JP2006053426A - Photocuring image recording material, color filter and manufacturing method therefor - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a photocuring image recording material having high sensitivity and high squareness of a pattern profile, and to provide a color filter using the material, and a manufacturing method therefor. <P>SOLUTION: The photocuring image recording material has a photopolymerizable layer containing a polymerizable compound having an ethylenically unsaturated bond and a polysaccharide layer containing polysaccharides, layered in this order on a support. The color filter and the manufacturing method therefor are also provided. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a photocurable image recording material suitable for forming a colored image constituting a color filter used in a liquid crystal display element (LCD), a solid-state imaging element (CCD, CMOS, etc.), and a photocurable image recording material. The present invention relates to a color filter using the above and a manufacturing method thereof.

  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 the pigment dispersion method is patterned by a photolithographic method, it has been widely used as a method suitable for producing a color filter for a large screen and a high-definition color display with high positional accuracy.

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

  Here, examples of the pigment dispersion method include negative photosensitive compositions 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).

  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 with conventional pigment dispersion systems, and there are problems such as color unevenness caused by coarse particles of the pigment, so that it is used for applications that require fine patterns such as solid-state imaging devices. Was not suitable.

  In order to solve this problem, a technique of using a dye instead of a pigment has been proposed (for example, see Patent Document 5). However, the dye-containing curable composition has a problem that it is generally inferior to the pigment in various performances such as light resistance, heat resistance, solubility, and coating uniformity. Particularly in the case of a color filter production application for a solid-state image sensor, a film thickness of 1.5 μm or less is required, so a large amount of dye must be added to the curable composition. For this reason, for example, a binder is insufficient. Insufficient adhesion to the substrate or insufficient photopolymerizable compound, etc., and sufficient curing may not be obtained. There was also a problem that it was extremely difficult.

  It is also known that when a film is cured by radical polymerization, the polymerization is inhibited by oxygen. For this reason, there is a demand for a technique that can perform a curing reaction in an environment with little oxygen that causes polymerization inhibition.

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

  An object of the present invention is to provide a photocurable image-recording material having high sensitivity and a highly rectangular pattern shape, and a color filter using the same. It is another object of the present invention to provide a color filter manufacturing method with high cost performance.

Specific means for solving the above problems are as follows.
<1> A photocurable image-recording material comprising a photopolymerizable layer containing a polymerizable compound having an ethylenically unsaturated bond and a polysaccharide layer containing a polysaccharide on a support. .

  <2> The photocurable image recording material according to <1>, wherein the polysaccharide is a microorganism-producing polysaccharide.

  <3> The photocurable image recording material according to <2>, wherein the microorganism-producing polysaccharide is at least one selected from pullulan, xanthan gum, and dextran.

  <4> The photocurable image recording material according to <1> to <3>, wherein the photopolymerizable layer contains a dye.

  <5> A color filter comprising the photocurable image recording material according to <1> to <4>.

<6> A photopolymerizable composition solution containing a dye and a polymerizable compound is applied on a support, and then an aqueous solution containing a polysaccharide is applied, and then exposed through a mask and developed to form a pattern. It is a manufacturing method of the color filter characterized by having a process.
The method for producing the color filter may include a step of curing the pattern by heating and / or exposure as necessary, or may repeat these steps a plurality of times. Further, the dye may be changed to form a plurality of types of color filters.

  According to the present invention, it is possible to provide a photocurable image recording material having high sensitivity and a high pattern shape rectangularity, and a color filter using the same. In addition, a method for manufacturing a color filter with high cost performance can be provided.

<< Photocurable image recording material >>
The photocurable image recording material of the present invention comprises a photopolymerizable layer containing a polymerizable compound having an ethylenically unsaturated bond (hereinafter sometimes simply referred to as “polymerizable compound”) on a support, And a polysaccharide layer containing saccharides. According to this invention, a sensitivity and pattern rectangularity can be improved by laminating | stacking the polysaccharide layer containing a polysaccharide on a photopolymerizable layer.
This is because the polysaccharide layer functions as a gas barrier layer and prevents oxygen, which is an inhibitory element of the polymerization reaction, from entering the photopolymerizable layer, thereby increasing the polymerizability of the photopolymerizable layer and increasing the rectangular shape of the pattern. It is estimated that the property is improved. Further, since the polymerization reaction is not inhibited by oxygen, the sensitivity can be improved at the same time.

