JP2012068374A - Color resist composition, color filter and liquid crystal display device - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a color resist composition excellent in defoaming property, showing good smoothness of a coating film with suppressed pigment aggregation and less color irregularity, and using a fluorine-based surfactant having low accumulating property in an environment and in a living body, and to provide a color filter and a liquid crystal display device using the composition.SOLUTION: The color resist composition contains an alkali soluble resin (A), a polymerizable compound (B), a colorant (C) and a fluorine-based surfactant (D). The fluorine-based surfactant (D) is a copolymer prepared by copolymerizing, as essential components, a monomer (d1) having a fluorinated alkyl group having 4 to 6 carbon atoms and a monomer (d2) having a polyoxyalkylene chain.

Description

  The present invention provides a color resist composition using a fluorine-containing surfactant that has excellent antifoaming properties, good coating smoothness, can suppress pigment aggregation, and has low accumulation in the environment and living organisms. The present invention relates to a used color filter and a liquid crystal display device.

  The color filter used in the color liquid crystal display device is generally a basic in which each pixel of red (R), green (G), and blue (B) and a black matrix (BM) are formed between them for the purpose of improving display contrast. It has a configuration. In the production of a color filter, a color resist composition is generally applied on a glass substrate by a coating method such as spin coating or slit coating, and after drying, exposed using a mask and then developed to form a colored pattern. If the coating smoothness is not good and the film thickness is uneven, or if there is application unevenness, repellency, etc., pixel color unevenness occurs. When a color liquid crystal display device is manufactured using a color filter having such color unevenness, there arises a problem that color unevenness occurs in an image obtained on the display. That is, the surface of these R, G, B pixels and BM in the color filter is required to have high smoothness. For this purpose, when the color resist composition is applied, it has a uniform film thickness and uneven coating. It is necessary to apply the coating so as not to cause repelling and color unevenness.

  In order to prevent color unevenness due to coating unevenness, repelling, etc., a method of using a fluorosurfactant has been proposed, and in order to improve its effect, the constituent components of the copolymer used for the surfactant have been improved. (For example, refer to Patent Documents 1 to 4.) The leveling property is improved by the effect of reducing the surface tension of the color resist composition by these fluorosurfactants, and the smoothness of the coating film can be improved.

  However, in recent years, compounds having a perfluoroalkyl group having 8 carbon atoms are decomposed, so that perfluorooctane sulfonic acid (hereinafter abbreviated as “PFOS”) or perfluoro, which has high accumulation in the environment and living organisms. It was revealed that octanoic acid (hereinafter abbreviated as “PFOA”) can be produced. The fluorine-based surfactants described in Patent Documents 1 to 4 use a compound having a C8 perfluoroalkyl group that has a high possibility of producing PFOS and PFOA having high accumulation in the environment and living body. There was a problem. On the other hand, the color filter composition is stirred at the time of preparation to obtain a uniform liquid, but there is also a problem that the foam is generated by the action of the fluorosurfactant and the foam does not disappear for a long time.

  Under the circumstances as described above, in the market, a fluorine-containing surfactant having excellent defoaming property, good coating smoothness, suppressing pigment aggregation, and low accumulation in the environment and living body was used. There is a need for color resist compositions.

JP-A-10-230154 JP-A-10-309455 JP 2002-139830 A JP 2004-109179 A

  The problem to be solved by the present invention is a fluorine-containing surfactant that has excellent defoaming properties, good coating smoothness, can suppress pigment aggregation, has little color unevenness, and has low accumulation in the environment and living body. It is an object to provide a color resist composition using the above, a color filter using the same, and a liquid crystal display device.

  As a result of intensive studies to solve the above-mentioned problems, the present inventors have obtained a fluorine-based material using a monomer having a fluorinated alkyl group having 4 to 6 carbon atoms and a monomer having a polyoxyalkylene chain as a raw material. By using a surfactant, it was found that a color resist composition having excellent defoaming property, smoothness of a coating film, suppression of pigment aggregation, and low accumulation in the environment and living body can be obtained. The invention has been completed.

  That is, the present invention is a composition containing an alkali-soluble resin (A), a polymerizable compound (B), a colorant (C) and a fluorosurfactant (D), wherein the fluorosurfactant ( D) is a copolymer obtained by copolymerizing the monomer (d1) having a fluorinated alkyl group having 4 to 6 carbon atoms and the monomer (d2) having a polyoxyalkylene chain as essential components. The present invention relates to a featured color resist composition.

  Furthermore, the present invention relates to a color filter having a cured coating film of the color resist composition, and a liquid crystal display device provided with the color filter on at least a part of a substrate.

  The color resist composition of the present invention is a material that has excellent defoaming properties, good coating film smoothness, can suppress pigment aggregation, and has low accumulation in the environment and living organisms. Therefore, by using the color resist composition, it is possible to provide a color filter that is excellent in color reproducibility without color unevenness and has a colored pattern formed with high accuracy. In addition, by using the color filter, a liquid crystal display device having excellent display characteristics can be provided.

  The alkali-soluble resin (A) used in the present invention is not particularly limited as long as it is soluble in an alkali developer, but at least one acid group selected from the group of a carboxyl group, a phenolic hydroxyl group, and a sulfonic acid group. Or the resin which has the salt is preferable.

  More specifically, the alkali-soluble resin (A) is obtained by polymerizing a monomer having an acidic group. Examples of the monomer having a carboxyl group as an acid group as a raw material of the alkali-soluble resin (A) include, for example, acrylic acid, methacrylic acid, vinyl acetic acid, crotonic acid, itaconic acid, maleic acid, fumaric acid, cinnamic acid, These salts are mentioned.

  As a monomer which has a phenolic hydroxyl group as an acidic group used as the raw material of alkali-soluble resin (A), o-hydroxy styrene, m-hydroxy styrene, p-hydroxy styrene etc. are mentioned, for example. In addition, one or more hydrogen atoms other than the phenolic hydroxyl group and vinyl group bonded to the aromatic ring of these monomers were substituted with an alkyl group, an alkoxyl group, a halogen atom, a nitro group, a cyano group, or an amide group. A compound etc. are also mentioned.

  Examples of the monomer having a sulfonic acid group as an acidic group as a raw material for the alkali-soluble resin (A) include vinyl sulfonic acid, styrene sulfonic acid, (meth) allyl sulfonic acid, and 2-hydroxy-3- (meth). Allyloxypropanesulfonic acid, (meth) acrylic acid-2-sulfoethyl, (meth) acrylic acid-2-sulfopropyl, 2-hydroxy-3- (meth) acryloxypropanesulfonic acid, 2- (meth) acrylamide-2 -Methylpropanesulfonic acid or a salt thereof.

  Moreover, although the monomer which has said acidic group can superpose | polymerize independently and can be set as alkali-soluble resin (A), you may make it copolymerize with another monomer. Such other monomers include hydrocarbon olefins, vinyl ethers, isopropenyl ethers, allyl ethers, vinyl esters, allyl esters, (meth) acrylic esters, (meth) acrylamides. , Aromatic vinyl compounds, chloroolefins, conjugated dienes and the like. Among these, (meth) acrylic acid esters are preferable.

  Examples of the (meth) acrylate esters include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, and n- (meth) acrylate. Butyl, isobutyl (meth) acrylate, sec-butyl (meth) acrylate, t-butyl (meth) acrylate, n-pentyl (meth) acrylate, 3-methylbutyl (meth) acrylate, (meth) acrylic acid n-hexyl, 2-ethyl- (meth) acrylate-n-hexyl, n-octyl (meth) acrylate, cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, (Meth) acrylic acid 2-hydroxypropyl, (meth) acrylic acid 3-hydroxypropyl, (meth) a 4-hydroxybutyl toluate, 5-hydroxypentyl (meth) acrylate, 6-hydroxyhexyl (meth) acrylate, 4-hydroxycyclohexyl (meth) acrylate, neopentyl glycol mono (meth) acrylate, (meth) acryl Acid 3-chloro-2-hydroxypropyl, glycerin mono (meth) acrylate, 1,1-dimethyl-3-oxobutyl (meth) acrylate, (meth) acrylic acid 2-acetoacetoxyethyl, (meth) acrylic acid 2- Examples include methoxyethyl, 2-ethoxyethyl (meth) acrylate, and benzyl (meth) acrylate.

  The monomer having an acidic group that is a raw material of the alkali-soluble resin (A) and the other monomer may be used alone or in combination of two or more.

  In the present invention, “(meth) acrylic acid” refers to one or both of methacrylic acid and acrylic acid, and “(meth) acryloyl” refers to one or both of methacryloyl and acryloyl. ) "Acrylate" refers to one or both of methacrylate and acrylate.

  Among the alkali-soluble resins (A), as a preferred specific example, at least a part of the epoxy group of the copolymer with respect to a copolymer of an epoxy group-containing (meth) acrylate and another radical polymerizable monomer A resin obtained by adding an unsaturated monocarboxylic acid to a resin, and an alkali-soluble resin (A-) obtained by addition-reacting an acid anhydride of polycarboxylic acid to at least a part of the hydroxyl group generated by the addition reaction of the unsaturated monocarboxylic acid 1).

  Examples of the epoxy group-containing (meth) acrylate that is a raw material of the alkali-soluble resin (A-1) include glycidyl (meth) acrylate, 3,4-epoxybutyl (meth) acrylate, and (3,4-epoxycyclohexyl). Examples thereof include methyl (meth) acrylate and 4-hydroxybutyl (meth) acrylate glycidyl ether. Of these, glycidyl (meth) acrylate is preferred. These epoxy group-containing (meth) acrylates can be used alone or in combination of two or more.

  Further, as a radical polymerizable monomer other than the epoxy group-containing (meth) acrylate that is a raw material of the alkali-soluble resin (A-1), a monomer having an alicyclic structure such as a norbornene skeleton or a dicyclopentadiene skeleton is used. Since the heat resistance and mechanical strength of the cured product of the color resist composition of the present invention can be improved, it is preferable.

  Moreover, you may use the monomer which does not have an alicyclic structure as other radically polymerizable monomers other than the said epoxy-group-containing (meth) acrylate. Examples of such polymerizable monomers include styrene, vinyl aromatics such as α-, o-, m-, p-alkyl, nitro, cyano, amide and ester derivatives of styrene; butadiene, 2,3-dimethyl. Dienes such as butadiene, isoprene, chloroprene; methyl (meth) acrylate, ethyl (meth) acrylate, (meth) acrylic acid-n-propyl, (meth) acrylic acid-i-propyl, (meth) acrylic acid- n-butyl, (meth) acrylic acid-s-butyl, (meth) acrylic acid-t-butyl, (meth) acrylic acid pentyl, (meth) acrylic acid neopentyl, (meth) acrylic acid isoamyl, (meth) acrylic acid Hexyl, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, dodecyl (meth) acrylate, (meth Cyclopentyl acrylate, cyclohexyl (meth) acrylate, (meth) acrylate-2-methylcyclohexyl, dicyclohexyl (meth) acrylate, isobornyl (meth) acrylate, adamantyl (meth) acrylate, propargyl (meth) acrylate, Phenyl (meth) acrylate, naphthyl (meth) acrylate, anthracenyl (meth) acrylate, anthraninonyl (meth) acrylate, piperonyl (meth) acrylate, salicyl (meth) acrylate, furyl (meth) acrylate , Furfuryl (meth) acrylate, tetrahydrofuryl (meth) acrylate, pyranyl (meth) acrylate, benzyl (meth) acrylate, phenethyl (meth) acrylate, cresyl (meth) acrylate, (meth) acrylic acid- 1,1,1-trif Fluoroethyl, perfluoroethyl (meth) acrylate, perfluoro-n-propyl (meth) acrylate, perfluoro-iso-propyl (meth) acrylate, triphenylmethyl (meth) acrylate, (meth) acrylic acid (Meth) acrylic acid esters such as cumyl, (meth) acrylic acid-3- (N, N-dimethylamino) propyl, (meth) acrylic acid-2-hydroxyethyl, (meth) acrylic acid-2-hydroxypropyl ; (Meth) acrylic acid amide, (meth) acrylic acid N, N-dimethylamide, (meth) acrylic acid N, N-diethylamide, (meth) acrylic acid N, N-dipropylamide, (meth) acrylic acid- (Meth) acrylic amides such as N, N-di-i-propylamide, (meth) acrylic acid anthracenyl amide; T) Vinyl compounds such as acrylic acid anilide, (meth) acryloylnitrile, acrolein, vinyl chloride, vinylidene chloride, vinyl fluoride, vinylidene fluoride, N-vinyl pyrrolidone, vinyl pyridine, vinyl acetate; diethyl citraconic acid, maleic acid Unsaturated dicarboxylic acid diesters such as diethyl, diethyl fumarate and diethyl itaconate; monomaleimides such as N-phenylmaleimide, N-cyclohexylmaleimide, N-laurylmaleimide and N- (4-hydroxyphenyl) maleimide; N- (Meth) acryloylphthalimide and the like.

