JP4316998B2 - Coloring agent-containing curable composition, color filter and method for producing the same - Google Patents

Description

  The present invention relates to a colorant-containing curable composition suitable for forming a colored image constituting a color filter used in a liquid crystal display element, a solid-state imaging element, and the like, a color filter using the colorant-containing curable composition, and It relates to the manufacturing method.

  As a method for producing a color filter used for a liquid crystal display device, a solid-state imaging device or the like, a dyeing method, a printing method, an electrodeposition method, or a pigment dispersion method is known.

  Among these, the pigment dispersion method is a method for producing a color filter by a photolithography method using a colored radiation-sensitive composition in which a pigment is dispersed in various photosensitive compositions. This method is stable to light and heat due to the use of pigments, and is patterned by a photolithographic method, so that sufficient positional accuracy can be secured and suitable for the production of color filters for large screens and high-definition color displays. It is a simple method.

  In order to produce a color filter by the pigment dispersion method, a radiation-sensitive composition is applied onto a substrate with a spin coater, a roll coater or the like, dried to form a coating film, and the coating film is subjected to pattern exposure and development. Thus, a colored pixel is obtained, and a color filter composed of a plurality of colors can be produced by repeating this operation for the hue.

  As the pigment dispersion method, a negative photosensitive composition in which a photopolymerizable monomer and a photopolymerization initiator are used in combination with an alkali-soluble resin is disclosed (for example, see Patent Documents 1 and 2). However, in recent years, color filters for solid-state imaging devices have been demanded to have higher definition. In the conventional pigment dispersion method, since the pigment exists in a particle state having a size, the resolution is essentially improved. In addition, there is a problem such as color unevenness due to coarse pigment particles, which is not suitable for applications requiring a fine pattern such as a solid-state imaging device.

In order to achieve the above high resolution, a technique using a dye soluble in a solvent or water has been studied (for example, see Patent Document 3). However, it has been found that the curable composition containing a dye has further new problems. That is,
(1) Since ordinary dyes have low solubility in an alkaline aqueous solution or an organic solvent (hereinafter also simply referred to as a solvent), it is difficult to obtain a liquid curable composition having a desired spectrum;
(2) The dye often exhibits an interaction with other components in the curable composition, and it is difficult to adjust the solubility (developability) of the cured part and the non-cured part;
(3) When the molar extinction coefficient (ε) of the dye is low, a large amount of dye must be added. For this purpose, the polymerizable compound (monomer), binder, photopolymerization initiator, etc. in the curable composition Other components must be reduced, causing problems such as reduced curability of the composition, heat resistance after curing, and developability of the (non) cured portion;
(4) Dyes are generally inferior in light resistance and heat resistance compared to pigments;
Etc.

  In addition, unlike a semiconductor manufacturing application or the like, particularly in the case of a color filter manufacturing application for a solid-state imaging device, a thin film of 1.5 μm or less is required. Therefore, it is necessary to add a relatively large amount of pigment to the curable composition, resulting in the above-mentioned problems.

In particular, for magenta dyes, there are those described as γ-acid-phenylazo type dyes (see, for example, Patent Document 4), but it is difficult to satisfy both heat resistance and light resistance with this dye. .
JP-A-2-199403 Japanese Patent Laid-Open No. 5-273411 JP-A-6-75375 JP-A-9-291241

  As described above, the performance required for practical use as a high-definition color filter, particularly for solid-state imaging devices, that is, the miniaturization and thinning of the colored pattern, the fastness to light and heat, and the developability (pattern formability) It was difficult to satisfy.

  The present invention has been made in view of the above problems, and has high sensitivity, wide development latitude, and suppression of elution of the dye after curing. In particular, the color value, light resistance, heat resistance, pattern formability (developability) ), And a colorant-containing curable composition having excellent liquid storage stability when made into a liquid composition, and high productivity with excellent color density, excellent light resistance and heat resistance, high transmittance, and high resolution. An object is to provide a color filter and a method for manufacturing the color filter, and to achieve the object. The color value is the concentration of a solution formed by dissolving the powder of the colorant in water, and can be indicated by using the value ε / Mw obtained by dividing the molar extinction coefficient ε by the average molecular weight Mw of the colorant. .

Specific means for solving the above problems are as follows.
<1> A colorant-containing curable composition containing a colorant, wherein the colorant contains a compound represented by the following general formula (I).
<2> The compound represented by the following general formula (I) is characterized in that ^one of the electron-withdrawing groups represented by the following R ¹ is a substituted sulfamoyl group represented by the following general formula (II). It is a coloring agent containing curable composition as described in said <1>.
<3> The colorant-containing curability according to <1> or <2>, wherein the compound represented by the following general formula (I) is a compound represented by the following general formula (III): It is a composition.

In the general formula (I) or general formula (III) , R ¹ represents an electron-withdrawing group, and R ² represents a hydrogen atom, a cation of a monovalent metal atom, or a cation composed of a nitrogen-containing compound. n represents an integer of 2 to 5. m represents an integer of 1 to 4. In General Formula (II) or General Formula (III), R ³ and R ⁴ are each independently a hydrogen atom, an alkyl group having 1 to 21 carbon atoms, an alkenyl group having 2 to 21 carbon atoms, or 6 to 6 carbon atoms. 21 represents an aryl group and an aralkyl group having 7 to 21 carbon atoms.

< 4 > The colorant-containing curable composition according to any one of <1> to <3>, further including a polymerizable compound.
< 5 > The colorant-containing curable composition according to <4> , wherein the polymerizable compound includes a (meth) acrylic ester-based polymerizable compound.
< 6 > The colorant-containing curable composition according to < 5 >, wherein the (meth) acrylic ester polymerizable compound is a tetrafunctional or higher functional (meth) acrylic ester monomer.
< 7 > The colorant-containing curable composition according to any one of <1> to < 6 >, further including a binder.
< 8 > The colorant-containing curable composition according to < 7 >, wherein the binder includes a (meth) acrylic alkali-soluble resin.
< 9 > The colorant-containing curable composition according to < 8 >, wherein the (meth) acrylic alkali-soluble resin has a polymerizable side chain.

< 10 > The colorant-containing curable composition according to any one of <1> to < 9 >, further including a photopolymerization initiator.
< 11 > The photopolymerization initiator is a trihalomethyltriazine compound, a benzyldimethyl ketal compound, an α-hydroxyketone compound, an α-aminoketone compound, a phosphine oxide compound, a metallocene compound, an oxime compound, or a triallylimidazole dimer. At least one selected from the group consisting of benzothiazole compounds, benzophenone compounds, acetophenone compounds and derivatives thereof, cyclopentadiene-benzene-iron complexes and salts thereof, halomethyloxadiazole compounds, and 3-aryl-substituted coumarin compounds It is a coloring agent containing curable composition as described in said < 10 >.
< 12 > The colorant-containing curable composition according to < 10 > or < 11 >, wherein the photopolymerization initiator includes at least one compound that does not generate an acid by decomposition.
<13> The photopolymerization initiator is, alpha-amino ketone compounds, phosphine oxide compounds, metallocene compounds, oxime compounds, and the containing at least one selected from the group consisting of triallyl imidazole dimer <10> - < 12 > A curable composition containing a colorant according to any one of < 12 >.

< 14 > The colorant-containing curable composition according to any one of <1> to < 9 >, further including an o-quinonediazide compound and configured in a positive type.
< 15 > The colorant-containing curable composition according to < 14 >, wherein the o-quinonediazide compound is o-benzoquinonediazidesulfonic acid ester or o-naphthoquinonediazidesulfonic acid ester.
< 16 > The colorant-containing curable composition according to any one of <1> to < 9 >, further including a photoacid generator and configured in a positive type.

< 17 > The colorant-containing curable composition according to any one of <1> to < 16 >, further including a crosslinking agent.
< 18 > A color filter comprising a compound represented by the following general formula (I).
<19> The compound represented by the following general formula (I) is characterized in that ^one of the electron-withdrawing groups represented by the following R ¹ is a substituted sulfamoyl group represented by the following general formula (II). <18> The color filter according to <18>.
<20> The color filter according to <18> or <19>, wherein the compound represented by the following general formula (I) is a compound represented by the following general formula (III).

In the general formula (I) or general formula (III), R ¹ represents an electron-withdrawing group, and R ² represents a hydrogen atom, a cation of a monovalent metal atom, or a cation composed of a nitrogen-containing compound . n represents an integer of 2 to 5. m represents an integer of 1 to 4. In General Formula (II) or General Formula (III), R ³ and R ⁴ are each independently a hydrogen atom, an alkyl group having 1 to 21 carbon atoms, an alkenyl group having 2 to 21 carbon atoms, or 6 to 6 carbon atoms. 21 represents an aryl group and an aralkyl group having 7 to 21 carbon atoms.
The color filter in any one of <18>-<20> can be suitably comprised using the coloring agent containing curable composition in any one of said <1>-<17>.

< 21 > A step of applying the colorant-containing curable composition according to any one of <1> to < 17 > onto a support, exposing through a mask, and developing to form a pattern image. It is a manufacturing method of the color filter characterized.
In the method for producing a color filter, when producing a color filter having a desired hue, the above steps are repeated according to the desired number of hues. Moreover, the aspect which has the process of hardening | curing the said pattern image by heating and / or exposure as needed is also suitable.

According to the present invention, high sensitivity, wide development latitude, and elution of a dye after curing can be suppressed, and in particular, a liquid having a color value, light resistance, heat resistance, pattern formability (developability), and a liquid composition. A colorant-containing curable composition having excellent storage stability can be provided. Also,
A highly productive color filter having good color density, excellent light resistance and heat resistance, high transmittance and high resolution, and a method for producing the color filter can be provided.

  Hereinafter, the coloring agent containing curable composition of this invention, a color filter, and its manufacturing method are explained in full detail.

<< Colorant-containing curable composition >>
The colorant-containing curable composition of the present invention comprises at least a colorant, generally an organic solvent (solvent), and the phenyl represented by the following general formula (I) as the colorant. It includes a phenylazonaphthalene-based compound having a plurality of electron-withdrawing groups in its group. In addition, the colorant-containing curable composition of the present invention is a binder or a negative type together with the colorant, and further includes a photopolymerization initiator and a polymerizable compound when the positive type is used. An o-quinonediazide compound or a photoacid generator can be used. Furthermore, a cross-linking agent and other components may be included. Moreover, when comprising in a positive type, you may further contain a photoinitiator and a polymeric compound as needed.