<Polysaccharide layer>
The polysaccharide layer is a layer containing a polysaccharide and functions as a gas barrier layer.
The polysaccharide is not particularly limited, but is preferably a water-soluble polysaccharide, and is preferably a microbially produced polysaccharide. As used herein, “microorganism-producing polysaccharide” means a water-soluble polysaccharide produced by a microorganism, and is preferably a polysaccharide that is not found in general animals or plants and is produced by fermentation of microorganisms. . Representative examples of the microbially produced polysaccharide include pullulan, xanthan gum, and dextran. For these, see Shinji Nagatomo, “Application and Market of New Water-Soluble Polymers,” p. 20-21, P.I. 256-258 (1988), published in detail by CMC Co., Ltd.

  The pullulan is produced by fermenting monosaccharides and disaccharides such as sucrose, glucose and maltose with pullularia pullulans. The weight average molecular weight of the pullulan is about 50,000 to about 200,000. The xanthan gum is a neutral viscous polysaccharide produced by the genus Zantomonas campestris, and has a degree of polymerization of about 1000 to 10,000. The dextran is a polymer based on D-glucopyranose produced from sucrose by bacteria belonging to Lactovacilluse, and has a polymerization degree of 1000 to 10,000.

  The microorganism-producing polysaccharide is produced by fermentation of microorganisms, but the polysaccharide used in the present invention is not limited to this, and is not necessarily limited to microorganisms as long as it is equivalent to the microorganism-producing polysaccharide described above. For example, it may be obtained by chemical synthesis.

  It is preferable that 0.01-100 mass parts is contained with respect to 100 mass parts of total solids, and, as for content of the polysaccharide contained in the said polysaccharide layer, 1-95 mass parts is contained. Further preferred. Moreover, as a film thickness of the said polysaccharide layer, 0.01 micrometer-5 micrometers are preferable, and 0.02 micrometer-2.5 micrometers are still more preferable.

  In the present invention, it is preferable to form a polysaccharide layer by coating an aqueous solution containing a polysaccharide such as a microbially produced polysaccharide after coating a curable composition described later on a support. The concentration of the aqueous solution containing the polysaccharide is not particularly limited as long as the polysaccharide (preferably microbially produced polysaccharide) is dissolved, and is preferably about 0.1 to 70% by mass, for example, 0.5 to 50 About mass% is more preferable. In order to improve the coated surface, it is possible to add a surfactant to the aqueous solution. In addition, as a compound contained in the said aqueous solution, the thing similar to the alkali-soluble binder contained in the photopolymerization layer mentioned later as a binder can be used.

<Photopolymerizable layer>
The photopolymerizable layer is a layer containing a polymerizable compound having at least an ethylenically unsaturated bond, and includes a dye, an alkali-soluble binder, a photopolymerization initiator, and the like as necessary. In particular, when producing a color filter using the photocurable image recording material of the present invention, it is preferable that the photopolymerizable layer contains a dye. The photopolymerizable layer contains at least the polymerizable compound, and further contains a dye, an alkali-soluble binder, a photopolymerization initiator, a crosslinking agent, an organic solvent, a dispersant, and the like as necessary. It is formed by applying an adhesive composition on a support.
Hereinafter, the curable composition used for forming the photopolymerizable layer in the present invention will be described using a dye-containing curable composition as an example. .

(Dye-containing curable composition)
The dye-containing curable composition contains at least the polymerizable compound, and may further contain other components such as an alkali-soluble binder, a dye, a photopolymerization initiator, a crosslinking agent, and an organic solvent.

