JP2005338452A - Dye-containing negative curable composition, color filter and method for producing the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a dye-containing negative curable composition free of occurrence of residue in an unexposed portion in pattern formation; a color filter using the composition; and a method for producing the color filter. <P>SOLUTION: The dye-containing negative curable composition comprises at least (A) an alkali-soluble binder, (B) an organic-solvent-soluble dye, (C) a photopolymerization initiator, (D) a photopolymerizable compound, (E) an organic solvent and (F) a compound containing an acid group within a molecule and having a molecular weight of ≤3,000. The color filter using the composition and the method for producing the color filter are also provided. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a dye-containing negative curable composition suitable for forming a colored image constituting a color filter used in a liquid crystal display device (LCD), a solid-state image pickup device (CCD, CMOS, etc.), and the dye-containing negative. The present invention relates to a color filter using a mold curable composition and a method for producing the same.

  As a method for producing a color filter used for a liquid crystal display device or a solid-state imaging device, a dyeing method, a printing method, an electrodeposition method, and a pigment dispersion method are 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. It has the advantage of being stable to heat and the like. Further, since patterning is performed by a photolithography method, it has been widely used as a suitable method for manufacturing a color filter for a large-screen, high-definition color display with high positional accuracy.

  When producing a color filter by a pigment dispersion method, a radiation sensitive composition is applied on a glass substrate by a spin coater or a roll coater and dried to form a coating film, and the coating film is subjected to pattern exposure and development. Colored pixels are formed, and a color filter can be obtained by repeating this operation for each color.

  Examples of the pigment dispersion method include a negative photosensitive composition in which a photopolymerizable monomer and a photopolymerization initiator are used in combination with an alkali-soluble resin (see, for example, Patent Documents 1 to 4).

  On the other hand, in recent years, there has been a demand for higher definition in color filters for solid-state imaging devices. However, it is difficult to further improve the resolution in the conventional pigment dispersion system, and there is a problem that color unevenness occurs due to the coarse particles of the pigment. For this reason, it was not suitable for uses requiring a fine pattern such as a solid-state imaging device.

  In order to solve such a problem, a technique of using a dye instead of a pigment has been conventionally proposed (for example, see Patent Document 5). However, in general, a curable composition containing a dye is inferior to a curable composition using a pigment in terms of various properties such as light resistance, heat resistance, solubility, and coating uniformity. there were. In particular, in the case of use for producing a color filter for a solid-state image sensor, a film thickness of 1.5 μm or less is required, so a large amount of a dye must be added to the curable composition, thereby ensuring close contact with the substrate. There have also been problems that pattern formation is extremely difficult, such as insufficientness, insufficient curing, and loss of dye even in exposed areas.

JP-A-2-181704 JP-A-2-199403 Japanese Patent Laid-Open No. 5-273411 JP-A-7-140654 JP-A-6-75375

  Accordingly, an object of the present invention is to provide a curable composition suitable for using a dye, and specifically, a dye-containing negative curable composition in which an unexposed portion residue does not occur during pattern formation. Is to provide. Another object of the present invention is to provide a color filter having excellent pattern forming properties and high cost performance, and a method for manufacturing the color filter.

Specific means for solving the above problems are as follows.
<1> (A) Alkali-soluble binder, (B) Organic solvent-soluble dye, (C) Photopolymerization initiator, (D) Photopolymerizable compound, (E) Organic solvent, (F) Intramolecular A dye-containing negative curable composition comprising at least an acid group-containing compound having a molecular weight of 3000 or less.

  <2> The content of the compound (F) having a molecular weight of 3000 or less containing an acid group in the molecule is 0.1 to 20 parts by mass with respect to 100 parts by mass of the total solid content. It is a dye-containing negative curable composition of <1>.

  <3> The above <1> or <2>, wherein the compound (F) having an acid group in the molecule and having a molecular weight of 3000 or less is a compound having at least one alicyclic group or aromatic ring group. The dye-containing negative curable composition.

  <4> The compound (F) having an acid group in the molecule and having a molecular weight of 3000 or less has at least one alicyclic group or aromatic ring group, and the acid group is a carboxylic acid or a phenolic hydroxyl group. It is a dye-containing negative curable composition according to <1> or <2>, which is a compound.

  <5> The compound (F) having a molecular weight of 3000 or less containing an acid group in the molecule has at least two acid groups, and the acid group is a carboxylic acid or a phenolic hydroxyl group. The dye-containing negative curable composition according to the above <1> or <2>.

  <6> A color filter comprising the dye-containing negative curable composition according to <1> to <5>.

  <7> A color comprising the steps of applying the dye-containing negative curable composition of the above <1> to <5> onto a support, exposing through a mask, and developing to form a pattern. It is a manufacturing method of a filter.

  ADVANTAGE OF THE INVENTION According to this invention, the dye-containing negative curable composition which does not generate | occur | produce the unexposed part residue at the time of pattern formation can be provided. Further, according to the present invention, it is possible to provide a color filter excellent in pattern formability and high cost performance, and a manufacturing method thereof.

  Hereinafter, the dye-containing negative curable composition of the present invention, a color filter constituted using the dye-containing negative curable composition, and a method for producing the same will be described in detail.

<< Dye-containing negative curable composition >>
The dye-containing negative curable composition of the present invention comprises (A) an alkali-soluble binder, (B) an organic solvent-soluble dye, (C) a photopolymerization initiator, (D) a photopolymerizable compound, and (E ) An organic solvent and (F) a compound containing a hydroxyl group in the molecule and having a molecular weight of 3000 or less, and may further contain other components such as a crosslinking agent.

<Alkali-soluble binder>
First, the alkali-soluble binder will be described. The alkali-soluble binder in the present invention 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 alkali-soluble binder is preferably a linear organic polymer, soluble in an organic solvent, and developable with a weak alkaline aqueous solution. Examples of such linear organic high molecular polymers include polymers having a carboxylic acid in the side chain, such as JP-A-59-44615, JP-B-54-34327, JP-B-58-12777, 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 a polymer, a maleic acid copolymer, and a partially esterified maleic acid copolymer. Similarly, acidic cellulose derivatives having a carboxylic acid in the side chain are useful.