(Coloring agent)
~ Compound represented by formula (I) ~
The colorant-containing curable composition of the present invention contains at least one phenylazonaphthalene-based compound having two or more electron-withdrawing groups in the phenyl group represented by the following general formula (I) as a colorant. . This compound is a dye compound that exhibits a high color value, which is not found in conventional azo compounds, satisfies both high light resistance and high heat resistance at the same time, and can ensure good pattern formability (that is, developability and development latitude). It is. Furthermore, if necessary, it can be freely dissolved in water or an organic solvent.

In the general formula (I), R ¹ represents an electron withdrawing group. The electron-withdrawing group represented by R ¹ can be selected from those having a positive value according to Hammett's σ value (Hammett rule—structure and reactivity—written by Naoki Inamoto, Maruzen Co., Ltd.). Suitable electron withdrawing groups include, for example, ethynyl group, trifluoromethyl group, cyano group, formyl group, acyl group, carboxy group, alkoxycarbonyl group, aryloxycarbonyl group, nitro group, acetoxy group, mercapto group, alkylthio group. Alkylsulfinyl group, substituted sulfonyl group (alkylsulfonyl group, arylsulfonyl group etc.), sulfamoyl group, substituted sulfamoyl group (alkylsulfamoyl group, arylsulfamoyl group etc.), acylthio group, fluoro group, chloro group, bromo Group and iodo group.

  Among these, ethynyl group, trifluoromethyl group, cyano group, acyl group, carboxy group, alkoxycarbonyl group, aryloxycarbonyl group, nitro group, acetoxy group, alkylthio group, alkylsulfinyl group, alkylsulfonyl group, arylsulfonyl group , Sulfamoyl group, substituted sulfamoyl group (alkylsulfamoyl group, arylsulfamoyl group, etc.), fluoro group, chloro group, bromo group, iodo group are more preferable, and trifluoromethyl group, cyano group, acyl group, Carboxy group, alkoxycarbonyl group, aryloxycarbonyl group, nitro group, acetoxy group, alkylthio group, alkylsulfinyl group, alkylsulfonyl group, arylsulfonyl group, sulfamoyl group, substituted sulfamoyl group (alkyls Famoiru group, an aryl sulfamoyl group), a fluoro group, chloro group, bromo group is particularly preferable.

  These electron-withdrawing groups are further the same groups as described above, or acyl groups, acylamino groups, acylaminocarbonylamino groups, aralkylaminocarbonylamino groups, arylaminocarbonylamino groups, methacryloylaminocarbonylamino groups, trifluoromethyl groups, fluoro groups. Group, chloro group, bromo group, iodo group, hydroxy group, nitro group, methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, sec-butyl group, t- Butyl group, pentyl group, hexyl group, heptyl group, octyl group, vinyl group, methoxy group, ethoxy group, butoxy group, isopropoxy group, t-butoxy group, cyclohexyloxy group, vinyloxy group, phenyloxy group, methylthio group, Ethylthio group, pyrrolidinyl group, piperidinyl group, amino group Dimethylamino group, diethylamino group, may be substituted with a phenyl group.

Of the electron-withdrawing groups represented by R ¹ , the substituted sulfamoyl group is preferably a group represented by the following general formula (II).

R ³ and R ⁴ are each independently a hydrogen atom, an alkyl group having 1 to 21 carbon atoms, an alkenyl group having 2 to 21 carbon atoms, an aryl group having 6 to 21 carbon atoms, or an aralkyl group having 7 to 21 carbon atoms. R ³ and R ⁴ may be the same or different, and R ³ and R ⁴ may form a heterocycle together with the nitrogen atom bonded thereto. Further, the alkyl group, alkenyl group, aryl group and aralkyl group represented by R ³ or R ⁴ may be unsubstituted or have a substituent.

The alkyl group having 1 to 21 carbon atoms represented by R ³ or R ⁴ may be a linear, branched, or cyclic alkyl group, preferably an alkyl group having 1 to 15 carbon atoms, and 1 carbon atom. 10 to 10 alkyl groups are more preferred. Specific examples include methyl group, ethyl group, n-propyl group, n-butyl group, n-amyl group, n-hexyl group, n-heptyl, n-octyl group, n-nonyl group, n-decyl group, n-undecyl group, n-dodecyl group, n-tridecyl group, n-tetradecyl group, n-pentadecyl group, n-hexadecyl group, n-heptadecyl group, n-octadecyl group, n-nonadecyl group, n-eicosanyl group, i-propyl group, sec-butyl group, i-butyl group, t-butyl group, 1-methylbutyl group, 1-ethylpropyl group, 2-methylbutyl group, i-amyl group, neopentyl group, 1,2-dimethylpropyl Group, 1,1-dimethylpropyl group, t-amyl group, 1,3-dimethylbutyl group, 3,3-dimethylbutyl group, 2-ethylbutyl group, 2-ethyl-2-methylpro Group,

Linear or branched heptyl group, 1-methylheptyl group, 2-ethylhexyl group, 1,5-dimethylhexyl group, t-octyl group, branched nonyl group, branched decyl group, branched undecyl group, branched dodecyl group Group, branched tridecyl group, branched tetradecyl group, branched pentadecyl group, branched hexadecyl group, branched heptadecyl group, branched octadecyl group, linear or branched nonadecyl group, linear or branched eicosanyl group, cyclopropyl Group, cyclopropylmethyl group, cyclobutyl group, cyclobutylmethyl group, cyclopentyl group, cyclohexyl group, cyclohexylmethyl group, cycloheptyl group, cyclooctyl group, cyclohexylpropyl group, cyclododecyl group, norbornyl group, bornyl group, cis-miltanyl Group, isopi Preferred examples include camphenyl, noradamantyl, adamantyl, adamantylmethyl, 1- (1-adamantyl) ethyl, 3,5-dimethyladamantyl, quinuclidinyl, cyclopentylethyl, and bicyclooctyl. .

  Among the above, methyl group, ethyl group, n-propyl group, n-butyl group, n-amyl group, n-hexyl group, n-heptyl group, n-octyl group, n-nonyl group, n-decyl group, n-undecyl group, n-dodecyl group, n-tridecyl group, n-tetradecyl group, i-propyl group, sec-butyl group, i-butyl group, t-butyl group, 1-methylbutyl group, 1-ethylpropyl group 2-methylbutyl group, i-amyl group, neopentyl group, 1,2-dimethylpropyl group, 1,1-dimethylpropyl group, t-amyl group, 1,3-dimethylbutyl group, 3,3-dimethylbutyl group 2-ethylbutyl group, 2-ethyl-2-methylpropyl group, linear or branched heptyl group, 1-methylheptyl group, 2-ethylhexyl group, 1,5-dimethylhexyl group, t-octyl Branched nonyl group, branched decyl group, branched undecyl group, branched dodecyl group, branched tridecyl group, branched tetradecyl group, cyclopropyl group, cyclopropylmethyl group, cyclobutyl group, cyclobutylmethyl group, cyclopentyl group , Cyclohexyl group, cyclohexylmethyl group, cycloheptyl group, cyclooctyl group, cyclohexylpropyl group, cyclododecyl group, norbornyl group, bornyl group, cis-miltanyl group, isopinocamphenyl group, noradamantyl group, adamantylmethyl, adamantylmethyl Group, 1- (1-adamantyl) ethyl group, 3,5-dimethyladamantyl group, quinuclidinyl group, cyclopentylethyl group, and bicyclooctyl group are more preferable,

  Further, methyl group, ethyl group, n-propyl group, n-butyl group, n-amyl group, n-hexyl group, n-heptyl group, n-octyl group, n-nonyl group, n-decyl group, i- Propyl group, sec-butyl group, i-butyl group, t-butyl group, 1-methylbutyl group, 1-ethylpropyl group, 2-methylbutyl group, i-amyl group, neopentyl group, 1,2-dimethylpropyl group, 1,1-dimethylpropyl group, t-amyl group, 1,3-dimethylbutyl group, 3,3-dimethylbutyl group, 2-ethylbutyl group, 2-ethyl-2-methylpropyl group, linear or branched heptyl Group, 1-methylheptyl group, 2-ethylhexyl group, 1,5-dimethylhexyl group, t-octyl group, branched nonyl group, branched decyl group, cyclopropyl group, cyclopropylmethyl group Cyclobutyl group, cyclobutylmethyl group, cyclopentyl group, cyclohexyl group, cyclohexylmethyl group, cycloheptyl group, cyclooctyl group, cyclohexylpropyl group, cyclododecyl group, norbornyl group, bornyl group, noradamantyl group, adamantyl group, adamantylmethyl group 1- (1-adamantyl) ethyl group, 3,5-dimethyladamantyl group, cyclopentylethyl group, and bicyclooctyl group are particularly preferable.

  Further, among the above groups, in order to improve heat resistance, ethyl group, n-propyl group, n-butyl group, n-amyl group, n-hexyl group, n-heptyl group, n-octyl group, n- Nonyl group, n-decyl group, i-propyl group, sec-butyl group, i-butyl group, t-butyl group, 1-methylbutyl group, 1-ethylpropyl group, 2-methylbutyl group, i-amyl group, Neopentyl group, 1,2-dimethylpropyl group, 1,1-dimethylpropyl group, t-amyl group, 1,3-dimethylbutyl group, 3,3-dimethylbutyl group, 2-ethylbutyl group, 2-ethyl-2 -Methylpropyl group, branched heptyl group, 1-methylheptyl group, 1,5-dimethylhexyl group, t-octyl group, branched nonyl group, branched decyl group, cyclopropyl group, cyclopropylmethyl , Cyclobutyl group, cyclobutylmethyl group, cyclopentyl group, cyclohexyl group, cyclohexylmethyl group, cycloheptyl group, cyclooctyl group, cyclohexylpropyl group, cyclododecyl group, norbornyl group, bornyl group, noradamantyl group, adamantylmethyl, adamantylmethyl Particularly preferred are branched alkyl groups such as 1- (1-adamantyl) ethyl group, 3,5-dimethyladamantyl group, cyclopentylethyl group, and bicyclooctyl group, and cyclic alkyl groups.