-Polymerizable compound having an ethylenically unsaturated bond-
First, a polymerizable compound having an ethylenically unsaturated bond will be described. As the polymerizable compound having an ethylenically unsaturated bond, a compound 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 using the polymerizable compound together with a photopolymerization initiator, which will be described later, the photopolymerizable layer (dye-containing curable composition) can be formed into a negative type.

  Examples of the polymerizable compound include monofunctional acrylates and methacrylates such as polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, and 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) Acrylate, hexanediol (meth) acrylate,

Trimethylolpropane tri (acryloyloxypropyl) ether, tri (acryloyloxyethyl) isocyanurate, polyfunctional alcohols such as glycerin and trimethylolethane and then (meth) acrylated after addition of 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, Polyester acrylates described in JP-B-52-30490; polyfunctional acrylates and methacrylates such as epoxy acrylates, which are reaction products of epoxy resin and (meth) acrylic acid, and mixtures thereof Can do. Furthermore, the Japan Adhesion Association Vol. 20, No. 7, pages 300 to 308, which are introduced as photocurable monomers and oligomers.

  The content of the polymerizable compound in the dye-containing curable composition is from 0.1 to the total solid content (mass) of the composition from the viewpoint of improving the curability of the photocurable layer. 90 mass% is preferable, 1.0-80 mass% is still more preferable, 2.0-70 mass% is especially preferable.

<Alkali-soluble binder>
Next, the alkali-soluble binder will be described. The alkali-soluble binder that can be used in the present invention is not particularly limited as long as it is water-soluble or 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 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, an acid anhydride added to a polymer having a hydroxyl group, a polyhydroxystyrene resin, a polysiloxane resin, poly (2-hydroxyethyl (meth) acrylate), polyvinylpyrrolidone, polyethylene oxide, Polyvinyl alcohol, etc. 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 a tetrahydrofurfuryl group, phosphoric acid, phosphate ester, quaternary ammonium salt, ethyleneoxy chain, propyleneoxy chain, sulfonic acid and its salt, morpholinoethyl group, and the like. 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 a polymerizable group include KS resist-106 (manufactured by Osaka Organic Chemical Industry Co., Ltd.), Cyclomer P series (manufactured by Daicel Chemical Industries, Ltd.), and the like. In addition, in order to increase the strength of the cured film, alcohol-soluble nylon, polyether of 2,2-bis- (4-hydroxyphenyl) -propane and epichlorohydrin, and the like are also useful.

  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 composed of monomers selected from benzyl (meth) acrylate, (meth) acrylic acid, hydroxyethyl (meth) acrylate, (meth) acrylamide, and the like, KS resist-106 (Osaka Organic Chemical Industry). And Cyclomer P series (manufactured by Daicel Chemical Industries, Ltd.).

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.

  As content in the dye-containing curable composition of the said alkali-soluble binder, 10-90 mass% is preferable with respect to the total solid (mass) of this composition from a developability viewpoint, and 20-80 mass% is preferable. More preferred is 30 to 70% by mass.

<Dye>
The dye can be used without particular limitation, and an organic solvent-soluble dye can be suitably used. Examples of the dye include conventionally known dyes for color filters. For example, JP-A 64-90403, JP-A 64-91102, JP-A-1-94301, JP-A 6-94301. No. 11614, No. 2592207, U.S. Pat. No. 4,808,501, U.S. Pat. No. 5,667,920, U.S. Pat. No. 5,059,500, JP-A-5-333207. And dyes described in JP-A-6-35183, JP-A-6-51115, JP-A-6-194828, and the like. From the viewpoint of the chemical structure of the dye, dyes such as triphenylmethane, anthraquinone, benzylidene, oxonol, cyanine, phenothiazine, pyrrolopyrazole azomethine, xanthene, phthalocyanine, benzopyran, indigo, etc. Can be used. Particularly preferably, pyrazole azo dyes, anilinoazo dyes, pyrazolotriazole azo dyes, pyridone azo dyes, anthraquinone dyes and anthrapyridone dyes can be suitably used.

