JP2007099840A - Colored curable composition, color filter, and its production method - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a colorant-containing photosensitive composition which has a good hue, high transmittance characteristics, high light fastness, high heat fastness, improved stability with time, and improved solvent resistance in a cured state and is useful for color filters, etc. <P>SOLUTION: The curable composition contains an acidic-substituent-containing colorant compound represented by formula (T) (wherein R<SP>1</SP>and R<SP>2</SP>are each independently a colorant residue or a substituent). <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a colored curable composition suitable for forming a color filter used in a liquid crystal display device or a solid-state imaging device, a color filter using the colored curable composition, and a method for producing the same.

  A yellow filter layer formed adjacent to each other on the same plane of the substrate as a color filter formed on the element for colorizing a solid-state imaging element (for example, CCD, CMOS, etc.) or a liquid crystal display element (LCD) There are known color filters composed of a magenta filter layer and a cyan filter layer, and color filters composed of a red filter layer, a green filter layer and a blue filter layer. A band-like pattern or a mosaic pattern is formed by these filter layers.

  Various methods have been proposed so far for producing the color filter as described above. In particular, a so-called color resist method in which a photosensitive resin composition containing a dye is exposed and developed to repeatedly perform a patterning process a required number of times has been widely put into practical use.

  The color resist method is a method for producing a color filter by a photolithographic method using a colored radiation-sensitive composition in which pigments are dispersed in various photosensitive compositions. This method uses pigments. It is stable to light, heat, and the like, and has a sufficient positional accuracy because it is patterned by a photolithography method, and is a suitable method for manufacturing a color filter for a large screen and a high-definition color display.

  When a color filter is produced by a pigment dispersion method in which a pigment is dispersed as described above, a coating film is formed by applying a radiation sensitive composition on a glass substrate using a spin coater or a roll coater. A colored pixel is obtained by pattern exposure and development, and a color filter is obtained by performing this operation in accordance with a desired number of hues. As a pigment dispersion method, a negative photosensitive composition using a photopolymerizable monomer and a photopolymerization initiator in an alkali-soluble resin is known. (For example, refer to Patent Documents 1 to 8, 12 and 13.)

  However, in recent years, further enhancement in definition has been desired for color filters for solid-state imaging devices. However, the conventional pigment dispersion system as described above does not improve the resolution, and also has problems such as color unevenness due to coarse pigment particles. Was not suitable for applications that required

Conventionally, the use of dyes has been proposed for such problems (see, for example, Patent Documents 9 to 10). There are also positive photosensitive compositions (see, for example, Patent Documents 11 to 12). However, the dye-containing curable composition has the following problems, and further improvement has been demanded. That is,
(1) Dyes are generally inferior in heat resistance, light resistance, etc. compared to pigments, and have insufficient fastness.
(2) When the molar absorption coefficient of the dye is low, a large amount of dye must be added. In this case, other compounds such as a polymerizable compound, a binder, and a photopolymerization initiator in the curable composition are added. The components must be relatively reduced, and the curability at the time of curing the composition, the heat resistance of the cured portion that has been cured, the developability of the non-cured portion, and the like are reduced.
(3) Even if the molar absorption coefficient of the dye is high, a poorly soluble dye has a large molecular weight in order to improve the solubility in the liquid preparation and to improve the stability of the liquid preparation. When the molecular weight is increased, a large amount (mass) of dye must be added, and other components such as a polymerizable compound, a binder, and a photopolymerization initiator in the curable composition are relatively In other words, the curability at the time of curing the composition, the heat resistance of the cured portion cured, the solvent resistance at the time of coating the next layer, the developability of the non-cured portion, and the like are reduced.
(4) Dyes often interact with other components in the curable composition, and it is difficult to adjust the developability (solubility) of the cured and uncured areas.

  As described above, the dyes conventionally used in the colored curable composition are not particularly satisfactory in fastness, and further have low solubility in the photosensitive composition, and are either in the liquid or coated. In some cases, the dye may precipitate in the state of the coating film, and it is difficult to contain the dye at a high concentration, and further, there are many that are difficult to develop.

  In order to improve the above problems, particularly (2) and (3), those having specific substituents have been studied, but were insufficient (for example, see Patent Document 13).

  On the other hand, in the color filter, yellow dye and magenta dye are used for the red filter array, yellow dye and cyan dye are used for the green filter array, and long wave magenta dye and cyan dye are used for the blue filter array. It is known (see, for example, Patent Document 10). However, there are no dyes that satisfy light fastness and heat fastness, improve solubility and stability over time of colored curable compositions, and can sufficiently satisfy solvent resistance, and further improvement is desired. Yes.

Japanese Patent Laid-Open No. 1-102469 Japanese Patent Laid-Open No. 1-152499 JP-A-2-181704 JP-A-2-199403 Japanese Patent Laid-Open No. 4-76062 Japanese Patent Laid-Open No. 5-273411 JP-A-6-184482 JP-A-7-140654 JP-A-6-75375 JP 2002-14221 A Japanese Patent Publication No.7-111485 JP 2002-14223 A JP-A-7-72323

  As described above, dye-containing colored curable compositions are useful in applications such as solid-state imaging devices that require particularly high definition and uniform color. Stability, and when using organic solvent-soluble dyes, the solvent resistance of the colored pattern is insufficient, and the solvent in the existing colored pattern elutes when the next color is overcoated on the existing pattern. Improvement of pattern property and pattern formation is a problem. In addition, due to the low solubility of the dye, improvement of the dye precipitation property when a liquid preparation is applied and a coating film is formed is also an issue.

The present invention has been made in view of the above, has a good hue and high transmittance characteristics, high light fastness and heat fastness, excellent temporal stability, and good solvent resistance after curing. The purpose of the present invention is to provide a color curable composition and a color filter, and a method for producing a color filter using the color curable composition and capable of producing a color filter with high productivity. This is an object of the present invention.
Another object of the present invention is to provide a colored curable composition which contains a dye having higher solubility in addition to the above and has excellent developability and pattern formability, a color filter using the same, and a method for producing the same. .

In the present invention, various substituents of various dyes have been examined in detail, and a dye having a specific substituent is not only excellent in fastness to light and heat but also particularly useful for improving solubility and developability. Based on this knowledge, a colored curable composition having the following constitution, a color filter and a method for producing the same are provided, and the above object has been achieved.
Specific means for achieving the above object are as follows.

  <1> A colored curable composition containing at least one compound represented by the following general formula (T).

In the general formula (T), R ¹ and R ² each independently represent a substituent or a dye residue, and at least one of R ¹ and R ² represents a dye residue.

  <2> A color filter containing at least one compound represented by the following general formula (T).

As described above, in general formula (T), R ¹ and R ² each independently represent a substituent or a dye residue, and at least one of R ¹ and R ² represents a dye residue.

  <3> A method for producing a color filter, comprising: applying the colored curable composition according to <1> onto a support, exposing the film through a mask, and developing to form a pattern image.

According to the present invention, a colored curable composition and color having good hue and high transmittance characteristics, high light fastness and heat fastness, excellent temporal stability, and good solvent resistance after curing. The filter and the colored curable composition are used, and a method for producing a color filter capable of producing a color filter with high productivity can be provided.
In addition, a colored curable composition containing a dye having high solubility and excellent in developability and pattern forming property, a color filter using the same, and a method for producing the same can be provided.

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

[Colored curable composition]
The colored curable composition of the present invention may be any pigment as long as it contains a compound represented by the following general formula (T) as a pigment and can be cured by light or heat. It comprises a radiation sensitive compound and a polymerizable monomer. Moreover, it can generally comprise using a solvent, and it can comprise using other components, such as a crosslinking agent, as needed.

For the general formula shown below, in the present specification, the term “aliphatic” means that the aliphatic moiety may be linear, branched or cyclic, and may be saturated or unsaturated. For example, an alkyl group, an alkenyl group, a cycloalkyl group, and a cycloalkenyl group are included, and these may be unsubstituted or substituted with a substituent.
In the present specification, aryl may be either a single ring or a condensed ring, and may be unsubstituted or substituted with a substituent. In addition, in this specification, a heterocyclic ring has a hetero atom (for example, a nitrogen atom, a sulfur atom, an oxygen atom) in the ring portion, and is either a saturated ring or an unsaturated ring. It may be either a single ring or a condensed ring, and may be unsubstituted or substituted with a substituent.

  In the present specification, the “substituent” may be any group that can be substituted, for example, an aliphatic group, an aryl group, a heterocyclic group, an acyl group, an imide group, an azo group, an acyloxy group, an acylamino group, an aliphatic group. Oxy group, aryloxy group, heterocyclic oxy group, aliphatic oxycarbonyl group, aryloxycarbonyl group, heterocyclic oxycarbonyl group, carbamoyl group, aliphatic sulfonyl group, arylsulfonyl group, heterocyclic sulfonyl group, aliphatic sulfonyloxy Group, arylsulfonyloxy group, heterocyclic sulfonyloxy group, sulfamoyl group, aliphatic sulfonamide group, arylsulfonamide group, heterocyclic sulfonamide group, amino group, aliphatic amino group, arylamino group, heterocyclic amino group, Aliphatic oxycarbonylamino group, aryloxycarbonyl Amino group, heterocyclic oxycarbonylamino group, aliphatic sulfinyl group, arylsulfinyl group, aliphatic thio group, arylthio group, heterocyclic thio, hydroxy group, cyano group, sulfo group, carboxyl group, aliphatic oxyamino group, aryl Oxyamino group, carbamoylamino group, sulfamoylamino group, halogen atom, sulfamoylcarbamoyl group, carbamoylsulfamoyl group, dialiphatic oxyphosphinyl group, diaryloxyphosphinyl group, etc. it can.

-Compound represented by general formula (T)-
The colored curable composition of the present invention contains at least one compound represented by the following general formula (T) (hereinafter sometimes referred to as “the pigment according to the present invention”). Hereinafter, the compound represented by the general formula (T) will be described in detail.