  Among the alkyl groups exemplified above, an alkyl group substituted with fluorine is also particularly suitable. Examples of the fluorine-substituted alkyl group include a trifluoromethyl group, a trifluoroethyl group, a pentafluoroethyl group, a heptafluoropropyl group, Nonafluorobutyl group, tridecafluorohexyl group, pentadecafluoroheptyl group, heptadecafluorooctyl group, tridecafluorooctyl group, nonadecafluorononyl group, heptadecafluorodecyl group, perfluorodecyl group are preferred, Among these, a trifluoromethyl group, a pentafluoroethyl group, a heptafluoropropyl group, a nonafluorobutyl group, a tridecafluorohexyl group, and a pentadecafluoroheptyl group are more preferable, and a trifluoromethyl group, a pentafluoroethyl group, Heptafluoropropyl group, a nonafluorobutyl group, tridecafluorohexyl group are particularly preferred.

As a C2-C21 alkenyl group represented by said R < ³ > or R < ⁴ >, a C2-C15 alkenyl group is preferable and a C2-C10 alkenyl group is more preferable. For example, vinyl group, isopropenyl group, 2-propenyl group, 2-methyl-propenyl group, 1-methyl-1-propenyl group, 1-butenyl group, 3-butenyl group, 1-methyl-1-butenyl group, 1 , 1-dimethyl-3-butenyl group, 1-pentenyl group, 2-pentenyl group, 1-ethyl-1-pentenyl group, 1-hexenyl group, 1-heptenyl group, 2,6-dimethyl-5-heptenyl group, 9-decenyl group, 1-cyclopentenyl group, 2-cyclopentenylmethyl group, cyclohexenyl group, 1-methyl-2-cyclohexenyl group, 1,4-dihydro-2-methylphenyl group, octenyl group, citronellyl group, Preferable examples include oleyl group, geranyl group, farnesyl group, 2- (1-cyclohexenyl) ethyl group and the like.

  Among the above, vinyl group, isopropenyl group, 2-propenyl group, 2-methyl-propenyl group, 1-methyl-1-propenyl group, 1-butenyl group, 3-butenyl group, 1-methyl-1-butenyl group 1,1-dimethyl-3-butenyl group, 1-pentenyl group, 2-pentenyl group, 1-ethyl-1-pentenyl group, 1-hexenyl group, 1-heptenyl group, 1-cyclopentenyl group, 2-cyclo Pentenylmethyl group, cyclohexenyl group, 1-methyl-2-cyclohexenyl group and 1,4-dihydro-2-methylphenyl group are more preferable, and vinyl group, isopropenyl group, 2-propenyl group, 2-methyl- Propenyl, 1-methyl-1-propenyl, 1-butenyl, 3-butenyl, 1-methyl-1-butenyl, 1,1-dimethyl-3-but Nyl group, 1-pentenyl group, 2-pentenyl group, 1-ethyl-1-pentenyl group, 1-hexenyl group, 1-cyclopentenyl group, 2-cyclopentenylmethyl group, cyclohexenyl group, 1-methyl-2- A cyclohexenyl group and a 1,4-dihydro-2-methylphenyl group are particularly preferable.

The aryl group having 6 to 21 carbon atoms represented by R ³ or R ⁴ is preferably an aryl group having 6 to 15 carbon atoms, and more preferably an aryl group having 6 to 10 carbon atoms. For example, a phenyl group, a naphthyl group, a biphenylenyl group, an acenaphthenyl group, a fluorenyl group, an anthracenyl group, an anthraquinonyl group, a pyrenyl group, and the like are preferable, among which a phenyl group, a naphthyl group, a biphenylenyl group, an acenaphthenyl group, A fluorenyl group and an anthracenyl group are more preferable, and a phenyl group, a naphthyl group, a biphenylenyl group, and a fluorenyl group are particularly preferable.

The aralkyl group having 7 to 21 carbon atoms represented by R ³ or R ⁴ is preferably an aralkyl group having 7 to 15 carbon atoms, and more preferably an aralkyl group having 7 to 10 carbon atoms. For example, benzyl group, diphenylmethyl group, 1,2-diphenylethyl group, phenyl-cyclopentylmethyl group, α-methylbenzyl group, phenylethyl group, α-methyl-phenylethyl group, β-methyl-phenylethyl group, 3 -Phenylpropyl group, 3,3-diphenylpropyl group, 4-phenylbutyl group, naphthylmethyl group, styryl group, cinnamyl group, fluorenyl group, 1-benzocyclobutenyl group, 1,2,3,4-tetrahydronaphthyl A group, an indanyl group, a piperonyl group, a pyrenemethyl group, and the like are preferable.

  Among these, benzyl group, phenyl-cyclopentylmethyl group, α-methylbenzyl group, phenylethyl group, α-methyl-phenylethyl group, β-methyl-phenylethyl group, 3-phenylpropyl group, 4-phenylbutyl group , Styryl group, cinnamyl group, fluorenyl group, 1-benzocyclobutenyl group, 1,2,3,4-tetrahydronaphthyl group, more preferably benzyl group, α-methylbenzyl group, phenylethyl group, α-methyl. -Phenylethyl group, β-methyl-phenylethyl group, 3-phenylpropyl group, styryl group, cinnamyl group, fluorenyl group, 1-benzocyclobutenyl group, 1,2,3,4-tetrahydronaphthyl group are particularly preferred .

The groups represented by R ³ and R ⁴ may contain an ether group, and a tetrahydrofurfuryl group, a tetrahydropyranylmethyl group, a 2,5-dihydro-2,5-dimethoxyfurfuryl group and the like are also preferable. .

R ³ and R ⁴ may form a heterocyclic ring with a nitrogen atom bonded thereto, and examples of the heterocyclic ring in this case include a 2-methylaziridine ring, an azetidine ring, a pyrrolidine ring, 3-pyrroline ring, piperidine ring, 1,2,3,6-tetrahydropyridine ring, hexamethyleneimine ring, piperazine ring, 1,3,3-trimethyl-6-azabicyclo [3.2.1] octane ring, deca Hydroquinoline ring, oxazolidine ring, morpholine ring, thiazolidine ring, thiomorpholine ring, indoline ring, isoindoline ring, 1,2,3,4-tetrahydrocarbazole ring, 1,2,3,4-tetrahydroquinoline ring, 1, 2,3,4-tetrahydroisoquinoline ring, iminodibenzyl ring, phenoxazine ring, phenothiazine ring, phenazine ring, etc. are preferred. Yes.

  Among these, pyrrolidine ring, 3-pyrroline ring, piperidine ring, 1,2,3,6-tetrahydropyridine ring, hexamethyleneimine ring, piperazine ring, decahydroquinoline ring, oxazolidine ring, morpholine ring, thiazolidine ring, thio More preferred are morpholine rings, and further pyrrolidine ring, 3-pyrroline ring, piperidine ring, 1,2,3,6-tetrahydropyridine ring, piperazine ring, decahydroquinoline ring, oxazolidine ring, morpholine ring, thiazolidine ring, thiomorpholine. A ring is particularly preferred.

Wherein R ³ or alkyl group represented by R ^4, an alkenyl group, aryl group and aralkyl group, and a heterocyclic ring formed by R ³ and R ⁴ and the nitrogen atom is represented further by the R ³ or R ⁴ Each group may be substituted.

In the case where each group represented by R ³ or R ⁴ and the heterocyclic ring formed by R ³ and R ⁴ and a nitrogen atom have a substituent, examples of the substituent include an acyl group (particularly an acetyl group), acylamino Group, acylaminocarbonylamino group, aralkylaminocarbonylamino group, arylaminocarbonylamino group, methacryloylaminocarbonylamino group, trifluoromethyl group, fluoro group, chloro group, bromo group, iodo group, hydroxy group, nitro group, methyl Group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, sec-butyl group, t-butyl group, pentyl group, hexyl group, heptyl group, octyl group, vinyl group, Methoxy group, ethoxy group, butoxy group, isopropoxy group, t-butoxy group, cyclohexyloxy group, vinyloxy group Methylthio group, ethylthio group, a pyrrolidinyl group, a piperidinyl group, an amino group, dimethylamino group, diethylamino group, a phenyl group is preferable.

Among them, acyl group (especially acetyl group), acylamino group, trifluoromethyl group, fluoro group, chloro group, bromo group, hydroxy group, nitro group, methyl group, ethyl group, n-propyl group, i-propyl group , N-butyl group, i-butyl group, sec-butyl group, t-butyl group, pentyl group, hexyl group, vinyl group, methoxy group, ethoxy group, butoxy group, isopropoxy group, t-butoxy group, cyclohexyloxy Group, vinyloxy group, methylthio group, ethylthio group, pyrrolidinyl group, piperidinyl group, amino group, dimethylamino group, diethylamino group, and phenyl group are more preferable, and acyl group (particularly acetyl group), acylamino group, trifluoromethyl group, Fluoro group, chloro group, bromo group, hydroxy group, nitro group, methyl group, ethyl N-propyl group, i-propyl group, n-butyl group, i-butyl group, t-butyl group, hexyl group, vinyl group, methoxy group, ethoxy group, isopropoxy group, cyclohexyloxy group, vinyloxy group, methylthio A group, ethylthio group, pyrrolidinyl group, piperidinyl group, amino group, dimethylamino group, diethylamino group and phenyl group are particularly preferred.
These substituents may be further substituted with the same substituents as described above.

  In particular, when the substituent is a group having an active hydrogen such as a hydroxy group or an amino group, it is reacted with various acid chlorides, acid anhydrides, halides or various isocyanates to produce acetyl groups, acyl groups, (meth) It may be substituted with a group such as acryloyl group, alkylaminocarbonyl group, arylaminocarbonyl group (for example, butylaminocarbonyl group, phenylaminocarbonyl group, etc.), alkyl group, aralkyl group and the like.