  In the case of a resist system that performs water or alkali development, an acid dye and / or a derivative thereof may be preferably used from the viewpoint of completely removing the alkali-soluble binder and / or dye by development. In addition, direct dyes, basic dyes, mordant dyes, acid mordant dyes, azoic dyes, disperse dyes, oil-soluble dyes, food dyes, and / or derivatives thereof can also be used effectively.

-Acid dyes-
The upper 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, 163, 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, 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 , 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, etc. can be used, and a curable composition solution Is not particularly limited as long as it can be dissolved, but it requires solubility in organic solvents and developers, absorbance, interaction with other components in the curable composition, light resistance, heat resistance, etc. It is selected considering all of the performance.

  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 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. n is a value that determines the molar ratio between the acid dye molecule and the amine compound that is a counter ion, and can be freely selected according to the salt forming conditions of the acid 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 addition, the acidic dye may suitably act during alkali development, but on the other hand, it may be over-developed, and a non-acidic dye may be preferably used.
The concentration of the dye in the dye-containing curable composition will be described. The content concentration of the dye in the total solid component of the dye-containing curable composition of the present invention varies depending on the dye, but is preferably 0.5 to 80% by mass, more preferably 0.5 to 60% by mass, and 0 0.5 to 50% by mass is particularly preferable.

<Photopolymerization initiator>
Next, the photopolymerization initiator will be described. A photoinitiator is contained with the said polymeric compound, when comprising the said dye-containing curable composition in a negative type. The photopolymerization initiator is not particularly limited as long as it can polymerize the polymerizable compound, but is preferably selected from the viewpoints 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 that is the 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.

  Specifically, 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)- , 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-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.

  In addition, TAZ series (for example, TAZ-107, TAZ-110, TAZ-104, TAZ-109, TAZ-140, TAZ-204, TAZ-113, TAZ-123) manufactured by Midori Chemical Co., Ltd., manufactured by PANCHIM T series (for example, T-OMS, T-BMP, T-R, TB), Irgacure series (for example, Irgacure 651, Irgacure 184, Irgacure 500, Irgacure 1000, Irgacure, manufactured by Ciba Specialty Chemicals) 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 Ciro acetophenone, 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.

A sensitizer and a light stabilizer can be used in combination with these photopolymerization initiators.
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 for the dye-containing curable composition in 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 (and known initiator) is preferably 0.01% by mass to 50% by mass with respect to the solid content (mass) of the polymerizable compound, and 1% by mass to 30% by mass. % Is more preferable, and 1% by mass to 20% by mass is particularly preferable. When the amount used is in the range of 0.01% by mass to 50% by mass, the polymerization sufficiently proceeds and the film strength can be improved.

<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 (a) epoxy resin 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 di Divalent glycidyl group-containing low molecular weight compounds such as glycidyl ether, hexanediol diglycidyl ether, dihydroxybiphenyl diglycidyl ether, diglycidyl phthalate, and N, N-diglycidyl aniline; similarly, trimethylolpropane triglycidyl ether , Trivalent glycidyl group-containing low molecular weight compounds represented by trimethylolphenol triglycidyl ether, TrisP-PA triglycidyl ether and the like; similarly, pentaerythritol tetraglycidyl ether, tetramethylo Tetravalent glycidyl group-containing low molecular weight compounds typified by bisphenol A tetraglycidyl ether and the like; similarly, 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 component (b) is 2 to 6 for melamine compounds, 2 to glycoluril compounds, guanamine compounds, and urea compounds. 4, preferably 5 to 6 in the case of a melamine compound, and 3 to 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 the component (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. Examples thereof include compounds obtained by acylating 1 to 3 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, As in the case of such a compound, intermixing with the top-coated photoresist is suppressed by thermal crosslinking, and the film strength is further increased. Hereinafter, these compounds may be collectively referred to as compounds (containing methylol group, alkoxymethyl group or acyloxymethyl group) according to (c).

