the present invention contains a photopolymerization initiator.
The photopolymerization initiator in the present invention is a compound that is decomposed by light and starts and accelerates polymerization of a polymerizable compound described later, 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, biimidazoles. 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 biimidazole compound, for example, a hexaarylbiimidazole compound is preferable.
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 '-Tetraphenylbiimidazole, 2,2'- (O-nitrophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole, 2,2′-bis (o-methylphenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole 2,2′-bis (o-trifluorophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole and the like.

  Examples of the organic borate compound include 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.

  The photopolymerization initiator used in the present invention is most preferably at least one compound selected from the group consisting of a trihalomethyltriazine compound, a biimidazole compound, and an oxime compound from the viewpoint of increasing sensitivity, and a biimidazole compound. Compounds are most preferred.

  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 of a curable composition, More preferably, it is 0.1 30% by mass, particularly preferably 0.3 to 20% by mass. Within this range, good sensitivity and pattern formability can be obtained.

  In the present invention, from the viewpoint of the decomposition efficiency of the initiator, the mass ratio [(B) / (A)] of (B) the photopolymerization initiator and (A) the specific sensitizer is 0.1. It is preferably 10 or less, more preferably 0.3 or more and 5 or less, and further preferably 0.5 or more and 3 or less.

<(C) Polymerizable compound>
The polymerizable compound that can be used in the present invention is an addition polymerizable compound having at least one ethylenically unsaturated double bond, and is a compound having at least one terminal ethylenically unsaturated bond, preferably two or more. To be elected. Such a compound group is widely known in the industrial field, and can be used without any particular limitation in the present invention. These have chemical forms such as monomers, prepolymers, i.e. dimers, trimers and oligomers, or mixtures thereof and copolymers thereof. Examples of monomers and copolymers thereof include unsaturated carboxylic acids (for example, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.), and esters and amides thereof. In this case, an ester of an unsaturated carboxylic acid and an aliphatic polyhydric alcohol compound, or an amide of an unsaturated carboxylic acid and an aliphatic polyvalent amine compound is used. In addition, an addition reaction product of an unsaturated carboxylic acid ester or amide having a nucleophilic substituent such as a 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, isocyanuric acid There are EO-modified triacrylate and the like.

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

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

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

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

  In addition, urethane-based addition polymerizable compounds produced by using an addition reaction of isocyanate and hydroxyl group are also suitable, and specific examples thereof include, for example, one molecule described in JP-B-48-41708. 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 (A) 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 (A)
(In the general formula (A), 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 photopolymerizable composition excellent in the photosensitive speed.

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

About these addition polymerizable compounds, the details of usage, such as the structure, single use or combination, addition amount, etc. can be arbitrarily set according to the final performance design of the curable composition. For example, it is selected from the following viewpoints.
From the viewpoint of sensitivity, a structure having a large unsaturated group content per molecule is preferable, and in many cases, a bifunctional or higher functionality is preferable. Further, in order to increase the strength of the cured film, those having three or more functionalities are preferable, and further, different functional numbers and different polymerizable groups (for example, acrylic acid ester, methacrylic acid ester, styrene compound, vinyl ether compound). A method of adjusting both sensitivity and intensity by using a combination of these materials is also effective.
In addition, the compatibility of the addition polymerization compound with other components (for example, photopolymerization initiators, colorants (pigments, dyes, etc.), binder polymers, etc.) contained in the curable composition is also improved. The selection / use method is an important factor. For example, the compatibility may be improved by using a low-purity compound or using two or more kinds in combination. In addition, a specific structure may be selected for the purpose of improving adhesion with a substrate or the like.

<(D) Colorant>
The curable composition of the present invention contains a colorant.
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 light resistance.

  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 an 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 the pigment 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. When the mass ratio is less than 100: 5, it is difficult to suppress the light transmittance of 400 nm to 450 nm, and the color purity may not be improved. When the ratio exceeds 100: 150, the dominant wavelength becomes longer and the deviation from the NTSC target hue may increase. 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. If it is 100: 61 or more, the dispersion stability may decrease.

In the present invention, when the colorant is a dye, it can be uniformly dissolved in the composition to obtain a curable composition.
The dye that can be used as the colorant contained in the curable composition of the present invention is not particularly limited, and conventionally known dyes for color filters can be used. For example, Japanese Patent Application Laid-Open No. 64-90403, Japanese Patent Application Laid-Open No. 64-91102, Japanese Patent Application Laid-Open No. 1-94301, Japanese Patent Application Laid-Open No. 6-11614, No. 2592207, US Pat. No. 4,808,501. Specification, US Pat. No. 5,667,920, US Pat. No. 5,059,500, JP-A-5-333207, JP-A-6-35183, JP-A-6-51115 JP-A-6-194828, JP-A-8-21599, JP-A-4-249549, JP-A-10-123316, JP-A-11-302283, JP-A-7-286107, JP 2001-4823, JP-A-8-15522, JP-A-8-29771, JP-A-8-146215, JP-A-11-3434. 7, JP-A-8-62416, JP-A-2002-14220, JP-A-2002-14221, JP-A-2002-14222, JP-A-2002-14223, JP-A-8-302224 The dyes disclosed in JP-A-8-73758, JP-A-8-179120, JP-A-8-151531, and the like can be used.