  As a number of the said substituent, 0-4 are preferable, 0-3 are more preferable, and 0-2 are especially preferable.

Among the compounds represented by the general formula (I), as a preferable compound, a combination of a plurality of R ¹ groups includes a [1] sulfamoyl group and a halogen atom (for example, 1-sulfamoyl-4-chloro, etc.) , [2] a combination containing a sulfamoyl group and a trifluoromethyl group (for example, 1-sulfamoyl-4-trifluoromethyl), [3] a combination containing a sulfamoyl group and a nitro group (for example, 1-sulfamoyl-3 -Nitro and the like). These are suitable in view of synthesis, light resistance, heat resistance, and color value (molar extinction coefficient).

Of the compounds represented by the general formula (I), the substituted sulfamoyl group represented by the general formula (II) is represented by the following general formula (III) bonded to the ortho position of the azo group bonding position. Compounds are more preferred. In general formula (III), m represents the integer of 1-4. In general formula (III) R ¹ and R ² and R ³ and R ⁴ in has the same meaning as R ¹ and R ² and R ³ and R ⁴ in above formula (I) or (II) The preferred embodiment is also the same.

Also in the general formula (III), a compound having a structure of a combination [1] to [3] of a plurality of R ¹ described above is particularly suitable.
In terms of color value, the formula weight of the group represented by R ³ or R ⁴ in each of the above general formulas is preferably 500 or less, more preferably 400 or less, and more preferably 300 or less in total of R ³ and R ^4. Is particularly preferred.

R ² is preferably a hydrogen atom, Li, Na, K, Rb, Cs, Ag, or a cation composed of a nitrogen-containing compound, and particularly, a hydrogen atom, Na, K, Rb, Cs, Ag, or a nitrogen-containing compound. A cation is more preferable, and a cation composed of a hydrogen atom, Na, K, Cs, or a nitrogen-containing compound is particularly preferable.

The nitrogen-containing compound represented by R ² is selected in consideration of all of solubility in organic solvents and water, salt-forming properties, dye absorbance / color value, heat resistance as a colorant, and light resistance. The When selecting only from the viewpoint of absorbance and color value, the nitrogen-containing compound preferably has a molecular weight as low as possible. Among them, those having a molecular weight of 300 or less are preferred, those having a molecular weight of 280 or less are more preferred, and those having a molecular weight of 250 or less are particularly preferred. Further, in order to prevent light fading of dyes and to improve heat resistance, nitrogen-containing compounds generally known as anti-fading agents may be used. From this viewpoint, the acid value potential (vs. Ag ^/ Ag ⁺ ) is A lower compound (smaller ionization potential), a tertiary amine compound, an aliphatic cyclic amine compound, an aniline compound, a hydrazine compound, and the like are preferable.

  Hereinafter, although the specific example of the said nitrogen-containing compound is given, in this invention, it is not limited to these.

N in the general formula (I) represents an integer of 2 to 5, preferably 2 to 3. Particularly when n = 2, a structure in which two R ¹ are in the para position is preferable. Similarly, m in the general formula (III) is preferably 1 to 2, and one R ¹ is preferably a structure in the meta or para position of the substituted sulfamoyl group.

  Hereinafter, specific examples (exemplary compounds (1) to (14)) of the compound represented by the general formula (I) will be given. However, the present invention is not limited to these.

  The compound represented by the general formula (I) or (III) can be synthesized by a known general method. Hereinafter, the synthesis of the exemplified compound (1) will be specifically described as an example (Synthesis Example 1). However, the present invention is not limited to the following synthesis method as long as the gist thereof is not exceeded.

-Synthesis Example 1
The synthesis | combination of exemplary compound (1) can be performed according to the following scheme.

  5.00 g of the above compound (1), 2.20 g of aniline, and 15 g of dichlorobenzene were mixed, stirred at room temperature for 1 hour, and heated to 50 ° C. Thereafter, 2.48 g of sodium carbonate was added thereto and stirred at 70 ° C. for 1 hour. The resulting reaction mixture was poured into water, extracted with ethyl acetate, and the ethyl acetate phase was washed with 4% aqueous sulfuric acid. Magnesium sulfate and activated carbon were added to the ethyl acetate phase, dried and decolored, filtered through Celite, and the ethyl acetate phase was concentrated to obtain 4.52 g of Compound (2) (yield 70%).

  Next, 2.07 g of reduced iron, 2.0 g of acetic acid, and 5.0 g of water were mixed and stirred at 80 ° C. To this, 4.52 g of the compound (2) obtained above was gradually added and stirred at 80 ° C. for 2 hours. Further, 1.39 g of sodium carbonate was added and stirred at 80 ° C. for 30 minutes. Subsequently, Celite and activated carbon were added and filtered through Celite, and then the organic layer was subjected to steam distillation to obtain 3.51 g of Compound (3) (yield 84%).

Next, 3.51 g of compound (3), 0.12 g of tetraethylammonium chloride, 3.1 ml of acetic acid, and 3.7 ml of 36% hydrochloric acid were mixed, cooled to 0 ° C., and then added to a sodium nitrite aqueous solution (NaNO ₂ : 0.74 g, water: 1.7 g) was added dropwise while maintaining the internal temperature at 5 ° C. or lower. Thereafter, the mixture was maintained at 5 to 10 ° C. and further stirred for 3 hours (diazo solution).

  The obtained diazo solution was dropped into a separately prepared slurry of γ acid (γ acid: 2.79 g, water: 16.5 g, 36% hydrochloric acid: 0.5 ml) at 0 ° C. over 30 minutes. . Subsequently, 5 ml of 40% aqueous sodium acetate solution was added dropwise over 1 hour, and the mixture was stirred at 0 ° C. for 2 hours. Subsequently, 20 ml of 10% aqueous sodium carbonate solution was added dropwise thereto and stirred overnight, and 7.0 g of 50% aqueous NaOH solution was further added dropwise, stirred for 1 hour while warming to 65 ° C., and then cooled to room temperature. The obtained mixture was filtered and washed with alkaline brine to obtain 6.21 g of phenylazonaphthalene compound [Exemplary Compound (1)] (yield 99%).

The structure obtained by the above-described method was actually confirmed by NMR. As a result, ¹ H-NMR (300 MHz, solvent: dimethyl-d ₆ sulfoxide, standard substance: tetramethylsilane) δ 12.4 ppm (1H, s ), 10.7 (1H, br.s), 9.00 (1H, br.s), 8.10 (1H, d), 7.90-7.80 (3H, m), 7.55 ( 1H, s), 7.25 (1H, s), 7.18 to 6.90 (6H, m), 3.60 (2H, q), 0.90 (3H, t). .
In addition, about other above-mentioned exemplary compounds, it can synthesize | combine similarly to the above by changing the compound (2) shown to the said scheme into a desired compound.

~ Acid dye ~
The compound represented by the above general formula (I) may be used simultaneously with other acid dyes, salts of other acid dyes with metals or nitrogen-containing compounds, derivatives of other acid dyes, and the like. Hereinafter, the acid dye will be described.

  The acidic dye is not particularly limited as long as it has an acidic group such as a sulfonic acid or a carboxylic acid, and is soluble in an organic solvent or a developer used for the preparation of a composition or a development treatment, a salt forming property, an absorbance, The curable composition is selected in consideration of all required performances such as interaction with other components, light resistance, heat resistance and the like.

Specific examples of the acid dye are shown below, but the invention is 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;
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 1,4,8,14,17,18,26,27,29,31,34,35,37,42,44,50,51,52,57,66,73,80,87,88, 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 1,3,7,9,11,17,23,25,29,34,36,42,54,65,72,73,76,79,98,99,111,112,114,116, 169, 243;
Food Yellow 3;
And derivatives of these dyes.

Among these, particularly, acid black 24;
acid blue 23, 25, 29, 62, 86, 87, 92, 138, 158;
acid orange 8, 51, 56, 74, 63;
acid red 1,4,8,34,37,42,52,57,80,97,114,143,145,151,183,217;
acid violet 7;
Acid yellow 17, 23, 25, 29, 34, 42, 72, 76, 99, 111, 112, 114, 116, 163, 243, and the like, and derivatives of these dyes are preferred.

Other than the above, azo, xanthene and phthalocyanine acid dyes are also preferable. I. Solvent Blue 44, 38, C.I. I. Solvent Orange 45, Rhodamine B, Rhodamine 110, 2,7-Naphthalenedisulfonic acid, 3-[(5-chloro-2-phenoxyphenyl) hydrazono] -3,4-dihydro-4-oxo-5- [minyl] ulyl] Preferable examples include acidic dyes such as and the like, and derivatives of these dyes.
As the derivative of the acid dye, a compound obtained by converting the sulfonic acid of the acid dye into a sulfonic acid amide or a sulfonic acid ester can be used effectively.

  Next, the atomic group that forms a salt with the acid dye will be described. The atomic group that forms a salt with the acid dye is not particularly limited as long as it is a cationic group that forms a salt with the anion of the acid dye. For example, Li, Na, K, Rb, Cs, Ag, or a nitrogen-containing compound And cations.

  Nitrogen-containing compounds that form salts with acidic dyes are soluble in organic solvents and developers used in the preparation and development of compositions, salt-forming properties, dye absorbance, and other components in the curable composition. It is selected in consideration of all interactions and the like. When selecting only from the viewpoint of absorbance, those having a molecular weight as low as possible are preferred, those having a molecular weight of 245 or less are preferred, those having a molecular weight of 240 or less are more preferred, and those having a molecular weight of 230 or less are particularly preferred.

Further, for the purpose of preventing light fading of dyes and improving heat resistance, nitrogen-containing compounds generally known as anti-fading agents may be used. From this viewpoint, the acid value potential is lower (the ionization potential is smaller). Compounds, tertiary amine compounds, aliphatic cyclic amine compounds, aniline compounds, hydrazine compounds, and the like are preferable.
Preferable specific examples of the nitrogen-containing compound here are the same as the nitrogen-containing compounds listed as R ² in the general formula (I).