In Formula (T), the substituent represented by R ¹ or R ^2, capable substitutions include a group described in the section of the above-described substituents, preferably the substituent of R ¹ Is an aliphatic group, aryl group, heterocyclic group, aliphatic oxy group, aryloxy group, heterocyclic oxy group, aliphatic oxycarbonyl group, aryloxycarbonyl group, heterocyclic oxycarbonyl group, carbamoyl group, aliphatic sulfone Amido group, arylsulfonamido group, heterocyclic sulfonamido group, amino group, aliphatic amino group, arylamino group, heterocyclic amino group, aliphatic oxyamino group, aryloxyamino group, sulfamoylamino group, etc. , Aliphatic group, aryl group, heterocyclic group, aliphatic sulfonamide group, arylsulfonamide group, heterocyclic sulfonamide group, amino group More preferably, it is an aliphatic amino group, an arylamino group, or a heterocyclic amino group, particularly an aliphatic group, an aryl group, a heterocyclic group, an aliphatic amino group, an arylamino group, or a heterocyclic amino group. preferable. In addition, as a substituent for R ² , an aliphatic group, an aryl group, a heterocyclic group, an acylamino group, an aliphatic sulfonamido group, an arylsulfonamido group, a heterocyclic sulfonamido group, an amino group, an aliphatic amino group, Arylamino group, heterocyclic amino group, aliphatic oxycarbonylamino group, aryloxycarbonylamino group, heterocyclic oxycarbonylamino group, carbamoylamino group, sulfamoylamino group, etc., aliphatic group, aryl group, hetero A cyclic group, an acylamino group, an aliphatic sulfonamido group, an arylsulfonamido group, an amino group, an aliphatic amino group, an arylamino group, a heterocyclic amino group, etc. are more preferred, and an aliphatic group, aryl group, heterocyclic ring Especially when it is a group, an aliphatic amino group, an arylamino group, or a heterocyclic amino group Masui.

The pigment residue represented by R ¹ or R ² is a pigment residue (also referred to as a dye in the present invention) based on an appropriate position. Examples of the dye include review synthetic dyes (Hiroguchi Horiguchi). , Sankyo Shuppan Co., Ltd., published in 1968), and preferred are azo dyes, azomethine dyes, indophenol dyes, diphenylmethane dyes, triphenylmethane dyes, stilbene dyes, quinoline dyes, India Examples include aniline dyes, azine dyes, oxazine dyes, indigo dyes, phthalocyanine dyes, and more preferably azo dyes, azomethine dyes, quinoline dyes, phthalocyanine dyes, and more preferably azo dyes, tetraazaporphyrin dyes. preferable.

  A preferable azo dye is represented by the following general formula (T1). In the following general formula (T1), A represents a coupler residue, and B represents a diazo component residue.

  In the general formula (T1), the coupler residue represented by A may be any group that can be coupled to a diazonium salt, and examples thereof include a hydrocarbon ring, a heterocyclic ring, and a substituted methylene group. A coupler residue which may be a non-dissociative dye or a dissociative dye (a dye containing a group that is dissociated by alkalinity and becomes a target hue), represented by the general formula (T1). To express. More specifically, the following formulas (A-1) to (A-13) may be mentioned.

In the formula, R ^{a6 to} R ^{a47 each} represents a hydrogen atom or a substituent, and the substituent here may be any group that can be substituted as long as it is a group described in the above description of the substituent. Preferred substituents include aliphatic groups, aryl groups, heterocyclic groups, acyl groups, imide groups, acylamino groups, aliphatic oxy groups, aliphatic oxycarbonyl groups, carbamoyl groups, sulfamoyl groups, aliphatic sulfonamido groups, An arylsulfonamide group, an amino group, an aliphatic amino group, an arylamino group, a hydroxy group, a cyano group, a sulfo group, a carboxyl group, and the like.

R ^{a6 to} R ^a10 , R ^{a11 to} R ^a14 , R ^{a15 to} R ^a17 , R ^{a45 to} R ^a47 , two adjacent ^groups , R ^a19 and R ^a20 , R ^a21 and R ^a22 , R ^a23 and R ^a24 , R ^a29 and R ^a30, R ^a31 and R ^a32, R ^a33 and R ^a34, R ^a35 and R ^a36, R ^a38 and R ^a39, R ^a42 and R ^a43 is as far as possible, hydrocarbon ring bonded 5- to 7-membered ring; A heterocycle may be formed. Q ^{a1 to} Q ^a3 represent a nonmetallic atom group necessary for forming a 5- to 7-membered ring with the nitrogen atom.

In view of the effect of the present invention, R ^a6 and R ^a8 , R ^a11 and R ^a13 , R ^a15 and R ^a17 and R ^a18 , R ^a19 and R ^a22 , R ^a24 and R ^a25 , R ^a26 and R ^a27 and R ^a28 At least one of each is preferably a hydroxy group, an amino group, a substituted amino group or an arylamino group, and more preferably a substituted amino group. In view of the effects of the present invention, R ^a31 is preferably an aliphatic group or an aromatic group, and more preferably an aliphatic group. In view of the effects of the present invention, R ^a32 is preferably a hydroxy group, R ^a39 is preferably a hydroxy group or an amino group which may be substituted, and R ^a39 is further an amino group which may be substituted. preferable. Of the above formulas, (A-1), (A-3), (A-6), and (A-7) are preferred in terms of the effects of the present invention, and (A-3), (A The case of −6) is more preferable.

In the general formula (T1), the diazo component residue represented by B is a residue of B—NH ₂ . B in this B—NH ₂ represents an aryl group, a heterocyclic group, etc., preferably a 5-membered heterocyclic group, and examples of preferable 5-membered heterocyclic groups include pyrazoles, imidazoles, 1, Examples include 2,4-triazoles, 1,2,3-triazoles, thiazoles, isothiazoles, benzoisothiazoles, thiadiazoles, benzothiazoles, and benzoxazoles. Each heterocyclic ring may further have a substituent, or may be condensed with another aliphatic ring, aromatic ring, or heterocyclic ring. Especially, the case where it represents with following formula (B-1)-(B-7) is preferable.

R ^{b7 to} R ^b23 in the formulas (B-1) to (B-7) represent a hydrogen atom or a substituent, and the substituent here is the group described in the description of the substituent. The preferred substituents are aliphatic groups, aryl groups, heterocyclic groups, acyl groups, imide groups, acylamino groups, aliphatic oxy groups, aliphatic oxycarbonyl groups, carbamoyl groups, A sulfamoyl group, an aliphatic sulfonamido group, an arylsulfonamido group, an amino group, an aliphatic amino group, an arylamino group, a hydroxy group, a cyano group, a sulfo group, a carboxyl group, and the like.

R ^b7 and R ^b8 , R ^b10 and R ^b11 , R ^b14 and R ^b15 , R ^b15 and R ^b16 , R ^b16 and R ^b17 , R ^b18 and R ^b19 , R ^b19 and R ^b20 , R ^b21 and R ^b22 , R ^b22 And R ^b23 may combine with each other to form a 5- to 7-membered hydrocarbon ring or heterocyclic ring as much as possible. From the standpoint of the effects of the present invention, the case of formulas (B-1), (B-2), and (B-7) is preferred, and the case of formulas (B-1) and (B-7) is more preferred. .

  In terms of the effects of the present invention, the general formula (T1) is such that when A is the formula (A-3) and B is the formula (B-1) or (B-7), The case where it is Formula (A-6) and B is the Formula (B-1) or (B-7) is preferable.

  Preferable tetraazaporphyrin-based dyes include compounds represented by the following general formula (T2).

In the general formula (T2), M represents two hydrogen atoms or metals, which are Zn, Mg, Si, Sn, Rh, Pt, Pd, Mo, Mn, Pb, Cu, In addition to Ni, Co, Fe and the like, metal chlorides such as AlCl, InCl, FeCl, TiCl ₂ , SnCl ₂ , SiCl ₂ and GeCl ₂ , metal oxides such as TiO and VO, metals such as Si (OH) ₂ Hydroxides are also included.

In the general formula (T2), Z ¹ , Z ² , Z ³ , and Z ⁴ are each independently an atom necessary for forming a 6-membered ring composed of atoms selected from a carbon atom and a nitrogen atom. Represents a group.
The 6-membered ring represented by Z ¹ , Z ² , Z ³ , or Z ⁴ may be a saturated ring or an unsaturated ring, and may be unsubstituted or substituted. Also good. Furthermore, other 5-membered or 6-membered rings may be condensed.

The substituent of the 6-membered ring represented by Z ¹ , Z ² , Z ³ , or Z ⁴ may be any substitutable group described in the above-mentioned substituent group, and includes, for example, a halogen atom, Alkyl group, alkenyl group, aryl group, heterocyclic group, silyl group, hydroxyl group, cyano group, nitro group, alkoxy group, cycloalkyloxy group, aryloxy group, heterocyclic oxy group, silyloxy group, acyloxy group, alkoxy Carbonyloxy group, aryloxycarbonyloxy group, carbamoyloxy group, sulfamoyloxy group, alkylsulfonyloxy group, arylsulfonyloxy group, acyl group, alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, amino group, anilino group , Heterocyclic amino group, carbonamido group, ureido group, imide group, Coxycarbonylamino group, aryloxycarbonylamino group, sulfonamido group, sulfamoylamino group, azo group, alkylthio group, arylthio group, heterocyclic thio group, sulfinyl group, arylsulfinyl group, alkylsulfonyl group, arylsulfonyl group , Sulfamoyl group, sulfo group, phosphonyl group, phosphinoylamino group and the like.
When Z ¹ , Z ² , Z ³ , Z ⁴ in the general formula (T2) have two or more substituents, these substituents may be the same or different.

  The tetraazaporphyrin-based dye represented by the general formula (T2) is preferably represented by the following general formula (T2-1).

Z ^C1 , Z ^C2 , Z ^C3 and Z ^C4 represent a nonmetallic atom group necessary for forming a 6-membered ring together with the carbon atom, and R ^C1 , R ^C2 , R ^C3 and R ^C4 are the substituents described above. Any substitutable group described in the above section may be used. For example, halogen atom, aliphatic group, aryl group, heterocyclic group, carbamoyl group, aliphatic oxycarbonyl group, aryloxycarbonyl group, acyl group, aliphatic oxy group, aryloxy group, acyloxy group, carbamoyloxy group, hetero Ring oxy group, aliphatic oxycarbonyloxy group, acylamino group, carbamoylamino group, sulfamoylamino group, aliphatic oxycarbonylamino group, aryloxycarbonylamino group, aliphatic sulfonylamino group, arylsulfonylamino group, aliphatic A thio group, an arylthio group, an aliphatic sulfonyl group, an arylsulfonyl group, a sulfamoyl group, an imide group, a heterocyclic thio group and the like are represented.