  Among the above other radical polymerizable monomers, since the heat resistance and mechanical strength of the cured product of the color resist composition of the present invention can be improved, at least one of styrene, benzyl (meth) acrylate and monomaleimide is selected. It is preferable to use it. In addition, the content of styrene, benzyl (meth) acrylate and monomaleimide is preferably 1 to 70 mol%, and preferably 3 to 50 mol% in the whole of other radical polymerizable monomers used as raw materials. Is more preferable.

  The copolymerization reaction between the epoxy group-containing (meth) acrylate and the other radical polymerizable monomer can be performed by a known polymerization method such as a solution polymerization method using a radical polymerization initiator. The solvent to be used is not particularly limited as long as it is inert to radical polymerization, and a commonly used organic solvent can be used.

  Examples of the copolymer of the epoxy group-containing (meth) acrylate and the other radical polymerizable monomer include 5 to 90 mol% of repeating units derived from the epoxy group-containing (meth) acrylate, and other radical polymerizable monomers. What consists of 10-95 mol% of derived repeating units is preferable, what consists of the former 20-80 mol% and the latter 80-20 mol% is more preferable, the former 30-70 mol%, and the latter 70- What consists of 30 mol% is still more preferable.

  The alkali-soluble resin (A-1) includes an unsaturated monocarboxylic acid (polymerizable component) on the epoxy group portion of a copolymer of the epoxy resin-containing (meth) acrylate and another radical polymerizable monomer, A polycarboxylic acid anhydride (alkali-soluble component) is reacted.

  Examples of the unsaturated monocarboxylic acid include (meth) acrylic acid, crotonic acid, o-, m-, p-vinylbenzoic acid, α-position is a haloalkyl group, an alkoxyl group, a halogen atom, a nitro group, or cyano. And monocarboxylic acids such as (meth) acrylic acid substituted with a group. Among these, (meth) acrylic acid is preferable. These unsaturated monocarboxylic acids can be used alone or in combination of two or more. By using this unsaturated monocarboxylic acid, polymerizability can be imparted to the alkali-soluble resin (A-1).

  The unsaturated monocarboxylic acid is usually preferably added to 10 to 100 mol% of the epoxy group of the copolymer, more preferably 30 to 100 mol%, and more preferably 50 to 100 mol%. More preferably, it is added.

  Examples of the acid anhydride of the polycarboxylic acid include dicarboxylic acid anhydrides such as maleic anhydride, succinic anhydride, itaconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, and chlorendic anhydride. A carboxylic acid anhydride having three or more carboxyl groups, such as trimellitic anhydride, pyromellitic anhydride, benzophenone tetracarboxylic acid anhydride, biphenyltetracarboxylic acid anhydride; Among these, tetrahydrophthalic anhydride and succinic anhydride are preferable. These polycarboxylic acid anhydrides can be used alone or in combination of two or more. By using this polycarboxylic acid anhydride, alkali solubility can be imparted to the alkali-soluble resin (A-1).

  The acid anhydride of the polycarboxylic acid is usually preferably added to 10 to 100 mol% of the hydroxyl group generated by adding an unsaturated monobasic acid to the epoxy group of the copolymer. It is more preferable to add to mol%, and it is further preferable to add to 30 to 80 mol%.

  The polystyrene-converted weight average molecular weight (Mw) measured by GPC of the alkali-soluble resin (A-1) is preferably in the range of 3,000 to 100,000, and more preferably in the range of 5,000 to 50,000. The dispersity (Mw / Mn) of the alkali-soluble resin (A-1) is preferably in the range of 2.0 to 5.0.

  Examples of the alkali-soluble resin (A) include an alkali-soluble resin (A-2) obtained by polymerizing a carboxyl group-containing polymerizable monomer.

  Examples of the carboxyl group-containing polymerizable monomer include (meth) acrylic acid, maleic acid, crotonic acid, itaconic acid, fumaric acid, 2- (meth) acryloyloxyethyl succinic acid, and 2- (meth) acryloyloxyethyl adipine. Acid, 2- (meth) acryloyloxyethylmaleic acid, 2- (meth) acryloyloxyethylhexahydrophthalic acid, 2- (meth) acryloyloxyethylphthalic acid, 2- (meth) acryloyloxypropylsuccinic acid, 2- (Meth) acryloyloxypropyladipic acid, 2- (meth) acryloyloxypropylmaleic acid, 2- (meth) acryloyloxypropylhydrophthalic acid, 2- (meth) acryloyloxypropylphthalic acid, 2- (meth) acryloyloxy Butyl succinic acid, 2- Vinyl monomers such as (meth) acryloyloxybutyladipic acid, 2- (meth) acryloyloxybutylmaleic acid, 2- (meth) acryloyloxybutylhydrophthalic acid, 2- (meth) acryloyloxybutylphthalic acid; acrylic acid Monomers obtained by adding lactones such as ε-caprolactone, β-propiolactone, γ-butyrolactone, and δ-valerolactone; succinic acid, maleic acid, phthalic acid, or acid anhydrides thereof to hydroxyalkyl (meth) acrylate Examples include added monomers. These carboxyl group-containing polymerizable monomers can be used alone or in combination of two or more. Among the carboxyl group-containing polymerizable monomers, (meth) acrylic acid and 2- (meth) acryloyloxyethyl succinic acid are preferable.

  As a raw material of the alkali-soluble resin (A-2), in addition to the carboxyl group-containing polymerizable monomer, a copolymerizable monomer having no carboxyl group may be used for copolymerization. Examples of the polymerizable monomer having no carboxyl group include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, Benzyl (meth) acrylate, phenyl (meth) acrylate, cyclohexyl (meth) acrylate, phenoxyethyl (meth) acrylate, phenoxymethyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, isobornyl (meth) acrylate, 2-hydroxyethyl (Meth) acrylates such as (meth) acrylate, glycerol mono (meth) acrylate, tetrahydrofurfuryl (meth) acrylate; 2-hydroxyethyl (meth) acrylate Relates, hydroxyalkyl (meth) acrylates such as hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, (meth) acrylic acid esters having a hydroxyl group such as glycerol mono (meth) acrylate; styrene and its derivatives, etc. Aromatic vinyl compounds; Vinyl compounds such as N-vinylpyrrolidone; N-substituted maleimides such as N-cyclohexylmaleimide, N-phenylmaleimide and N-benzylmaleimide; Polymethyl (meth) acrylate macromonomers, polystyrene macromonomers, poly-2- Macromonomer such as hydroxyethyl (meth) acrylate macromonomer, polyethylene glycol macromonomer, polypropylene glycol macromonomer, polycaprolactone macromonomer And the like. These polymerizable monomers having no carboxyl group can be used alone or in combination of two or more.

  Among the polymerizable monomers having no carboxyl group, styrene, methyl (meth) acrylate, cyclohexyl (meth) acrylate, benzyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 2-hydroxyethyl ( Preferred are (meth) acrylate, hydroxypropyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, N-cyclohexylmaleimide, N-benzylmaleimide, and N-phenylmaleimide.

  Specific examples of the alkali-soluble resin (A-2) include, for example, (meth) acrylic acid, methyl (meth) acrylate, benzyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, cyclohexyl ( Copolymerization of a polymerizable monomer not containing a hydroxyl group such as (meth) acrylate or cyclohexylmaleimide and a hydroxyl group-containing monomer such as 2-hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate or 4-hydroxybutyl (meth) acrylate Copolymerization: Copolymerization of (meth) acrylic acid with (meth) acrylic acid esters such as methyl (meth) acrylate, benzyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, 2-hydroxyethyl methacrylate Body; copolymer of (meth) acrylic acid and styrene; copolymer of (meth) acrylic acid, styrene and α-methylstyrene; copolymer of (meth) acrylic acid and cyclohexylmaleimide . Moreover, the alkali-soluble resin (A-2) using benzyl (meth) acrylate is preferable from the viewpoint of excellent pigment dispersibility.

  The acid value of the alkali-soluble resin (A-2) is preferably in the range of 30 to 500, more preferably in the range of 40 to 350, and still more preferably in the range of 50 to 300. The polystyrene-converted weight average molecular weight (Mw) measured by GPC of the alkali-soluble resin (A-2) is preferably in the range of 2,000 to 80,000, more preferably in the range of 3,000 to 5,000. The range of 4,000 to 30,000 is more preferable.

  An alkali-soluble resin (A-3) obtained by adding an epoxy group-containing unsaturated compound to the carboxyl group of the alkali-soluble resin (A-2) can also be used.

  Examples of the epoxy group-containing unsaturated compound include glycidyl (meth) acrylate, allyl glycidyl ether, glycidyl-α-ethyl acrylate, crotonyl glycidyl ether, (iso) crotonic acid glycidyl ether, N- (3,5-dimethyl). -4-glycidyl) benzylacrylamide, 4-hydroxybutyl (meth) acrylate glycidyl ether, and the like. In addition, an alicyclic epoxy group-containing unsaturated compound is preferable because heat resistance can be improved and dispersibility can be improved when a pigment is used as the colorant (C) described later.

  Examples of the alicyclic epoxy group-containing unsaturated compound include alicyclic epoxy groups such as 2,3-epoxycyclopentyl group, 3,4-epoxycyclohexyl group, 7,8-epoxy [tricyclo [5.2. .1.0] dec-2-yl] group and the like. The ethylenically unsaturated group is preferably a (meth) acryloyl group. The alicyclic epoxy group-containing unsaturated compound can be used alone or in combination of two or more.

  A known technique can be used to add the epoxy group-containing unsaturated compound to the carboxyl group portion of the alkali-soluble resin (A-2). For example, a carboxyl group-containing resin and an epoxy group-containing unsaturated compound are converted into a tertiary amine such as triethylamine or benzylmethylamine; dodecyltrimethylammonium chloride, tetramethylammonium chloride, tetraethylammonium chloride, tetrabutylammonium chloride, benzyltriethylammonium chloride. A quaternary ammonium salt such as pyridine, triphenylphosphine, etc. in an organic solvent at a reaction temperature of 50 to 150 ° C. for several hours to several tens of hours. Saturated compounds can be introduced.

  The acid value of the alkali-soluble resin (A-3), which is a carboxyl group-containing resin to which an epoxy group-containing unsaturated compound is added, is preferably in the range of 10 to 200, more preferably in the range of 20 to 150, and in the range of 30 to 150. Is more preferable. In addition, the polystyrene-converted weight average molecular weight measured by GPC of the alkali-soluble resin (A-3) is preferably in the range of 2,000 to 100,000, more preferably in the range of 4,000 to 50,000, The range of 000 to 30,000 is more preferable.