  Next, a ratio of “a compound (or acidic dye) represented by the general formula (I) and a chemical group represented by the general formula (I) (or an acidic dye) / a compound forming the salt (or acidic dye)” (hereinafter, will be described. k is a value that determines the molar ratio between the compound represented by the general formula (I) or the molecule of the acid dye and the atomic group that is a counter ion, and the compound represented by the general formula (I) or the acid dye − It can be freely selected according to the salt formation conditions of the atomic group. Specifically, k is a numerical value satisfying 0 <k ≦ 10 among the number of functional groups of the acid in the acid dye, and is soluble in organic solvents and developers, salt-forming properties, absorbance, and other values in the curable composition. It is selected in consideration of all necessary performance priorities, such as interaction with other components, light resistance, heat resistance and the like. When selecting only from the viewpoint of absorbance, it is preferable to take a numerical value between 0 <k ≦ 7, more preferably a numerical value between 0 <k ≦ 6, and a numerical value between 0 <k ≦ 5. It is particularly preferred to take.

In the colorant-containing curable composition of the present invention, the ratio of the solid content in the composition is preferably 3 to 60% by mass, more preferably 10 to 40% by mass.
In addition, the amount of the compound represented by the above general formula (I) and, if necessary, the acidic dye in the solid content (including the case of a color filter) is preferably 3 to 90% by mass, 70 mass% is more preferable. The proportion of the compound represented by the general formula (I) and, if necessary, the acid dye in the curable composition is preferably 0.1 to 50% by mass, more preferably 1 to 30% by mass. .

(binder)
The colorant-containing curable composition of the present invention can contain at least one binder. The binder is not particularly limited as long as it is alkali-soluble, but is preferably selected from the viewpoints of heat resistance, developability, availability, and the like.

  The 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-58-12777, and JP-B-54-25957. Methacrylic acid copolymer, acrylic acid copolymer, itaconic acid copolymer, crotonic acid copolymer, as described in JP-A-59-53836 and JP-A-59-71048. Examples thereof include polymers, maleic acid copolymers, partially esterified maleic acid copolymers, and acidic cellulose derivatives having a carboxylic acid in the side chain are also useful.

In addition to the above, those obtained by adding an acid anhydride to a polymer having a hydroxyl group, polyhydroxystyrene resins, polysiloxane resins, poly (2-hydroxyethyl (meth) acrylate), polyvinylpyrrolidone and polyethylene oxide, Polyvinyl alcohol, etc. are also useful.
Moreover, you may copolymerize the monomer which has hydrophilic property, As an example, alkoxyalkyl (meth) acrylate, hydroxyalkyl (meth) acrylate, glycerol (meth) acrylate, (meth) acrylamide, N-methylol acrylamide, Secondary or tertiary alkylacrylamide, dialkylaminoalkyl (meth) acrylate, morpholine (meth) acrylate, N-vinylpyrrolidone, N-vinylcaprolactam, vinylimidazole, vinyltriazole, methyl (meth) acrylate, ethyl (meth) acrylate Branched or linear propyl (meth) acrylate, branched or linear butyl (meth) acrylate, phenoxyhydroxypropyl (meth) acrylate, and the like.

  Other examples of the hydrophilic monomer include tetrahydrofurfuryl group, phosphoric acid, phosphoric ester, quaternary ammonium salt, ethyleneoxy chain, propyleneoxy chain, sulfonic acid and its salt, and morpholinoethyl group. Useful.

  In order to improve the crosslinking efficiency, a polymerizable group may be included in the side chain, and 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 containing these polymerizable groups are shown below, but the polymer is not limited to these as long as it contains an alkali-soluble group such as COOH group, OH group, and ammonium group and a carbon-carbon unsaturated bond.

  As a specific example, a copolymer of an OH group such as 2-hydroxyethyl acrylate, a COOH group such as methacrylic acid, and a monomer such as an acrylic or vinyl compound copolymerizable with these, an OH group A compound obtained by reacting an epoxy ring having reactivity with a compound having a carbon-carbon unsaturated bond group (for example, a compound such as glycidyl acrylate) can be used.

  As the compound having reactivity with the OH group, a compound having an acid anhydride, an isocyanate group, and an acryloyl group can be used in addition to the epoxy ring. Further, a compound obtained by reacting an unsaturated carboxylic acid such as acrylic acid with a compound having an epoxy ring described in JP-A-6-102669 and JP-A-6-1938 is saturated or unsaturated polybasic. A reaction product obtained by reacting an acid anhydride can also be used.

  Examples of the compound having both an alkali solubilizing group such as a COOH group and a carbon-carbon unsaturated group include, for example, Dainar NR series (manufactured by Mitsubishi Rayon Co., Ltd.); Photomer 6173 (COOH group-containing Polyurethane acrylic oligomer, Diamond Shamrock Co.) Ltd.); Biscote R-264, KS resist 106 (both manufactured by Osaka Organic Chemical Industry Co., Ltd.); Cyclomer P series, Plaxel CF200 series (both manufactured by Daicel Chemical Industries, Ltd.); Ebecryl 3800 (Daicel) And UCB Co., Ltd.).

  Among these various binders, from the viewpoint of heat resistance, polyhydroxystyrene resins, polysiloxane resins, acrylic resins, acrylamide resins, and acrylic / acrylamide copolymer resins are preferable, and acrylic resins and polyhydroxystyrenes are used. More preferred are resin based resins and polysiloxane based resins. From the viewpoint of control of developability, an acrylic resin, an acrylamide resin, and an acrylic / acrylamide copolymer resin are preferable.

  Examples of the acrylic resin include copolymers composed of monomers selected from benzyl (meth) acrylate, (meth) acrylic acid, hydroxyethyl (meth) acrylate, (meth) acrylamide, and the like, and cyclomer P series, Placcel CF200 series (all manufactured by Daicel Chemical Industries, Ltd.), Ebecryl 3800 (manufactured by Daicel UC Corporation), Dinar NR series (manufactured by Mitsubishi Rayon Co., Ltd.), Biscote R264, KS resist 106 (all Osaka Organic Chemical) Kogyo Co., Ltd.) is preferred.

  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.

  Furthermore, an alkali-soluble phenol resin can be used. The alkali-soluble phenol resin can be suitably used when the colorant-containing curable composition of the present invention is configured as a positive type. Examples of the alkali-soluble phenol resin 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. These phenols can be used alone or in combination of two or more. Examples of aldehydes include formaldehyde, paraformaldehyde, acetaldehyde, propionaldehyde, benzaldehyde, and the like.

  Specific examples of the novolak resin include, for example, 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 phenolic hydroxyl groups, such as bisphenol C and bisphenol A, in said novolak resin.

  Among these, it is preferable to use an acrylic or methacrylic alkali-soluble resin. Among these, an alkali-soluble resin having a polymerizable group (polymerizable side chain) at a side chain site bonded to the main chain is particularly preferable. When having a polymerizable group, the crosslinking efficiency is increased regardless of the presence or absence of the monomer, and the degree of curing can be effectively improved by the presence of the polymerizable group in the side chain.

The above binder is preferably a polymer having a weight average molecular weight (polystyrene conversion value measured by GPC method) of 1000 to 2 × 10 ⁵ , more preferably 2000 to 1 × 10 ⁵ , and 5000 to ⁵ × 10. The polymer of ⁴ is particularly preferred.

  As content in the coloring agent containing curable composition of the said binder, 10-90 mass% is preferable with respect to the total solid of this composition, 20-80 mass% is more preferable, 30-70 mass% Is particularly preferred.

(Crosslinking agent)
The colorant-containing curable composition of the present invention contains the compound represented by the general formula (I) or (III) described above as a colorant, and further enhances the curing reaction of the coating film as compared with the prior art. It is possible to obtain a film having good curability by proceeding, but it is also possible to form a more highly cured film by additionally using a crosslinking agent.
Hereinafter, the crosslinking agent will be described.

  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) epoxy resin, (b) methylol group, alkoxymethyl group, and acyloxymethyl. At least one substituent selected from a melamine compound, a guanamine compound, a glycoluril compound or a urea compound, (c) a methylol group, an alkoxymethyl group, and an acyloxymethyl group, which is substituted with at least one substituent selected from the group A phenol compound, a naphthol compound or a hydroxyanthracene compound substituted with Of these, polyfunctional epoxy resins are preferred.

  The epoxy resin (a) may be any epoxy resin as long as it has an epoxy group and has crosslinkability, for example, bisphenol A diglycidyl ether, ethylene glycol diglycidyl ether, butanediol diglycidyl ether. , Hexanediol diglycidyl ether, dihydroxybiphenyl diglycidyl ether, diphthalic acid diglycidyl ester, N, N-diglycidyl aniline and other divalent glycidyl group-containing low molecular weight compounds, as well as trimethylolpropane triglycidyl ether, Trivalent glycidyl group-containing low molecular weight compounds represented by methylolphenol triglycidyl ether, TrisP-PA triglycidyl ether, etc., as well as pentaerythritol tetraglycidyl ether, tetramethylol vinyl Tetravalent glycidyl group-containing low molecular weight compounds typified by phenol A tetraglycidyl ether, polyvalent glycidyl group-containing low molecular weight compounds such as dipentaerythritol pentaglycidyl ether and dipentaerythritol hexaglycidyl ether, polyglycidyl ( And glycidyl group-containing polymer compounds represented by 1,2-epoxy-4- (2-oxiranyl) cyclohexane adduct of 2,2-bis (hydroxymethyl) -1-butanol and the like. .

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

  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 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 obtained by acyloxymethylating 1 to 3 methylol groups of guanamine 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.
These 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 the crosslinking agent (b). As in the case of, the thermal cross-linking suppresses intermixing with the overcoated photoresist and further increases the film strength. 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 group-containing compound).

The number of methylol groups, acyloxymethyl groups or alkoxymethyl groups contained in the crosslinking agent (c) is at least 2 per molecule, and from the viewpoint of thermal crosslinkability and storage stability, phenol as a skeleton Compounds in which the 2nd and 4th positions of the compound are all substituted are 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 3rd or 5th position of the phenolic compound serving as the skeleton may be unsubstituted or may have a substituent.
The naphthol compound may be unsubstituted or substituted except for the ortho position of the OH group.