Examples of M include VO, TiO, Zn, Mg, Si, Sn, Rh, Pt, Pd, Mo, Mn, Pb, Cu, Ni, Co, Fe, AlCl, InCl, FeCl, TiCl ₂ , SnCl ₂ , It represents an _{SiCl 2, GeCl 2, Si (} OH) 2, H 2 or the like.
cn ₁ , cn ₂ , cn ₃ and cn ₄ each independently represents a substitutable integer of 0 to 3 (preferably 0 or 1), and cn ₁ , cn ₂ , cn ₃ and cn ₄ are plural. In some cases, a plurality of R ^C1 , R ^C2 , R ^C3 and R ^C4 may be the same or different. cr1, cr2, cr3 and cr4 represent 0 or 1, and satisfy cr1 + cr2 + cr3 + cr4 ≧ 1. cm1, cm2, cm3, and cm4 represent an integer of 0 to 2 (preferably 0 or 2).

Z ^C1 , Z ^C2 , Z ^C3 , and Z ^C4 each independently represent a nonmetallic atom group necessary for forming a 6-membered ring with a carbon atom, and may be an aromatic ring or a heterocyclic ring. May be condensed, and the condensed ring may have a substituent, for example, a phenyl ring, a pyridine ring, a cyclohexene ring, or a naphthalene ring.

Examples of the halogen atom represented by R ^C1 , R ^C2 , R ^C3 , or R ^C4 include fluorine, chlorine, and bromine.
The aliphatic group represented by R ^C1 , R ^C2 , R ^C3 , or R ^C4 may be unsubstituted or substituted, and may be saturated or unsaturated. It may be cyclic and preferably has 1 to 15 carbon atoms in total, and examples thereof include a methyl group, an ethyl group, a vinyl group, an allyl group, an ethynyl group, an isopropenyl group, and a 2-ethylhexyl group.

The aryl group represented by R ^C1 , R ^C2 , R ^C3 , or R ^C4 may be unsubstituted or substituted, and is preferably an aryl group having 6 to 16 carbon atoms in total. An aryl group of ˜12 is more preferred. For example, phenyl group, 4-nitrophenyl group, 2-nitrophenyl group, 2-chlorophenyl group, 2,4-dichlorophenyl group, 2,4-dimethylphenyl group, 2-methylphenyl group, 4-methoxyphenyl group, 2 -Methoxyphenyl group, 2-methoxycarbonyl-4-nitrophenyl group and the like.

The heterocyclic group represented by R ^C1 , R ^C2 , R ^C3 , or R ^C4 may be saturated or unsaturated, and is preferably a heterocyclic group having 1 to 15 carbon atoms in total. A heterocyclic group having 3 to 10 carbon atoms in total is more preferable. For example, 3-pyridyl group, 2-pyridyl group, 2-pyrimidinyl group, 2-pyrazinyl group, 1-piperidyl group and the like can be mentioned. Furthermore, you may have a substituent.

The carbamoyl group represented by R ^C1 , R ^C2 , R ^C3 , or R ^C4 may be unsubstituted or substituted, and is preferably a carbamoyl group having 1 to 16 carbon atoms in total. A carbamoyl group of ˜12 is more preferred. For example, a carbamoyl group, a dimethylcarbamoyl group, a dimethoxyethylcarbamoyl group, etc. are mentioned.

The aliphatic oxycarbonyl group represented by R ^C1 , R ^C2 , R ^C3 , or R ^C4 may be unsubstituted or substituted, may be saturated or unsaturated, It may be cyclic and is preferably an aliphatic oxycarbonyl group having 2 to 16 carbon atoms, more preferably an aliphatic oxycarbonyl group having 2 to 10 carbon atoms. Examples thereof include a methoxycarbonyl group and a butoxycarbonyl group.

The aryloxycarbonyl group represented by R ^C1 , R ^C2 , R ^C3 , or R ^C4 may be unsubstituted or substituted and may be an aryloxycarbonyl group having 7 to 17 carbon atoms in total. Is preferable, and an aliphatic oxycarbonyl group having 2 to 10 carbon atoms is more preferable. For example, a phenoxycarbonyl group, 4-methylphenoxycarbonyl group, etc. are mentioned.

The acyl group represented by R ^C1 , R ^C2 , R ^C3 , or R ^C4 may be aromatic or aliphatic, may be saturated or unsaturated, may be cyclic, An acyl group having 2 to 15 carbon atoms is preferred, and an acyl group having 2 to 10 carbon atoms is more preferred. For example, acetyl group, pivaloyl group, benzoyl group and the like can be mentioned. Furthermore, you may have a substituent.

The aliphatic oxy group represented by R ^C1 , R ^C2 , R ^C3 , or R ^C4 may be unsubstituted or substituted, and is preferably an aliphatic oxy group having 1 to 12 carbon atoms in total. An aliphatic oxy group having 1 to 10 carbon atoms is more preferable. For example, a methoxy group, an ethoxyethoxy group, a phenoxyethoxy group, a thiophenoxyethoxy group, and the like can be given.

The aryloxy group represented by R ^C1 , R ^C2 , R ^C3 , or R ^C4 may be unsubstituted or substituted, and is preferably an aryloxy group having 6 to 18 carbon atoms in total. An aryloxy group having 6 to 14 carbon atoms in total is more preferable. For example, a phenoxy group, 4-methylphenoxy group, etc. are mentioned.

The acyloxy group represented by R ^C1 , R ^C2 , R ^C3 , or R ^C4 may be unsubstituted or substituted, and is preferably an acyloxy group having 2 to 14 carbon atoms in total. An acyloxy group having 2 to 10 carbon atoms is more preferable. Examples include an acetoxy group, a methoxyacetoxy group, and a benzoyloxy group.

The carbamoyloxy group represented by R ^C1 , R ^C2 , R ^C3 , or R ^C4 may be unsubstituted or substituted, and is preferably a carbamoyloxy group having 1 to 16 carbon atoms in total. A carbamoyloxy group having 1 to 12 carbon atoms is more preferred. Examples thereof include a dimethylcarbamoyloxy group and a diisopropylpropylcarbamoyl group.

The heterocyclic oxy group represented by R ^C1 , R ^C2 , R ^C3 , or R ^C4 may be unsubstituted or substituted and may be a heterocyclic oxy group having 1 to 15 carbon atoms in total. Is preferable, and a heterocyclic oxy group having 3 to 10 carbon atoms is more preferable. For example, 3-furyloxy group, 3-pyridyloxy group, N-methyl 2-piperidyloxy group and the like can be mentioned.

The aliphatic oxycarbonyloxy group represented by R ^C1 , R ^C2 , R ^C3 , or R ^C4 may be unsubstituted or substituted, may be saturated or unsaturated, and is cyclic. The aliphatic oxycarbonyloxy group having 2 to 16 carbon atoms is preferable, and the aliphatic oxycarbonyloxy group having 2 to 10 carbon atoms is more preferable. Examples thereof include a methoxycarbonyloxy group and (t) butoxycarbonyloxy group.

The acylamino group represented by R ^C1 , R ^C2 , R ^C3 , or R ^C4 may be unsubstituted or substituted, and is preferably an acylamino group having 2 to 15 carbon atoms in total. An acylamino group having 2 to 12 carbon atoms is more preferable. Examples thereof include an acetylamino group, a benzoylamino group, and an N-methylmethoxyacetylamino group.

The carbamoylamino group represented by R ^C1 , R ^C2 , R ^C3 or R ^C4 may be unsubstituted or substituted, and preferably has 1 to 16 carbon atoms in total. 1-12 carbamoylamino groups are more preferred. Examples thereof include an N, N-dimethylcarbamoylamino group and an N-methyl-N-methoxyethylcarbamoylamino group.

The sulfamoylamino group represented by R ^C1 , R ^C2 , R ^C3 , or R ^C4 may be unsubstituted or substituted, and may be a sulfamoylamino group having 0 to 16 carbon atoms in total. It is preferable that a sulfamoylamino group having 0 to 12 carbon atoms is more preferable. Examples thereof include an N, N-dimethylsulfamoylamino group and an N, N-diethylsulfamoylamino group.

The aliphatic oxycarbonylamino group represented by R ^C1 , R ^C2 , R ^C3 , or R ^C4 may be unsubstituted or substituted, and the aliphatic oxycarbonylamino group having 2 to 15 carbon atoms in total. Is preferably an aliphatic oxycarbonylamino group having 2 to 10 carbon atoms in total. For example, a methoxycarbonylamino group, a methoxyethoxycarbonylamino group, etc. are mentioned.

The aryloxycarbonylamino group represented by R ^C1 , R ^C2 , R ^C3 , or R ^C4 may be unsubstituted or substituted, and may be an aryloxycarbonylamino group having 7 to 17 carbon atoms in total. It is preferable that an aryloxycarbonylamino group having a total carbon number of 7 to 15 is more preferable. Examples thereof include a phenoxycarbonylamino group and a 4-methoxycarbonylamino group.

The aliphatic sulfonylamino group represented by R ^C1 , R ^C2 , R ^C3 , or R ^C4 may be unsubstituted or substituted, may be saturated or unsaturated, It may be cyclic and is preferably an aliphatic sulfonylamino group having 1 to 12 carbon atoms, more preferably an aliphatic sulfonylamino group having 1 to 8 carbon atoms. Examples thereof include a methanesulfonylamino group and a butanesulfonylamino group.

The arylsulfonylamino group represented by R ^C1 , R ^C2 , R ^C3 or R ^C4 may be unsubstituted or substituted, and is an arylsulfonylamino group having 6 to 15 carbon atoms in total. Are preferred, and arylsulfonylamino groups having 6 to 12 carbon atoms in total are more preferred. Examples thereof include a benzenesulfonylamino group and a 4-toluenesulfonylamino group.

The aliphatic thio group represented by R ^C1 , R ^C2 , R ^C3 , or R ^C4 may be unsubstituted or substituted, may be saturated or unsaturated, and may be cyclic. The aliphatic thio group having 1 to 16 carbon atoms is preferable, and the aliphatic thio group having 1 to 10 carbon atoms is more preferable. Examples thereof include a methylthio group, an ethylthio group, and an ethoxyethylthio group.

The arylthio group represented by R ^C1 , R ^C2 , R ^C3 or R ^C4 may be unsubstituted or substituted, and is preferably an arylthio group having 6 to 22 carbon atoms in total. The arylthio group of several 6-14 is more preferable. For example, a phenylthio group, 2-t-butylthio group, etc. are mentioned.

The aliphatic sulfonyl group represented by R ^C1 , R ^C2 , R ^C3 , or R ^C4 may be unsubstituted or substituted, may be saturated or unsaturated, and may be cyclic. It is preferable that it is a C1-C15 aliphatic sulfonyl group, and a C1-C8 aliphatic sulfonyl group is more preferable. For example, a methanesulfonyl group, a butanesulfonyl group, a methoxyethanesulfonyl group, and the like can be given.