  Moreover, alkali-soluble resin (A-4) which is (meth) acrylic-type resin can also be used. The (meth) acrylic resin is a polymer obtained by polymerizing (meth) acrylic acid and / or (meth) acrylic acid ester as monomer components. Among these (meth) acrylic resins, those having (meth) acrylic acid ester having an alicyclic structure such as ether dimer or adamantyl group as a monomer component are preferable.

  Examples of the ether dimer include dimethyl-2,2 ′-[oxybis (methylene)] bis-2-propenoate, diethyl-2,2 ′-[oxybis (methylene)] bis-2-propenoate, di (n- Propyl) -2,2 ′-[oxybis (methylene)] bis-2-propenoate, di (isopropyl) -2,2 ′-[oxybis (methylene)] bis-2-propenoate, di (n-butyl) -2 , 2 ′-[oxybis (methylene)] bis-2-propenoate, di (isobutyl) -2,2 ′-[oxybis (methylene)] bis-2-propenoate, di (t-butyl) -2,2′- [Oxybis (methylene)] bis-2-propenoate, di (t-amyl) -2,2 ′-[oxybis (methylene)] bis-2-propenoate, (Stearyl) -2,2 ′-[oxybis (methylene)] bis-2-propenoate, di (lauryl) -2,2 ′-[oxybis (methylene)] bis-2-propenoate, di (2-ethylhexyl)- 2,2 ′-[oxybis (methylene)] bis-2-propenoate, di (1-methoxyethyl) -2,2 ′-[oxybis (methylene)] bis-2-propenoate, di (1-ethoxyethyl)- 2,2 ′-[oxybis (methylene)] bis-2-propenoate, dibenzyl-2,2 ′-[oxybis (methylene)] bis-2-propenoate, diphenyl-2,2 ′-[oxybis (methylene)] bis 2-propenoate, dicyclohexyl-2,2 ′-[oxybis (methylene)] bis-2-propenoate, di (t-butylsilane) Rohexyl) -2,2 ′-[oxybis (methylene)] bis-2-propenoate, di (dicyclopentadienyl) -2,2 ′-[oxybis (methylene)] bis-2-propenoate, di (tricyclo Decanyl) -2,2 ′-[oxybis (methylene)] bis-2-propenoate, di (isobornyl) -2,2 ′-[oxybis (methylene)] bis-2-propenoate, diadamantyl-2,2 ′ -[Oxybis (methylene)] bis-2-propenoate, di (2-methyl-2-adamantyl) -2,2 '-[oxybis (methylene)] bis-2-propenoate and the like. Among these, dimethyl-2,2 ′-[oxybis (methylene)] bis-2-propenoate, diethyl-2,2 ′-[oxybis (methylene)] bis-2-propenoate, dicyclohexyl-2,2 ′-[ Oxybis (methylene)] bis-2-propenoate and dibenzyl-2,2 ′-[oxybis (methylene)] bis-2-propenoate are preferred. These ether dimers can be used alone or in combination of two or more.

  When using an ether dimer as a raw material of the alkali-soluble resin (A-4) that is a (meth) acrylic resin, the ratio of the ether dimer in the monomer component is obtained by suppressing gelation to obtain a low molecular weight one. Since high transparency and heat resistance can be obtained, a range of 2 to 60% by mass is preferable in all monomer components, a range of 5 to 55% by mass is more preferable, and a range of 5 to 50% by mass is further preferable.

  On the other hand, when a (meth) acrylic acid ester having an alicyclic structure such as an adamantyl group is used as a raw material for the alkali-soluble resin (A-4) which is a (meth) acrylic resin, the ratio of the ether dimer in the monomer component is The pigment dispersibility when using a pigment in the colorant (C) can be improved, and the soil stain suitability can be improved. Therefore, the range of 0.5 to 60% by mass is preferable in all monomer components, and 1 to 55% by mass. % Is more preferable, and a range of 5 to 50% by weight is more preferable.

  Moreover, in order to introduce an acid group into the alkali-soluble resin (A-4), for example, a monomer having a carboxyl group such as (meth) acrylic acid or itaconic acid; a monomer having a phenolic hydroxyl group such as N-hydroxyphenylmaleimide; A monomer having a carboxylic anhydride group such as maleic anhydride or itaconic anhydride may be used as a raw material. Among these, (meth) acrylic acid is preferable.

  Examples of the monomer capable of introducing an acid group after the polymerization include, for example, a monomer having a hydroxyl group such as 2-hydroxyethyl (meth) acrylate; a monomer having an epoxy group such as glycidyl (meth) acrylate; 2-isocyanatoethyl (meth) And monomers having an isocyanate group such as acrylate. Examples of monomers capable of introducing an acid group after polymerization include, for example, monomers having a hydroxyl group such as 2-hydroxyethyl (meth) acrylate; monomers having an epoxy group such as glycidyl (meth) acrylate; 2-isocyanatoethyl (meta ) Monomers having an isocyanate group such as acrylate. These monomers can be used alone or in combination of two or more. The amount of the monomer capable of introducing these acid groups is preferably in the range of 5 to 70% by mass, more preferably in the range of 10 to 60% by mass, based on all monomer components.

  Moreover, you may introduce | transduce a radically polymerizable double bond into alkali-soluble resin (A-4). Examples of monomers capable of introducing a radical polymerizable double bond after polymerization include, for example, monomers having a carboxyl group such as (meth) acrylic acid and itaconic acid; monomers having a carboxylic acid anhydride group such as maleic anhydride and itaconic anhydride A monomer having an epoxy group such as glycidyl (meth) acrylate, 3,4-epoxycyclohexylmethyl (meth) acrylate, vinylbenzyl glycidyl ether, and the like. These monomers for introducing radical polymerizable double bonds can be used alone or in combination of two or more. The amount of the monomer capable of introducing these radical polymerizable double bonds is preferably in the range of 5 to 70% by mass and more preferably in the range of 10 to 60% by mass in the total monomer components.

  Furthermore, you may introduce | transduce an epoxy group into alkali-soluble resin (A-4). Examples of the monomer capable of introducing an epoxy group after polymerization include glycidyl (meth) acrylate, 3,4-epoxycyclohexylmethyl (meth) acrylate, vinylbenzyl glycidyl ether, and the like. These monomers for introducing an epoxy group can be used alone or in combination of two or more. The amount of the monomer capable of introducing these epoxy groups is preferably in the range of 5 to 70% by mass and more preferably in the range of 10 to 60% by mass in the total monomer components.

  As the raw material monomer of the alkali-soluble resin (A-4), other copolymerizable monomers can be used. Examples of such a monomer include methyl (meth) acrylate, ethyl (meth) acrylate, ( (Meth) acrylic acid-n-propyl, (meth) acrylic acid isopropyl, (meth) acrylic acid-n-butyl, (meth) acrylic acid isobutyl, (meth) acrylic acid-t-butyl, (meth) acrylic acid methyl- (Meth) acrylates such as 2-ethylhexyl, cyclohexyl (meth) acrylate, benzyl (meth) acrylate, (meth) acrylate-2-hydroxyethyl; aromatics such as styrene, vinyltoluene, α-methylstyrene Vinyl compounds; N-substituted maleimides such as N-phenylmaleimide and N-cyclohexylmaleimide; Tajien, butadiene or substituted butadiene compounds such as isoprene, ethylene, propylene, vinyl chloride, ethylene or substituted ethylene compound such as acrylonitrile; and vinyl esters such as vinyl acetate and the like. These other copolymerizable monomers can be used alone or in combination of two or more. The amount of these other copolymerizable monomers used is preferably 95% by mass or less, more preferably 85% by mass or less, based on all monomer components.

  Among the other copolymerizable monomers, methyl (meth) acrylate, cyclohexyl (meth) acrylate, benzyl (meth) acrylate, and styrene are excellent in transparency and are difficult to impair heat resistance. preferable. Furthermore, when using a part or all of alkali-soluble resin (A-4) as a dispersing agent, it is preferable to use benzyl (meth) acrylate, and the usage-amount is 1-70 mass normally in all the monomer components. % Range is preferable, and the range of 5-60 mass% is more preferable.

  There is no restriction | limiting in particular as a manufacturing method of the said alkali-soluble resin (A-4), Although conventionally well-known various methods can be employ | adopted, It is especially preferable by the solution polymerization method. The polymerization temperature and polymerization concentration (polymerization concentration = [total weight of monomer components / (total weight of monomer components + solvent weight)] × 100) depend on the type and ratio of monomer components used and the molecular weight of the target polymer. Different. Regarding polymerization temperature, the range of 40-150 degreeC is preferable, and the range of 60-130 degreeC of polymerization temperature is more preferable. The polymerization concentration is preferably in the range of 5 to 50%, more preferably in the range of 10 to 40%.

  The solvent used in the solution polymerization method may be one used in a normal radical polymerization reaction. Specifically, for example, ethers such as tetrahydrofuran, dioxane, ethylene glycol dimethyl ether and diethylene glycol dimethyl ether; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone; ethyl acetate, butyl acetate, propylene glycol monomethyl ether acetate, 3-methoxybutyl Examples include esters such as acetate; alcohols such as methanol, ethanol, isopropanol, n-butanol, ethylene glycol monomethyl ether, and propylene glycol monomethyl ether; aromatic hydrocarbons such as toluene, xylene, and ethylbenzene; chloroform; dimethyl sulfoxide, and the like. These solvents can be used alone or in combination of two or more.

  When polymerizing the monomer component, if necessary, a polymerization initiator may be used. For example, cumene hydroperoxide, diisopropylbenzene hydroperoxide, di-t-butyl peroxide, lauroyl peroxide, Organic peroxides such as benzoyl peroxide, t-butylperoxyisopropyl carbonate, t-amylperoxy-2-ethylhexanoate, t-butylperoxy-2-ethylhexanoate; 2,2′-azobis (Isobutyronitrile), 1,1′-azobis (cyclohexanecarbonitrile), 2,2′-azobis (2,4-dimethylvaleronitrile), dimethyl 2,2′-azobis (2-methylpropionate) An azo compound such as These polymerization initiators can be used alone or in combination of two or more. The amount used of these polymerization initiators may be appropriately set according to the combination of monomers used, reaction conditions, target polymer molecular weight, etc., and is not particularly limited, but the weight average molecular weight is several times without gelation. Since 1,000 to several tens of thousands of polymers can be obtained, a range of 0.1 to 15% by mass is preferable with respect to all monomer components, and a range of 0.5 to 10% by mass is more preferable.

  Moreover, you may add a chain transfer agent for molecular weight adjustment. Examples of the chain transfer agent include mercaptan chain transfer agents such as n-dodecyl mercaptan, mercaptoacetic acid, methyl mercaptoacetate, α-methylstyrene dimer, etc., but the chain transfer effect is high and the residual monomer can be reduced. N-dodecyl mercaptan and mercaptoacetic acid, which are easily available, are preferred. The amount used in the case of using a chain transfer agent may be appropriately set according to the combination of monomers used, reaction conditions, the molecular weight of the target polymer, etc., and is not particularly limited, but the weight average molecular weight without gelation Can obtain several thousand to several tens of thousands of polymers, the range of 0.1 to 15% by mass is preferable with respect to all monomer components, and the range of 0.5 to 10% by mass is more preferable.