The number of methylol groups, acyloxymethyl groups or alkoxymethyl groups contained in the component (c) is at least two per molecule, and from the viewpoint of thermal crosslinkability and storage stability, a phenolic compound that serves as a skeleton A compound in which all of the 2- and 4-positions are substituted is preferred. In addition, the naphthol compound and hydroxyanthracene compound as the skeleton are preferably compounds in which all of the ortho-position and para-position of the OH group are substituted. The 3-position or 5-position of the 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 compound (c) include a phenol compound, naphthol, hydroxyanthracene compound, etc., in which the ortho-position or para-position of the phenolic OH group is unsubstituted. For example, phenol, cresol isomers, 2,3-xylenol, 2,5-xylenol, 3,4-xylenol, 3,5-xylenol, bisphenols such as bisphenol A, 4,4′-bishydroxybiphenyl, TrisP-PA (Honshu Chemical) Kogyo Co., Ltd.), naphthol, dihydroxynaphthalene, 2,7-dihydroxyanthracene, and the like are used.

  Specific examples of the compound according to the above (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 , Tetramethylol bisphenol A, tetramethoxymethyl bisphenol A, compounds obtained by methoxymethylating 1 to 3 methylol groups of tetramethylol bisphenol A, tetramethylol-4,4′-bishydroxybiphenyl, tetramethoxymethyl-4, 4'-bishydroxybiphenyl, hexamethylol form of TrisP-PA, hexamethoxymethyl form of TrisP-PA, compound obtained by methoxymethylating 1 to 5 methylol groups of the hexamethylol form of TrisP-PA, bishydroxymethylnaphthalene Diols, and the like.

  In addition, 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.

  Although the total content of the crosslinking agent in the dye-containing curable composition varies depending on the material, it is 1 to 70% by mass with respect to the solid content (mass) of the curable composition from the viewpoint of film curability. 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 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 preparing the dye-containing curable composition in the present invention is basically not particularly limited as long as the solubility of each component and the coating property of the dye-containing curable composition are satisfied. It is preferably selected in consideration of the solubility, coating property and safety of the binder. Moreover, it is preferable to use together two or more types of organic solvents as the organic solvent.

  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.

  In the present invention, among these organic solvents, two or more kinds of organic solvents can be arbitrarily mixed, but an organic solvent having a hydroxyl group (for example, methyl lactate, ethyl lactate, propylene glycol monomethyl ether, propylene glycol mono It is preferable to mix ethyl ether and the like and an organic solvent having no hydroxyl group. As the organic solvent not having a hydroxyl group, an organic solvent having a ketone group is preferable, and an organic solvent having a cyclic ketone group is more preferable from the viewpoint of increasing the exposed portion residual color rate. As the organic solvent having no hydroxyl group, for example, methyl ethyl ketone, cyclohexanone, 2-heptanone, propylene glycol monomethyl ether acetate and the like are preferable, and methyl ethyl ketone, cyclohexanone and 2-heptanone are more preferable, and cyclohexanone is particularly preferable.

  In addition, when combining 2 or more types of organic solvents, each addition amount can be suitably determined in the range which does not impair the effect of this invention. For example, when using together the organic solvent which has a hydroxyl group, and the organic solvent which does not have a hydroxyl group, the content ratio (molar ratio; the organic solvent which has a hydroxyl group / the organic solvent which does not have a hydroxyl group) is 5 / 95-95. / 5 is preferable, and 10/90 to 90/10 is more preferable. When the content ratio is in the range of 5/95 to 95/5, it is favorable from the viewpoints of solubility and coatability, and a good coating film can be formed.

<Various additives>
In the dye-containing curable composition of the present invention, various additives such as a filler, a polymer compound other than the above, a surfactant, an adhesion promoter, an antioxidant, an ultraviolet absorber, and an aggregation preventive agent are added as necessary. An agent or the like can be added.

  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.

Moreover, when the dye-containing curable composition in the present invention is configured as a negative type, the alkali solubility of the non-cured portion is promoted, and the developability of the dye-containing curable composition of the present invention is further improved. In this case, an organic carboxylic acid, preferably a low molecular weight organic carboxylic acid having a molecular weight of 1000 or less can be added to the composition.
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.