The arylsulfonyl group represented by R ^C1 , R ^C2 , R ^C3 , or R ^C4 may be unsubstituted or substituted, and is preferably an arylsulfonyl group having 6 to 16 carbon atoms in total. An arylsulfonyl group having 6 to 12 carbon atoms in total is more preferable. Examples thereof include a benzenesulfonyl group, a 4-tbutylbenzenesulfonyl group, a 4-toluenesulfonyl group, and a 2-toluenesulfonyl group.

The sulfamoyl group represented by R ^C1 , R ^C2 , R ^C3 , or R ^C4 may be unsubstituted or substituted, and is preferably a sulfamoyl group having 0 to 16 carbon atoms in total. A sulfamoyl group having 0 to 12 carbon atoms is more preferable. For example, a sulfamoyl group, a dimethylsulfamoyl group, etc. are mentioned.

The imide group represented by R ^C1 , R ^C2 , R ^C3 , or R ^C4 may be further condensed, and is preferably an imide group having 3 to 22 carbon atoms in total, and 3 to 3 carbon atoms in total. 15 imide groups are more preferred. For example, a succinimide group, a phthalimide group, and the like can be given.

The heterocyclic thio group represented by R ^C1 , R ^C2 , R ^C3 , or R ^C4 may be unsubstituted or substituted, and is a 5- to 7-membered ring having a total number of carbon atoms of 1 to 20 heterocyclic thio groups are preferable, and heterocyclic thio groups having 1 to 12 carbon atoms in total are preferable. For example, 3-furylthio group, 3-pyridylthio group and the like can be mentioned.

In view of the effect of the present invention, R ^C1 , R ^C2 , R ^C3 , and R ^C4 are each a halogen atom, an aliphatic group, a carbamoyl group, an aliphatic oxycarbonyl group, an aryloxycarbonyl group, an aliphatic oxy group, or an acyloxy group. Carbamoyloxy group, acylamino group, aliphatic sulfonylamino group, arylsulfonylamino group, aliphatic thio group, arylthio group, sulfamoyl group, preferably carbamoyl group, aliphatic oxycarbonyl group, aliphatic oxy group, acylamino More preferred is a group, an aliphatic sulfonylamino group, an arylsulfonylamino group, or a sulfamoyl group.

As M, the aspect which is VO, Zn, Mn, Cu, Ni, Co is preferable.
Further, an embodiment in which cr1 + cr2 + cr3 + cr4 is 3 or 4 is preferable, and an embodiment in which cr1 + cr2 + cr3 + cr4 is 4 is particularly preferable.

In terms of the effect of the present invention, the general formulas (T2) and (T2-1) are preferably the following general formula (T2-2).

In the general formula (T2-2), R ^C1 , R ^C2 , R ^C3 , R ^C4 , M, cn1, cn2, cn3, cn4, cm1, cm2, cm3, and cm4 represent the general formula (T2) and It is synonymous with what was defined by (T2-1), and R ^C5 , R ^C6 , R ^C7 and R ^C8 represent a hydrogen atom or a substituent.

  The substituent may be any group that can be substituted with the group described in the above-mentioned substituent group, and is preferably a halogen atom, aliphatic group, aryl group, heterocyclic group, carbamoyl group, aliphatic oxycarbonyl. Group, aryloxycarbonyl group, acyl group, aliphatic oxy group, aryloxy group, acyloxy group, carbamoyloxy group, heterocyclic oxy group, aliphatic oxycarbonyloxy group, acylamino group, carbamoylamino group, sulfamoylamino group , Aliphatic oxycarbonylamino group, aryloxycarbonylamino group, aliphatic sulfonylamino group, arylsulfonylamino group, aliphatic thio group, arylthio group, aliphatic sulfonyl group, arylsulfonyl group, sulfamoyl group, imide group, heterocyclic ring Represents a thio group.

In view of the effects of the present invention, R ^C5 , R ^C6 , R ^C7 and R ^C8 are preferably hydrogen atoms.
In terms of the effect of the present invention, in the general formula (T), R ¹ is a dye residue, and R ² is an aliphatic group, an aryl group, a heterocyclic group, an aliphatic amino group, an arylamino group, a heterogeneous group. When it is a cyclic amino group or the like, it is preferable that R ² is a pigment residue and R ¹ is an aliphatic group, an aryl group, a heterocyclic group, an aliphatic amino group, an arylamino group, or a heterocyclic amino group. .

In terms of the effect of the present invention, the general formula (T) is such that the dye residue of R ¹ is the general formula (T1), (T2), (T2-1), or (T2-2), More preferably, R ² is an aliphatic group, an aryl group, an aliphatic amino group, or an arylamino group, and the dye residue of R ¹ is represented by the general formula (T2), (T2-1), or (T2-2). And R ² is more preferably an aliphatic group, an aryl group, an aliphatic amino group, or an arylamino group, and the dye residue of R ¹ is represented by the general formula (T2), (T2-1), Or (T2-2), and R ² is more preferably an aliphatic group or an aryl group, and the dye residue of R ¹ is the general formula (T2-2), and R ² is aliphatic. Most preferred when it is a group.

  Hereinafter, specific examples (Exemplary compounds M-1 to M-25, Exemplified compounds Y-1 to Y-25, Exemplified compounds C-1 to C-39) of the dye compound represented by the general formula (T) are shown. . However, the present invention is not limited to the following examples.

  The compound of the present invention can be dyed by the method described in the review synthetic dye "Horiguchi Hiroshi, Sankyo Publishing Co., Ltd., 1968" or the method described in the literature. The introduction of the sulfonylcarbamoyl group can be synthesized by heating and refluxing a carboxylic acid chloride compound and a sulfonamide compound in toluene.

  The total concentration of the dye according to the present invention in the colored curable composition varies depending on the molecular weight and the molar extinction coefficient, but is preferably 0.5 to 80% by mass based on the total solid components of the composition. -60% by mass is more preferred, and 0.5-50% by mass is particularly preferred.

  The dye represented by the general formula (T) according to the present invention is a color filter for recording and reproducing a color image, which is used for a solid-state imaging device such as a CCD or CMOS, or a display such as an LCD or PDP. Or it can utilize suitably for the colored curable composition for producing these color filters.

  The color filter of the present invention can be produced by any method as long as it is an embodiment configured using at least one of the dyes according to the present invention, that is, the compound represented by the general formula (T). A colored curable composition containing the dye according to the present invention is prepared, the prepared colored curable composition is applied to a support, exposed as a mask, developed, and uncured in the case of a negative type, for example. The present invention is preferably performed by performing a step of forming a pattern image by removing a portion (unexposed portion) (repeating a desired number of hues constituting a color filter so as to obtain a desired hue as necessary). The color filter can be manufactured. Details will be described later.

-Binder-
The colored curable composition of the present invention can contain at least one binder. Although it will not specifically limit if it is alkali-soluble as a binder based on this invention, It is preferable to select from viewpoints, such as heat resistance, developability, and availability.

  The alkali-soluble binder is preferably a linear organic polymer, soluble in an organic solvent, and developable with a weak alkaline aqueous solution. Examples of such linear organic high molecular polymers include polymers having a carboxylic acid in the side chain, such as JP-A-59-44615, JP-B-54-34327, JP-B-58-12577, and JP-B-54-. Methacrylic acid copolymer, acrylic acid copolymer, itaconic acid copolymer, crotonic acid as described in the specifications of No. 25957, JP-A-59-53836, JP-A-59-71048, etc. There are a copolymer, a maleic acid copolymer, a partially esterified maleic acid copolymer, and the like. Similarly, an acidic cellulose derivative having a carboxylic acid in the side chain is useful. In addition to this, an acid anhydride added to a polymer having a hydroxyl group, a polyhydroxystyrene resin, a polysiloxane resin, poly (2-hydroxyethyl (meth) acrylate), polyvinylpyrrolidone, polyethylene oxide, polyvinyl alcohol, etc. Is also useful.

In addition, a monomer having a hydrophilic group may be copolymerized, and examples thereof include alkoxyalkyl (meth) acrylate, hydroxyalkyl (meth) acrylate, glycerol (meth) acrylate, (meth) acrylamide, and N-methylolacrylamide. Secondary and tertiary alkyl acrylamide, dialkylaminoalkyl (meth) acrylate, morpholino (meth) acrylate, N-vinylpyrrolidone, N-vinylcaprolactam, vinylimidazole, vinyltriazole, methyl (meth) acrylate, ethyl (meth) Examples include acrylate, branched or linear propyl (meth) acrylate, branched or linear butyl (meth) acrylate, phenoxyhydroxypropyl (meth) acrylate, and the like.
In addition to the above, the monomer having a hydrophilic group includes a tetrahydrofurfuryl group, a phosphoric acid site, a phosphate ester site, a quaternary ammonium salt site, an ethyleneoxy chain, a propyleneoxy chain, a sulfonic acid or its salt site, a morpholinylethyl group, etc. Also useful are monomers containing.

Further, from the viewpoint of improving the crosslinking efficiency, a polymer having a polymerizable group in the side chain, a polymer containing an allyl group, a (meth) acryl group, an allyloxyalkyl group or the like in the side chain is also useful. .
Examples of the polymer having these polymerizable groups include KS resist-106 (manufactured by Osaka Organic Chemical Industry Co., Ltd.), cyclomer P series (manufactured by Daicel Chemical Industries, Ltd.) and the like.
In addition, 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.

  Of the various binders described above, from the viewpoint of heat resistance, polyhydroxystyrene resins, polysiloxane resins, acrylic resins, acrylamide resins, and acryl / acrylamide copolymer resins are preferable, and from the viewpoint of development control. An acrylic resin, an acrylamide resin, and an acrylic / acrylamide copolymer resin are preferable. Examples of the acrylic resin include a copolymer composed of monomers selected from benzyl (meth) acrylate, (meth) acryl, hydroxyethyl (meth) acrylate, (meth) acrylamide, and the like, and KS-resist-106 (Osaka Organic Chemical). Industrial Co., Ltd.) and Cyclomer P-series (Daicel Chemical Industries, Ltd.) are preferred.

  Moreover, an alkali-soluble phenol resin can also be used as a binder. The alkali-soluble phenol resin can be suitably used when the colored curable composition of the present invention is configured as a positive type, and examples thereof include novolak resins and vinyl polymers.

  Examples of the novolak resin include those obtained by condensing phenols and aldehydes in the presence of an acid catalyst. Examples of phenols include phenol, cresol, ethylphenol, butylphenol, xylenol, phenylphenol, catechol, resorcinol, pyrogallol, naphthol, and bisphenol A. Phenols can be used alone or in combination of two or more. Examples of aldehydes include formaldehyde, paraformaldehyde, acetaldehyde, propionaldehyde, or benzaldehyde.