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

In 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, and other components in the composition. It is selected in consideration of all required performance such as interaction with components, light resistance, heat resistance and the like.
Specific examples of the acid dye are shown below, but are not limited thereto. For example,
acid alizarin violet N; acid black 1, 2, 24, 48; acid blue 1, 7, 9, 15, 18, 23, 25, 27, 29, 40, 45, 62, 70, 74, 80, 83, 86 , 87, 90, 92, 103, 112, 113, 120, 129, 138, 147, 158, 171, 182, 192, 243, 324: 1; acid chroma violet K; acid Fuchsin; acid green 1, 3, 5 , 9, 16, 25, 27, 50; acid orange 6, 7, 8, 10, 12, 50, 51, 52, 56, 63, 74, 95; acid red 1, 4, 8, 14, 17, 18 , 26, 27, 29, 31, 34, 35, 37, 42, 44, 50, 51, 52, 57, 66, 73, 0, 87, 88, 91, 92, 94, 97, 103, 111, 114, 129, 133, 134, 138, 143, 145, 150, 151, 158, 176, 183, 198, 211, 215, 216 217,249,252,257,260,266,274; acid violet 6B, 7,9,17,19; acid yellow 1,3,7,9,11,17,23,25,29,34,36, 42, 54, 72, 73, 76, 79, 98, 99, 111, 112, 114, 116, 184, 243; Food Yellow 3; and derivatives of these dyes.

Among these, acid black 24; acid blue 23, 25, 29, 62, 80, 86, 87, 92, 138, 158, 182, 243, 324: 1; acid orange 8, 51, 56, 63 , 74; acid red 1,4,8,34,37,42,52,57,80,97,114,143,145,151,183,217; acid violet 7; acid yellow 17, 25, 29, 34 42, 72, 76, 99, 111, 112, 114, 116, 184, 243; acidgreen 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 them, as the colorant (D), 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.

The colorant that can be used in the present invention is a dye or a pigment having an average particle size r (unit: nm) satisfying 20 ≦ r ≦ 300, preferably 125 ≦ r ≦ 250, particularly preferably 30 ≦ r ≦ 200. desirable. By using such a pigment having an average particle diameter r, red and green pixels having a high contrast ratio and a high light transmittance can be obtained. The “average particle diameter” as used herein means the average particle diameter of secondary particles in which primary particles (single microcrystals) of the pigment are aggregated.
In addition, the particle size distribution of the secondary particles of the pigment that can be used in the present invention (hereinafter, simply referred to as “particle size distribution”) is 70% by mass of the secondary particles falling within (average particle size ± 100) nm. As mentioned above, it is desirable that it is 80 mass% or more.

  The pigment having the above average particle size and particle size distribution is preferably a commercially available pigment mixed with other pigments optionally used (average particle size is usually above 300 nm), preferably with a dispersant and a solvent. The pigment mixture can be prepared by mixing and dispersing while pulverizing using a pulverizer such as a bead mill or a roll mill. The pigment thus obtained is usually in the form of a pigment dispersion.

As content of (D) coloring agent contained in the curable composition of this invention, it is preferable that it is 25-95 mass% in the total solid of a curable composition, and 30-90 mass% is more. Preferably, 40-80 mass% is still more preferable.
When the amount of the colorant is too small, there is a tendency that an appropriate chromaticity cannot be obtained when a color filter is produced with the curable composition of the present invention. On the other hand, if the amount is too large, the photocuring does not proceed sufficiently and the strength as a film is lowered, or the development latitude during alkali development tends to be narrow, but the specific sensitizer according to the present invention has a light absorption efficiency. Since it is high, even if it is a case where a coloring agent is contained in a high concentration in a curable composition, the sensitivity improvement effect is exhibited notably.

  The curable composition of the present invention, together with the above-described (A) specific sensitizer, (B) photopolymerization initiator, (C) polymerizable compound, and (D) colorant, is described in detail below as necessary. You may further contain the optional component described. Hereinafter, optional components that can be contained in the curable composition of the present invention will be described.

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

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

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

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

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

As content of the dispersing agent in this invention, it is preferable that it is 1-80 mass% with respect to a pigment, 5-70 mass% is more preferable, and 10-60 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) 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.

<(G) 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.

<(H) Other sensitizers>
In the curable composition of the present invention, (H) and the like other than the specific sensitizer are used for the purpose of improving the radical generation efficiency of the radical initiator and increasing the photosensitive wavelength within a range not impairing the effects of the present invention. The sensitizer may be contained.
Other sensitizers that can be used in the present invention are preferably those that sensitize radical initiators with an electron transfer mechanism or an energy transfer mechanism.
Other sensitizers that can be used in the present invention include those that belong to the compounds listed below and have an absorption wavelength in the wavelength region of 300 nm to 450 nm.
Examples of other preferable sensitizers include those belonging to the following compounds and having an absorption wavelength in the range of 330 nm to 450 nm.