In addition to the above, the alkali-soluble binder in the present invention includes a polymer having a hydroxyl group and an acid anhydride added thereto, a polyhydroxystyrene resin, a polysiloxane resin, and poly (2-hydroxyethyl (meth) acrylate). ), Polyvinylpyrrolidone, polyethylene oxide, polyvinyl alcohol, and the like are also useful.
The linear organic polymer may be a copolymer of hydrophilic monomers, and examples thereof include alkoxyalkyl (meth) acrylate, hydroxyalkyl (meth) acrylate, glycerol (meta ) Acrylate, (meth) acrylamide, N-methylolacrylamide, secondary or tertiary alkylacrylamide, dialkylaminoalkyl (meth) acrylate, morpholine (meth) acrylate, N-vinylpyrrolidone, N-vinylcaprolactam, vinylimidazole, vinyl Triazole, methyl (meth) acrylate, ethyl (meth) acrylate, branched or linear propyl (meth) acrylate, branched or linear butyl (meth) acrylate, or phenoxyhydroxypropyl Meth) acrylate.

  In addition, examples of the hydrophilic monomer include tetrahydrofurfuryl group, phosphoric acid, phosphate ester, quaternary ammonium salt, ethyleneoxy chain, propyleneoxy chain, sulfonic acid and its salt, morpholinoethyl group and the like Is also useful.

  In addition, the alkali-soluble binder in the present invention may have a polymerizable group in the side chain in order to improve the crosslinking efficiency, for example, an allyl group, a (meth) acryl group, an allyloxyalkyl group, etc. Polymers contained in are also useful. Examples of the polymer containing the above-described polymerizable group include commercially available KS resist-106 (manufactured by Osaka Organic Chemical Industry Co., Ltd.), cyclomer P series (manufactured by Daicel Chemical Industries, Ltd.), and the like. In addition, in order to increase the strength of the cured film, alcohol-soluble nylon, polyether of 2,2-bis- (4-hydroxyphenyl) -propane and epichlorohydrin, and the like are also useful.

  Among these various alkali-soluble binders, from the viewpoint of heat resistance, polyhydroxystyrene resins, polysiloxane resins, acrylic resins, acrylamide resins, and acrylic / acrylamide copolymer resins are preferable, and from the viewpoint of development control. Are preferably acrylic resins, acrylamide resins, and acrylic / acrylamide copolymer resins.

  Examples of the acrylic resin include a copolymer made of a monomer selected from benzyl (meth) acrylate, (meth) acrylic acid, hydroxyethyl (meth) acrylate, (meth) acrylamide, and the like, and a commercially available KS resist 106 ( Osaka Organic Chemical Industry Co., Ltd.) and Cyclomer P Series (Daicel Chemical Industries, Ltd.) are preferred.

As the alkali-soluble binder, a polymer having a weight average molecular weight (polystyrene conversion value measured by GPC method) of 1000 to 2 × 10 ⁵ is preferable, a polymer of 2000 to 1 × 10 ⁵ is more preferable, and 5000 to ⁵ is preferable. A polymer of × 10 ⁴ is particularly preferred.

  The content of the alkali-soluble binder in the dye-containing negative curable composition is preferably 10 to 90% by mass with respect to the total solid content (mass) of the composition from the viewpoint of adjusting alkali developability. 20-80 mass% is more preferable, and 30-70 mass% is especially preferable.

<Organic solvent soluble dye>
The organic solvent-soluble dye in the present invention can be used without particular limitation, and examples thereof include conventionally known dyes for color filters. Examples of the known dye include, for example, JP-A 64-90403, JP-A 64-91102, JP-A-1-94301, JP-A-6-11614, JP-T-2592207, US Patent. No. 4,808,501, U.S. Pat.No. 5,667,920, U.S. Pat.No. 5,059,500, JP-A-5-333207, JP-A-6-35183, Examples thereof include dyes described in JP-A-6-51115 and JP-A-6-194828. The chemical structure of the dye that can be used as the organic solvent-soluble dye in the present invention includes triphenylmethane, anthraquinone, benzylidene, oxonol, cyanine, phenothiazine, pyrrolopyrazole azomethine, xanthene, phthalocyanine, A benzopyran type, an indigo type, etc. are mentioned. Particularly preferred as the organic solvent-soluble dye in the present invention are pyrazole azo dyes, anilinoazo dyes, pyrazolotriazole azo dyes, pyridone azo dyes, anthraquinone dyes, and anthrapyridone dyes.

  In the case of a resist system that performs water or alkali development, an acid dye and / or a derivative thereof can be preferably used as the organic solvent-soluble dye in the present invention from the viewpoint of completely removing the binder and / or dye by development. There is. In addition, as organic solvent-soluble dyes in the present invention, direct dyes, basic dyes, mordant dyes, acid mordant dyes, azoic dyes, disperse dyes, oil-soluble dyes, food dyes, and / or derivatives thereof are also useful. can do.

(Acid dyes)
The acid dye will be described. The acidic dye is not particularly limited as long as it is a dye having an acidic group such as sulfonic acid, carboxylic acid, phenolic hydroxyl group, etc., but is soluble in an organic solvent or a developer, salt-forming with a basic compound, absorbance, curability. It is selected in consideration of all required performance such as interaction with other components in the composition, light resistance, heat resistance and the like.

Hereinafter, specific examples of the acid dye will be given. However, the present invention is not limited to these. For example,
acid alizarin violet N;
acid black 1, 2, 24, 48;
acid blue 1,7,9,15,18,23,25,27,29,40,42,45,51,62,70,74,80,83,86,87,90,92,96,103, 112, 113, 120, 129, 138, 147, 150, 158, 171, 182, 192, 210, 242, 243, 256, 259, 267, 278, 280, 285, 290, 296, 315, 324: 1, 335, 340;
acid chroma violet K;
acid Fuchsin;
acid green 1,3,5,9,16,25,27,50,58,63,65,80,104,105,106,109;
acid orange 6, 7, 8, 10, 12, 26, 50, 51, 52, 56, 62, 63, 64, 74, 75, 94, 95, 107, 108, 169, 173;

acid red 1,4,8,14,17,18,26,27,29,31,34,35,37,42,44,50,51,52,57,66,73,80,87,88, 91, 92, 94, 97, 103, 111, 114, 129, 133, 134, 138, 143, 145, 150, 151, 158, 176, 182, 183, 198, 206, 211, 215, 216, 217, 227,228,249,252,257,258,260,261,266,268,270,274,277,280,281,195,308,312,315,316,339,341,345,346,349, 382, 383, 394, 401, 412, 417, 418, 422, 426;
acid violet 6B, 7, 9, 17, 19;
acid yellow 1,3,7,9,11,17,23,25,29,34,36,38,40,42,54,65,72,73,76,79,98,99,111,112, 113, 114, 116, 119, 123, 128, 134, 135, 138, 139, 140, 144, 150, 155, 157, 160, 161, 163, 168, 169, 172, 177, 178, 179, 184 190,193,196,197,199,202,203,204,205,207,212,214,220,221,228,230,232,235,238,240,242,243,251;