  When the acid group is introduced by using a monomer capable of introducing the acid group as a monomer component when obtaining the alkali-soluble resin (A-4), it is necessary to perform a treatment for introducing the acid group after polymerization. is there. This treatment varies depending on the type of monomer used. For example, when a monomer having a hydroxyl group such as 2-hydroxyethyl (meth) acrylate is used, succinic anhydride, tetrahydrophthalic anhydride, maleic anhydride An acid anhydride such as a product may be added. When a monomer having an epoxy group such as glycidyl (meth) acrylate is used, a compound having an amino group and an acid group such as N-methylaminobenzoic acid or N-methylaminophenol is added, or first ( An acid such as meth) acrylic acid may be added, and an acid anhydride such as succinic anhydride, tetrahydrophthalic anhydride, maleic anhydride or the like may be added to the resulting hydroxyl group. When a monomer having an isocyanate group such as 2-isocyanatoethyl (meth) acrylate is used, for example, a compound having a hydroxyl group and an acid group such as 2-hydroxybutyric acid may be added.

  In addition, when the alkali-soluble resin (A-4) is obtained, when a radical polymerizable double bond is introduced by using the monomer capable of imparting the radical polymerizable double bond described above as the monomer component, It is necessary to perform a treatment for imparting a radically polymerizable double bond. The treatment varies depending on the type of monomer used. For example, when a monomer having a carboxyl group such as (meth) acrylic acid or itaconic acid is used, glycidyl (meth) acrylate, 3,4-epoxycyclohexylmethyl ( A compound having an epoxy group and a radically polymerizable double bond such as (meth) acrylate or vinylbenzyl glycidyl ether may be added. When a monomer having a carboxylic acid anhydride group such as maleic anhydride or itaconic anhydride is used, a compound having a hydroxyl group and a radical polymerizable double bond such as 2-hydroxyethyl (meth) acrylate is added. Just do it. When a monomer having an epoxy group, such as glycidyl (meth) acrylate, 3,4-epoxycyclohexylmethyl (meth) acrylate, or vinylbenzyl glycidyl ether, is used, radical polymerization with acid groups such as (meth) acrylic acid A compound having a double bond may be added.

  Since the weight-average molecular weight of the alkali-soluble resin (A-4) can impart a viscosity with good coating film formation and sufficient heat resistance, the weight-average molecular weight in terms of polystyrene measured by GPC is 1,000 to 200, Is preferably in the range of 2,000 to 50,000, more preferably in the range of 2,000 to 30,000.

  Moreover, alkali-soluble resin (A-5) which is epoxy (meth) acrylate resin which has a carboxyl group can also be used. An epoxy (meth) acrylate resin having a carboxyl group is obtained by adding an α, β-unsaturated monocarboxylic acid to an epoxy resin or an α, β-unsaturated monocarboxylic acid ester having a carboxyl group in an ester moiety, It is obtained by reacting an acid anhydride.

  As an epoxy resin used as the raw material of the alkali-soluble resin (A-5), for example, a bisphenol A type epoxy resin (as a commercially available product, “Epicoat 828”, “Epicoat 1001”, “Epicoat 1002” manufactured by Japan Epoxy Resin Co., Ltd.) ”,“ Epicoat 1004 ”, etc.), epoxy resin obtained by reaction of alcoholic hydroxyl group of bisphenol A type epoxy resin and epichlorohydrin (as a commercial product,“ NER-1302 ”(epoxy equivalent 323, softened by Nippon Kayaku Co., Ltd.) Point 76 ° C.)), bisphenol F type resin (as a commercially available product, “Epicoat 807”, “EP-4001”, “EP-4002”, “EP-4004”, etc., manufactured by Japan Epoxy Resin Co., Ltd.)), bisphenol F type Epoxy resin alcoholic hydroxyl groups and epic Epoxy resin obtained by the reaction of ruhydrin (as a commercial product, “NER-7406” manufactured by Nippon Kayaku Co., Ltd. (epoxy equivalent 350, softening point 66 ° C.)), bisphenol S type epoxy resin, biphenyl glycidyl ether (as a commercial product) "YX-4000" manufactured by Japan Epoxy Resin Co., Ltd.), phenol novolac type epoxy resin (as a commercial product, "EPPN-201" manufactured by Nippon Kayaku Co., Ltd., "EP-152" manufactured by Japan Epoxy Resin Co., Ltd.) , “EP-154”, “DEN-438” manufactured by Dow Chemical Japan Co., Ltd.), cresol novolac type epoxy resin (commercially available products “EOCN-102S”, “EOCN-1020” manufactured by Nippon Kayaku Co., Ltd., “EOCN-104S”), triglycidyl isocyanurate (commercially available product) "TEPIC" manufactured by Nissan Chemical Industries, Ltd.), trisphenolmethane type epoxy resin (as commercial products, "EPPN-501", "EPN-502", "EPPN-503" manufactured by Nippon Kayaku Co., Ltd.) ), Fluorene epoxy resin (as a commercial product, cardo epoxy resin “ESF-300” manufactured by Nippon Steel Chemical Co., Ltd.), alicyclic epoxy resin (“Celoxide 2021P”, “Celoxide EHPE” manufactured by Daicel Chemical Industries, Ltd.) ), Dicyclopentadiene type epoxy resin obtained by glycidylation of phenol resin by reaction of dicyclopentadiene and phenol (for example, “XD-1000” manufactured by Nippon Kayaku Co., Ltd., “EXA-7200” manufactured by DIC Corporation, Japan “NC-3000” and “NC-7300” manufactured by Kayaku Co., Ltd.), fluorene skeleton An epoxy resin (see JP-A-4-355450) or the like can be used. These epoxy resins can be used alone or in combination of two or more.

  Another example of the epoxy resin is a copolymer type epoxy resin. As copolymerizable epoxy resins, monomers having an epoxy group such as glycidyl (meth) acrylate, (meth) acryloylmethylcyclohexene oxide, vinylcyclohexene oxide, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) Acrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl (meth) acrylate, (meth) acrylic acid, styrene, phenoxyethyl (meth) acrylate, benzyl (meth) acrylate, α-methylstyrene, glycerin mono (meth) acrylate, The copolymer obtained by copolymerizing the monomer which does not have epoxy groups, such as (meth) acrylate which has a polyoxyalkylene chain, is mentioned.

  Examples of the (meth) acrylate having a polyoxyalkylene chain include polyethylene glycol mono (meth) acrylates such as diethylene glycol mono (meth) acrylate, triethylene glycol mono (meth) acrylate, and tetraethylene glycol mono (meth) acrylate; Examples thereof include alkoxy polyethylene glycol (meth) acrylates such as methoxydiethylene glycol mono (meth) acrylate, methoxytriethylene glycol mono (meth) acrylate, and methoxytetraethylene glycol mono (meth) acrylate.

  The molecular weight of the copolymerization type epoxy resin is preferably in the range of 1,000 to 200,000. Further, the amount of the monomer having an epoxy group used as a raw material for the copolymerization type epoxy resin is preferably in the range of 10 to 70% by mass, more preferably in the range of 20 to 50% by mass with respect to the monomer having no epoxy group. preferable.

  As a commercial item of the copolymerization type epoxy resin, for example, “CP-15”, “CP-30”, “CP-50”, “CP-20SA”, “CP-510SA” manufactured by NOF Corporation, “CP-50S”, “CP-50M”, “CP-20MA” and the like can be mentioned.

  The molecular weight of the epoxy resin is 200 to 200, as the weight average molecular weight in terms of polystyrene measured by GPC, since the coating film formation is good and gelation during the addition reaction of α, β-unsaturated monocarboxylic acid can be prevented. The range of 000 is preferable, and the range of 300 to 100,000 is more preferable.

  Examples of the α, β-unsaturated monocarboxylic acid include itaconic acid, crotonic acid, cinnamic acid, acrylic acid, methacrylic acid and the like. Acrylic acid and methacrylic acid are preferable, and acrylic acid has good reactivity. Is more preferable. The α, β-unsaturated monocarboxylic acid ester having a carboxyl group in the ester portion includes acrylic acid-2-succinoyloxyethyl, acrylic acid-2-malenoyloxyethyl, acrylic acid-2-phthaloyloxyethyl, Acrylic acid-2-hexahydrophthaloyloxyethyl, methacrylic acid-2-succinoyloxyethyl, methacrylic acid-2-malenoyloxyethyl, methacrylic acid-2-phthaloyloxyethyl, methacrylic acid-2-hexahydrophthalo Yloxyethyl, crotonic acid-2-succinoyloxyethyl, and the like, acrylate-2-malenoyloxyethyl acrylate and 2-phthaloyloxyethyl acrylate are preferred, and acrylate-2-maleinoyloxyethyl acrylate is preferred. More preferred. These α, β-unsaturated monocarboxylic acid and α, β-unsaturated monocarboxylic acid ester can be used alone or in combination of two or more.

  A known method can be used for the addition reaction of α, β-unsaturated monocarboxylic acid or an ester thereof and an epoxy resin. Can be mentioned. As the esterification catalyst, tertiary amines such as triethylamine, trimethylamine, benzyldimethylamine, and benzyldiethylamine; quaternary ammonium salts such as tetramethylammonium chloride, tetraethylammonium chloride, and dodecyltrimethylammonium chloride can be used.

  The amount of α, β-unsaturated monocarboxylic acid or ester thereof used is preferably in the range of 0.5 to 1.2 equivalents, preferably 0.7 to 1.1 equivalents, based on 1 equivalent of the epoxy group of the epoxy resin as a raw material. The range of is more preferable.

  Examples of the polybasic acid anhydride to be further added to the epoxy resin to which an α, β-unsaturated carboxylic acid or ester thereof is added include, for example, maleic anhydride, succinic anhydride, itaconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride Acid, hexahydrophthalic anhydride, pyromellitic anhydride, trimellitic anhydride, benzophenonetetracarboxylic dianhydride, anhydrous methylhexahydrophthalic anhydride, endomethylenetetrahydrophthalic anhydride, chlorendic anhydride, methyltetrahydrophthalic anhydride, Biphenyltetracarboxylic dianhydride etc. are mentioned. Among these, maleic anhydride, succinic anhydride, itaconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, pyromellitic anhydride, trimellitic anhydride, and biphenyltetracarboxylic dianhydride are preferable. More preferred are tetrahydrophthalic anhydride and biphenyltetracarboxylic dianhydride. These polybasic acid anhydrides can be used alone or in combination of two or more.

  A known method can be used for the addition reaction of the polybasic acid anhydride, and the reaction can be continued continuously under the same conditions as in the addition reaction of the α, β-unsaturated carboxylic acid or its ester. The amount of the polybasic acid anhydride used is preferably such that the acid value of the epoxy (meth) acrylate resin to be produced is in the range of 10 to 150, since the alkali developability and coating formation can be made favorable. An amount that is in the range of 20 to 140 is more preferred.

  Moreover, the epoxy (meth) acrylate resin which has a carboxyl group can also be used. Examples of the epoxy (meth) acrylate resin having a carboxyl group include naphthalene-containing resins described in JP-A-6-49174; JP-A 2003-89716, JP-A 2003-165830, JP-A 2005-325331. Examples include fluorene-containing resins described in JP-A-2001-354735; JP-A-2005-126684, JP-A-2005-55814, JP-A-2004-295084, and the like. Commercially available products include “ACA-200M” manufactured by Daicel Chemical Industries, Ltd.

  The alkali-soluble resin (A) may be used alone or in combination of two or more of the alkali-soluble resins (A-1) to (A-5). In addition, the alkali-soluble resin (A) is used in combination with a pigment dispersant described later, so that an undissolved substance does not remain in a non-pixel portion on the substrate, and has a high density color with excellent adhesion to the substrate. This is preferable because a pixel can be formed. Specifically, it is preferable to use a part of the alkali-soluble resin (A) together with a pigment dispersant described later in the dispersion treatment step. In this case, it is preferable to use alkali-soluble resin (A) in the range of 5-200 mass% with respect to a pigment, and it is more preferable to use it in the range of 10-100 mass%.