  Examples of other sensitizers include 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), coumarins (eg, 7-diethylamino-4-methylcoumarin), ketocoumarins, 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.

<(I) Polymerization inhibitor>
In the present invention, a small amount of a thermal polymerization inhibitor may be added 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.

<(J) Adhesion improver>
In the present invention, it is preferable to add an adhesion improver in order to improve adhesion to a hard surface (substrate) as a base material. Examples of the adhesion improver include a silane coupling agent and a titanium coupling agent.

Examples of the silane coupling agent include γ- (2-aminoethyl) aminopropyltrimethoxysilane, γ- (2-aminoethyl) aminopropyldimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxy. Silane, γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropyltriethoxysilane, γ-acryloxypropyltrimethoxysilane, γ-acryloxypropyl Triethoxysilane, γ-isocyanatopropyltrimethoxysilane, γ-isocyanatopropyltriethoxysilane, N-β- (N-vinylbenzylaminoethyl) -γ-aminopropyltrimethoxysilane / hydrochloride, γ-glycidoxypro Pyrtrimethoxysilane, γ-glycidoxypropyltriethoxysilane, aminosilane, γ-mercaptopropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, vinyltriacetoxysilane, γ- Chloropropyltrimethoxysilane, hexamethyldisilazane, γ-anilinopropyltrimethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (β-methoxyethoxy) silane, octadecyldimethyl [3- (trimethoxysilyl) propyl ] Ammonium chloride, γ-chloropropylmethyldimethoxysilane, γ-mercaptopropylmethyldimethoxysilane, methyltrichlorosilane, dimethyldichlorosilane, trimethyl Chlorosilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, bisallyltrimethoxysilane, tetraethoxysilane, bis (trimethoxysilyl) hexane, phenyltrimethoxysilane, N- (3-acryloxy-2-hydroxy Propyl) -3-aminopropyltriethoxysilane, N- (3-methacryloxy-2-hydroxypropyl) -3-aminopropyltriethoxysilane, (methacryloxymethyl) methyldiethoxysilane, (acryloxymethyl) methyldimethoxysilane , Etc.
Among them, γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropyltriethoxysilane, γ-acryloxypropyltrimethoxysilane, γ-acryloxypropyltriethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-aminopropyl Triethoxysilane and phenyltrimethoxysilane are preferable, and γ-methacryloxypropyltrimethoxysilane is most preferable.

  0.5-30 mass% is preferable in the total solid of a curable composition, and, as for the addition amount of a contact | adherence improving agent, 0.7-20 mass% is more preferable.

<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.

<Diluent>
When the curable composition of the present invention is applied on a support in the production of a color filter, it may be dissolved in various organic solvents and used.
The organic solvent used here is acetone, methyl ethyl ketone, cyclohexane, ethyl acetate, ethylene dichloride, tetrahydrofuran, toluene, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol dimethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether. , Acetylacetone, cyclohexanone, diacetone alcohol, ethylene glycol monomethyl ether acetate, ethylene glycol ethyl ether acetate, ethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether acetate, 3-methoxypropanol, methoxymethoxyethanol, diethylene glycol monomethyl ether , Diethylene glycol monoethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, 3-methoxypropyl acetate, N, N-dimethylformamide, dimethyl sulfoxide, γ-butyrolactone, methyl lactate, lactic acid There are ethyl and the like.
These solvents can be used alone or in combination. The concentration of the solid content in the organic solvent is preferably 2 to 60% by mass.

  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.

[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 on the support using the curable composition for color filters of the present invention.
Hereinafter, the color filter of the present invention will be described in detail through its manufacturing method (color filter manufacturing method of the present invention).

  The method for producing a color filter of the present invention comprises a step of applying a curable composition for a color filter of the present invention on a support to form a colored curable composition layer (hereinafter appropriately referred to as “colored curable composition layer”). Abbreviated as “formation step”), a step of exposing the colored curable composition layer through a mask (hereinafter abbreviated as “exposure step” as appropriate), and the curable composition layer after exposure. And a step of forming a colored pattern by development (hereinafter abbreviated as “development step” as appropriate).

Specifically, the curable composition of the present invention is applied directly or via another layer onto a support (substrate) to form a photopolymerizable composition layer (colored curable composition layer formation) Process), exposing through a predetermined mask pattern, curing only the irradiated film portion (exposure process), and developing with a developer (development process), each color (3 colors or 4 colors) A color film of the present invention can be produced by forming a pattern-like film composed of pixels.
Hereafter, each process in the manufacturing method of this invention is demonstrated.

<Colored curable composition layer forming step>
In the colored curable composition layer forming step, the colored curable composition layer is formed by applying the curable composition of the present invention on the support.

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.

  The curable composition applied on the support is usually dried at 70 to 110 ° C. for about 2 to 4 minutes to form a colored curable composition layer.

<Exposure process>
In the exposure step, the colored curable composition layer formed in the colored curable composition layer forming step is exposed through a mask, and only the coating film portion irradiated with light is cured.
The exposure is preferably performed by irradiation of radiation, and as radiation that can be used for exposure, ultraviolet rays such as g-line and i-line are preferably used, and a high-pressure mercury lamp is more preferable. The irradiation intensity is preferably 5 mJ to 1500 mJ, more preferably 10 mJ to 1000 mJ, and most preferably 10 mJ to 800 mJ.