  Specific examples of the novolak resin include a condensation product of metacresol, paracresol or a mixture thereof and formalin. The novolak resin may be adjusted in molecular weight distribution using means such as fractionation. Moreover, you may mix the low molecular weight component which has bisphenol C or bisphenol A, and Uno phenolic hydroxyl group in the said novolak resin.

The binder preferably has a mass average molecular weight (polystyrene equivalent value measured by GPC method) of 1000 to 2 × 10 ⁵ , more preferably 2000 to 1 × 10 ⁵ , and 5000 to ⁵ × 10 ⁴ . Polymers are particularly preferred.

  As content in the colored curable composition of this invention of a binder, 10-90 mass% is preferable with respect to the total solid in this composition, and 20-80 mass% is still more preferable. 30-70 mass% is especially preferable.

-Crosslinking agent-
Including the dye according to the present invention described above, the curing reaction of the film proceeds to a higher degree than before, and a film having good curability can be obtained. It is also possible to obtain a highly cured film. This is useful from the viewpoint of achieving high resolution of the colored curable composition of the present invention.

  The crosslinking agent that can be used in the present invention is not particularly limited as long as the film can be cured by a crosslinking reaction. For example, (a) an epoxy resin, (b) a methylol group, an alkoxymethyl group, and an acyloxymethyl group. Substituted with at least one group selected from melamine compound, guanamine compound, glycoluril compound, or urea compound substituted with at least one group selected from: (c) methylol group, alkoxymethyl group, and acyloxymethyl group Phenolic compounds, naphthol compounds or hydroxyanthracene compounds. Of these, polyfunctional epoxy resins are particularly preferred.

  The (a) epoxy resin may be any epoxy resin having an epoxy group and crosslinkability. For example, bisphenol A-glycidyl ether, ethylene glycol diglycidyl ether, ethylene glycol diglycidyl ether, butanediol Divalent glycidyl group-containing low molecular weight compounds such as diglycidyl ether, hexanediol diglycidyl ether, dihydroxybiphenyl diglycidyl ether, diglycidyl phthalate, and N, N-diglycidylaniline, as well as trimethylolpropane triglycidyl Trivalent glycidyl group-containing low molecular weight compounds represented by ether, trimethylolphenol triglycidyl ether, TrisP-PA triglycidyl ether, etc., as well as pentaerythritol tetraglycol Tetravalent glycidyl group-containing low molecular weight compounds typified by dil ether, tetramethylol bisphenol-A-tetraglycidyl ether and the like, as well as polyvalent glycidyl groups such as dipentaerythritol pentaglycidyl ether and dipentaerythritol hexaglycidyl ether Low molecular weight compounds, polyglycidyl (meth) acrylate, 2,2-bis (hydroxymethyl) -1-butanol 1,2-epoxy-4- (2-oxiranyl) cyclohexane adducts and the like containing glycidyl groups Examples thereof include molecular compounds.

  The number of methylol groups, alkoxymethyl groups, and acyloxymethyl groups substituted in the crosslinking agent (b) is 2 to 6 for melamine compounds, 2 for glycoluril compounds, guanamine compounds, and urea compounds. Although it is -4, Preferably it is 5-6 in the case of a melamine compound, and is 3-4 in the case of a glycoluril compound, a guanamine compound, and a urea compound.

  Hereinafter, the melamine compound, guanamine compound, glycoluril compound and urea compound of (b) are collectively referred to as a compound according to (b) (methylol group-containing compound, alkoxymethyl group-containing compound, or acyloxymethyl group-containing compound). There is.

The methylol group-containing compound according to (b) can be obtained by heating the alkoxymethyl group-containing compound according to (b) in an alcohol in the presence of an acid catalyst such as hydrochloric acid, sulfuric acid, nitric acid, methanesulfonic acid or the like.
The acyloxymethyl group-containing compound according to (b) can be obtained by mixing and stirring the methylol group-containing compound according to (b) with an acyl chloride in the presence of a basic catalyst.

Hereinafter, specific examples of the compound according to (b) having the substituent will be given.
Examples of the melamine compound include hexamethylol melamine, hexamethoxymethyl melamine, a compound in which 1 to 5 methylol groups of hexamethylol melamine are methoxymethylated, or a mixture thereof, hexamethoxyethyl melamine, hexaacyloxymethyl melamine, hexamethylol. Examples thereof include compounds in which 1 to 5 methylol groups of melamine are acyloxymethylated, or mixtures thereof.

  Examples of the guanamine compound include tetramethylol guanamine, tetramethoxymethyl guanamine, a compound obtained by methoxymethylating 1 to 3 methylol groups of tetramethylol guanamine or a mixture thereof, tetramethoxyethyl guanamine, tetraacyloxymethyl guanamine, tetramethylol. Examples thereof include compounds in which 1 to 3 methylol groups of guanamine are acyloxymethylated or a mixture thereof.

  Examples of the glycoluril compound include tetramethylol glycoluril, tetramethoxymethylglycoluril, a compound obtained by methoxymethylating 1 to 3 methylol groups of tetramethylolglycoluril, or a mixture thereof, or a methylol group of tetramethylolglycoluril. Examples thereof include compounds in which 1 to 3 are acyloxymethylated or a mixture thereof.

  Examples of the urea compound include tetramethylol urea, tetramethoxymethyl urea, a compound obtained by methoxymethylating 1 to 3 methylol groups of tetramethylol urea, a mixture thereof, and tetramethoxyethyl urea. The compounds according to (b) may be used alone or in combination.

  The crosslinking agent (c), that is, a phenol compound, a naphthol compound or a hydroxyanthracene compound substituted with at least one group selected from a methylol group, an alkoxymethyl group, and an acyloxymethyl group is a component of the crosslinking agent (b). As in the case, intermixing with the overcoated photoresist is suppressed by thermal crosslinking, and the film strength is further increased.

  Hereinafter, these compounds may be collectively referred to as a compound according to (c) (a methylol group-containing compound, an alkoxymethyl group-containing compound, or an acyloxymethyl compound).

  The number of methylol groups, acyloxymethyl groups or alkoxymethyl groups contained in the crosslinker (c) component is at least 2 per molecule, and from the viewpoint of thermal crosslinkability and storage stability, A compound in which all of the 2- and 4-positions are substituted is preferred. In addition, the naphthol compound and hydroxyanthracene compound as the skeleton are preferably compounds in which all of the ortho-position and para-position of the OH group are substituted.

  The 3-position or 5-position of the phenolic compound that serves as the skeleton may be unsubstituted or may have a substituent. Also in the naphthol compound, other than the ortho position of the OH group may be unsubstituted or may have a substituent.

The methylol group-containing compound according to (c) is a compound in which the ortho-position or para-position (2-position or 4-position) of the phenolic OH group is a hydrogen atom, and this is used as sodium hydroxide, potassium hydroxide, It can be obtained by reacting with formalin in the presence of a basic catalyst such as ammonia or tetraalkylammonium hydroxide.
The alkoxymethyl group-containing compound according to (c) can be obtained by heating the methylol group-containing compound according to (c) in an alcohol in the presence of an acid catalyst such as hydrochloric acid, sulfuric acid, nitric acid, methanesulfonic acid or the like.
The acyloxymethyl group-containing compound according to (c) can be obtained by reacting the methylol group-containing compound according to (c) with an acyl chloride in the presence of a basic catalyst.

  Examples of the skeletal compound in the crosslinking agent (c) include phenol compounds in which the ortho-position or para-position of the phenolic OH group are unsubstituted, naphthol, hydroxyanthracene compounds, and the like. For example, phenol, cresol isomers, 2 , 3-xylenol, 2,5-xylenol, 3,4-xylenol, 3,5-xylenol, bisphenols such as bisphenol-A, 4,4_-bishydroxybiphenyl, TrisP-PA (Honshu Chemical Industry) Naphthol, dihydroxynaphthalene, 2,7-dihydroxyanthracene, etc. are used.

  Specific examples of the crosslinking agent (c) include trimethylolphenol, tri (methoxymethyl) phenol, a compound obtained by methoxymethylating one or two methylol groups of trimethylolphenol, trimethylol-3-cresol, tri ( Methoxymethyl) -3-cresol, a compound obtained by methoxymethylating one or two methylol groups of trimethylol-3-cresol, dimethylolcresol such as 2,6-dimethylol-4-cresol, tetramethylolbisphenol-A, Tetramethoxymethyl bisphenol-A, a compound obtained by methoxymethylating 1 to 3 methylol groups of tetramethylol bisphenol-A, tetramethylol-4,4-bishydroxybiphenyl, tetramethoxymethyl-4,4-bishydroxybiphenyl, T Hexamethylol of ISP-PA, hexamethoxymethyl of Tris P-PA, compounds in which 1 to 5 methylol groups have been methoxymethylated hexamethylol of Tris P-PA, there is bishydroxymethyl naphthalene diol.

Examples of the hydroxyanthracene compound include 1,6-dihydroxymethyl-2,7-dihydroxyanthracene.
Examples of the acyloxymethyl group-containing compound include compounds in which the methylol group of the methylol group-containing compound is partially or fully acyloxymethylated.

  Among these compounds, trimethylol phenol, bishydroxymethyl-p-cresol, tetramethylol bisphenol A, hexamethylol body of TrisP-PA (manufactured by Honshu Chemical Industry Co., Ltd.) or their methylol group is alkoxy. Mention may be made of phenolic compounds substituted with methyl and both methylol and alkoxymethyl groups. These compounds according to (c) may be used alone or in combination.

  When it contains a crosslinking agent in the present invention, the total content of the crosslinking agents (a) to (c) in the colored curable composition varies depending on the material, but is 1 to the solid content of the composition. 70 mass% is preferable, 5-50 mass% is more preferable, and 7-30 mass% is especially preferable.

-Polymerizable monomer-
The colored curable composition of this invention can be conveniently comprised using at least 1 sort (s) of a polymerizable monomer. The polymerizable monomer is mainly contained when the colored curable composition is configured as a negative type. In addition, it can also contain in the positive type | system | group containing the below-mentioned naphthoquinone diazide compound with the below-mentioned photoinitiator, and in this case, the hardening degree of the pattern formed can be promoted more.

  This polymerizable monomer is useful in that it can achieve high sensitivity and high resolution of the colored curable composition of the present invention by using it together with a photopolymerization initiator described later. Hereinafter, the polymerizable monomer will be described.