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 skeleton compound in the crosslinking agent (c) include phenol compounds, naphthols, hydroxyanthracene compounds, etc., in which the ortho-position or para-position of the phenolic OH group is unsubstituted. , 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, as a phenol compound or a naphthol compound, for example, trimethylolphenol, tri (methoxymethyl) phenol, a compound obtained by methoxymethylating one or two methylol groups of trimethylolphenol, Trimethylol-3-cresol, tri (methoxymethyl) -3-cresol, compounds obtained by methoxymethylating 1 to 2 methylol groups of trimethylol-3-cresol, 2,6-dimethylol-4-cresol and the like Methylol cresol, tetramethylol bisphenol A, tetramethoxymethyl bisphenol A, a compound obtained by methoxymethylating 1 to 3 methylol groups of tetramethylol bisphenol A, tetramethylol-4,4′-bishydroxybiphenyl, tetramethyl A compound obtained by methoxymethylating 1 to 5 methylol groups of cymethyl-4,4′-bishydroxybiphenyl, hexamethylol of TrisP-PA, hexamethoxymethyl of TrisP-PA, hexamethylol of TrisP-PA, Bishydroxymethyl naphthalene diol, etc. are mentioned.

Examples of the hydroxyanthracene compound include 1,6-dihydroxymethyl-2,7-dihydroxyanthracene.
Examples of the acyloxymethyl group-containing compound include compounds obtained by partially or fully acyloxymethylating the methylol group of the methylol group-containing compound.

Among these compounds, trimethylolphenol, bishydroxymethyl-p-cresol, tetramethylolbisphenol A, trisP-PA (manufactured by Honshu Chemical Industry Co., Ltd.) or a methylol group thereof is preferable. Examples thereof include an alkoxymethyl group and a phenol compound substituted with both a methylol group and an alkoxymethyl group.
These compounds according to (c) may be used alone or in combination.

  In the present invention, it is not always necessary to contain a cross-linking agent, but in the case where it is contained, the total content of the cross-linking agents (a) to (c) in the colorant-containing curable composition may be a material. Depending on the solid content (mass) of the composition, it is preferably 1 to 70 mass%, more preferably 5 to 50 mass%, and particularly preferably 7 to 30 mass%.

(Polymerizable compound)
The colorant-containing curable composition of the present invention can be suitably constituted by containing at least one polymerizable compound (hereinafter also referred to as a monomer as appropriate). The monomer is mainly contained when the colorant-containing curable composition is configured as a negative type. In addition, it can further contain in the positive type | system | group containing the below-mentioned o-quinonediazide compound with the below-mentioned photoinitiator and photoacid generator, and in this case, the hardening degree of the pattern formed can be promoted more. . Hereinafter, the polymerizable compound will be described.

  As the polymerizable compound, a compound having an ethylenically unsaturated group having at least one addition-polymerizable ethylene group and having a boiling point of 100 ° C. or higher under normal pressure is preferable. Monofunctional acrylates and methacrylates such as (meth) acrylate, polypropylene glycol mono (meth) acrylate, phenoxyethyl (meth) acrylate; polyethylene glycol di (meth) acrylate, trimethylolethane tri (meth) acrylate, neopentyl glycol di (Meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) a Ethylene oxide and propylene oxide were added to polyfunctional alcohols such as relate, hexanediol (meth) acrylate, trimethylolpropane tri (acryloyloxypropyl) ether, tri (acryloyloxyethyl) isocyanurate, glycerin and trimethylolethane Later (meth) acrylates, urethane acrylates described in JP-B-48-41708, JP-B-50-6034, JP-A-51-37193, JP-A-48-64183, JP-B-37 No. 49-43191, Japanese Patent Publication No. 52-30490, polyester acrylates, polyfunctional acrylates and methacrylates such as epoxy acrylates which are reaction products of epoxy resin and (meth) acrylic acid, and these Mixture can be mentioned. Furthermore, the Journal of Japan Adhesion Association Vol. 20, no. 7, pages 300 to 308 are introduced as photocurable monomers and oligomers. In particular, a (meth) acrylic ester-based polymerizable compound is preferable, and a tetrafunctional or higher (meth) acrylic ester-based monomer is more preferable.

  The content of the polymerizable compound in the colorant-containing curable composition is preferably 0.1 to 90 mass%, more preferably 1.0 to 80 mass%, based on the solid content of the composition. 0.0 to 70% by mass is particularly preferable.

(Radiosensitive compounds)
The coloring agent containing curable composition of this invention can be comprised suitably by containing at least 1 type of a radiation sensitive compound. The radiation-sensitive compound according to the present invention is a compound capable of causing a chemical reaction such as radical generation, acid generation, base generation, etc., against 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.

  The colorant-containing curable composition preferably contains a photopolymerization initiator, particularly when it is configured as a negative type, and when it is configured as a positive type, an o-quinonediazide compound or photoacid generator. It is preferable to contain an agent.

  First, the photopolymerization initiator will be described. The photopolymerization initiator is not particularly limited as long as it can polymerize the polymerizable compound (a monomer having a polymerizable group), but is selected from the viewpoints of characteristics, initiation efficiency, absorption wavelength, availability, cost, and the like. It is preferable. The photopolymerization initiator can be configured as a negative type, and the photopolymerization initiator here includes a compound capable of generating acid with respect to radiation, so-called photoacid generator. It can also be configured into a mold. In addition, you may further contain a photoinitiator in the positive type | system | group containing said o-quinonediazide compound, In this case, the hardening degree of the pattern formed can be accelerated | stimulated more.

  Examples of the photopolymerization initiator include trihalomethyltriazine compounds, benzyldimethyl ketal compounds, α-hydroxyketone compounds, α-aminoketone compounds, phosphine oxide compounds, metallocene compounds, oxime compounds, triallylimidazole dimers, benzoates. Examples include thiazole compounds, benzophenone compounds, acetophenone compounds and derivatives thereof, cyclopentadiene-benzene-iron complexes and salts thereof, halomethyloxadiazole compounds, and 3-aryl-substituted coumarin compounds.

  Examples of active halogen compounds such as halomethyloxadiazole compounds include 2-halomethyl-5-vinyl-1,3,4-oxadiazole compounds 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. Alternatively, as a romethyl-s-triazine compound, a vinyl-halomethyl-s-triazine compound described in JP-B-59-1281 and 2- (naphth-1-yl)-described in JP-A-53-133428 are disclosed. Examples include 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-trichloro Methyl-s-triazine, 4- [p-N, 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- [p-N, N-di (chloroethyl) aminophenyl] -2,6-di (trichloro Methyl) -s-triazine, 4- [o-methyl-pN, N-di (chloroethyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- (pN-chloroethyla) Nophenyl) -2,6-di (trichloromethyl) -s-triazine, 4- (pN-ethoxycarbonylmethylaminophenyl) -2,6-di (trichloromethyl) -s-triazine, 4- [p- N, N-di (phenyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- (p-N-chloroethylcarbonylaminophenyl) -2,6-di (trichloromethyl)- s-triazine, 4- [p-N- (p-methoxyphenyl) carbonylaminophenyl] -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) aminophen L] -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 (chloroethyl) 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-p-N, 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-pN-ethoxycarbonylmethylamino) Phenyl) -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-ethoxycarbonylmethylaminophenyl) -2 , 6-Di (trichloromethyl) -s-triazine, 4- (o-chloro-pN-ethoxycarbonylmethylaminophenyl) -2,6-di (trichloro) Methyl) -s-triazine, 4- (o-fluoro-pN-ethoxycarbonylmethylaminophenyl) -2,6-di (trichloromethyl) -s-triazine, 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-pN-chloroethylaminophenyl) -2 , 6-Di (trichloromethyl) -s-triazine, 4- (o-chloro-pN-chloroethylaminophenyl) -2,6-di (trichloromethyl) -s-triazine, 4 (O-FLUORO -p-N-chloroethyl aminophenyl) -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, etc.) manufactured by Midori Chemical, manufactured by PANCHIM T series (for example, T-OMS, T-BMP, TR, T-B, etc.), Irgacure series (for example, Irgacure 651, Irgacure 184, Irgacure 500, Irgacure 1000, Irgacure 149, Irgacure 819) manufactured by Ciba Geigy , Irgacure 261, etc.), Darocur series (eg Darocur 1173),

4,4′-bis (diethylamino) -benzophenone, 2- (O-benzoyloxime) -1- [4- (phenylthio) phenyl] -1,2-octanedione, 2-benzyl-2-dimethylamino-4- Morpholinobyrophenone, 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-methoxyphenyl) -4,5-diphenylimidazolyl dimer, 2- (p-dimethoxyphenyl) -4 , 5-Diphenylimidazolyl dimer, 2- (2,4-dimethoxyphenyl) -4,5-diphenylimidazolyl dimer , 2-(p-methyl) -4,5-diphenyl imidazolyl dimer, benzoin isopropyl ether, etc. are also useful.

  The α-aminoketone-based compound is not particularly limited, but examples thereof include Irgacure series (Irgacure 907, Irgacure 369, etc.) manufactured by Ciba Geigy, 2-methyl-1-phenyl-2-morpholinopropan-1-one. 2-methyl-1- [4- (hexyl) phenyl] -2-morpholinopropan-1-one, 2-ethyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1, etc. Is mentioned.

  Although it does not specifically limit as an oxime type compound, For example, 2- (O-benzoyloxime) -1- [4- (phenylthio) phenyl] -1,2-octanedione, 1- (4-methylsulfanyl-phenyl) -Butane-1,2-butane 2-oxime-O-acetate, 1- (4-methylsulfanyl-phenyl) -butan-1-one oxime-O-acetate, hydroxyimino- (4-methylsulfanyl-phenyl) -acetic acid Examples include ethyl ester-O-acetate, hydroxyimino- (4-methylsulfanyl-phenyl) -acetic acid ethyl ester-O-benzoate, and the like.

  From the viewpoints of availability and stability, Irgacure 651 and the like are used as the benzyldimethyl ketal compound, Irgacure 184, 1173, 500, 1000, and 2959 are used as the α-hydroxyketone compound, and Irgacure is used as the α-aminoketone compound. 907, 369, etc. are preferably Irgacure 1700, 149, 1850, 819, 184, etc. as phosphine oxide compounds (blends), and Irgacure 784, 261, etc. as metallocene compounds (all manufactured by Ciba Specialty Chemicals) These analogs / peripheral compounds and the like are also preferable.