<Development process>
Subsequent to the exposure step, an alkali development treatment (development step) is performed, and the light non-irradiated portion in the exposure step is eluted in an alkaline aqueous solution. Thereby, only the photocured part 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 alkali used in the developer include ammonia water, ethylamine, diethylamine, dimethylethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, choline, pyrrole, piperidine, 1,8-diazabicyclo- [5, 4, 0. ] -7- An alkaline aqueous solution obtained by diluting an organic alkaline compound such as undecene with pure water so as to have a concentration of 0.001 to 10% by mass, preferably 0.01 to 1% by mass is used. 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.

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

  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 has excellent development resistance. It is possible to form a high-resolution pattern that is excellent in 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. Unless otherwise specified, “%” and “part” are based on mass.

<Synthesis of specific sensitizer>
Synthesis examples of compounds 1 to 7, which are specific sensitizers according to the present invention, are shown below.

(Synthesis Example 1)
After 27 g of diphenylaminobenzaldehyde and 3.5 g of piperidine were dissolved in 450 ml of methanol, the mixture was stirred for 1 hour while refluxing. Next, 17 g of 3-ethyl-2-allylimino-oxazolidine-4-one was added and stirred while refluxing for 1 hour. After completion of the reaction, the mixture was allowed to cool to room temperature, whereby yellow crystals were precipitated. The precipitated crystals were filtered, added to 1000 ml of methanol, and stirred for 1 hour. The crystals were filtered and dried to obtain 23 g of Compound 1 having the following structure (yield 55%). Identification was performed by ¹ H-NMR (solvent CDCl ₃ ), infrared absorption spectrum, mass spectrometry spectrum, and elemental analysis. Melting point (67 ° C.), electron absorption spectrum (THF): absorption maximum wavelength 388 nm, absorption maximum molar extinction coefficient 29400. Oxidation potential (CH ₃ CN, vs Ag / AgCl) + 0.89V.

(Synthesis Example 2)
After 35 g of diphenylaminobenzaldehyde and 2.0 g of piperidine were dissolved in 500 ml of methanol, the mixture was stirred for 1 hour while refluxing. Next, 20 g of 3-ethyl-2-thioxo-4-oxazolidione was added and stirred while refluxing for 4 hours. After completion of the reaction, the mixture was allowed to cool to room temperature, whereby yellow crystals were precipitated. The precipitated crystals were filtered, added to 1000 ml of methanol, and stirred for 1 hour. The crystals were filtered and dried to obtain 48 g of Compound 2 having the following structure (yield 91%). Identification was performed by ¹ H-NMR.

Next, 1.7 g of silver nitrate was dissolved in 20 ml of acetonitrile, 2.0 g of compound 2 was added, and the mixture was stirred at room temperature for 0.5 hour. Next, 1.0 g of benzylamine was added dropwise and stirred for 1.5 hours, then 1.0 g of triethylamine was added dropwise, and the mixture was further stirred for 1.5 hours. After completion of the reaction, 30 ml of acetone was added, the precipitated silver salt was filtered off using celite, and the filtrate was poured into 150 ml of water. The precipitated crystals were collected by filtration and reslurried in methanol to obtain 1.9 g of Compound 1 similar to that obtained in Synthesis Example 1 (yield 88%). Identification was performed by ¹ H-NMR.

(Synthesis Example 3)
After dissolving 20 g of 2,3,6,7-tetrahydro-1H, 5H-pyrido- [3,2,1-η] -quinoline-9-carbaldehyde and 3.5 g of pyrrolidine in 400 ml of methanol, 1.5 g Stirring at reflux for an hour. Next, 21 g of 3-phenylethyl-1,3-oxazolidine-2,4-dione was added and stirred while refluxing for 4 hours. After completion of the reaction, the mixture was allowed to cool to room temperature, whereby yellow crystals were precipitated. The precipitated crystals were filtered, added to 800 ml of methanol, and stirred for 1 hour. The crystals were filtered and dried to obtain 33 g of Compound 3 having the following structure (yield: 85%). Identification was performed by ¹ H-NMR (solvent CDCl ₃ ), infrared absorption spectrum, mass spectrometry spectrum, and elemental analysis. Melting point (162 ° C.), electron absorption spectrum (THF): absorption maximum wavelength 412 nm, absorption maximum molar extinction coefficient 35500. Oxidation potential (CH ₃ CN, vs Ag / AgCl)
+ 0.64V.