  As the polymerizable monomer, a compound having an ethylenically unsaturated group having a boiling point of 100 ° C. or higher under normal pressure is preferable. Examples thereof include polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, and phenoxyethyl. Monofunctional acrylates and methacrylates such as (meth) acrylate; polyethylene glycol di (meth) acrylate, trimethylolethane tri (meth) acrylate, neopentyl glycol di (meth) acrylate, pentaerythritol tri (meth) acrylate, penta Erythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, hexanediol (meth) acrylate, (Meth) acrylated after adding ethylene oxide or propylene oxide to polyfunctional alcohols such as dimethylolpropane tri (acryloyloxypropyl) ether, tri (acryloyloxyethyl) isocyanurate, glycerin and trimethylolethane, Urethane acrylates as described in JP-B-48-41708, JP-B-50-6034, JP-A-51-37193, JP-A-48-64183, JP-B-49-43191, Mention polyfunctional acrylates and methacrylates such as polyester acrylates and epoxy acrylates, which are reaction products of epoxy resin and (meth) acrylic acid, and mixtures thereof described in JP-B 52-30490 Can do.

  Furthermore, the Japan Adhesion Association Vol. 20, no. 7, pages 300 to 308 can be listed as photocurable monomers and oligomers.

  As content in the colored curable composition of a polymerizable monomer, 0.1-90 mass% is preferable with respect to solid content of this composition, 1.0-80 mass% is further more preferable, 2.0 -70 mass% is especially preferable.

-Radiosensitive compounds-
The colored curable composition of this invention can be comprised suitably using at least 1 sort (s) of a radiation sensitive compound. The radiation-sensitive compound according to the present invention is a compound that can cause a chemical reaction such as generation of a radical, generation of an acid, generation of a base with respect to radiation such as UV, Deep UV, visible light, infrared light, and electron beam. The coating film is alkali-developed by insolubilizing the above-mentioned alkali-soluble resin by reactions such as crosslinking, polymerization, decomposition of acidic groups, polymerization of polymerizable monomers and oligomers coexisting in the coating film, crosslinking of the crosslinking agent, etc. It is used for the purpose of making it insoluble in liquid.

  This radiation sensitive compound is useful from the viewpoint of achieving high sensitivity and high resolution of the colored curable composition of the present invention. When the colored curable composition is configured as a negative type, it contains a photopolymerization initiator, and when it is configured as a positive type, it contains a naphthoquinone diazide compound as an essential component.

<Photopolymerization initiator, etc.>
First, the photopolymerization initiator in the case of forming a negative type will be described.
The photopolymerization initiator is not particularly limited as long as it can cause the polymerization monomer (a monomer having a polymerizable group) to undergo a polymerization reaction, but is selected from the viewpoints of characteristics, initiation efficiency, absorption wavelength, availability, cost, and the like. It is preferable. In addition, you may further contain in the positive type | system | group containing a naphthoquinone diazide compound, In this case, the hardening degree of the pattern formed can be promoted more.

  The photopolymerization initiator includes at least one active halogen compound selected from a halomethyloxadiazole compound and a halomethyl-s-triazine compound, a 3-aryl-substituted coumarin compound, a lophine dimer, a benzophenone compound, and an acetophenone compound. And derivatives thereof, cyclopentadiene-benzene-iron complex and salts thereof, and oxime compounds.

  Examples of the active halogen compound which is the halomethyloxadiazole include 2-halomethyl-5-vinyl-1,3,4-oxadiazole compound described in JP-B-57-6096, 2-trichloromethyl- 5-styryl-1,3,4-oxadiazole, 2-trichloromethyl-5- (p-cyanostyryl) -1,3,4-oxadiazole, 2-trichloromethyl-5- (p-methoxystyryl) ) -1,3,4-oxadiazole and the like.

  Examples of the active halogen compound that is the halomethyl-s-triazine compound include vinyl-halomethyl-s-triazine compounds described in Japanese Patent Publication No. 59-1281 and 2- (naphtho) described in JP-A-53-133428. -1-yl) -4,6-bis-halomethyl-s-triazine compounds and 4- (p-aminophenyl) -2,6-di-halomethyl-s-triazine compounds.

  Other specific examples include 2,4-bis (trichloromethyl) -6-p-methoxystyryl-s-triazine, 2,6-bis (trichloromethyl) -4- (3,4-methylenedioxyphenyl)- 1,3,5-triazine, 2,6-bis (trichloromethyl) -4- (4-methoxyphenyl) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- (1- p-dimethylaminophenyl-1,3-butadienyl) -s-triazine, 2-trichloromethyl-4-amino-6-p-methoxystyryl-s-triazine, 2- (naphth-1-yl) -4,6 -Bis-trichloromethyl-s-triazine, 2- (4-methoxy-naphth-1-yl) -4,6-bis-trichloromethyl-s-triazine, 2- (4-ethoxy-naphth-1) Yl) -4,6-bis-trichloromethyl-s-triazine, 2- (4-butoxy-naphth-1-yl) -4,6-bis-trichloromethyl-s-triazine, 2- [4- (2 -Methoxyethyl) -naphth-1-yl] -4,6-bis-trichloromethyl-s-triazine, 2- [4- (2-ethoxyethyl) -naphth-1-yl] -4,6-bis- Trichloromethyl-s-triazine, 2- [4- (2-butoxyethyl) -naphth-1-yl] -4,6-bis-trichloromethyl-s-triazine, 2- (2-methoxy-naphth-1- Yl) -4,6-bis-trichloromethyl-s-triazine, 2- (6-methoxy-5-methyl-naphth-2-yl) -4,6-bis-trichloromethyl-s-triazine, 2- ( 6-methoxy-naphtho 2-yl) -4,6-bis-trichloromethyl-s-triazine, 2- (5-methoxy-naphth-1-yl) -4,6-bis-trichloromethyl-s-triazine, 2- (4 7-dimethoxy-naphth-1-yl) -4,6-bis-trichloromethyl-s-triazine, 2- (6-ethoxy-naphth-2-yl) -4,6-bis-trichloromethyl-s-triazine 2- (4,5-dimethoxy-naphth-1-yl) -4,6-bis-trichloromethyl-s-triazine, 4- [pN, N-di (ethoxycarbonylmethyl) aminophenyl] -2 , 6-Di (trichloromethyl) -s-triazine, 4- [o-methyl-pN, N-di (ethoxycarbonylmethyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4 -[PN, N-di (chloroethyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- [o-methyl-pN, N-di (chloroethyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- (p-N-chloroethylaminophenyl) -2,6-di (trichloromethyl) -s-triazine, 4- (pN-ethoxy) Carbonylmethylaminophenyl) -2,6-di (trichloromethyl) -s-triazine, 4- [pN, N-di (phenyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine 4- (pN-chloroethylcarbonylaminophenyl) -2,6-di (trichloromethyl) -s-triazine, 4- [pN- (p-methoxyphenyl) carbonylaminophenyl Nyl] 2,6-di (trichloromethyl) -s-triazine, 4- [m-N, N-di (ethoxycarbonylmethyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4 -[M-bromo-pN, N-di (ethoxycarbonylmethyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine,

4- [m-chloro-pN, N-di (ethoxycarbonylmethyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- [m-fluoro-pN, N- Di (ethoxycarbonylmethyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- [o-bromo-pN, N-di (ethoxycarbonylmethyl) aminophenyl] -2,6 -Di (trichloromethyl) -s-triazine, 4- [o-chloro-pN, N-di (ethoxycarbonylmethyl) aminophenyl-2,6-di (trichloromethyl) -s-triazine, 4- [ o-Fluoro-pN, N-di (ethoxycarbonylmethyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- [o-bromo-pN, N-di (chloro) Ethyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- [o-chloro-pN, N-di (chloroethyl) aminophenyl] -2,6-di (trichloromethyl) -S-triazine, 4- [o-fluoro-pN, N-di (chloroethyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- [m-bromo-pN , N-di (chloroethyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- [m-chloro-pN, N-di (chloroethyl) aminophenyl] -2,6- Di (trichloromethyl) -s-triazine, 4- [m-fluoro-pN, N-di (chloroethyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- (m- Bromo-p N-ethoxycarbonylmethylaminophenyl) -2,6-di (trichloromethyl) -s-triazine, 4- (m-chloro-pN-ethoxycarbonylmethylaminophenyl) -2,6-di (trichloromethyl) -S-triazine, 4- (m-fluoro-pN-ethoxycarbonylmethylaminophenyl) -2,6-di (trichloromethyl) -s-triazine, 4- (o-bromo-pN-ethoxycarbonyl) Methylaminophenyl) -2,6-di (trichloromethyl) -s-triazine, 4- (o-chloro-pN-ethoxycarbonylmethylaminophenyl) -2,6-di (trichloromethyl) -s-triazine 4- (o-fluoro-pN-ethoxycarbonylmethylaminophenyl) -2,6-di (trichloromethyl) -s-tri Azine, 4- (m-bromo-pN-chloroethylaminophenyl) -2,6-di (trichloromethyl) -s-triazine, 4- (m-chloro-pN-chloroethylaminophenyl)- 2,6-di (trichloromethyl) -s-triazine, 4- (m-fluoro-pN-chloroethylaminophenyl) -2,6-di (trichloromethyl) -s-triazine, 4- (o- Bromo-p-N-chloroethylaminophenyl) -2,6-di (trichloromethyl) -s-triazine, 4- (o-chloro-pN-chloroethylaminophenyl) -2,6-di (trichloro Methyl) -s-triazine, 4- (o-fluoro-pN-chloroethylaminophenyl) -2,6-di (trichloromethyl) -s-triazine, and the like.

  In addition, TAZ series (for example, TAZ-107, TAZ-110, TAZ-104, TAZ-109, TAZ-140, TAZ-204, TAZ-113, TAZ-123, TAZ-104) manufactured by Midori Chemical, PANCHIM T series (for example, T-OMS, T-BMP, T-R, T-B) manufactured by the company, Irgacure series (for example, Irgacure 369, Irgacure 784, Irgacure 651, Irgacure 184) manufactured by Ciba Specialty Chemicals , Irgacure 500, Irgacure 1000, Irgacure 149, Irgacure 819, Irgacure 261), Darocur Series, Darocur 1173, 4,4′-bis (diethylamino) -benzophenone, 2- (O-benzoyloxime) -1- [4- (Fe Ruthio) phenyl] -1,2-octanedione, 2-benzyl-2-dimethylamino-4-morpholinobutyrophenone, 2,2-dimethoxy-2-phenylacetophenone, 2- (o-chlorophenyl) -4,5- Diphenylimidazolyl dimer, 2- (o-fluorophenyl) -4,5-diphenylimidazolyl dimer, 2- (o-methoxyphenyl) -4,5-diphenylimidazolyl dimer, 2- (p-methoxy) Phenyl) -4,5-diphenylimidazolyl dimer, 2- (p-dimethoxyphenyl) -4,5-diphenylimidazolyl dimer, 2- (2,4-dimethoxyphenyl) -4,5-diphenylimidazolyl dimer 2-mer, 2- (p-methylmercaptophenyl) -4,5-diphenylimidazolyl dimer, benzoin isopro Ether and the like are also useful.