Direct Yellow 2,33,34,35,38,39,43,47,50,54,58,68,69,70,71,86,93,94,95,98,102,108,109,129, 136, 138, 141;
Direct Orange 34, 39, 41, 46, 50, 52, 56, 57, 61, 64, 65, 68, 70, 96, 97, 106, 107;
Direct Red 79, 82, 83, 84, 91, 92, 96, 97, 98, 99, 105, 106, 107, 172, 173, 176, 177, 179, 181, 182, 184, 204, 207, 211, 213, 218, 220, 221, 222, 232, 233, 234, 241, 243, 246, 250;
Direct Violet 47, 52, 54, 59, 60, 65, 66, 79, 80, 81, 82, 84, 89, 90, 93, 95, 96, 103, 104;

Direct Blue 57, 77, 80, 81, 84, 85, 86, 90, 93, 94, 95, 97, 98, 99, 100, 101, 106, 107, 108, 109, 113, 114, 115, 117, 119,137,149,150,153,155,156,158,159,160,161,162,164,166,167,170,171,172,173,188,189,190,192,193 194,196,198,199,200,207,209,210,212,213,214,222,228,229,237,238,242,243,244,245,247,248,250,251,252, 256, 257, 259, 260, 268, 274, 275, 293;
Direct Green 25, 27, 31, 32, 34, 37, 63, 65, 66, 67, 68, 69, 72, 77, 79, 82;
Modern Yellow 5, 8, 10, 16, 20, 26, 30, 31, 33, 42, 43, 45, 56, 50, 61, 62, 65;
Modern Orange 3, 4, 5, 8, 12, 13, 14, 20, 21, 23, 24, 28, 29, 32, 34, 35, 36, 37, 42, 43, 47, 48;

Modern Red 1, 2, 3, 4, 9, 11, 12, 14, 17, 18, 19, 22, 23, 24, 25, 26, 30, 32, 33, 36, 37, 38, 39, 41, 43, 45, 46, 48, 53, 56, 63, 71, 74, 85, 86, 88, 90, 94, 95;
Modern Violet 2, 4, 5, 7, 14, 22, 24, 30, 31, 32, 37, 40, 41, 44, 45, 47, 48, 53, 58;
Modern Blue 2, 3, 7, 8, 9, 12, 13, 15, 16, 19, 20, 21, 22, 23, 24, 26, 30, 31, 32, 39, 40, 41, 43, 44, 48, 49, 53, 61, 74, 77, 83, 84;
Modern Green 1, 3, 4, 5, 10, 15, 19, 26, 29, 33, 34, 35, 41, 43, 53;
Food Yellow 3;
And derivatives of these dyes.

Among the acid dyes,
acid black 24;
acid blue 23, 25, 29, 62, 80, 86, 87, 92, 138, 158, 182, 243, 324: 1;
acid orange 8, 51, 56, 74, 63, 74;
acid red 1,4,8,34,37,42,52,57,80,97,114,143,145,151,183,217,249;
acid violet 7;
acid yellow 17, 25, 29, 34, 42, 72, 76, 99, 111, 112, 114, 116, 134, 155, 169, 172, 184, 220, 228, 230, 232, 243;
Acid Green 25;
And the like and derivatives of these dyes are preferred.

  Other than the above, azo, xanthene and phthalocyanine acid dyes are also preferred. I. Solvent Blue 44, 38; I. Solvent Orange 45; Rhodamine B; Rhodamine 110; 2,7-Naphthalendisulfonic acid; 3-[(5-chloro-2-phenoxyphenyl) hydrazono] -3,4-dihydro-4-oxo-5- [minyl]-[ulphonyl] , Etc. and derivatives of these dyes can also be suitably used.

  As the derivative of the acid dye, an inorganic salt of an acid dye having an acid group such as sulfonic acid or carboxylic acid, a salt of an acid dye and a nitrogen-containing compound, a sulfonamide of an acid dye, or the like can be used, and a curable composition It is not particularly limited as long as it can be dissolved as a solution, but it is necessary to have solubility in organic solvents and developers, absorbance, interaction with other components in the curable composition, light resistance, heat resistance, etc. It is selected in consideration of all the performance to be performed.

  The salt of the acidic dye and the nitrogen-containing compound will be described. The method of forming a salt of an acid dye and a nitrogen-containing compound may be effective for improving the solubility of the acid dye (providing solubility in an organic solvent) and improving heat resistance and light resistance.

The nitrogen-containing compound that forms a salt with the acid dye and the nitrogen-containing compound that forms an amide bond with the acid dye will be described.
Nitrogen-containing compounds are the solubility of salts or amide compounds in organic solvents and developers, salt-forming properties, dye absorbance / color value, interaction with other components in the curable composition, and heat resistance as a colorant. In addition, it is selected in consideration of all of light resistance and the like. When selecting only in terms of absorbance and color value, the nitrogen-containing compound is preferably as low as possible in molecular weight, more preferably having a molecular weight of 300 or less, more preferably having a molecular weight of 280 or less, and more preferably having a molecular weight of 250 or less. Those are particularly preferred.

  The molar ratio (hereinafter referred to as “n”) of the nitrogen-containing compound / acid dye in the salt of the acid dye and the nitrogen-containing compound will be described. Said n is a value which determines the molar ratio of an acidic dye molecule and the amine compound which is a counter ion, and can be freely selected according to the salt forming conditions of the acidic dye-amine compound. Specifically, a number between 0 <n ≦ 5 of the number of functional groups of the acid in the acid dye is practically used, and the solubility in organic solvents and developers, salt formation, absorbance, and curable composition It is selected in consideration of all necessary performance such as interaction with other components, light resistance, heat resistance and the like. When selecting from the standpoint of absorbance only, n is preferably a value between 0 <n ≦ 4.5, more preferably a value between 0 <n ≦ 4, and 0 <n. It is particularly preferable to take a numerical value between ≦ 3.5.