(Synthesis Example 4)
Compound 2 was synthesized by a method similar to that described in Synthesis Example 2.
Next, after 2.8 g of silver nitrate was dissolved in 40 ml of acetonitrile, 3.0 g of compound 2 was added and stirred for 0.5 hour. Next, 5 g of 2,4,6-trimethylaniline was added and stirred for 1.5 hours, then 1.0 g of triethylamine was added dropwise, and the mixture was further stirred at 70 ° C. for 1 hour. After completion of the reaction, 60 ml of acetone was added, the precipitated silver salt was filtered off using Celite, and the filtrate was poured into 300 ml of water. The precipitated crystals were collected by filtration and reslurried in methanol to obtain 3.5 g of compound 4 having the following structure (yield 92%). Identification was performed by ¹ H-NMR (solvent CDCl ₃ ), infrared absorption spectrum, mass spectrometry spectrum, and elemental analysis. Melting point (117 ° C.), electron absorption spectrum (THF): absorption maximum wavelength 395 nm, absorption maximum molar extinction coefficient 30900. Oxidation potential (CH ₃ CN, vs Ag / AgCl) + 0.82V.

(Synthesis Example 5)
After 1.8 g of diethylaminobenzaldehyde, 0.7 g of piperidine and 2.1 g of 3-ethyl-2-cyclohexylimino-oxazolidine-4-one were dissolved in 50 ml of ethanol, the mixture was stirred for 8 hours while refluxing. After completion of the reaction, the mixture was allowed to cool to room temperature, whereby yellow crystals were precipitated. The precipitated crystals were filtered, added to 50 ml of methanol, and stirred for 1 hour. The crystals were filtered and dried to obtain 1.4 g of Compound 5 having the following structure (yield 38%). Identification was performed by ¹ H-NMR (solvent CDCl ₃ ), infrared absorption spectrum, mass spectrometry spectrum, and elemental analysis. Electronic absorption spectrum (THF): absorption maximum wavelength 385 nm, absorption maximum molar extinction coefficient 37200.

(Synthesis Example 6)
17.7 g of diethylaminobenzaldehyde and 1.0 g of piperidine were dissolved in 250 ml of methanol and stirred for 1 hour while refluxing. Next, 19.9 g of 3-cyclohexyl-2-thioxo-4-oxazolidione was added and stirred while refluxing for 4 hours. After completion of the reaction, the reaction mixture was allowed to cool to room temperature to precipitate orange crystals. The precipitated crystals were filtered, added to 500 ml of methanol, and stirred for 1 hour. The crystals were filtered and dried to obtain 30.4 g of Compound 6 having the following structure as a dye precursor (yield 85%). Identification was performed by ¹ H-NMR.

(Synthesis Example 7)
After 1.7 g of silver nitrate was dissolved in 20 ml of acetonitrile, 1.8 g of compound 6 obtained by the same method as in Synthesis Example 6 was added and stirred at room temperature for 0.5 hour. Next, 1.0 g of cyclohexylamine was added dropwise and stirred for 1.5 hours, then 1.0 g of triethylamine was added dropwise, and the mixture was further stirred for 1.5 hours. After completion of the reaction, 30 ml of acetone was added, the precipitated silver salt was filtered off using celite, and the filtrate was poured into 150 ml of water. The precipitated crystals were collected by filtration and reslurried in methanol to obtain 1.9 g of Compound 7 having the following structure (yield 88%). Identification was performed by ¹ H-NMR (solvent CDCl ₃ ), infrared absorption spectrum, mass spectrometry spectrum, and elemental analysis. Electronic absorption spectrum (THF): absorption maximum wavelength 384 nm, absorption maximum molar extinction coefficient 38300.

  The structures of compounds 1 to 7 are summarized in Table 1 below. Table 2 shows the structures of Comparative Compounds 1 to 3 used in Comparative Examples described later.

  Hereinafter, the color filter of the present invention and the method for producing the same will be described more specifically with reference to examples. However, the present invention is not limited to the following examples unless it exceeds the gist.

[Example 1-1]
Here, an example will be described in which a colored curable composition A-1 containing a colorant (pigment) is prepared, and a color filter for use in a liquid crystal display device is prepared using the colored curable composition A-1. .

[1. Preparation of colored curable composition A-1]

1-1. Preparation of Pigment Dispersion (P1) As a pigment, C.I. I. Pigment Green 36 and C.I. I. 40 parts by mass of a 30/70 (mass ratio) mixture with Pigment Yellow 219, and 10 parts by mass (approximately 4. 51 parts by mass) and 150 parts by mass of ethyl 3-ethoxypropionate as a solvent were mixed and dispersed by a bead mill for 15 hours to prepare a pigment dispersion (P1).
With respect to the obtained pigment dispersion (P1), the average particle diameter of the pigment was measured by a dynamic light scattering method and found to be 200 nm.

1-2. Preparation of colored curable composition A-1 (coating liquid) The components of the following composition A-1 were mixed and dissolved to prepare a colored curable composition A-1.
<Composition A-1>
Pigment dispersion (P1) 600 parts by mass Alkali-soluble resin (benzyl methacrylate / methacrylic acid / hydroxyethyl methacrylate copolymer, molar ratio: 80/10/10,
Mw: 10000) 190 parts by mass • Dipentaerythritol hexaacrylate [polymerizable compound] 60 parts by mass • 2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetraphenyl-
1,2'-biimidazole [photopolymerization initiator] 60 parts by mass Compound 1 [specific sensitizer] 40 parts by mass Co-sensitizer: 40 parts by mass of 2-mercaptobenzimidazole Surfactant: (trade name : Tetranic 150R1, BASF) 1 part by mass Solvent: 1000 parts by mass of propylene glycol monomethyl ether acetate 10 parts by mass of γ-methacryloxypropyltriethoxysilane