  In the color resist composition of the present invention, the content ratio of the alkali-soluble resin (A) is 0.1 to 80% by mass in the total solid content because the appearance of the coating film and the adhesion to the substrate are good. The range of 1-60 mass% is more preferable.

  The polymerizable compound (B) used in the present invention is not particularly limited as long as it is a compound having a photopolymerizable functional group that can be polymerized or cross-linked by irradiation with active energy rays such as ultraviolet rays. Examples of such a polymerizable compound (B) include unsaturated carboxylic acids such as (meth) acrylic acid, esters of monohydroxy compounds and unsaturated carboxylic acids, aliphatic polyhydroxy compounds and unsaturated carboxylic acids. Esters of esters, esters of aromatic polyhydroxy compounds with unsaturated carboxylic acids, unsaturated carboxylic acids and polyvalent carboxylic acids, and polyhydric hydroxy compounds such as the above-mentioned aliphatic polyhydroxy compounds and aromatic polyhydroxy compounds And a polymerizable compound having a urethane skeleton obtained by reacting a polyisocyanate compound and a (meth) acryloyl group-containing hydroxy compound.

  Examples of the ester of the aliphatic polyhydroxy compound and the unsaturated carboxylic acid include ethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, trimethylolethanetri ( (Meth) acrylate, pentaerythritol di (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (Meth) acrylates such as (meth) acrylate and glycerol (meth) acrylate are exemplified. Moreover, itaconic acid ester in which the (meth) acrylic acid portion of these acrylates is replaced with itaconic acid, crotonic acid ester in which crotonic acid is replaced, or maleic acid ester in which maleic acid is replaced.

  Examples of the ester of the aromatic polyhydroxy compound and the unsaturated carboxylic acid include hydroquinone di (meth) acrylate, resorcin di (meth) acrylate, pyrogallol tri (meth) acrylate, and the like. Moreover, the ester obtained by esterification reaction of unsaturated carboxylic acid, polyvalent carboxylic acid and polyvalent hydroxy compound may be a single substance or a mixture. Examples of such esters include esters obtained from (meth) acrylic acid, phthalic acid and ethylene glycol, esters obtained from (meth) acrylic acid, maleic acid and diethylene glycol, (meth) acrylic acid, terephthalic acid and penta Examples thereof include esters obtained from erythritol, esters obtained from (meth) acrylic acid, adipic acid, butanediol and glycerin.

  Examples of the polymerizable compound having a urethane skeleton obtained by reacting the polyisocyanate compound with a (meth) acryloyl group-containing hydroxy compound include aliphatic diisocyanates such as hexamethylene diisocyanate and trimethylhexamethylene diisocyanate; fats such as cyclohexane diisocyanate and isophorone diisocyanate. Cyclic diisocyanates; aromatic diisocyanates such as tolylene diisocyanate and diphenylmethane diisocyanate; (meth) such as 2-hydroxyethyl (meth) acrylate and 3-hydroxy [1,1,1-tri (meth) acryloyloxymethyl] propane A reaction product with a hydroxy compound having an acryloyl group may be mentioned.

  Examples of the polymerizable compound (B) used in the present invention other than those described above include (meth) acrylamides such as ethylenebis (meth) acrylamide; allyl esters such as diallyl phthalate; compounds having a vinyl group such as divinyl phthalate. Is mentioned.

  Moreover, you may use the monomer which has an acid group as said polymeric compound (B). The monomer having an acid group is, for example, an ester of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid, and a non-aromatic carboxylic acid anhydride is reacted with an unreacted hydroxyl group of the aliphatic polyhydroxy compound. A polyfunctional monomer having a group is preferred. Further, those using pentaerythritol or dipentaerythritol as the aliphatic polyhydroxy compound are particularly preferred. These monomers can be used alone or in combination of two or more. Moreover, you may use together the monomer which has an acid group, and the monomer which does not have an acid group.

  Furthermore, as preferable specific examples of the polyfunctional monomer having an acid group, for example, dipentaerythritol hexaacrylate, dipentaerythritol pentaacrylate and dipentaerythritol pentaacrylate commercially available as “Aronix TO-1382” from Toagosei Co., Ltd. And a mixture containing succinic acid ester as a main component. This polyfunctional monomer can also be used in combination with other polyfunctional monomers.

  The acid value of the polyfunctional monomer having an acid group is preferably in the range of 0.1 to 40, and more preferably in the range of 5 to 30, because developability and curability are improved. When two or more polyfunctional monomers having different acid values are used in combination or when a polyfunctional monomer having no acid group is used in combination, the acid value of the mixture after mixing all the polyfunctional monomers is within the above range. It is preferable that

  In the color resist composition of the present invention, the content of the polymerizable compound (B) is preferably in the range of 5 to 80% by mass and in the range of 10 to 70% by mass in the total solid content. More preferably, it is in the range of 20 to 50% by mass. Moreover, it is preferable that the ratio of the said polymeric compound (B) with respect to the coloring agent (C) mentioned later is 5-200 mass%, It is more preferable that it is the range of 10-100 mass%, 20-80 mass More preferably, it is in the range of%.

  As the colorant (C) used in the present invention, any pigment or dye can be used without particular limitation as long as it can be colored. The pigment can be either an organic pigment or an inorganic pigment. As the organic pigment, pigments of various hues such as a red pigment, a green pigment, a blue pigment, a yellow pigment, a purple pigment, an orange pigment, and a brown pigment can be used. Examples of the chemical structure of the organic pigment include azo, phthalocyanine, quinacridone, benzimidazolone, isoindolinone, dioxazine, indanthrene, and perylene. The following “CI” means a color index.

  Examples of the red pigment include C.I. I. Pigment Red 1, 2, 3, 4, 5, 6, 7, 8, 9, 12, 14, 15, 16, 17, 21, 22, 23, 31, 32, 37, 38, 41, 47, 48, 48: 1, 48: 2, 48: 3, 48: 4, 49, 49: 1, 49: 2, 50: 1, 52: 1, 52: 2, 53, 53: 1, 53: 2, 53: 3, 57, 57: 1, 57: 2, 58: 4, 60, 63, 63: 1, 63: 2, 64, 64: 1, 68, 69, 81, 81: 1, 81: 2, 81: 3, 81: 4, 83, 88, 90: 1, 101, 101: 1, 104, 108, 108: 1, 109, 112, 113, 114, 122, 123, 144, 146, 147, 149, 151 166, 168, 169, 170, 172, 173, 174, 175, 176, 177, 178, 17 9, 181, 184, 185, 187, 188, 190, 193, 194, 200, 202, 206, 207, 208, 209, 210, 214, 216, 220, 221, 224, 230, 231, 232, 233, 235, 236, 237, 238, 239, 242, 243, 245, 247, 249, 250, 251, 253, 254, 255, 256, 257, 258, 259, 260, 262, 263, 264, 265, 266, 267, 268, 269, 270, 271, 272, 273, 274, 275, 276 and the like. Among these, C.I. I. Pigment Red 48: 1, 122, 168, 177, 202, 206, 207, 209, 224, 242, or 254 is preferred, and C.I. I. Pigment Red 177, 209, 224 or 254 is more preferable.

  Examples of the green pigment include C.I. I. Pigment green 1, 2, 4, 7, 8, 10, 13, 14, 15, 17, 18, 19, 26, 36, 45, 48, 50, 51, 54, 55, 58 and the like. Among these, C.I. I. Pigment Green 7, 36 or 58 is preferable.

  Examples of the blue pigment include C.I. I. Pigment Blue 1, 1: 2, 9, 14, 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, 16, 17, 19, 25, 27, 28, 29, 33, 35, 36, 56, 56: 1, 60, 61, 61: 1, 62, 63, 66, 67, 68, 71, 72, 73, 74, 75, 76, 78, 79 and the like. Among these, C.I. I. Pigment Blue 15, 15: 1, 15: 2, 15: 3, 15: 4, or 15: 6 is preferable. I. Pigment Blue 15: 6 is more preferable.

  Examples of the yellow pigment include C.I. I. Pigment Yellow 1, 1: 1, 2, 3, 4, 5, 6, 9, 10, 12, 13, 14, 16, 17, 24, 31, 32, 34, 35, 35: 1, 36, 36: 1, 37, 37: 1, 40, 41, 42, 43, 48, 53, 55, 61, 62, 62: 1, 63, 65, 73, 74, 75, 81, 83, 87, 93, 94, 95, 97, 100, 101, 104, 105, 108, 109, 110, 111, 116, 117, 119, 120, 126, 127, 127: 1, 128, 129, 133, 134, 136, 138, 139, 142, 147, 148, 150, 151, 153, 154, 155, 157, 158, 159, 160, 161, 162, 163, 164, 165, 166, 167, 168, 169, 170, 172, 17 174, 175, 176, 180, 181, 182, 183, 184, 185, 188, 189, 190, 191, 191: 1, 192, 193, 194, 195, 196, 197, 198, 199, 200, 202 , 203, 204, 205, 206, 207, 208 and the like. Among these, C.I. I. Pigment Yellow 83, 117, 129, 138, 139, 150, 154, 155, 180 or 185 is preferable. I. Pigment Yellow 83, 138, 139, 150 or 180 is more preferable.

  Examples of the purple pigment include C.I. I. Pigment Violet 1, 1: 1, 2, 2: 2, 3, 3: 1, 3: 3, 5, 5: 1, 14, 15, 16, 19, 23, 25, 27, 29, 31, 32, 37, 39, 42, 44, 47, 49, 50 and the like. Among these, C.I. I. Pigment violet 19 or 23 is preferred; I. Pigment Violet 23 is more preferable.

  Examples of the orange pigment include C.I. I. Pigment Orange 1, 2, 5, 13, 16, 17, 19, 20, 21, 22, 23, 24, 34, 36, 38, 39, 43, 46, 48, 49, 61, 62, 64, 65, 67, 68, 69, 70, 71, 72, 73, 74, 75, 77, 78, 79 and the like. Among these, C.I. I. Pigment Orange 38 or 71 is preferred.

  Since each pixel of the three primary colors of the color filter used in the liquid crystal display device is red (R), green (G), and blue (B), the color reproducibility is mainly composed of the red pigment, the green pigment, and the blue pigment. In order to improve the color, organic pigments of colors such as yellow, purple and orange may be used for hue adjustment.

  Examples of the inorganic pigment include barium sulfate, lead sulfate, titanium oxide, yellow lead, bengara, and chromium oxide.

  The average particle size of the organic pigment is preferably 1 μm or less, more preferably 0.5 μm or less, and further preferably 0.3 μm or less in order to increase the luminance of the color liquid crystal display device. It is preferable to use the organic pigment after being subjected to a dispersion treatment so as to obtain these average particle diameters. The average primary particle size of the organic pigment is preferably 100 nm or less, more preferably 50 nm or less, further preferably 40 nm or less, and particularly preferably in the range of 10 to 30 nm. The average particle size of the organic pigment is measured with a dynamic light scattering type particle size distribution meter. -EX250 "or the like.

  On the other hand, the colorant (C) used when the color resist composition of the present invention is used to form a black matrix (BM) is not particularly limited as long as it is black, but carbon black, lamp Examples thereof include black, acetylene black, bone black, thermal black, channel black, furnace black, graphite, iron black, and titanium black. Moreover, the combination which mixed 2 or more types of organic pigments and made it black by mixing colors may be sufficient. Among these, carbon black and titanium black are preferable from the viewpoints of light shielding rate and image characteristics.