Since the acidic dye shown above is an acidic dye due to the introduction of an acidic group in its structure, it can be made a non-acidic dye by changing its substituent.
In some cases, the acid dye works favorably during alkali development, but on the other hand, it may become over-developed, and a non-acid dye may be preferably used.

  The content concentration of the organic solvent-soluble dye will be described. The content concentration of the organic solvent-soluble dye in the total solid component (mass) of the dye-containing negative curable composition of the present invention varies depending on the dye, but from the viewpoint of spectral characteristics and pattern formability, 0.5 to 80 % By mass is preferable, 0.5 to 60% by mass is more preferable, and 0.5 to 50% by mass is particularly preferable.

<Photopolymerization initiator>
Next, the photopolymerization initiator will be described. The photopolymerization initiator is contained in the dye-containing negative curable composition of the present invention together with a photopolymerizable compound (radical polymerizable monomer) described later. The photopolymerization initiator in the present invention is not particularly limited as long as it can polymerize the photopolymerizable compound, but is preferably selected from the viewpoint of characteristics, initiation efficiency, absorption wavelength, availability, cost, and the like. .

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

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

  Examples of the active halogen compound which is a halomethyl-s-triazine compound include vinyl-halomethyl-s-triazine compounds described in JP-B-59-1281 and 2- (naphtho-) described in JP-A-53-133428. 1-yl) -4,6-bis-halomethyl-s-triazine compound and 4- (p-aminophenyl) -2,6-di-halomethyl-s-triazine compound.

  Specific examples of the halomethyl-s-triazine compound 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- (naphtho) -1-yl) -4,6-bis-trichloromethyl-s-triazine, 2- (4-methoxy-naphth-1-yl) -4,6-bis-trichloromethyl-s-tria 2- (4-Ethoxy-naphth-1-yl) -4,6-bis-trichloromethyl-s-triazine, 2- (4-butoxy-naphth-1-yl) -4,6-bis-trichloro Methyl-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-naphth-2-yl) -4,6-bis-trichloromethyl-s-triazine, 2 -(5-Methoxy-naphth-1-yl) -4,6-bis-trichloromethyl-s-triazine, 2- (4,7-dimethoxy-naphth-1-yl) -4,6-bis-trichloromethyl -S-triazine, 2- 6-Ethoxy-naphth-2-yl) -4,6-bis-trichloromethyl-s-triazine, 2- (4,5-dimethoxy-naphth-1-yl) -4,6-bis-trichloromethyl-s -Triazine,

4- [pN, N-di (ethoxycarbonylmethyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- [o-methyl-pN, N-di (ethoxycarbonyl) Methyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- [pN, N-di (chloroethyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine 4- [o-methyl-pN, N-di (chloroethyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- (pN-chloroethylaminophenyl) -2 , 6-Di (trichloromethyl) -s-triazine, 4- (p-N-ethoxycarbonylmethylaminophenyl) -2,6-di (trichloromethyl) -s-triazine, 4- [p-N, -Di (phenyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- (pN-chloroethylcarbonylaminophenyl) -2,6-di (trichloromethyl) -s-triazine ,

4- [pN- (p-methoxyphenyl) carbonylaminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- [mN, N-di (ethoxycarbonylmethyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- [m-bromo-pN, N-di (ethoxycarbonylmethyl) aminophenyl] -2,6-di (trichloromethyl) -s- Triazine, 4- [m-chloro-pN, N-di (ethoxycarbonylmethyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- [m-fluoro-pN, N-di (ethoxycarbonylmethyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- [o-bromo-pN, N-di (ethoxycarbonylmethyl) Minophenyl] -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 (trichloro Methyl) -s-triazine, 4- [o-fluoro-p-N, N-di (chloroethyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- [m-bromo-p -N, N-di (chloroethyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- [m-chloro-pN, N-di (chloroethyl) aminophenyl] -2, 6-di (trick Romechiru) -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-pN-chloro) Ethylamino) -2,6-di (trichloromethyl) -s-triazine.

  Other examples of the photopolymerization initiator include TAZ series (for example, TAZ-107, TAZ-110, TAZ-104, TAZ-109, TAZ-140, TAZ-204, TAZ-113, TAZ- 123), T series (for example, T-OMS, T-BMP, TR, TB) manufactured by PANCHIM, Irgacure series (for example, Irgacure 651, Irgacure 184, Irgacure 500, Irgacure 1000) manufactured by Ciba Geigy. , Irgacure 149, Irgacure 819, Irgacure 261), 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-morpholinobutyrophenone, 2,2-dimethoxy-2-phenylacetophenone,

2- (o-chlorophenyl) -4,5-diphenylimidazolyl dimer, 2- (o-fluorophenyl) -4,5-diphenylimidazolyl dimer, 2- (o-methoxyphenyl) -4,5 -Diphenylimidazolyl dimer, 2- (p-methoxyphenyl) -4,5-diphenylimidazolyl dimer, 2- (p-dimethoxyphenyl) -4,5-diphenylimidazolyl dimer, 2- (2, 4-Dimethoxyphenyl) -4,5-diphenylimidazolyl dimer, 2- (p-methylmercaptophenyl) -4,5-diphenylimidazolyl dimer, benzoin isopropyl ether, and the like are also useful.

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, dibenzylacetone, p- (dimethylamino) phenylstyryl ketone, p- ( Dimethylamino) phenyl-p-methyls Rilketone, benzophenone, p- (dimethylamino) benzophenone (or Michler's ketone), p- (diethylamino) benzophenone, benzoanthrone, benzothiazole compounds described in Japanese Patent Publication No. 51-48516, tinuvin 1130, 400, etc. Can be mentioned.