[2. (Production of color filter)
2-1. Formation of the curable composition layer The colored curable composition A-1 containing the pigment obtained as described above was applied as a resist solution to a 550 mm × 650 mm glass substrate by slit coating under the following conditions, and then left as it was for 10 minutes. It was made to wait, apply | coated to a new glass substrate, vacuum-dried and prebaked (100 degreeC80 second), and the colored curable composition coating film (colored curable composition layer) was formed.
(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

2-2. Exposure and development Thereafter, the colored curable composition coating film is exposed in a pattern using a 2.5 kW ultra-high pressure mercury lamp, and after the exposure, the entire surface of the coating film is organic developer (trade name: CD, Fuji Film Arch). The product was covered with a 10% aqueous solution (made by Co., Ltd.) and left stationary for 60 seconds.

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 development treatment was heated in an oven at 220 ° C. for 1 hour (post-baking). Thereby, a colored pattern was formed on the glass substrate to obtain a color filter.

[3. (Performance evaluation)
Storage stability of the colored curable composition A-1 (coating liquid) prepared above, and a colored curable composition coating film formed on a glass substrate using the colored curable composition A-1 ( The exposure sensitivity and developability of the colored layer), and the substrate adhesion and cross-sectional shape of the colored pattern in the color filter were evaluated as follows. The results are shown in Table 3.

3-1. Storage Stability of Colored Curable Composition A-1 After the colored curable composition coating solution was stored at room temperature for 1 month, the degree of precipitation of foreign matters was visually evaluated according to the following criteria.
<Criteria>
○: No precipitation was observed.
Δ: Slight precipitation was observed.
X: Precipitation was recognized.

3-2. Exposure sensitivity of coating film (colored layer),
The colored curable composition A-1 (coating solution) was applied on a glass substrate and dried to a thickness of 1.0 μm. The spin coating conditions were 300 rpm for 5 seconds, 800 rpm for 20 seconds, and the drying conditions were 100 ° C. for 80 seconds. Next, it exposed with the various exposure amount of 10-1600mJ / cm < ² > using the photomask for a test with a line | wire width of 2.0 micrometers. Next, it developed on 25 degreeC and the conditions for 60 second using the developing solution of 60% CD-2000 (made by Fuji Film Electronics Materials). Then, after rinsing with running water for 20 seconds, spray drying was performed to complete patterning. The minimum exposure amount in which the film thickness after development of the region irradiated with light in the exposure step was 95% or more with respect to 100% of the film thickness before exposure was evaluated as the exposure sensitivity. A smaller exposure sensitivity value indicates higher sensitivity.

3-3. Developability, pattern cross-sectional shape, substrate adhesiveness Evaluation of developability, substrate adhesion, pattern cross-sectional shape by confirming the substrate surface and cross-sectional shape after post-baking with an optical microscope and SEM photograph observation in a normal manner. went. Details of the evaluation method are as follows.

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

<Board adhesion>
As an evaluation of substrate adhesion, it was observed whether or not a pattern defect occurred. About these evaluation items, it evaluated based on the following reference | standard: (circle): The pattern defect | deletion was not observed at all.
(Triangle | delta): Although the pattern defect | defect was hardly observed, the defect | deletion was partially observed.
X: A pattern defect was remarkably observed.

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

[Examples 1-2 to 1-10]
In Example 1-1, the specific sensitizer, photopolymerization initiator, and co-sensitizer in composition A-1 used for the preparation of colored curable composition A-1 are shown in Table 3 below. A colored curable composition A-2 to A-10 was prepared in the same manner as in Example 1-1 except that the color filter having a colored pattern was obtained. Furthermore, evaluation similar to Example 1-1 was performed. The results are shown in Table 3.

[Comparative Example 1-1]
In Example 1-1, except that the composition A-1 used for the preparation of the colored curable composition A-1 was changed to the following composition B-1, all were the same as in Example 1-1 for comparison. A colored curable composition B-1 was prepared and a colored pattern was formed to obtain a color filter. Furthermore, evaluation similar to Example 1-1 was performed. The results are shown in Table 3.

<Composition B-1>
Pigment dispersion (P1) 600 parts by mass Alkali-soluble resin (benzyl methacrylate / methacrylic acid / hydroxyethyl methacrylate copolymer, molar ratio: 80/10/10,
Mw: 10,000, 200 parts by mass Dipentaerythritol hexaacrylate [polymerizable compound] 60 parts by mass 1- [4- (phenylthio) phenyl] -2-
(O-benzoyloxime) [photopolymerizable initiator] 140 parts by mass Solvent: 1000 parts by mass of propylene glycol monomethyl ether acetate Surfactant (trade name: Tetranic 150R1, BASF) 1 part by mass

[Comparative Examples 1-2 to 1-4]
In the colored curable composition A-1 prepared in Example 1-1, specific sensitizers, photopolymerization initiators, and co-sensitizers were compared with the comparative compounds, photopolymerization initiators shown in Table 3 below, and A color filter having a colored pattern formed by preparing comparative colored curable compositions B-2 to B-4 in the same manner as in Example 1-1 except that the co-sensitizer was used. Got. Furthermore, evaluation similar to Example 1-1 was performed. The results are shown in Table 3.