  Examples of commercially available carbon black include MA7, MA8, MA11, MA100, MA100R, MA220, MA230, MA600, # 5, # 10, # 20, # 25, # 30, # 32 manufactured by Mitsubishi Chemical Corporation. , # 33, # 40, # 44, # 45, # 47, # 50, # 52, # 55, # 650, # 750, # 850, # 950, # 960, # 970, # 980, # 990, # 1000, # 2200, # 2300, # 2350, # 2400, # 2600, # 3050, # 3150, # 3250, # 3600, # 3750, # 3950, # 4000, # 4010, OIL7B, OIL9B, OIL11B, OIL30B, OIL31B Such as Printex3, Printex3OP, manufactured by Eponic Degussa Japan Co., Ltd. rintex30, Printex30OP, Printex40, Printex45, Printex55, Printex60, Printex75, Printex80, Printex85, Printex90, Printex A, Print ex L, Printex G, Printex P, Printex U, Printex V, PrintexG, SpecialBlack550, SpecialBlack 350, SpecialBlack250, SpecialBlack100, Special Black 6, Special Black 5, Special Black 4, Color Black FW1, Color Black FW2, Color Black FW2V, Color Black Examples include FW18, Color Black FW18, Color Black FW200, Color Black S160, Color Black S170, Monarch 120, Monch 280, Monch 480, Monch 480, Monch 880, Monch 880, Monch 880, Monch 880, Monch REGAL99, REGAL99R, REGAL415, REGAL415R, REGAL250, REGAL250R, REGAL330, REGAL400R, REGAL55R0, REGAL660R, BLACK PEARLS480, PEAR S130, VULCAN XC72R, ELFTEX-8, and the like, and Raven11, Raven14, Raven15, Raven16, Raven22Raven30, Raven35, Raven40, Raven410, Raven420, Raven450, Raven450, Raven450, Raven850, Raven850, Raven850, Raven850, Raven8 , RAVEN1040, RAVEN1060U, RAVEN1080U, RAVEN1170, RAVEN1190U, RAVEN1250, RAVEN1500, RAVEN2000, RAVEN2500U, RAVEN3500, RAVEN5000, RAVEN5250, RAVEN5750, RAVEN7 000 or the like.

  Among the above-described carbon blacks, it is preferable to use carbon black coated with a resin as having high optical density and high surface resistivity required for a black matrix of a color filter. The carbon black coated with resin is, for example, disclosed in JP-A-9-26571, JP-A-9-71733, JP-A-9-95625, JP-A-9-238863, or JP-A-11-60989. It can be obtained by treating a known carbon black by the method described in Japanese Patent Publication.

  Further, as a method for producing the titanium black, a method of heating and reducing a mixture of titanium dioxide and metal titanium described in JP-A-49-5432 under a reducing atmosphere, disclosed in JP-A-57-205322. A method of reducing ultrafine titanium dioxide obtained by high-temperature hydrolysis of titanium tetrachloride in a reducing atmosphere containing hydrogen, titanium dioxide or water described in JP-A-60-65069 and JP-A-61-201610 Examples thereof include a method of reducing titanium oxide at a high temperature in the presence of ammonia, and a method of reducing a high temperature in the presence of ammonia by attaching a vanadium compound to titanium dioxide or titanium hydroxide described in JP-A-61-201610. Examples of commercially available titanium black include Titanium Black 10S, 12S, 13R, 13M, and 13M-C manufactured by Mitsubishi Materials Corporation.

  Examples of the combination of two or more organic pigments mixed and blackened by mixing colors include black pigments in which red, green, and blue pigments are mixed. Color materials that can be mixed and used to prepare a black pigment include Victoria Pure Blue (C.I. 42595), Auramine O (C.I. 41000), Catillon Brilliant Flavin (Basic 13), Rhodamine 6GCP (C I.45160), rhodamine B (C.I. 45170), safranin OK70: 100 (C.I.50240), Erioglaucine X (C.I.42080), No. 120 / Lionol Yellow (C.I. 21090), Lionol Yellow GRO (C.I. 21090), Shimla First Yellow 8GF (C.I. 21105), Benzidine Yellow 4T-564D (C.I. 21095), Shimla Fast Red 4015 (C.I. 12355), Lionol Red 7B4401 (C.I. 15850), Fast Gen Blue TGR-L (C.I. 74160), Lionol Blue SM (C.I. 26150), Examples include Lionol Blue ES (CI Pigment Blue 15: 6), Lionogen Red GD (CI Pigment Red 168), and Lionol Green 2YS (CI Pigment Green 36).

  Examples of other colorants that can be mixed and used for preparing a black pigment include C.I. I. Yellow pigments 20, 24, 86, 93, 109, 110, 117, 125, 137, 138, 147, 148, 153, 154, 166, C.I. I. Orange pigments 36, 43, 51, 55, 59, 61, C.I. I. Red pigments 9, 97, 122, 123, 149, 168, 177, 180, 192, 215, 216, 217, 220, 223, 224, 226, 227, 228, 240, C.I. I. Violet pigments 19, 23, 29, 30, 37, 40, 50, C.I. I. Blue pigment 15, 15: 1, 15: 4, 22, 60, 64, C.I. I. Green pigment 7, C.I. I. Examples thereof include brown pigments 23, 25, and 26.

On the other hand, when carbon black is used as the black pigment, the average primary particle size is preferably in the range of 0.01 to 0.08 μm, and more preferably in the range of 0.02 to 0.05 μm because of good developability. Further, dibutyl phthalate of the carbon black to be used (hereinafter, abbreviated as "DBP".) Uptake, 50～80Cm ³ since preferably in the range of 40~100cm ³ / 100g, a good dispersibility and developing property The range of / 100 g is more preferable. Further, BET specific surface area of carbon black used is preferably in the range of 50~120m ² / g, and more preferably in a range of from 60~95m ² / g because a good dispersion stability.

  Carbon black, unlike organic pigments, has a structure called primary structure in which primary particles are fused in a skewer shape, and fine pores may be formed on the particle surface by post-treatment. is there. Therefore, in order to represent the particle shape of carbon black, in addition to the average particle diameter of primary particles obtained by the same method as that of the organic pigment, the DBP absorption amount (JIS K6221) and the specific surface area (BET method) JIS K6217) is preferably measured and used as an index of structure and pore volume.

  A dye can also be used as the colorant used in the present invention. Examples of such dyes include azo dyes, anthraquinone dyes, phthalocyanine dyes, quinoneimine dyes, quinoline dyes, nitro dyes, carbonyl dyes, and methine dyes.

  Examples of the azo dye include C.I. I. Acid Yellow 11, C.I. I. Acid Orange 7, C.I. I. Acid Red 37, C.I. I. Acid Red 180, C.I. I. Acid Blue 29, C.I. I. Direct Red 28, C.I. I. Direct Red 83, C.I. I. Direct Yellow 12, C.I. I. Direct Orange 26, C.I. I. Direct Green 28, C.I. I. Direct Green 59, C.I. I. Reactive Yellow 2, C.I. I. Reactive Red 17, C.I. I. Reactive Red 120, C.I. I. Reactive Black 5, C.I. I. Disperse Orange 5, C.I. I. Disperse thread 58, C.I. I. Disperse blue 165, C.I. I. Basic Blue 41, C.I. I. Basic Red 18, C.I. I. Molded Red 7, C.I. I. Moldant Yellow 5, C.I. I. Examples thereof include Moldant Black 7.

  Examples of the anthraquinone dye include C.I. I. Bat Blue 4, C.I. I. Acid Blue 40, C.I. I. Acid Green 25, C.I. I. Reactive Blue 19, C.I. I. Reactive Blue 49, C.I. I. Disperse thread 60, C.I. I. Disperse Blue 56, C.I. I. Disperse Blue 60 etc. are mentioned.

  Examples of the phthalocyanine dye include C.I. I. Pad blue 5 and the like, and examples of the quinoneimine dye include C.I. I. Basic Blue 3, C.I. I. Basic blue 9 and the like, and examples of the quinoline dye include C.I. I. Solvent Yellow 33, C.I. I. Acid Yellow 3, C.I. I. Disperse Yellow 64 and the like. Examples of the nitro dye include C.I. I. Acid Yellow 1, C.I. I. Acid Orange 3, C.I. I. Disperse Yellow 42 and the like.

  Among the colorants (C) listed above, it is preferable to use a pigment in terms of excellent light resistance, weather resistance and fastness of the coating film finally obtained, but in order to adjust the hue, If necessary, a dye may be used in combination with the pigment.

  The content ratio of the colorant (C) in the color resist composition of the present invention is preferably 1% by mass or more, more preferably in the range of 5 to 80% by mass, based on the total solid content. More preferably, it is in the range of -70% by mass.

  In addition, when the color resist composition of the present invention is used for forming red (R), green (G), and blue (B) pixels of a color filter, the colorant (C ) Is preferably in the range of 5 to 60% by mass, and more preferably in the range of 10 to 50% by mass in the total solid content.

  Furthermore, when using the color resist composition of this invention for formation of the black matrix of a color filter, the content ratio of the said coloring agent (C) in the color resist composition of this invention is 20-80 mass in a total solid. % Is preferable, and a range of 30 to 70% by mass is more preferable.

  In the color resist composition of the present invention, when the colorant (C) is a pigment, it is preferable to prepare and use a pigment dispersion prepared by dispersing it in an organic solvent using a dispersant. Examples of the dispersant include surfactants; pigment intermediates or derivatives; dye intermediates or derivatives; resin-type dispersants such as polyamide resins, polyurethane resins, polyester resins, and acrylic resins. Among these, a graft copolymer having a nitrogen atom, an acrylic block copolymer having a nitrogen atom, a urethane resin dispersant, and the like are preferable. Since these dispersants have a nitrogen atom, the nitrogen atom has an affinity for the pigment surface, and a portion other than the nitrogen atom increases the affinity for the medium, thereby improving the dispersion stability. In addition, these dispersing agents can be used alone or in combination of two or more.

  Commercially available dispersants include “Efka” series (“Efka 46”, etc.) manufactured by Fuka Chemicals, Inc .; “Disperbyk” series, “BYK” series (“BYK-160”, manufactured by Big Chemie Japan Ltd.) , “BYK-161”, “BYK-2001”, etc.); “Solsperse” series manufactured by Nippon Lubrizol Corporation; “KP” series manufactured by Shin-Etsu Chemical Co., Ltd .; “Polyflow” series manufactured by Kyoeisha Chemical Co., Ltd .; “Disparon” series manufactured by Enomoto Kasei Co., Ltd .; “Ajisper” series (“Ajisper PB-814”, etc.) manufactured by Ajinomoto Fine Techno Co., etc.

  Examples of the organic solvent used in the preparation of the pigment dispersion include acetate solvents such as propylene glycol monomethyl ether acetate and propylene glycol monoethyl ether acetate; propionate solvents such as ethoxypropionate; toluene Aromatic solvents such as xylene and methoxybenzene; ether solvents such as butyl cellosolve, propylene glycol monomethyl ether, diethylene glycol ethyl ether and diethylene glycol dimethyl ether; ketone solvents such as methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone; aliphatic carbonization such as hexane Hydrogen-based solvents; nitrogen compound-based solvents such as N, N-dimethylformamide, γ-butyrolactam, N-methyl-2-pyrrolidone; γ-butyrolacto Lactone solvents such as carbene; carbamates and the like. These solvents can be used alone or in combination of two or more.

  Examples of the method for preparing the pigment dispersion include a method in which the colorant (C) is kneaded and dispersed, a method in which the dispersion is performed, and a method in which only the fine dispersion step is performed. In the kneading and dispersing step, the colorant (C), a part of the alkali-soluble resin (A), and, if necessary, the dispersing agent are mixed and kneaded. Examples of the machine used for kneading include two rolls, three rolls, ball mills, tron mills, dispersers, kneaders, kneaders, homogenizers, blenders, single-screw or twin-screw extruders, and the like. The colorant can be dispersed by dispersing while applying force. The colorant (C) is preferably refined in particle size by a salt milling method or the like before the kneading.