  Other known photopolymerization initiators other than the photopolymerization initiator can be used in combination with the colored curable composition of the present invention. Specifically, the vicinal polyketol aldonyl compound described in U.S. Pat. No. 2,367,660, the α-form described in U.S. Pat. Nos. 2,367,661 and 2,367,670. Carbonyl compounds, acyloin ethers described in US Pat. No. 2,448,828, aryl acyloin compounds substituted with α-hydrocarbons described in US Pat. No. 2,722,512, US Pat. , 046,127 and 2,951,758, a triarylimidazole dimer / P-aminophenylketone combination described in US Pat. No. 3,549,367, Examples include benzothiazole compounds / trihalomethyl-s-triazine compounds described in JP-B 51-48516.

  The content of the photopolymerization initiator in the colored curable composition is preferably 0.01 to 50% by mass, more preferably 1 to 30% by mass, based on the solid content (mass) of the polymerizable monomer. -20% by weight is particularly preferred. When the content is within the above range, the polymerization is good, and the content is too high, the polymerization rate increases, while the molecular weight does not decrease and the film strength does not decrease.

A sensitizer and a light stabilizer can be used in combination with the photopolymerization initiator.
Specific examples thereof include benzoin, benzoin methyl ether, 9-fluorenone, 2-chloro-9-fluorenone, 2-methyl-9-fluorenone, 9-anthrone, 2-bromo-9-anthrone, and 2-ethyl-9-anthrone. 9,10-anthraquinone, 2-ethyl-9,10-anthraquinone, 2-t-butyl-9,10-anthraquinone, 2,6-dichloro-9,10-anthraquinone, xanthone, 2-methylxanthone, 2- Methoxyxanthone, 2-ethoxyxanthone, thioxanthone, 2,4-diethylthioxanthone, acridone, 10-butyl-2-chloroacridone, benzyl, dibenzalacetone, p- (dimethylamino) phenylstyryl ketone, p- (dimethyl Amino) phenyl-p-methylstyryl ketone Examples include benzophenone, p- (dimethylamino) benzophenone (or Michler's ketone), p- (diethylamino) benzophenone, benzoanthrone, benzothiazole compounds described in Japanese Patent Publication No. 51-48516, tinuvin 1130, 400, and the like. .

  In addition to the above, it is preferable to add a thermal polymerization inhibitor. For example, 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-tert-butylphenol), 2-mercaptobenzimidazole and the like are useful.

<Naphthoquinonediazide compound>
Next, the naphthoquinone diazide compound in the case of constituting the positive type will be described. A naphthoquinonediazide compound is a compound having at least one o-quinonediazide group.
For example, o-naphthoquinone diazide-5-sulfonic acid ester, o-naphthoquinone diazide-5-sulfonic acid amide, o-naphthoquinone diazide-4-sulfonic acid ester, o-naphthoquinone diazide-4-sulfonic acid amide and the like can be mentioned. These esters and amide compounds can be produced by a known method using, for example, a phenol compound described in general formula (I) in JP-A-2-84650 and JP-A-3-49437. it can.

  When the colored curable composition is constituted as a positive type, the binder and the crosslinking agent are usually dissolved in an organic solvent at a ratio of about 2 to 50% by mass and about 2 to 30% by mass, respectively. Is preferred. Moreover, each content of the said naphthoquinone diazide compound and the said pigment | dye is normally added in the ratio of about 2-30 mass% and about 2-50 mass%, respectively with respect to the mass of the solution which melt | dissolved the said binder and the crosslinking agent. Is preferred.

-Solvent-
In preparing the colored curable composition of the present invention, a solvent can generally be used. The solvent is basically not particularly limited as long as the solubility of each component and the coating property of the colored curable composition are satisfied, but it is particularly preferably selected in consideration of the solubility, coating property and safety of the binder.

  Specific examples of the solvent include esters such as ethyl acetate, n-butyl acetate, isobutyl acetate, amyl formate, isoamyl acetate, isobutyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, alkyl esters, and lactic acid. Methyl, ethyl lactate, methyl oxyacetate, ethyl oxyacetate, butyl oxyacetate, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, methyl 3-oxypropionate, ethyl 3-oxypropionate Alkyl esters of 3-oxypropionic acid such as methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl 2-oxypropionate, 2-oxypropionate Ethyl onate, propyl 2-oxypropionate, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, 2-oxy- Methyl 2-methylpropionate, ethyl 2-oxy-2-methylpropionate, methyl 2-methoxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate, methyl pyruvate, ethyl pyruvate, pyruvate Propyl, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutanoate, ethyl 2-oxobutanoate and the like; ethers such as diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoe Ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol methyl ether, propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate, propylene glycol propyl ether acetate, etc .; ketones, For example, methyl ethyl ketone, cyclohexanone, 2-heptanone, 3-heptanone and the like; aromatic hydrocarbons such as toluene and xylene are preferred.

  Among these, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl cellosolve acetate, ethyl lactate, diethylene glycol dimethyl ether, butyl acetate, methyl 3-methoxypropionate, 2-heptanone, cyclohexanone, ethyl carbitol acetate, butyl Carbitol acetate, propylene glycol methyl ether, propylene glycol methyl ether acetate and the like are more preferable.

-Various additives-
In the colored curable composition of the present invention, various additives as necessary, for example, fillers, polymer compounds other than the above, surfactants, adhesion promoters, antioxidants, ultraviolet absorbers, anti-aggregation agents, etc. Can be blended.

  Specific examples of the various additives include fillers such as glass and alumina; polymer compounds other than binder resins such as polyvinyl alcohol, polyacrylic acid, polyethylene glycol monoalkyl ether, and polyfluoroalkyl acrylate; nonionic, cationic And anionic surfactants: vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, N- (2 -Aminoethyl) -3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2- (3,4-epoxycyclohexyl) ) Ethyltrimetoki Adhesion promoters such as silane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane; 2,2-thiobis (4-methyl- 6-t-butylphenol), 2,6-di-t-butylphenol and other antioxidants; 2- (3-t-butyl-5-methyl-2-hydroxyphenyl) -5-chlorobenzotriazole, alkoxybenzophenone, etc. And an anti-aggregation agent such as sodium polyacrylate.

  Further, when the alkali solubility of the non-cured part is promoted and the developability of the colored curable composition of the present invention is further improved, the composition has an organic carboxylic acid, preferably a low molecular weight organic compound having a molecular weight of 1000 or less. Carboxylic acid can be added. Specifically, for example, aliphatic monocarboxylic acids such as formic acid, acetic acid, propionic acid, butyric acid, valeric acid, pivalic acid, caproic acid, diethyl acetic acid, enanthic acid, caprylic acid; oxalic acid, malonic acid, succinic acid, Aliphatic dicarboxylic acids such as glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, brassic acid, methylmalonic acid, ethylmalonic acid, dimethylmalonic acid, methylsuccinic acid, tetramethylsuccinic acid, citraconic acid; Aliphatic tricarboxylic acids such as tricarballylic acid, aconitic acid, camphoric acid; aromatic monocarboxylic acids such as benzoic acid, toluic acid, cumic acid, hemelitic acid, mesitylene acid; phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid, Aromatic polycarboxylic acids such as trimesic acid, melophanoic acid, pyromellitic acid; phenylacetic acid Hydratropic acid, hydrocinnamic acid, mandelic acid, phenyl succinic acid, atropic acid, cinnamic acid, methyl cinnamate, benzyl cinnamate, cinnamylidene acetic acid, coumaric acid, other carboxylic acids such as umbellic acid.

  The colored curable composition of the present invention is used for forming a colored pixel such as a color filter used in a liquid crystal display (LCD), a solid-state imaging device (for example, CCD, CMOS), and the like. It can be suitably used as a production application for paints and the like.

<< Color filter and manufacturing method thereof >>
Next, the color filter of the present invention will be described in detail through its manufacturing method.
In the method for producing a color filter of the present invention, the above-described colored curable composition of the present invention is used. The color filter of the present invention is formed by using the compound according to the present invention represented by the general formula (T) described above, and preferably, using the above-described colored curable composition of the present invention. A colored curable composition is applied onto a support by a coating method such as spin coating, cast coating, roll coating, etc. to form a radiation-sensitive composition layer, and the layer is exposed through a predetermined mask pattern, It can be produced by developing with a developer to form a negative or positive colored pattern (image forming step). At this time, if necessary, a curing step of curing the formed colored pattern by heating and / or exposure can be provided.
As light or radiation used at this time, ultraviolet rays such as g-line, h-line and i-line are particularly preferably used.
Further, when the colored curable composition is configured in a positive type, a step of post-baking the colored pattern after the image forming step can be provided.

  In the production of the color filter, in the case of the negative type, the image forming step (and the curing step if necessary) is repeated according to the desired number of hues, and in the case of the positive type, the image forming step and post-baking are performed as desired. By repeating according to the hue, a color filter configured to have a desired number of hues can be manufactured.

  Examples of the support include soda glass, Pyrex (registered trademark) glass, and quartz glass used for liquid crystal display elements and the like, and those obtained by attaching a transparent conductive film to these, and photoelectric conversion element substrates used for imaging elements and the like. Examples thereof include a silicon substrate and a complementary metal oxide semiconductor (CMOS). These substrates may have black stripes that separate pixels.

  Further, if necessary, an undercoat layer may be provided on these supports in order to improve adhesion to the upper layer, prevent diffusion of substances, or flatten the substrate surface.

  Any developer can be used as long as it has a composition that dissolves the portion (uncured portion) to be developed and removed of the colored curable composition of the present invention while the cured portion forming the filter does not dissolve. be able to. Specifically, a combination of various organic solvents or an alkaline aqueous solution can be used.

  As said organic solvent, the above-mentioned solvent which can be used when preparing the colored curable composition of this invention is mentioned.