Photopolymerization initiators D1 to D3 and cosensitizers F1 and F2 shown in Table 3 are the compounds shown below.
D1: 2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-
Tetraphenyl-1,2'-biimidazole D2: 1- [4- (phenylthio) phenyl] -2- (O-benzoyloxime)
D3: 4-Benzoxolane-2,6-di (trichloromethyl) -s-triazine F1: 2-mercaptobenzimidazole F2: 2-mercaptobenzothiazole

  From the results of Table 3, it can be seen that the colored curable composition of each Example containing the specific sensitizer (Compounds 1 to 7) is excellent in storage stability in the solution state. Further, when a colored pattern is formed on a support using this colored curable composition, it does not contain a specific sensitizer or uses Comparative Compounds 1 to 3 instead of the specific sensitizer. It can be seen that, for each of the comparative examples, a color filter having high exposure sensitivity, excellent developability, and excellent substrate adhesion and pattern cross-sectional shape is obtained.

  Hereinafter, an example of preparing a color curable composition containing a colorant (pigment) for use in a solid-state image sensor and producing a color filter for use in a solid-state image sensor using the color curable composition will be described.

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

[2. Fabrication of silicon wafer 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.

[3. Preparation of colored curable composition C-1]
A compound of the following composition C-1 was mixed and dissolved to prepare a colored photosensitive resin composition C-1.
<Composition C-1>
-Cyclohexanone (solvent) 80 parts by mass-C.I. I. Acid Blue 108 [colorant] 7.5 parts by mass C.I. I. Solvent Yellow 162 [colorant] 2.5 parts by mass-3: 7 mixture of pentaerythritol triacrylate and dipentaerythritol hexaacrylate [polymerizable compound] 7.0 parts by mass-2,2'-bis (2- Chlorophenyl) -4,4 ′, 5,5′-tetraphenyl-
1,1'-biimidazole [photopolymerization initiator] 1 part by mass Compound 1 [specific sensitizer] 0.7 part by mass Co-sensitizer: 0.8 part by mass of 2-mercaptobenzimidazole Glycerol propoxylate 0.5 parts by mass (number average molecular weight Mn: 1500, molar extinction coefficient ε = 0, colorless compound)

[4. Storage Stability Evaluation of Colored Curable Composition C-1 (Coating Liquid)]
After coloring curable composition C-1 was stored at room temperature for 1 month, the degree of precipitation of foreign matters was visually evaluated according to the following criteria.
<Criteria>
○: No precipitation was observed.
Δ: Slight precipitation was observed.
X: Precipitation was recognized.

[5. Production and Evaluation of Color Filter Using Colored Curable Composition C-1]
3 above. The colored photosensitive resin composition C-1 prepared in the above 2. It was applied on the undercoat layer of the silicon wafer substrate with the undercoat layer obtained in (1) to form a photocurable coating film. 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, irradiation was performed using an i-line stepper exposure apparatus FPA-3000i5 + (manufactured by Canon Inc.) at an exposure dose of 10 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). Paddle development was performed at 23 ° C. for 60 seconds using Electronics Materials Co., Ltd. to form a colored pattern on the silicon wafer substrate.

  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 rpm by a rotating device, while being pure from above the rotation center. Water was supplied in a shower form from the ejection nozzle to perform rinsing, and then spray-dried.

<Exposure sensitivity>
The minimum exposure amount in which the film thickness after development of the region irradiated with light in the exposure step was 95% or more with respect to 100% of the film thickness before exposure was evaluated as the exposure sensitivity. A smaller exposure sensitivity value indicates higher sensitivity. In addition, the size of the colored pattern was measured using a length measurement SEM “S-9260A” (manufactured by Hitachi High-Technologies Corporation). The closer the pattern size is to 2 μm, the better the curability and the better the sensitivity.
The results of measurement evaluation are shown in Table 4 below.

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

<Board adhesion>
As an evaluation of substrate adhesion, it was observed whether or not a pattern defect occurred. About these evaluation items, it evaluated based on the following reference | standard: (circle): The pattern defect | deletion was not observed at all.
(Triangle | delta): Although the pattern defect | defect was hardly observed, the defect | deletion was partially observed.
X: A pattern defect was remarkably observed.

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

[Comparative Example 2-1]
In Example 2-1, except that the composition C-1 used for the preparation of the colored curable composition C-1 was changed to the following composition D-1, all were the same as in Example 2-1, for comparison. A colored curable composition D-1 was prepared and a colored pattern was formed to obtain a color filter. Furthermore, evaluation similar to Example 2-1 was performed. The results are shown in Table 4.