In addition to the above-mentioned photopolymerization initiator, other known initiators can be used in the dye-containing negative curable composition of the present invention.
Specifically, the vicinal polykettle aldonyl compound disclosed in US Pat. No. 2,367,660, disclosed in US Pat. Nos. 2,367,661 and 2,367,670. Substituted α-carbonyl compounds, acyloin ethers disclosed in US Pat. No. 2,448,828, α-hydrocarbons disclosed in US Pat. No. 2,722,512 Aromatic acyloin compounds, polynuclear quinone compounds disclosed in US Pat. Nos. 3,046,127 and 2,951,758, disclosed in US Pat. No. 3,549,367. Triarylimidazole dimer / p-aminophenyl ketone combination, benzothiazole compound / triha disclosed in Japanese Patent Publication No. 51-48516 And lomethyl-s-triazine compounds.

  The total amount of the photopolymerization initiator used is preferably 0.01% by mass to 50% by mass, more preferably 1% by mass to 30% by mass, based on the solid content (mass) of the photopolymerizable compound described later. 1% by mass to 20% by mass is particularly preferable. When the use amount of the photopolymerization initiator is in the range of 0.01% by mass to 50% by mass, the polymerization reaction of the photopolymerizable compound is sufficiently advanced to prevent the molecular weight from being lowered and the film strength from being weakened. be able to.

<Photopolymerizable compound>
Next, the photopolymerizable compound will be described. Examples of the photopolymerizable compound include radical polymerizable monomers and cationic polymerizable monomers, and radical polymerizable monomers are particularly preferable.
The radical polymerizable monomer will be described. As the radical polymerizable monomer, a compound having an ethylenically unsaturated group having at least one addition-polymerizable ethylenic double bond and having a boiling point of 100 ° C. or higher under normal pressure is preferable. By including both the photopolymerizable compound in the present invention and the above-described photopolymerization initiator, the dye-containing negative curable composition of the present invention can be configured as a negative type.

  Examples of the compound having an ethylenically unsaturated group include monofunctional acrylates and methacrylates such as polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate and phenoxyethyl (meth) acrylate; (Meth) acrylate, trimethylolethane tri (meth) acrylate, neopentyl glycol di (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipenta Erythritol hexa (meth) acrylate, hexanediol (meth) acrylate,

Trimethylolpropane tri (acryloyloxypropyl) ether, tri (acryloyloxyethyl) isocyanurate, polymethic alcohol such as glycerin and trimethylolethane, and then (meth) acrylated after adding ethylene oxide or propylene oxide, Urethane acrylates as described in JP-B-48-41708, JP-B-50-6034, JP-A-51-37193, JP-A-48-64183, JP-B-49-43191, Mention polyfunctional acrylates and methacrylates such as polyester acrylates, epoxy resins and epoxy acrylates which are reaction products of (meth) acrylic acid described in JP-B 52-30490 and mixtures thereof Can do. Furthermore, the Japan Adhesion Association Vol. 20, no. 7, pages 300 to 308 are introduced as photocurable monomers and oligomers.

  As content in the dye-containing negative curable composition of the photopolymerizable compound in this invention, from a viewpoint of pattern formation, 0.1-90 mass with respect to the total solid (mass) of this composition. % Is preferable, 1.0 to 80% by mass is more preferable, and 2.0 to 70% by mass is particularly preferable.

<Compound with a molecular weight of 3000 or less containing an acid group in the molecule>
Next, a compound having an acid group in the molecule and having a molecular weight of 3000 or less, which is a feature of the present invention, will be described in detail. The compound having an acid group in the molecule and having a molecular weight of 3000 or less may have any structure as long as the compound has a molecular weight of 3000 or less and basically contains an acid group. As the acid group, all of the generally known structures are meant, but those showing good solubility in an alkaline developer are preferable, for example, sulfonic acid groups, carboxylic acid groups, phenolic hydroxyl groups, Examples thereof include a sulfonimide group. Of these, carboxylic acid groups and phenolic hydroxyl groups are particularly preferred. The number of acid groups present in the molecule is not particularly limited, but is selected depending on each system from the viewpoint of compatibility with other components. Preferred are compounds having 1 to 10 acid groups in the molecule, and particularly preferred are compounds having 1 to 6 acid groups in the molecule. For example, when the compound having an acid group in the molecule and having a molecular weight of 3000 or less is a compound having a carboxylic acid or a phenolic hydroxyl group as an acid group, the compound preferably has two or more acid groups.

  The compound having an acid group in the molecule and having a molecular weight of 3000 or less is preferably selected from those that do not impair the stability in the liquid and those that dissolve uniformly, and are assumed not to volatilize during film formation. A compound that is solid at room temperature (23 ° C.) is preferred. Furthermore, from the viewpoint of not lowering the Tg of the formed film, the compound having an acid group in the molecule and having a molecular weight of 3000 or less preferably has at least one alicyclic group or aromatic ring group. However, a compound having two or more acid groups does not necessarily have an alicyclic group or an aromatic ring.

  Examples of the alicyclic group include a cyclohexyl group, a cyclopentyl group, a cycloheptyl group, a cyclooctyl group, a water-added naphthyl group, a water-added anthranyl group, and the like, and a cyclohexyl group and a cyclopentyl group are preferable. Examples of the aromatic ring group include a phenyl group, a naphthyl group, and an anthranyl group, and a phenyl group is preferable. These alicyclic groups and aromatic ring groups may further have a substituent.

Further, the compound having an acid group in the molecule and having a molecular weight of 3000 or less preferably has at least one alicyclic group or aromatic ring group, and the acid group is a carboxylic acid or a phenolic hydroxyl group. .
Further, the molecular weight of the compound having an acid group in the molecule and having a molecular weight of 3000 or less is preferably 2500 or less, more preferably 2000 or less, particularly preferably 1000 or less from the viewpoint of compatibility in the system. preferable. Moreover, the minimum of molecular weight is although it does not specifically limit, From a sublimation viewpoint, 50 or more are preferable and 100 or more are especially preferable.