  Examples of the alkaline aqueous solution include sodium hydroxide, potassium hydroxide, sodium carbonate, sodium oxalate, sodium metasuccinate, aqueous ammonia, ethylamine, diethylamine, dimethylethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide. , Choline, pyrrole, piperidine, alkaline compounds such as 1,8-diazabicyclo- [5.4.0] -7-undecene, the concentration is 0.001 to 10% by mass, preferably 0.01 to 1% by mass. An alkaline aqueous solution obtained by dissolution is preferable. When a developer composed of such an alkaline aqueous solution is used, it is generally washed with water after development.

  The color filter of the present invention can be used for a solid-state image pickup device such as a liquid crystal display device or a CCD, and is particularly suitable for a high-resolution CCD device or a CMOS device having more than 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, the present invention 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. Unless otherwise specified, “part” is based on mass.
Example 1
1) Preparation of resist solution (negative type)
A compound having the following composition was mixed and dissolved to prepare a resist solution.
Propylene glycol monomethyl ether acetate ... 5.20 parts (PGMEA)
-Ethyl lactate (EL): 52.6 parts-Binder: 30.5 parts (41% EL of benzyl methacrylate / methacrylic acid / methacrylic acid-2-hydroxyethyl copolymer (molar ratio = 60: 20: 20)) solution)
Dipentaerythritol hexaacrylate 10.2 parts Polymerization inhibitor (p-methoxyphenol) 0.006 parts Fluorosurfactant 0.80 parts (trade name: F-475, Dainippon Ink & Chemicals, Inc. (Made by Co., Ltd.)
・ TAZ-107 (manufactured by Midori Chemical Co .; photopolymerization initiator): 0.58 parts

2) Production of glass substrate with undercoat layer A glass substrate (Corning 1737) was ultrasonically washed with 0.5% NaOH water, followed by washing with water and dehydration baking (200 ° C./20 minutes). Next, the resist solution obtained in 1) above was applied onto a cleaned glass substrate using a spin coater so as to have a film thickness of 2 μm, and dried by heating at 220 ° C. for 1 hour to prepare a cured film (undercoat layer). did.

3) Preparation of resist solution (colored curable composition [negative type]) 9.4 g of resist solution obtained in the above 1) and the exemplified compound C-1 described above which is a dye according to the present invention [the above general formula ( Compound represented by T2)] 0.75 g was mixed and dissolved to prepare a dye resist solution (colored curable composition [negative type] solution).

4) Exposure and development of dye resist (image formation)
The dye resist solution obtained in 3) above was applied onto the undercoat layer of the glass substrate with an undercoat layer obtained in 2) so as to have a film thickness of 1.0 μm at 100 ° C. Pre-baked for 120 seconds.
Next, using an exposure apparatus, the coating film was irradiated with an exposure dose of 500 mJ / cm ² through a mask having a wavelength of 365 nm and a line width of 20 μm. After the exposure, development was performed at 25 ° C. for 40 seconds using a CD-2000 (manufactured by Fuji Film Electromaterial) developer. Then, after rinsing with running water for 30 seconds, spray drying was performed. As described above, a pattern suitable as a cyan color constituting the color filter was obtained.

5) Evaluation Storage stability over time of the dye resist solution prepared above (storage stability over time), and heat resistance, light resistance, and pattern formability of the coating film coated on the glass substrate using the dye resist solution. Was evaluated as follows. The evaluation results are shown in Table 1 below.

-1. Storage over time
After the dye resist solution was stored at room temperature for 1 month, the degree of precipitation of foreign matters in the solution was visually evaluated according to the following criteria.
[Criteria]
○: No precipitation was observed.
Δ: Slight precipitation was observed.
X: Precipitation was recognized.

-2. Heat resistance
The glass substrate coated with the dye resist solution is placed on a hot plate at 200 ° C. so as to be in contact with the substrate surface, heated for 1 hour, and then heated with a chromaticity meter MCPD-1000 (manufactured by Otsuka Electronics Co., Ltd.). The color difference (ΔEab value) before and after the measurement was used as an index for evaluating heat resistance, and evaluated according to the following criteria. A smaller ΔEab value indicates better heat resistance.
[Criteria]
○: ΔEab value <5
Δ: 5 ≦ ΔEab value ≦ 10
×: ΔEab value> 10

-3. Light resistance
After irradiating a glass substrate coated with a dye resist solution with a xenon lamp at 50,000 lux for 20 hours (equivalent to 1 million lux · h), the color difference (ΔEab value) before and after irradiation is measured to evaluate the light resistance. And was evaluated according to the following criteria. A smaller ΔEab value indicates better light resistance.
[Criteria]
○: ΔEab value <3
Δ: 3 ≦ ΔEab value ≦ 10
×: ΔEab value> 10

-4. Solvent resistance
The spectra of the various coating films after post-baking obtained in 4) above were measured (spectrum A). On this coating film, the resist solution obtained in 1) above was applied so as to have a film thickness of 1 μm and prebaked, and then a CD-2000 (produced by Fuji Film Electromaterial) developer was used. Then, development was performed at 23 ° C. for 120 seconds, and the spectrum was measured again (spectrum B).
Then, a dye residual ratio (%) was calculated from the difference between the obtained spectra A and B, and used as an index for evaluating the solvent resistance. Therefore, the closer the value is to 100%, the better the solvent resistance.

(Examples 2 to 10)
Example 1 3) In the preparation of the dye resist solution, Exemplified Compound C-1 which is a dye according to the present invention was changed as shown in Table 1 below (but equimolar) in the same manner as in Example 1. Then, a pattern was formed, and the same evaluation was performed. The evaluation results are shown in Table 1 below.

(Comparative Examples 1-2)
In the preparation of the dye resist solution of Example 1, 3), the exemplified compound C-1 which is a dye according to the present invention was changed to the following comparative dye 1 (Comparative Example 1) or the following comparative dye 2 (Comparative Example 2) (however, A pattern was formed in the same manner as in Example 1 except that it was equimolar), and the same evaluation was performed. The evaluation results are shown in Table 1 below together with the results of the examples.

  As shown in Table 1, in Examples using the dyes according to the present invention, compared to Comparative Examples using other dyes, dye resist solutions (colored curable compositions) prepared in a solution state were used. ) Was excellent in storage stability over time, and the pattern formed using this colored curable composition showed good heat resistance, light resistance, and solvent resistance.

(Comparative dye 1)
Oreosol First Blue RL [Taoka Chemical Co., Ltd.]

(Comparative dye 2)

(Example 11)
1) Preparation of colored curable composition [positive type] The following compositions were mixed and dissolved to prepare a solution-like colored curable composition [positive type].
・ Ethyl lactate (EL): 30 parts ・ Resin P-1: 3.0 parts ・ Naphthoquinone diazide compound N-1: 1.8 parts ・ Hexamethoxymethylolated melamine (crosslinking agent): 0.6 parts ・ TAZ -107 (manufactured by Midori Chemical Co., Ltd .; photoacid generator) ... 1.2 parts, F-475 ... 0.0005 parts (Dainippon Ink Chemical Co., Ltd .; fluorinated surfactant)
-Dye according to the present invention (Exemplary Compound C-1 as described above) 1.5 parts (Compound represented by Formula (T2))

-Synthesis of Resin P-1-
A three-necked flask was charged with 70.0 g of benzyl methacrylate, 13.0 g of methacrylic acid, 17.0 g of methacrylic acid-2-hydroxyethyl, and 600 g of 2-methoxypropanol, and a stirrer, a reflux condenser, and a thermometer were attached. A polymerization amount of a polymerization initiator V-65 (manufactured by Wako Pure Chemical Industries, Ltd.) was added at ° C and stirred for 10 hours. The obtained resin solution was added dropwise to 20 L of ion exchange water with vigorous stirring to obtain a white powder. This white powder was vacuum-dried at 40 ° C. for 24 hours to obtain 145 g of resin P-1.
When this molecular weight was measured by GPC, the weight average molecular weight Mw = 28,000 and the number average molecular weight Mn = 11,000.

-Synthesis of naphthoquinonediazide compound N-1-
Trisp-PA (Honshu Chemical Co., Ltd.) 42.45 g, o-naphthoquinonediazide-5-sulfonyl chloride 61.80 g, and acetone 300 ml were charged into a three-necked flask, and 24.44 g of triethylamine was added dropwise at room temperature over 1 hour. After completion of the dropwise addition, the mixture was further stirred for 2 hours, and then the reaction solution was poured while stirring a large amount of water. Precipitated naphthoquinone diazide sulfonic acid ester was collected by suction filtration and vacuum dried at 40 ° C. for 24 hours to obtain photosensitive naphthoquinone azide compound N-1.

2) Exposure and development (image formation) of the colored curable composition
A glass substrate with an undercoat layer was prepared in the same manner as in Example 1, and the colored curable composition [positive type] prepared as described above was applied on the undercoat layer of the glass substrate with an undercoat layer in the same manner as in Example 1. It was coated, pre-baked, irradiated, developed and rinsed, and spray-dried to obtain a pattern, and then this pattern was heated at 180 ° C. for 5 minutes (post-baking). The formed cyan pattern showed a good rectangular profile.

  Subsequently, storage stability over time of the colored curable composition [positive type] prepared above (storage stability over time), and heat resistance of the coating film coated on the glass substrate using the dye resist solution, When the light resistance and the solvent resistance were evaluated in the same manner as in Example 1, the storage stability and the light resistance, heat resistance and solvent resistance were all good as in the case of the negative type.

(Examples 12 to 21)
Except having replaced the glass substrate of Examples 1-10 with the silicon wafer substrate, all the same operations as Example 1-10 were performed, and the coating film was coated on the silicon wafer substrate. Next, a 2 μm square pattern was exposed at an exposure amount of 500 mj / cm ² using an i-line reduction projection exposure apparatus, and a developer obtained by diluting CD-2000 (manufactured by Fuji Film Electromaterial) to 60% was used. And developed at 23 ° C. for 60 seconds. Subsequently, after rinsing with running water for 30 seconds, spray drying was performed. As a result, a pattern suitable as a color filter for CCD having a square cross section and a good profile was obtained.

Claims (3)

The colored curable composition containing at least 1 sort (s) of the compound represented by the following general formula (T).

[Wherein, R ¹ and R ² each independently represent a substituent or a dye residue, and at least one of R ¹ and R ² represents a dye residue. ] The color filter containing at least 1 sort (s) of the compound represented by the following general formula (T).

[Wherein, R ¹ and R ² each independently represent a substituent or a dye residue, and at least one of R ¹ and R ² represents a dye residue. ]   A method for producing a color filter, comprising: applying a colored curable composition according to claim 1 onto a support, exposing the film through a mask, and developing the pattern image to form a pattern image.