<< Photocurable image recording material, color filter >>
Next, the photocurable image recording material and color filter of the present invention will be described in detail through the production method thereof.
In the method for producing a color filter of the present invention, the aqueous solution and the photopolymerizable composition solution containing the polysaccharide described above are used. As the photopolymerizable composition solution, the aforementioned dye-containing curable composition can be preferably used.
The photocurable image recording material of the present invention is a spin coating, casting coating, roll coating or the like of a photopolymerizable composition solution (preferably the dye-containing curable composition) containing at least the polymerizable compound on a support. The coating method can be used to apply the solution containing an aqueous solution containing the polysaccharide, and a photopolymerizable layer and a polysaccharide layer can be provided in this order on the support.

  In the method for producing a color filter of the present invention, a photopolymerizable composition solution containing at least the polymerizable compound (preferably the dye-containing curable composition) is spin-coated, cast-coated, and rolled on a support. A photopolymerizable layer is formed by coating by a coating method such as coating, and then a polysaccharide layer is formed by coating an aqueous solution containing a polysaccharide. Then, the layer is exposed through a predetermined mask pattern and developed. By developing with a liquid, a negative colored pattern is formed (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 the color filter, a color filter having a desired hue can be produced by repeating the image forming step (and 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 (registered trademark) glass, and quartz glass used for liquid crystal display elements and the like, and those obtained by attaching a transparent conductive film thereto, and photoelectric conversion element substrates used for imaging elements and the like. Examples thereof include a silicon substrate and a complementary metal oxide semiconductor (CMOS). These 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.

  Any developer can be used as long as it has a composition that dissolves the uncured portion of the dye-containing curable composition and 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 above-mentioned solvent used when preparing the dye-containing 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.

[Example 1]
1) Preparation of dye-containing curable composition Each compound was mixed and dissolved in the composition shown below to prepare dye-containing curable composition A (photopolymerizable composition solution).
〔composition〕
・ Ethyl lactate 43.5 parts ・ Allyl methacrylate / methacrylic acid copolymer (= 80/20 [molar ratio])
(Alkali-soluble binder) 4.1 parts dipentaerythritol hexaacrylate 6.1 parts polymerization inhibitor (p-methoxyphenol) 0.0061 parts photopolymerization initiator 1.0 part (trade name: TAZ-107, (Midori Chemical Co., Ltd.)
・ Organic solvent soluble dye (Valifast yellow 1101) 7.0 parts

2) Production of silicon wafer with undercoat layer A resist solution (trade name: CT-2000L, manufactured by Fuji Film Arch Co., Ltd.) was applied to a 6-inch silicon wafer using a spin coater so as to have a film thickness of 2 μm. Heat-dried at 1 ° C. for 1 hour to form a cured film (undercoat layer).

3) Formation of pattern image (image forming process)
The dye-containing curable composition A obtained in 1) above was applied on the silicon wafer with an undercoat layer obtained in 2) so as to have a film thickness of 1 μm using a spin coater, and 120 ° C. Was pre-baked for 120 seconds to form a photopolymerizable layer.
Next, a 5% aqueous solution of pullulan having the following composition was applied on the photopolymerizable layer by a spin coater so as to have a film thickness of 1.0 μm to form a polysaccharide layer, and the photocurable image recording of the present invention. The material was made.
〔composition〕
・ Pullan 6 parts ・ Water 50 parts ・ Allyl methacrylate / methacrylic acid copolymer 4 parts (= 10/90 (molar ratio))

Next, using an i-line stepper exposure apparatus, the coating film was subjected to pattern exposure of 2 μm at a wavelength of 365 nm. After the exposure, development (development process) was performed at 23 ° C. for 60 seconds using a developer (trade name: CD-2000, 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. Thereafter, the wafer was heated (heating process) at 200 ° C. for 10 minutes to obtain a final image.
The rectangularity of the obtained pattern image was determined by SEM photograph observation of the cross section of the pattern.

[Example 2]
In Example 1, a photocurable image-recording material was prepared in the same manner as in Example 1 except that a polysaccharide layer was formed by applying a 5% aqueous solution of pullulan with a spin coater to a film thickness of 0.05 μm. It produced and also formed the pattern image.