  Among the above, it is desirable to use a compound that does not generate an acid by decomposition in terms of light resistance and heat resistance of the dye. That is, as a compound which does not generate an acid by decomposition among the above, a trihalomethyltriazine compound, a benzyldimethyl ketal compound, an α-hydroxyketone compound, an α-aminoketone compound, a phosphine oxide compound, a metallocene compound, an oxime compound, Preference is given to at least one compound selected from triallylimidazole dimer, benzothiazole compounds, benzophenone compounds, acetophenone compounds and derivatives thereof, cyclopentadiene-benzene-iron complexes and salts thereof. Furthermore, at least one compound selected from the group consisting of α-aminoketone compounds, phosphine oxide compounds, metallocene compounds, oxime compounds and triallylimidazole dimers is preferred.

  These photopolymerization initiators can be used in combination with a sensitizer and a light stabilizer. Specific examples thereof include benzoin, benzoin methyl ether, benzoin, 9-fluorenone, 2-chloro-9-fluorenone, 2-methyl-9-fluorenone, 9-anthrone, 2-bromo-9-anthrone, 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-methoxyxanthone, thioxanthone, 2,4-diethylthioxanthone, acridone, 10-butyl-2-chloroacridone, benzyl, dibenzalacetone, p- (dimethylamino) phenylstyryl ketone, p- (Dimethylamino) phenyl-p-methyls Tiny ketone, benzophenone, p- (dimethylamino) benzophenone (or Michler's ketone), p- (diethylamino) benzophenone, benzoanthrone, benzothiazole compounds described in Japanese Patent Publication No. 51-48516, etc. Etc.

  Other known photopolymerization initiators other than the photopolymerization initiator can be used in combination with the colorant-containing curable composition of the present invention. Specifically, the vicinal polykettle aldonyl compound described in US Pat. No. 2,367,660, the α described in US Pat. Nos. 2,367,661 and 2,367,670 Carbonyl compounds, acyloin ethers described in US Pat. No. 2,448,828, aromatic acyloin compounds substituted with α-hydrocarbons described in US Pat. No. 2,722,512, US Polynuclear quinone compounds described in Patent Nos. 3,046,127 and 2,951,758, and triallylimidazole dimer / p-aminophenyl ketone described in US Pat. No. 3,549,367. Combinations, benzothiazole compounds / trihalomethyl-s-triazine compounds described in JP-B 51-48516, and the like can be mentioned.

  The content of the photopolymerization initiator in the colorant-containing curable composition is preferably 0.01 to 50% by mass and preferably 1 to 30% by mass with respect to the solid content (mass) of the polymerizable compound (monomer). % Is more preferable, and 1 to 20% by mass is particularly preferable. When the content is less than 0.01% by mass, the polymerization may be difficult to proceed. When the content exceeds 50% by mass, the polymerization rate is increased, but the molecular weight is decreased and the film strength may be decreased.

  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-tert-butylphenol), 2,2′-methylenebis (4-methyl-6-tert-butylphenol), 2-mercaptobenzimidazole and the like are useful.

  Next, an o-quinonediazide compound suitable for a positive structure will be described. The o-quinonediazide compound is a compound having at least one o-quinonediazide group, and o-benzoquinonediazidesulfonic acid ester and o-naphthoquinonediazidesulfonic acid ester are particularly preferable. Specific examples include o-naphthoquinonediazide-5-sulfonic acid ester, o-naphthoquinonediazide-5-sulfonic acid amide, o-naphthoquinonediazide-4-sulfonic acid ester, o-naphthoquinonediazide-4-sulfonic acid amide. , Etc. These esters and amide compounds can be produced by a known method using, for example, the phenol compound described in the general formula (I) in JP-A-2-84650 and JP-A-3-49437. .

  In addition, when the colorant-containing curable composition is configured as a positive type, the alkali-soluble phenol resin and the crosslinking agent are usually about 2 to 50% by mass and about 2 to 30% by mass, respectively, in the organic solvent. It is preferable to dissolve at a ratio of In addition, each content of the o-quinonediazide compound and the colorant is usually preferably about 2 to 30% by mass and about 2 to 50% by mass with respect to the solution in which the binder and the crosslinking agent are dissolved. .

(Organic solvent)
In preparing the colorant-containing curable composition of the present invention, an organic solvent can generally be contained regardless of the negative type or the positive type. The organic solvent is not particularly limited as long as the solubility of each component and the coating property of the colorant-containing curable composition are satisfied, but especially considering the solubility, coating property, and safety of the colorant and binder. It is preferable to be selected.
Among these, non-amide organic solvents are particularly preferable from the viewpoints of coatability and safety.

  Specific examples of the organic 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, and alkyl esters. , Methyl lactate, ethyl lactate, methyl oxyacetate, ethyl oxyacetate, butyl oxyacetate, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, etc .;

3-oxypropionic acid alkyl esters such as methyl 3-oxypropionate and ethyl 3-oxypropionate, such as methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, 3-ethoxy Ethyl propionate, etc .; 2-oxypropionic acid alkyl esters such as methyl 2-oxypropionate, ethyl 2-oxypropionate, propyl 2-oxypropionate, such as methyl 2-methoxypropionate, 2-methoxypropion Acid ethyl, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, methyl 2-oxy-2-methylpropionate, ethyl 2-oxy-2-methylpropionate, 2-methoxy- 2-methylpropio Methyl acid, 2-ethoxy-2-methylpropionic acid ethyl, etc; methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutanoate, ethyl 2-oxobutanoate, etc .;

Ethers such as diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl 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 such as methyl ethyl ketone, cyclohexanone, 2-heptanone, 3-heptanone, etc .; aromatic hydrocarbons such as toluene, xylene, etc. Preferably mentioned .

  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)
The colorant-containing curable composition of the present invention includes various additives as necessary, for example, fillers, polymer compounds other than the above, surfactants, adhesion promoters, antioxidants, ultraviolet absorbers, and aggregation prevention. An agent or the like 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-image area is promoted and the developability of the colorant-containing curable composition of the present invention is further improved, the composition has an organic carboxylic acid, preferably a molecular weight of 1000 or less. Addition of a low molecular weight organic carboxylic acid can be performed.
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, and camphoric acid; aromatic monocarboxylic acids such as benzoic acid, toluic acid, cumic acid, hemelitic acid, and 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 colorant-containing curable composition of the present invention is used for forming colored pixels such as color filters used in liquid crystal display devices (LCDs), solid-state imaging devices (eg, CCDs, CMOSs, etc.), printing inks, and inkjets. It can be suitably used as a production application for inks and paints.

<< 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 aforementioned colorant-containing curable composition of the present invention is used.
When the colorant-containing curable composition of the present invention is configured as a negative type, the negative type colorant-containing curable composition is applied onto a support by a coating method such as spin coating, cast coating, or roll coating. Then, a radiation-sensitive composition layer is formed, the layer is exposed through a predetermined mask pattern, and developed with a developer to form a negative colored pattern (image forming step). At this time, if necessary, a curing step for curing the formed colored pattern by heating and / or exposure can be provided.

  When the colorant-containing curable composition of the present invention is configured as a positive type, the positive type colorant-containing curable composition is applied onto a support by a coating method such as spin coating, cast coating, roll coating, or the like. To form a radiation-sensitive composition layer, exposing the layer through a predetermined mask pattern, and developing with a developer to form a positive colored pattern (image forming step). Post-baking and curing the colored pattern.

  In the production of a color filter, in the case of a negative type, the image forming step (and a curing step if necessary) is repeated according to a desired number of hues. In the case of a positive type, the image forming step and post-baking are performed. By repeating according to the desired number of hues, a color filter configured with a desired number of hues can be produced. As light or radiation used at this time, ultraviolet rays such as g-line, h-line and i-line are particularly preferably used.

Examples of the support include soda glass, Pyrex (R) glass, and quartz glass used for liquid crystal display elements and the like, a transparent conductive film attached thereto, a photoelectric conversion element substrate used for an imaging element, and the like. For example, a silicon substrate, a complementary metal oxide semiconductor (CMOS), or the like can be given. These supports may be formed with black stripes that separate pixels.
Further, an undercoat layer may be provided on these supports, if necessary, in order to improve adhesion with the upper layer, prevent diffusion of substances, or flatten the substrate surface.

  As the developer, any developer can be used as long as it has a composition that dissolves the uncured portion of the colorant-containing curable composition of the present invention but does not dissolve the cured portion. Specifically, a combination of various organic solvents or an alkaline aqueous solution can be used. As said organic solvent, the organic solvent as stated above used for preparation of the coloring agent containing curable composition of this invention can be 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 thereof. Unless otherwise specified, “part” is based on mass.

Example 1
1) Preparation of resist solution-Propylene glycol monomethyl ether acetate ... 19.20 parts (PGMEA)
-Ethyl lactate-36.67 parts-Binder-30.51 parts [41% PGMEA solution of allyl methacrylate / methacrylic acid copolymer (molar ratio = 65/35)]
Dipentaerythritol hexaacrylate 12.20 parts Polymerization inhibitor (p-methoxyphenol) 0.0075 parts Fluorosurfactant 0.95 parts (F-475, Dainippon Ink & Chemicals, Inc.) Made)
Photopolymerization initiator [2- (O-benzoyloxime) -1- [4- (phenylthio) phenyl] -1,2-octanedione] ... 0.600 parts were mixed and dissolved to prepare a resist solution. .

2) Creation of glass substrate with undercoat layer A glass substrate (Corning 1737) was ultrasonically washed with 1% NaOH water, and then washed with water and dehydrated (200 ° C./30 minutes). Next, the resist solution obtained in 1) above was applied onto a glass substrate after washing 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 form a cured film (undercoat layer). Formed.

3) Preparation of colorant-containing resist solution 9.4 parts of the resist solution obtained in 1) above and the exemplified compound (1) described above as a colorant [compound represented by the general formula (I)] 0.6 Then, a negative colorant-containing resist solution (solution of the colorant-containing curable composition of the present invention) was obtained.