  Examples of the compound having an acid group in the molecule and having a molecular weight of 3000 or less include hexanoic acid, heptanoic acid, octanoic acid, decanoic acid, stearic acid, 2-bromo-3-methylbutanoic acid, shikimic acid, menthoxyacetic acid, tetrahydro -2-Floic acid, galacturonic acid, gluconic acid, lactobionic acid, mercaptopropionic acid, thioctic acid, succinic semialdehyde, pyruvic acid, cyclopentaneacetic acid, cyclohexaneacetic acid, cyclopentanoic acid, cyclohexane acid, dicyclohexylacetic acid, Cyclohexanepropionic acid, cyclohexanepentanoic acid, 4-methyl-1-cyclohexanecarboxylic acid, 4-t-butylcyclohexanecarboxylic acid, 4-methylcyclohexaneacetic acid, hexahydromandelic acid, 3-methoxycyclohexane Rubonic acid, 4-methoxycyclohexanecarboxylic acid, cycloheptanecarboxylic acid, 2-norbornaneacetic acid, 4-pentylbicyclo [2.2.2] octane-1-carboxylic acid, anti-3-oxotricyclo [2.2.1] .0 (2,6)]-heptane-7-carboxylic acid, 3-noradamantanecarboxylic acid, 1-adamantanecarboxylic acid, 1-adamantaneacetic acid, 1-cyclopentene-1-carboxylic acid, 1-cyclohexene-1-carboxyl Acid, ketopic acid, malonic acid, methylmalonic acid, ethylmalonic acid, butylmalonic acid, dimethylmalonic acid, diethylmalonic acid, succinic acid, methylsuccinic acid, dimethylsuccinic acid, methylglutaric acid, dimethylglutaric acid, pimelic acid, 1,11-undecanedicarboxylic acid, undecanedioic acid, 1,10-decane Dicarboxylic acid, 1,12-dodecanedicarboxylic acid, hexadecanediic acid, docosadic acid, tricarbaric acid, cyclobutanedicarboxylic acid, cyclopentanedicarboxylic acid, tetramethyleneglutaric acid, camphoric acid, camphoric acid, cyclohexylsuccinic acid, 1,1- Cyclohexane diacetic acid, 1,2-cyclohexane dicarboxylic acid, 1,3-cyclohexane dicarboxylic acid, 1,4-cyclohexane dicarboxylic acid, 1,3-adamantane carboxylic acid, 1,3-adamantane diacetic acid, norbornane dicarboxylic acid, cyclohexane tricarboxylic acid Acid, cyclohexanehexacarboxylic acid, cyclobutanetetracarboxylic acid, pentadecylphenol, ethoxyphenol, iodophenol, butoxyphenol, hexyloxyphenol, heptyloxy Phenol, dimethylphenol, 2,6-diisopropylphenol, 2,3-dihydro-2,2-dimethyl-7-benzofuranol, 5-indanol, thymol, 2-t-butyl-4-methylphenol, 2,4- Di-t-amylphenol, 2- (1-adamantyl) -4-phenol, 2,4,6-triphenylphenol, 3,3,3 ′, 3′-tetramethyl-1,1′-spirobisindane -5,5 ', 6,6'-tetrol, vitamin E, benzenetriol, naphthol, 2-methyl-1-naphthol, 1,2-dihydroxynaphthol, 2,3-dihydroxynaphthol, 1,5-dihydroxynaphthol, 2,7-dihydroxynaphthol, 2-hydroxyfluorene, 4,4 ′-(9-fluorenylidene) diphenol, a Surarobin, 9-phenanthrol, 1-hydroxypyrene, 4-phenoxyphenol, 4-phenylphenol, 4-cyclohexylphenol, bisphenol A, bis (4-hydroxyphenyl) methane, mesohexestol, calixarene, phenylacetic acid , Α-phenylcyclopentaneacetic acid, diphenylacetic acid, hydroxycinnamic acid, diphenylpropionic acid, triphenylpropionic acid, phenylbutanoic acid, phenoxyacetic acid, benzylic acid, benzoylpropionic acid, phenylmalonic acid, benzylmalonic acid, phenylsuccinic acid , Phenylglutaric acid, benzocyclobutenecarboxylic acid, phenylenediacetic acid, 3- (2-methoxyphenyl) propionic acid, 2-hydroxyphenylacetic acid, 3-methoxyphenylacetic acid, 4-methyl Examples thereof include tilphenyl acetic acid.

  Among these, as the compound having an acid group in the molecule and having a molecular weight of 3000 or less, cyclohexaneacetic acid, dicyclohexylacetic acid, cyclohexanepropionic acid, 4-t-butylcyclohexanecarboxylic acid, 2-norbornaneacetic acid, 1-adamantanecarboxylic acid 1-adamantaneacetic acid, malonic acid, butylmalonic acid, succinic acid, 1,2-cyclohexanedicarboxylic acid, 1,3-adamantanedicarboxylic acid, 1,3-adamantanediacetic acid, 2,6-diisopropylphenol, benzenetriol, Naphthol and diphenylacetic acid are preferred, dicyclohexylacetic acid, 2-norbornaneacetic acid, 1-adamantanecarboxylic acid, 1-adamantaneacetic acid, malonic acid, butylmalonic acid, 1,2-cyclohexanedicarboxylic acid, 1,3-adamantanedi Carboxylic acid, 1,3-adamantane diacetic acid, particularly preferred.

  From the viewpoint of alkali solubility, the content of the compound having an acid group in the molecule and having a molecular weight of 3000 or less is based on 100 parts by mass of the total solid content (mass) of the dye-containing negative curable composition of the present invention. It is preferably 0.1 to 20 parts by mass, more preferably 0.5 to 20 parts by mass, and particularly preferably 1 to 15 parts by mass. The content of the compound having a molecular weight of 3000 or less containing an acid group in the molecule is 0.1 to 20 mass with respect to 100 mass parts of the total solid content (mass) of the dye-containing negative curable composition of the present invention. When it is within the range of the part, it is possible to achieve both unexposed part dissolution and exposed part curability.

<Crosslinking agent>
In the present invention, it is also possible to obtain a film that has been further cured by using a crosslinking agent. Hereinafter, the crosslinking agent will be described.
The crosslinking agent usable in the present invention is not particularly limited as long as the film can be cured by a crosslinking reaction. For example, (a) an epoxy resin, (b) a methylol group, an alkoxymethyl group, and an acyloxymethyl group. 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 Substituted phenolic compounds, naphthol compounds or hydroxyanthracene compounds. 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, 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 for melamine compounds, 2 for glycoluril compounds, guanamine compounds, and urea compounds. Although it is -4, Preferably it is 5-6 in the case of a melamine compound, and is 3-4 in the case of a glycoluril compound, a guanamine compound, and a urea compound.
Hereinafter, the melamine compound, guanamine compound, glycoluril compound and urea compound of (b) are collectively referred to as a compound (containing a methylol group, an alkoxymethyl group or an acyloxymethyl group) 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 in which 1 to 3 methylol groups of guanamine are acyloxymethylated or a mixture thereof.