[Example 3]
In Example 1, a photocurable image-recording material was prepared in the same manner as in Example 1 except that a polysaccharide layer was formed by applying a 5% aqueous solution of pullulan to a film thickness of 0.3 μm using a spin coater. It produced and also formed the pattern image.

[Example 4]
In Example 1, a photocurable image-recording material was prepared in the same manner as in Example 1 except that a polysaccharide layer was formed by applying a 5% aqueous solution of pullulan to a film thickness of 0.6 μm using a spin coater. It produced and also formed the pattern image.

[Example 5]
In Example 1, a photocurable image-recording material was prepared in the same manner as in Example 1 except that a polysaccharide layer was formed by applying a 5% aqueous solution of pullulan with a spin coater to a thickness of 0.01 μm. It produced and also formed the pattern image.

[Example 6]
In Example 1, a photocurable image-recording material was prepared in the same manner as in Example 1 except that a polysaccharide layer was formed by applying a 5% aqueous solution of pullulan to a film thickness of 0.1 μm using a spin coater. It produced and also formed the pattern image.

[Comparative Example 1]
First, the dye-containing curable composition obtained in Example 1 was applied on a silicon wafer with an undercoat layer using a spin coater so as to have a film thickness of 1 μm, and prebaked at 120 ° C. for 120 seconds. A photocurable image recording material was produced.
Next, using an i-line stepper exposure apparatus, a pattern exposure of 2 μm was performed on the coating film of the photocurable image recording material at a wavelength of 365 nm. After the exposure, development was performed at 23 ° C. for 60 seconds using a developer (trade name: CD-2000, 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. Thereafter, the wafer was heated at 200 ° C. for 10 minutes to obtain a final image.

[Evaluation]
(1) Pattern rectangularity The rectangularity of the pattern was compared based on the values observed and measured by SEM. The measurement was performed by quantifying the rectangularity of the obtained pattern having a length of 1 μm and a width of 2 μm in the SEM image of the pattern cross section by the distance from the center of the cross-sectional photograph to the apex of the upper part of the film (the roundness of the determined corner is In the case of an ideal rectangle, the distance from the center to the corner is √ ((0.5) ² + (1.0) ² ) = 1.12.
In addition, the rectangularity of the pattern was measured for the pattern when the development was performed for 90 seconds after the development step, after the heating step, and in the development step.

(2) Sensitivity Regarding the sensitivity of each photocurable image recording material, the minimum exposure amount at which a 2 μm square pattern can be confirmed was measured, and the measured value was used as an index of sensitivity. The smaller the measured value, the higher the sensitivity.

  As shown in Table 1, it can be seen that the image pattern of each example has a very high rectangularity of the pattern, and further, the change due to heating after development is very small and preferable. It can also be seen that the shape stability when developing up to 90 seconds is high, and the latitude with respect to the development time is also widened. Furthermore, each Example was excellent in sensitivity. Moreover, it turns out that these performance is improved according to the layer thickness of the polysaccharide layer.

  Although dextran and xanthan gum were also evaluated in the same manner as in Examples 1 to 6, it was confirmed that the rectangularity was improved with respect to Comparative Example 1, the sensitivity was increased, and the latitude with respect to development time was also expanded. .

Claims (6)

  A photocurable image-recording material comprising a photopolymerizable layer containing a polymerizable compound having an ethylenically unsaturated bond and a polysaccharide layer containing a polysaccharide in this order on a support.   The photocurable image recording material according to claim 1, wherein the polysaccharide is a microbially produced polysaccharide.   3. The photocurable image recording material according to claim 2, wherein the microbially produced polysaccharide is at least one selected from pullulan, xanthan gum and dextran.   The photocurable image recording material according to claim 1, wherein the photopolymerizable layer contains a dye.   A color filter comprising the photocurable image recording material according to claim 1.   A step of applying a photopolymerizable composition solution containing a dye and a polymerizable compound on a support, and then applying an aqueous solution containing a polysaccharide, exposing through a mask, and developing to form a pattern. A method for producing a color filter characterized by the above.