<Composition D-1>
-Cyclohexanone 80 parts by mass-Colorant C.I. I. Acid Blue 108 7.5 parts by mass Colorant C.I. I. Solvent Yellow 162 2.5 parts by mass-3: 7 mixture of pentaerythritol triacrylate and dipentaerythritol hexaacrylate [polymerizable compound] 7.0 parts by mass-Oxime-based photopolymerization initiator
(CGI-124, manufactured by Ciba Specialty Chemicals,
Photopolymerization initiator) 2.5 parts by mass-Glycerol propoxylate (number average molecular weight Mn: 1500) 0.5 parts by mass

[Examples 2-2 to 2-10, Comparative Examples 2-2 to 2-4]
In Example 2-1, the specific sensitizer, photopolymerization initiator, and co-sensitizer in composition C-1 used for the preparation of colored photosensitive resin composition C-1 are shown in Table 4 below. A colored photosensitive resin composition C-2 to C-10 and a comparative colored curable composition C-11 to C-13 were prepared and supported in the same manner as in Example 2-1, except that each was changed. A colored filter was formed on the body to produce a color filter, and further evaluation was performed. The results are shown in Table 4 below.

[Example 2-11]
In Example 2-1, color hardening was performed in the same manner as in Example 2-1, except that the composition C-1 used for the preparation of the colored curable composition C-1 was changed to the following composition E-1. In addition to the preparation of the composition E-1, a colored pattern was formed to obtain a color filter. Furthermore, evaluation similar to Example 2-1 was performed. The results are shown in Table 4.

<Composition E-1>
-Cyclohexanone 80 parts by mass-Colorant C.I. I. Pigment Red 254 6.0 parts by mass Colorant C.I. I. Pigment Yellow 139 4.0 parts by mass-3: 7 mixture of pentaerythritol triacrylate and dipentaerythritol hexaacrylate [polymerizable compound] 7.0 parts by mass-2,2'-bis (2-chlorophenyl)-
4,4 ', 5,5'-tetraphenyl-
1,1'-biimidazole [photopolymerization initiator] 1 part by mass Compound 1 [specific sensitizer] 0.7 part by mass Co-sensitizer: 0.8 part by mass of 2-mercaptobenzimidazole Glycerol propoxylate (Number average molecular weight Mn: 1500) 0.5 parts by mass

[Comparative Example 2-5]
In Example 2-11, the specific sensitizer, photopolymerization initiator, and co-sensitizer in composition E-1 used for the preparation of colored photosensitive resin composition E-1 were respectively shown in Table 4 below. A comparative colored curable composition E-2 was prepared in the same manner as in Example 2-11 except that the color filter was changed, a colored pattern was formed on the support, and a color filter was prepared. I did it. The results are shown in Table 4 below.

[Comparative Example 2-6]
In Example 2-1, except that the composition C-1 used for the preparation of the colored curable composition C-1 was changed to the following composition F-1, all were the same as in Example 2-1, for comparison. A colored curable composition F-1 was prepared and a colored pattern was formed to obtain a color filter. Furthermore, evaluation similar to Example 2-1 was performed. The results are shown in Table 4.

<Composition F-1>
-Cyclohexanone 80 parts by mass-Colorant C.I. I. Pigment Red 254 6.0 parts by mass Colorant C.I. I. Pigment Yellow 139 4.0 parts by mass-3: 7 mixture of pentaerythritol triacrylate and dipentaerythritol hexaacrylate [polymerizable compound] 7.0 parts by mass-Oxime-based photopolymerization initiator
(CGI-124, manufactured by Ciba Specialty Chemicals,
Photopolymerization initiator) 2.5 parts by mass-Glycerol propoxylate (number average molecular weight Mn: 1500) 0.5 parts by mass

  Photopolymerization initiators D1 to D3, cosensitizers F1 and F2, and comparative compounds 1 to 3 shown in Table 4 are the compounds described above.

  From the results of Table 4, it can be seen that the colored curable composition of each Example containing the specific sensitizer (compounds 1 to 7) is excellent in storage stability in the solution state. Further, when a colored pattern is formed on a support using this colored curable composition, it does not contain a specific sensitizer or uses Comparative Compounds 1 to 3 instead of the specific sensitizer. It can be seen that, for each of the comparative examples, a color filter having high exposure sensitivity, excellent developability, and excellent substrate adhesion and pattern cross-sectional shape is obtained.

Claims (4)

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

[In General Formula (1), A represents an aromatic ring or a hetero ring which may have a substituent, X represents an oxygen atom, a sulfur atom or —N (R ³ ) —, Y represents an oxygen atom, sulfur atom or -N ^{(R 3)} - represents a. R ¹ , R ² , and R ³ each independently represent a hydrogen atom or a monovalent nonmetallic atomic group, and A, R ¹ , R ² , and R ³ are bonded to each other to form an aliphatic group Or you may form an aromatic ring. ]   The curable composition for a color filter according to claim 1, comprising a biimidazole compound as the photopolymerization initiator.   A color filter comprising a colored pattern formed using the curable composition for a color filter according to claim 1 or 2 on a support.   A step of applying a curable composition for a color filter according to claim 1 or 2 to form a colored curable composition layer on a support, and the colored curable composition layer through a mask. A method for producing a color filter, comprising: a step of exposing; and a step of developing the colored curable composition layer after exposure to form a colored pattern.