  Examples of the glycoluril compound include tetramethylol glycoluril, tetramethoxymethylglycoluril, a compound obtained by methoxymethylating 1 to 3 methylol groups of tetramethylolglycoluril, or a mixture thereof, or a methylol group of tetramethylolglycoluril. A compound obtained by acylating 1 to 3 or a mixture thereof, and the like.

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), intermixing with the overcoated photoresist is suppressed by thermal crosslinking, and the film strength is further increased. Hereinafter, these compounds may be collectively referred to as a compound according to (c) (containing a methylol group, an alkoxymethyl group or an acyloxymethyl group).

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 3-position or 5-position of the phenol compound 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 the above (c) uses a compound in which the phenolic OH group has a hydrogen atom at the 2nd or 4th position as a raw material, and this is used as sodium hydroxide, potassium hydroxide, ammonia, tetraalkylammonium hydroxide. It can be obtained by reacting with formalin in the presence of a basic catalyst.
The alkoxymethyl group-containing compound according to (c) can be obtained by heating the methylol group-containing compound according to (c) in an alcohol in the presence of an acid catalyst such as hydrochloric acid, sulfuric acid, nitric acid, methanesulfonic acid or the like.
The acyloxymethyl group-containing compound according to (c) can be obtained by reacting the methylol group-containing compound according to (c) with an acyl chloride in the presence of a basic catalyst.

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

  Specific examples of the crosslinking agent (c) include, as a phenol compound, for example, trimethylolphenol, tri (methoxymethyl) phenol, a compound obtained by methoxymethylating one or two methylol groups of trimethylolphenol, trimethylol- Compounds obtained by methoxymethylating one or two methylol groups of 3-cresol, tri (methoxymethyl) -3-cresol, trimethylol-3-cresol, dimethylol cresol such as 2,6-dimethylol-4-cresol, Compounds obtained by methoxymethylating 1 to 3 methylol groups of tetramethylol bisphenol A, tetramethoxymethyl bisphenol A, tetramethylol bisphenol A, tetramethylol-4,4′-bishydroxybiphenyl, tetramethoxymethyl-4,4 ′ − Suhydroxybiphenyl, TrisP-PA hexamethylol, TrisP-PA hexamethoxymethyl, TrisP-PA hexamethylol compound methoxymethylated from 1 to 5 methylol groups, Bishydroxymethylnaphthalenediol, etc. Is mentioned.

  Examples of the hydroxyanthracene compound include 1,6-dihydroxymethyl-2,7-dihydroxyanthracene, and examples of the acyloxymethyl group-containing compound include, for example, a part of the methylol group of the methylol group-containing compound or Examples include compounds that are all acyloxymethylated.

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.

  The total content of the crosslinking agent in the dye-containing negative curable composition varies depending on the material, but from the viewpoint of curability, 1 to 70% by mass with respect to the solid content (mass) of the curable composition. Is preferable, 5-50 mass% is more preferable, and 7-30 mass% is especially preferable.

<Thermal polymerization inhibitor>
In addition to the above, it is preferable to add a thermal polymerization inhibitor to the dye-containing negative curable composition of the present invention. For example, hydroquinone, p-methoxyphenol, di-t-butyl-p-cresol, pyrogallol, t-butylcatechol, benzoquinone, 4,4'-thiobis (3-methyl-6-t-butylphenol), 2,2 ' -Methylenebis (4-methyl-6-tert-butylphenol), 2-mercaptobenzimidazole, etc. are useful.

<Organic solvent>
The organic solvent used in the present invention is not particularly limited as long as the solubility of each component and the coating property of the dye-containing negative curable composition are satisfied, but particularly the solubility, coating property, and safety of the dye and binder. It is preferable to select in consideration of the properties. Moreover, when preparing the dye-containing negative curable composition of this invention, it is preferable that at least 2 type of organic solvent is included.

  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, alkyl esters, and lactic acid. Methyl, 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 monomethyl ether, propylene glycol monomethyl Ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, etc .;

Ketones such as methyl ethyl ketone, cyclohexanone, 2-heptanone, and 3-heptanone are preferred; aromatic hydrocarbons such as toluene and xylene are preferred.
As described above, these organic solvents may be used in admixture of two or more kinds from the viewpoints of solubility of dyes and alkali-soluble resins, improvement of the coated surface, and the like, and in particular, the above methyl 3-ethoxypropionate, 3- Ethyl 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, and propylene glycol methyl A mixed solution composed of two or more selected from ether acetate is preferably used.

  The amount of the organic solvent used in the present invention is preferably such that the total solid content concentration is 5 to 80% by mass, more preferably 5 to 60% by mass, and 10 to 50% by mass from the viewpoint of applicability. Particularly preferred.

<Various additives>
In the dye-containing negative curable composition of the present invention, various additives, for example, a filler, a polymer compound other than the above, a surfactant, an adhesion promoter, an antioxidant, an ultraviolet absorber, An anti-aggregation 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.

<< Color filter and manufacturing method thereof >>
Next, the color filter of the present invention will be described in detail through its manufacturing method.
In the method for producing a color filter of the present invention, the above-described dye-containing negative curable composition of the present invention is used.
A radiation-sensitive composition layer is formed by applying the dye-containing negative curable composition of the present invention on a support by a coating method such as spin coating, cast coating, roll coating, and the like, and the layer is formed into a predetermined mask pattern. And a negative coloring pattern is formed by developing with a developer (image forming step). Moreover, the hardening process which hardens | cures the formed coloring pattern by heating and / or exposure as needed may be included.

  In the production of a color filter, a color filter having a desired hue can be produced by repeating the image forming step (and the curing step if necessary) by the desired number of hues. 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, and 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 substrates may have black stripes that separate pixels.
Further, an undercoat layer may be provided on these supports, if necessary, in order to improve adhesion 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 dye-containing negative curable composition of the present invention but does not dissolve the irradiated portion. Specifically, a combination of various organic solvents or an alkaline aqueous solution can be used. As said organic solvent, the above-mentioned organic solvent used when preparing the dye-containing negative curable composition of this invention is mentioned.