  On the other hand, in the fine dispersion step, a composition obtained by adding the solvent to the composition containing the colorant (C) obtained in the kneading and dispersion step, or the colorant (C), the alkali-soluble resin (A), the solvent and necessary According to the above, the dispersion agent is mixed and dispersed together with a dispersion medium for fine particles of glass, zirconia or ceramic using a disperser, so that the colorant (C) particles are in a minute state close to primary particles. Can be dispersed.

  Further, from the viewpoint of improving the transmittance and contrast of the color filter, the average particle diameter of the primary particles of the colorant (C) is preferably 10 to 100 nm, and more preferably 10 to 60 nm. The average particle size of the colorant (C) was measured with a dynamic light scattering particle size distribution meter. For example, Nanotrac particle size distribution measuring device “UPA-EX150 manufactured by Nikkiso Co., Ltd.” ”,“ UPA-EX250 ”or the like.

  The fluorosurfactant (D) used in the present invention comprises a monomer (d1) having a fluorinated alkyl group having 4 to 6 carbon atoms and a monomer (d2) having a polyoxyalkylene chain as essential components. It is a copolymerized copolymer.

  As the monomer (d1), a compound having a (meth) acrylic ester group from the viewpoint of availability of raw materials, ease of controlling compatibility with compounding components in various coating compositions, or polymerization reactivity Are suitable, and examples thereof include fluorinated alkyl (meth) acrylates represented by the general formula (d1-1). The fluorinated alkyl group includes those having an ether type oxygen atom.

（上記一般式（１）中、Ｒ^１は水素原子、フッ素原子、メチル基、シアノ基、フェニル基、ベンジル基又は−Ｃ_ｎＨ_２ｎ−Ｒｆ’（ｎは１〜８の整数を表し、Ｒｆ’は下記式（Ｒｆ−１）〜（Ｒｆ−７）のいずれか１つの基を表す。）を表し、Ｘは、下記式（Ｘ−１）〜（Ｘ−１０）のいずれか１つの基を表し、Ｒｆは下記式（Ｒｆ−１）〜（Ｒｆ−７）のいずれか１つの基を表す。）

(In the general formula (1), R ¹ represents a hydrogen atom, a fluorine atom, a methyl group, a cyano group, a phenyl group, a benzyl group, or —C _n H _2n —Rf ′ (n represents an integer of 1 to 8, Rf 'Represents any one group of the following formulas (Rf-1) to (Rf-7)), and X represents any one group of the following formulas (X-1) to (X-10). Rf represents any one group of the following formulas (Rf-1) to (Rf-7).

（上記式（Ｘ−１）、（Ｘ−３）、（Ｘ−５）、（Ｘ−６）及び（Ｘ−７）中のｎは１〜８の整数を表す。上記式（Ｘ−８）、（Ｘ−９）及び（Ｘ−１０）中のｍは１〜８の整数を表し、ｎは０〜８の整数を表す。上記式（Ｘ−６）及び（Ｘ−７）中のＲｆ’’は下記式（Ｒｆ−１）〜（Ｒｆ−７）のいずれか１つの基を表す。）

(In the above formulas (X-1), (X-3), (X-5), (X-6) and (X-7), n represents an integer of 1 to 8. The above formula (X-8 M in (X-9) and (X-10) represents an integer of 1 to 8, and n represents an integer of 0 to 8. In the above formulas (X-6) and (X-7) Rf ″ represents any one of the following formulas (Rf-1) to (Rf-7).)

（上記式（Ｒｆ−１）〜（Ｒｆ−４）中のｎは４〜６の整数を表す。上記式（Ｒｆ−５）中のｍは１〜５の整数であり、ｎは０〜４の整数であり、かつｍ及びｎの合計は４〜５である。上記式（Ｒｆ−６）中のｍは０〜４の整数であり、ｎは１〜４の整数であり、ｐは０〜４の整数であり、かつｍ、ｎ及びｐの合計は４〜５である。）

(In the formulas (Rf-1) to (Rf-4), n represents an integer of 4 to 6. In the formula (Rf-5), m is an integer of 1 to 5, and n is 0 to 4). And the sum of m and n is 4 to 5. In the formula (Rf-6), m is an integer of 0 to 4, n is an integer of 1 to 4, and p is 0. ) Is an integer of -4, and the sum of m, n, and p is 4-5.)

  Moreover, the following monomers (d1-1-1)-(d1-1-15) etc. are mentioned as a more preferable specific example of the said monomer (d1).

  The monomer (d2) is a monomer having a polyoxyalkylene chain. By using this monomer (d2) as an essential component of the raw material of the fluorosurfactant (D), the leveling property of the surfactant can be improved. As said monomer (d2), what is represented by the following general formula (d2) is mentioned, for example.

（式中、Ｒ^１は水素原子又はメチル基であり、Ｙ^１及びＹ^２はそれぞれ独立のアルキレン基であり、ｐ及びｑはそれぞれ０または１以上の整数であり、かつｐとｑの合計は１以上であり、Ｒ^３は水素原子又は炭素原子数１〜６のアルキル基である。）

(Wherein R ¹ is a hydrogen atom or a methyl group, Y ¹ and Y ² are each an independent alkylene group, p and q are each 0 or an integer of 1 or more, and the sum of p and q is 1 or more, and R ³ is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.)

Although Y ¹ and Y ² in the general formula (d2) is an alkylene group, the alkylene group may have a substituent. Specific examples of the —O— (Y ¹ O) p— (Y ² O) q— moiety include ethylene glycol, in which the number of repeating units p is 1, q is 0, and Y ¹ is ethylene, the number of repeating units propylene glycol in which p is 1 and q is 0 and Y ¹ is propylene, the number of repeating units p is 1 and q is 0 and butylene glycol in which Y ¹ is butylene, the number of repeating units p is 2 or more Polyethylene glycol in which q is 0 and Y ¹ is ethylene, polypropylene glycol in which q is an integer of 2 or more and q is 0, and Y ¹ is 1-methylethylene (propylene) , the number of repeating units p and q are both an integer of 1 or more, and ethylene oxide and propylene oxy Y ¹ or Y ² is other ethylene 1-methylethylene (propylene) They include polyalkylene glycols and copolymers of. In addition, the thing whose polymerization degree of these polyalkylene glycol, ie, the sum total of p and q in general formula (B1), is 1-50 is preferable. Note that the repeating unit containing Y ¹ and the repeating unit containing Y ² may be arranged in a random manner or in a block shape.

  The monomer (d2) is a mono (meth) acrylic acid ester of an alkylene glycol such as ethylene glycol, propylene glycol, butylene glycol, or the like, when the number of repeating units p is 1 and q is 0. The terminal of the mono (meth) acrylic acid ester which is not a (meth) acrylic acid ester is sealed with an alkyl group having 1 to 6 carbon atoms, and the total number of repeating units p and q is an integer of 2 or more. In the case of poly (alkylene glycol) mono (meth) acrylic acid ester, this polyalkylene glycol mono (meth) acrylic acid ester which is not a (meth) acrylic acid ester is capped with an alkyl group having 1 to 6 carbon atoms. And the like.

  More specific examples of the monomer (d2) include polypropylene glycol mono (meth) acrylate, polyethylene glycol mono (meth) acrylate, polytetramethylene glycol (meth) acrylate, and poly (ethylene glycol / propylene glycol) mono. (Meth) acrylate, polyethylene glycol / polypropylene glycol mono (meth) acrylate, poly (ethylene glycol / tetramethylene glycol) mono (meth) acrylate, polyethylene glycol / polytetramethylene glycol mono (meth) acrylate, poly (propylene glycol / tetra) Methylene glycol) mono (meth) acrylate, polypropylene glycol polytetramethylene glycol mono (meth) acrylate, poly (pro Lenglycol / butylene glycol) mono (meth) acrylate, polypropylene glycol / polybutylene glycol mono (meth) acrylate, poly (ethylene glycol / butylene glycol) mono (meth) acrylate, polyethylene glycol / polybutylene glycol mono (meth) acrylate, Poly (tetraethylene glycol / butylene glycol) mono (meth) acrylate, polytetraethylene glycol / polybutylene glycol mono (meth) acrylate, polybutylene glycol mono (meth) acrylate, poly (ethylene glycol / trimethylene glycol) mono (meta) ) Acrylate, polyethylene glycol polytrimethylene glycol mono (meth) acrylate, poly (propylene glycol Limethylene glycol) mono (meth) acrylate, polypropylene glycol / polytrimethylene glycol mono (meth) acrylate, poly (trimethylene glycol / tetramethylene glycol) mono (meth) acrylate, polytrimethylene glycol / polytetramethylene glycol mono ( And (meth) acrylate, poly (butylene glycol / trimethylene glycol) mono (meth) acrylate, polybutylene glycol / polytrimethylene glycol mono (meth) acrylate, and the like. “Poly (ethylene glycol / propylene glycol)” means a random copolymer of ethylene glycol and propylene glycol, and “polyethylene glycol / polypropylene glycol” means a block copolymer of ethylene glycol and propylene glycol. Meaning, and so on. Among these monomers (d2), polypropylene glycol mono (meth) acrylate and polyethylene glycol mono (meth) acrylate are preferred because of compatibility with other components in the coating composition of the present invention. .

  Moreover, as a commercial item of the said monomer (d2), for example, “NK ester M-20G”, “NK ester M-40G”, “NK ester M-90G” manufactured by Shin-Nakamura Chemical Co., Ltd., “ "NK ester M-230G", "NK ester AM-90G", "NK ester AMP-10G", "NK ester AMP-20G", "NK ester AMP-60G", "Blemmer PE-90" manufactured by NOF Corporation ”,“ Blemmer PE-200 ”,“ Blemmer PE-350 ”,“ Blemmer PME-100 ”,“ Blemmer PME-200 ”,“ Blemmer PME-400 ”,“ Blemmer PME-4000 ”,“ Blemmer PP-1000 ” , "Blemmer PP-500", "Blemmer PP-800", "Blemmer 70PEP-350B", "Blenmer Over 55PET-800 "," Brenmer 50POEP-800B "," Blemmer 10PPB-500B "," Blemmer NKH-5050 "," Blemmer AP-400 ", such as" Blemmer AE-350 ", and the like. These monomers (d2) can be used alone or in combination of two or more.

  The fluorine-based surfactant (D) used in the color resist composition of the present invention contains the monomer (d1) and the monomer (d2) as essential components as raw materials, but as other monomers, You may use together the monomer (d3) which has an alkyl group. As said monomer (d3), what is represented by the following general formula (d3) is mentioned, for example.

（式中、Ｒ^４は水素原子又はメチル基であり、Ｒ^５は炭素原子数１〜１８の直鎖状、分岐状又は環構造を有するアルキル基である。）

(In the formula, R ⁴ is a hydrogen atom or a methyl group, and R ⁵ is an alkyl group having a linear, branched or ring structure having 1 to 18 carbon atoms.)

The above general formula (d3) in R ⁵ is a straight-chain having 1 to 18 carbon atoms, is an alkyl group having a branched or cyclic structure, the alkyl group, an aliphatic or aromatic hydrocarbon It may have a substituent such as a group or a hydroxyl group. Specific examples of the ethylenically unsaturated monomer having an alkyl group include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, and (meth) acrylic. Alkyl having 1 to 18 carbon atoms of (meth) acrylic acid such as octyl acid, (meth) acrylic acid-2-ethylhexyl, (meth) acrylic acid decyl, (meth) acrylic acid dodecyl, (meth) acrylic acid stearyl Esters: dicyclopentanyloxylethyl (meth) acrylate, isobornyloxylethyl (meth) acrylate, isobornyl (meth) acrylate, adamantyl (meth) acrylate, dimethyladamantyl (meth) acrylate, dicyclopentanyl (meth) acrylate , Dicyclopentenyl (meth) acryl Such as chromatography bets, etc. (meth) bridging cyclic alkyl ester having 1 to 18 carbon atoms of acrylic acid. These monomers (d3) can be used alone or in combination of two or more.