4) Exposure and development of colorant-containing curable composition (image forming process)
Using a spin coater, the negative colorant-containing resist solution obtained in 3) above is formed on the undercoat layer of the glass substrate with an undercoat layer obtained in 2) so that the film thickness becomes 1.0 μm. It was applied and prebaked at 120 ° C. for 120 seconds.

Next, using an exposure apparatus, the coating film was irradiated at a wavelength of 365 nm through a mask having a mask pattern of 20 μm square with an exposure amount of 800 mJ / cm ² . After irradiation, development was performed at 26 ° C. for 60 seconds using a 60% CD-2000 (Fuji Film Arch Co., Ltd.) developer. Then, after rinsing with running water for 20 seconds, spray drying was performed to obtain a pattern image. Formation of the pattern image was confirmed by an ordinary method by observation with an optical microscope and SEM photograph.

5) Evaluation The following evaluation was performed about the coloring agent containing curable composition and pattern image, and the used coloring agent. The evaluation results are shown in Table 1 below.
-Developability and remaining film rate-
The unexposed area developability and the exposed area residual film ratio in the image forming process were measured with a chromaticity meter MCPD-1000 (manufactured by Otsuka Electronics Co., Ltd.). The unexposed area developability refers to the rate of change [%] of the absorbance value of the film before and after development. When a negative colorant-containing resist solution is used, a larger value indicates better developability. . The exposed area residual film ratio refers to the maintenance ratio [%] of the absorbance value of the film before and after development. When a negative colorant-containing resist solution is used, the larger the value, the better the pattern shape. Indicates. A high value for both the unexposed area developability and the exposed area residual film ratio means that the pattern formability (developability) is good.
On the other hand, when prepared in a positive type in the examples described later (positive colorant-containing curable composition), the unexposed part developability and the exposed part residual film ratio should be small, and unexposed part development A low value of both the photosensitivity and the exposed portion residual film ratio means that the pattern formability (developability) is good.

-Heat resistance-
The glass substrate with the undercoat layer on which the pattern image was formed was heated with a hot plate at 200 ° C. for 1 hour so as to be in contact with the substrate surface, and then a chromaticity meter MCPD-1000 (manufactured by Otsuka Electronics Co., Ltd.) The chromaticity change in the pattern image, that is, the ΔEab value was measured. A smaller ΔEab value indicates better heat resistance.

-Light resistance-
The glass substrate with the undercoat layer on which the pattern image was formed was irradiated with a xenon lamp at 200,000 lux for 10 hours (equivalent to 2 million lux · h), and then the chromaticity change in the pattern image, that is, ΔEab value was measured. A smaller ΔEab value indicates better light resistance.

-Measurement of molar extinction coefficient (ε) and color value-
Separately from the above steps, the colorant used was dissolved in methanol, and the molar extinction coefficient (ε; l · mol ⁻¹ cm ⁻¹ ) was calculated from the absorbance measured using this. The color value was used as an evaluation index by a value (ε / Mw) obtained by dividing the calculated ε by the average molecular weight (Mw) of the colorant.

  Furthermore, the colorant used in the “3) Preparation of colorant-containing resist solution” is replaced with a different colorant, and the second color is applied to the glass substrate with the undercoat layer on which the pattern image has already been formed. The dye elution and color mixture were evaluated by the change in absorbance before and after the image formation of the second color.

(Examples 2-6, Comparative Example 1)
In Example 1, the same procedure as in Example 1 was conducted except that the exemplified compound (1) used as the colorant in “3) Preparation of colorant-containing resist solution” was replaced with the colorant shown in Table 1 below. A colorant-containing resist solution was prepared, a pattern image was formed, and the same evaluation was performed. The evaluation results are shown in Table 1 below.

As shown in Table 1, a colorant containing, as a colorant, the “compound represented by the general formula (I)” according to the present invention for various performances in Table 1 that have been difficult to satisfy at the same time. In the examples containing the curable composition, the colorant-containing curable composition prepared with a high molar extinction coefficient ε of the colorant has a good color value, and also has a high color density and heat resistance and light resistance. In addition to being excellent, it was possible to obtain a high-resolution pattern image (color filter) excellent in unexposed area developability and development residual film property (exposed area curability) and in developability (pattern formability). At the same time, the formed pattern did not impair the shape and hue even when contacted with a solvent, and exhibited excellent solvent resistance. Moreover, the stability after the preparation of each colorant-containing resist solution was good, and no precipitation of foreign substances or increase in liquid viscosity occurred over time.
On the other hand, in the comparative example using another colorant other than the “compound represented by the general formula (I)”, the developability and the light resistance were good, but the other performances in Table 1 were all inferior. .

(Examples 7 to 12)
A pattern image was obtained by performing the same operation as in Examples 1 to 6 except that the glass substrate used in Examples 1 to 6 was replaced with a silicon wafer substrate. The same results as in Examples 1 to 6 were obtained for heat resistance and light resistance, as well as unexposed area developability and exposed area residual film ratio. In Examples 7-12, a silicon wafer substrate is used, and the substrate is different from Examples 1-6, but the colorant-containing resist solution is substantially coated on the undercoat layer throughout Examples 1-12. The same performance was obtained without any difference.

(Example 13)
In Example 1, the exemplified compound (1) used as the colorant in “3) Preparation of colorant-containing resist solution” was replaced with the exemplified compound (14) [compound represented by the general formula (I)] described above. In the same manner as in Example 1, a colorant-containing resist solution was prepared, a pattern image was formed, and the same evaluation was performed. The evaluation results are shown in Table 1.

(Examples 14 to 15)
In Example 1, the photopolymerization initiator used in “1) Preparation of resist solution” was TAZ-107 (Example 14) and 2-benzyl-2-dimethylamino-4-morpholino manufactured by Midori Chemical Co., Ltd. A colorant-containing resist solution was prepared in the same manner as in Example 1 except that each was replaced with butyrophenone (Example 15), and a pattern image was formed, and the same evaluation was performed. The evaluation results are shown in Table 1.

(Example 16)
In Example 1, “3) Preparation of colorant-containing resist solution” was replaced with the following <Preparation of positive-type colorant-containing curable composition> in the same manner as in Example 1, but positive-type coloring. An agent-containing curable composition was prepared to form a pattern image, and the same evaluation was performed. The evaluation results are shown in Table 1.
<Preparation of positive colorant-containing curable composition>
-Ethyl lactate-210.0 parts-Novolak resin condensed with p-cresol and formaldehyde (polystyrene equivalent molecular weight 5500)-20.0 parts-Hexamethoxymethylol melamine-15.0 parts-Exemplified compound (1) [general formula Compound represented by (I)] ... 35.0 parts · Esterified product of 2,3,4-trihydroxybenzophenone and o-naphthoquinonediazide-5-sulfonyl chloride (esterification rate: 80 mol%; o-quinonediazide compound) 15.0 parts · Esterified product of [4- (7,8-dihydroxy-2,4,4-trimethyl-2-chromanyl) pyrogallol] and o-naphthoquinonediazide-5-sulfonic acid
... 15.0 parts The compound having the above composition was mixed and dissolved to obtain a positive colored photosensitive resin composition.

Claims (7)

A colorant-containing curable composition containing a colorant, wherein the colorant contains a compound represented by the following general formula (I).

[Wherein, R ¹ represents an electron-withdrawing group, and R ² represents a hydrogen atom, a cation of a monovalent metal atom, or a cation composed of a nitrogen-containing compound. n represents an integer of 2 to 5. ] The compound represented by the general formula (I) is the R ¹ The colorant-containing curable composition according to claim 1, wherein one of the electron-withdrawing groups represented by the formula is a substituted sulfamoyl group represented by the following general formula (II).

[In the formula, R ^Three And R ^Four Each independently represents a hydrogen atom, an alkyl group having 1 to 21 carbon atoms, an alkenyl group having 2 to 21 carbon atoms, an aryl group having 6 to 21 carbon atoms, or an aralkyl group having 7 to 21 carbon atoms. ] The colorant-containing curable composition according to claim 1 or 2, wherein the compound represented by the general formula (I) is a compound represented by the following general formula (III).

[In the formula, R ¹ Represents an electron-withdrawing group and R ² Represents a cation composed of a hydrogen atom, a cation of a monovalent metal atom, or a nitrogen-containing compound. m represents an integer of 1 to 4. R ^Three And R ^Four Each independently represents a hydrogen atom, an alkyl group having 1 to 21 carbon atoms, an alkenyl group having 2 to 21 carbon atoms, an aryl group having 6 to 21 carbon atoms, or an aralkyl group having 7 to 21 carbon atoms. ] A color filter comprising a compound represented by the following general formula (I):

[Wherein, R ¹ represents an electron-withdrawing group, and R ² represents a hydrogen atom, a cation of a monovalent metal atom, or a cation composed of a nitrogen-containing compound. n represents an integer of 2 to 5. ] The compound represented by the general formula (I) is the R ¹ 5. The color filter according to claim 4, wherein one of the electron-withdrawing groups represented by the formula (I) is a substituted sulfamoyl group represented by the following general formula (II).

[In the formula, R ^Three And R ^Four Each independently represents a hydrogen atom, an alkyl group having 1 to 21 carbon atoms, an alkenyl group having 2 to 21 carbon atoms, an aryl group having 6 to 21 carbon atoms, or an aralkyl group having 7 to 21 carbon atoms. ] The color filter according to claim 4 or 5, wherein the compound represented by the general formula (I) is a compound represented by the following general formula (III).

[In the formula, R ¹ Represents an electron-withdrawing group and R ² Represents a cation composed of a hydrogen atom, a cation of a monovalent metal atom, or a nitrogen-containing compound. m represents an integer of 1 to 4. R ^Three And R ^Four Each independently represents a hydrogen atom, an alkyl group having 1 to 21 carbon atoms, an alkenyl group having 2 to 21 carbon atoms, an aryl group having 6 to 21 carbon atoms, or an aralkyl group having 7 to 21 carbon atoms. ] It has the process of, after apply | coating the coloring agent containing curable composition of any one of Claims 1-3 on a support body, exposing through a mask, and developing, and forming a pattern image. A method for manufacturing a color filter.