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

  The color filter of the present invention can be used for a solid-state imaging device such as a liquid crystal display device or a CCD, and is particularly suitable for a high-resolution CCD device or a CMOS that exceeds 1 million pixels. The color filter of the present invention can be used as, for example, a color filter disposed between a light receiving portion of each pixel constituting a CCD and a microlens for condensing light.

  EXAMPLES Hereinafter, 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.

1) Preparation of dye-containing negative curable composition Each compound was mixed and dissolved in the composition shown below to prepare the dye-containing negative curable composition of the present invention.
〔composition〕
・ Ethyl lactate (organic solvent) 43.5 parts ・ Allyl methacrylate / methacrylic acid copolymer (= 80/20 [molar ratio])
(Alkali-soluble binder) 4.1 parts dipentaerythritol hexaacrylate 6.1 parts (photopolymerizable compound)
・ Polymerization inhibitor (p-methoxyphenol) 0.0061 part ・ Photopolymerization initiator (trade name: TAZ-107, manufactured by Midori Chemical Co., Ltd.) 1.0 part ・ Organic solvent soluble dye 7.0 part (Valifast yellow) 1101)
Additive A (dicyclohexylacetic acid) 2.0 parts (compound with a molecular weight of 3000 or less containing an acid group in the molecule)

2) Production of glass substrate with undercoat layer A glass substrate (trade name: Corning 1737, manufactured by Corning) was ultrasonically washed with 1% NaOH water, followed by washing with water and dehydration baking (200 ° C./30 minutes). Next, a resist solution (trade name: CT-2000L, manufactured by Fuji Film Arch Co., Ltd.) is applied on the glass substrate after cleaning to a thickness of 2 μm using a spin coater and heated at 220 ° C. for 1 hour. It dried and formed the cured film (undercoat layer).

3) Exposure and development of dye-containing negative curable composition (image forming process)
The dye-containing negative curable composition obtained in 1) above was applied on the undercoat layer of the glass substrate with an undercoat layer obtained in 2) above using a spin coater so that the film thickness became 1 μm. And prebaking at 100 ° C. for 120 seconds.
Next, using an i-line reduction projection exposure apparatus, the coating film was irradiated at a wavelength of 365 nm through a 20 μm mask with an exposure amount of 800 mJ / cm ² . After irradiation, development was performed at 23 ° C. for 60 seconds using a developer (trade name: CD-2000, 60%, manufactured by Fuji Film Arch Co., Ltd.). Subsequently, after rinsing with running water for 20 seconds, spray drying was performed to obtain a pattern image. The image formation was confirmed by an ordinary method using an optical microscope and SEM photograph observation.

[Examples 2 to 10]
In Example 1, a dye-containing negative curable property was obtained in the same manner as in Example 1 except that the additive A (a compound having an acid group in the molecule and having a molecular weight of 3000 or less) was replaced with the one shown in Table 1 below. A composition was prepared and a pattern image was formed.

[Comparative Example 1]
In Example 1, a dye-containing negative curable composition was prepared in the same manner as in Example 1 except that additive A (a compound having a molecular weight of 3000 or less containing an acid group in the molecule) was not used. An image was formed.

[Comparative Examples 2-3]
In Example 1, a dye-containing negative curable property was obtained in the same manner as in Example 1 except that the additive A (a compound having an acid group in the molecule and having a molecular weight of 3000 or less) was replaced with the one shown in Table 1 below. A composition was prepared and a pattern image was formed. In addition, the adamantane of the comparative example 2 is a compound which does not contain an acid group.

4) Evaluation (1) At the time of pattern formation, observation of unexposed part residue The following evaluation was performed about the obtained pattern. The results are shown in Table 1 below.
The observation of the unexposed portion residue at the time of pattern formation was confirmed by visual observation with an optical microscope and SEM photograph observation as described above. In the visual observation, “◯” indicates that the residual was not confirmed, “Δ” indicates that the residual was somewhat recognized, and “×” indicates that the residual was clearly confirmed.
Further, as quantitative data, at the time of exposure, exposure is performed with a 5 mm square mask (island pattern), the unexposed portion is measured with a spectrophotometer, and the transmittance (%) at a wavelength of 430 nm is measured. Based on the above, the degree of residue was estimated. When the transmittance is 0%, there is no residue, and a larger transmittance value indicates that more residue remains.

  As shown in Table 1 above, the dye-containing negative curable compositions of Examples 1 to 9 to which a compound having an acid group in the molecule and having a molecular weight of 3000 or less was added had a residue of an unexposed portion at the time of pattern formation. It is clear that it has been improved.

Claims (7)

  (A) an alkali-soluble binder, (B) an organic solvent-soluble dye, (C) a photopolymerization initiator, (D) a photopolymerizable compound, (E) an organic solvent, and (F) an acid group in the molecule. A dye-containing negative curable composition comprising at least a compound having a molecular weight of 3000 or less.   The content of the compound having a molecular weight of 3000 or less containing an acid group in the molecule (F) is 0.1 to 20 parts by mass with respect to 100 parts by mass of the total solid content. The dye-containing negative curable composition as described.   The dye-containing negative according to claim 1 or 2, wherein the compound (F) having a molecular weight of 3000 or less containing an acid group in the molecule is a compound having at least one alicyclic group or aromatic ring group. Mold curable composition.   (F) The compound having an acid group in the molecule and having a molecular weight of 3000 or less has at least one alicyclic group or aromatic ring group, and the acid group is a carboxylic acid or a phenolic hydroxyl group. The dye-containing negative curable composition according to claim 1 or 2, wherein   (F) The compound having an acid group in the molecule and having a molecular weight of 3000 or less has at least two acid groups, and the acid group is a carboxylic acid or a phenolic hydroxyl group. The dye-containing negative curable composition according to claim 1 or 2.   A color filter comprising the dye-containing negative curable composition according to any one of claims 1 to 5.   It includes a step of applying the dye-containing negative curable composition according to any one of claims 1 to 5 on a support, exposing through a mask, and developing to form a pattern. A method for producing a color filter.