  Furthermore, as a raw material for the fluorosurfactant (D), as a monomer other than the monomer (d1), the monomer (d2) and the monomer (d3), styrene, α-methylstyrene, p -Aromatic vinyls such as methylstyrene and p-methoxystyrene; maleimides such as maleimide, methylmaleimide, ethylmaleimide, propylmaleimide, butylmaleimide, hexylmaleimide, octylmaleimide, dodecylmaleimide, stearylmaleimide, phenylmaleimide, cyclohexylmaleimide Etc. can also be used.

  In order to impart good leveling properties to the color resist composition of the present invention, the mass ratio of the monomer (d1) and the monomer (d2) as the raw material of the fluorosurfactant (D) [(d1 ) / (D2)] is preferably in the range of 10/90 to 90/10, more preferably in the range of 20/80 to 80/20. Moreover, when using monomers other than the said monomer (d1) and monomer (d2), it is preferable to set it as 30 mass% or less in all the monomers.

  The method for producing the fluorine-based surfactant (D) is not particularly limited, but the fluorine-based monomer (d1) and monomer (d2), and the monomer (d3) as necessary. The method of polymerizing monomers other than these in an organic solvent using a radical polymerization initiator is mentioned. As the organic solvent used here, ketones, esters, amides, sulfoxides, ethers, hydrocarbons are preferable. Specifically, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, ethyl acetate, butyl acetate, Examples include propylene glycol monomethyl ether acetate, dimethylformamide, dimethylacetamide, N-methylpyrrolidone, dimethyl sulfoxide, diethyl ether, diisopropyl ether, tetrahydrofuran, dioxane, toluene, xylene and the like. These are appropriately selected in consideration of boiling point, compatibility, and polymerizability. Examples of the radical polymerization initiator include peroxides such as benzoyl peroxide and azo compounds such as azobisisobutyronitrile. Furthermore, chain transfer agents such as lauryl mercaptan, 2-mercaptoethanol, thioglycerol, ethylthioglycolic acid, octylthioglycolic acid and the like can be used as necessary.

  The number average molecular weight (Mn) of the fluorosurfactant (D) has good compatibility with other compounding components when added to a resin composition such as a coating composition, and realizes a high leveling property. Therefore, the range of 2,000 to 100,000 is preferable, and the range of 2,500 to 50,000 is more preferable. The number average molecular weight (Mn) is a value in terms of polystyrene based on gel permeation chromatography (hereinafter abbreviated as “GPC”) measurement. The measurement conditions for GPC are as follows.

[GPC measurement conditions]
Measuring device: “HLC-8220 GPC” manufactured by Tosoh Corporation
Column: Guard column “HHR-H” manufactured by Tosoh Corporation (6.0 mm ID × 4 cm)
+ "TSK-GEL GMHHR-N" (7.8 mm ID x 30 cm) manufactured by Tosoh Corporation
+ "TSK-GEL GMHHR-N" (7.8 mm ID x 30 cm) manufactured by Tosoh Corporation
+ "TSK-GEL GMHHR-N" (7.8 mm ID x 30 cm) manufactured by Tosoh Corporation
+ "TSK-GEL GMHHR-N" (7.8 mm ID x 30 cm) manufactured by Tosoh Corporation
Detector: ELSD ("ELSD2000" manufactured by Oltec)
Data processing: “GPC-8020 Model II data analysis version 4.30” manufactured by Tosoh Corporation
Measurement conditions: Column temperature 40 ° C
Developing solvent Tetrahydrofuran (THF)
Flow rate 1.0 ml / min Sample: A 1.0% by mass tetrahydrofuran solution filtered in terms of resin solids through a microfilter (100 μl).
Standard sample: The following monodisperse polystyrene having a known molecular weight was used in accordance with the measurement manual of “GPC-8020 Model II Data Analysis Version 4.30”.

(Monodispersed polystyrene)
“A-500” manufactured by Tosoh Corporation
"A-1000" manufactured by Tosoh Corporation
"A-2500" manufactured by Tosoh Corporation
"A-5000" manufactured by Tosoh Corporation
“F-1” manufactured by Tosoh Corporation
"F-2" manufactured by Tosoh Corporation
“F-4” manufactured by Tosoh Corporation
“F-10” manufactured by Tosoh Corporation
“F-20” manufactured by Tosoh Corporation
“F-40” manufactured by Tosoh Corporation
“F-80” manufactured by Tosoh Corporation
“F-128” manufactured by Tosoh Corporation
“F-288” manufactured by Tosoh Corporation
“F-550” manufactured by Tosoh Corporation

  In addition, the fluorine content in the fluorosurfactant of the present invention can make the leveling property of the color resist composition sufficient, and can have good compatibility with other components in the color resist composition. Therefore, the range of 2 to 40% by mass is preferable, the range of 5 to 30% by mass is more preferable, and the range of 10 to 25% by mass is further preferable. The fluorine content is calculated from the mass ratio of fluorine atoms to the total amount of raw materials used.

  Since leveling properties can be obtained and the occurrence of defects such as foaming during coating can be suppressed, the blending amount of the fluorosurfactant (D) in the color resist composition of the present invention is the total solid content in the color resist composition. 0.0001-10 mass parts is preferable with respect to 100 mass parts per minute, 0.001-5 mass parts is more preferable, and 0.01-2 mass parts is still more preferable.

  When irradiating active energy rays such as ultraviolet rays and visible light to cure the color resist composition of the present invention, a photopolymerization initiator (E) is added to the color resist composition of the present invention. Examples of the photopolymerization initiator (E) include titanocene derivatives, biimidazole derivatives, halomethylated oxadiazole derivatives, halomethyl-s-triazine derivatives, α-aminoalkylphenone derivatives, oxime ester derivatives, benzoin alkyl ether derivatives, Anthraquinone derivatives, benzophenone derivatives, acetophenone derivatives, thioxanthone derivatives, benzoate derivatives, acridine derivatives, acridine derivatives, anthrone derivatives, N-aryl-α-amino acids such as N-phenylglycine, N-aryl-α-amino acid salts, N -Aryl-α-amino acid ester and the like.

  Specific examples of the titanocene derivative include dicyclopentadienyl titanium dichloride, dicyclopentadienyl titanium bisphenyl, dicyclopentadienyl titanium bis (2,3,4,5,6-pentafluoropheny-1). Yl), dicyclopentadienyl titanium bis (2,3,5,6-tetrafluorophen-1-yl), dicyclopentadienyl titanium bis (2,4,6-trifluorophen-1-yl) Dicyclopentadienyl titanium di (2,6-difluorophen-1-yl), dicyclopentadienyl titanium di (2,4-difluorophen-1-yl), di (methylcyclopentadienyl) titanium Bis (2,3,4,5,6-pentafluorophen-1-yl), di (methylcyclopentadi Nyl) titanium bis (2,6-difluorophen-1-yl), dicyclopentadienyltitanium [2,6-difluoro-3- (pyro-1-yl) -phen-1-yl] and the like Can be mentioned.

  Specific examples of the biimidazole derivative include 2- (2′-chlorophenyl) -4,5-diphenylimidazole dimer, 2- (2′-chlorophenyl) -4,5-bis (3′-methoxy). Phenyl) imidazole dimer, 2- (2′-fluorophenyl) -4,5-diphenylimidazole dimer, 2- (2′-methoxyphenyl) -4,5-diphenylimidazole dimer, (4 And '-methoxyphenyl) -4,5-diphenylimidazole dimer.

  Specific examples of the halomethylated oxadiazole derivative include 2-trichloromethyl-5- (2′-benzofuryl) -1,3,4-oxadiazole, 2-trichloromethyl-5- [β- (2 ′ -Benzofuryl) vinyl] -1,3,4-oxadiazole, 2-trichloromethyl-5-[[beta]-(2 '-(6' '-benzofuryl) vinyl)]-1,3,4-oxadiazole 2-trichloromethyl-5-furyl-1,3,4-oxadiazole and the like.

  Specific examples of the halomethylated oxadiazole derivative include 2-trichloromethyl-5- (2′-benzofuryl) -1,3,4-oxadiazole, 2-trichloromethyl-5- [β- (2′- Benzofuryl) vinyl] -1,3,4-oxadiazole, 2-trichloromethyl-5- [β- (2 ′-(6 ″ -benzofuryl) vinyl)]-1,3,4-oxadiazole, 2-trichloromethyl-5-furyl-1,3,4-oxadiazole and the like.

  Specific examples of the halomethyl-s-triazine derivative include 2- (4-methoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4-methoxynaphthyl) -4,6-bis. (Trichloromethyl) -s-triazine, 2- (4-ethoxynaphthyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4-ethoxycarbonylnaphthyl) -4,6-bis (trichloromethyl) ) -S-triazine and the like.

  Specific examples of the α-aminoalkylphenone derivative include 2-methyl-1 [4- (methylthio) phenyl] -2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1- (4 -Morpholinophenyl) -butanone-1,2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butan-1-one, 4-dimethylaminoethylbenzoate, 4-dimethylaminoisoamylbenzo Eat, 4-diethylaminoacetophenone, 4-dimethylaminopropiophenone, 2-ethylhexyl-1,4-dimethylaminobenzoate, 2,5-bis (4-diethylaminobenzal) cyclohexanone, 7-diethylamino-3- ( 4-diethylaminobenzoyl) coumarin, 4- (diethylamino) chalcone, etc. And the like.

  Specific examples of the oxime ester derivative include 1,2-octanedione, 1- [4- (phenylthio) phenyl], 2- (o-benzoyloxime), ethanone, 1- [9-ethyl-6- (2 -Methylbenzoyl) -9H-carbazol-3-yl], 1- (o-acetyloxime) and the like.

  Specific examples of the benzoin alkyl ether derivative include benzoin methyl ether, benzoin phenyl ether, benzoin isobutyl ether, and benzoin isopropyl ether.

  Specific examples of the anthraquinone derivative include 2-methylanthraquinone, 2-ethylanthraquinone, 2-t-butylanthraquinone, 1-chloroanthraquinone and the like.

  Specific examples of the benzophenone derivative include benzophenone, Michler's ketone, 2-methylbenzophenone, 3-methylbenzophenone, 4-methylbenzophenone, 2-chlorobenzophenone, 4-bromobenzophenone, 2-carboxybenzophenone and the like.

  Specific examples of the acetophenone derivative include 2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxyacetophenone, 1-hydroxycyclohexyl phenyl ketone, α-hydroxy-2-methylphenylpropanone, 1- Hydroxy-1-methylethyl- (p-isopropylphenyl) ketone, 1-hydroxy-1- (p-dodecylphenyl) ketone, 2-methyl- (4′-methylthiophenyl) -2-morpholino-1-propanone, 1 1,1-trichloromethyl- (p-butylphenyl) ketone and the like.

  Specific examples of the thioxanthone derivative include thioxanthone, 2-ethylthioxanthone, 2-isopropylthioxanthone, 2-chlorothioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2,4-diisopropylthioxanthone, and the like;

  Specific examples of the benzoate derivative include ethyl p-dimethylaminobenzoate and ethyl p-diethylaminobenzoate. Specific examples of the acridine derivative include 9-phenylacridine, 9- (pmethoxyphenyl) acridine and the like. Specific examples of the phenazine derivative include 9,10-dimethylbenzphenazine. Specific examples of the anthrone derivative include benzanthrone and the like. These photopolymerization initiators (E) can be used alone or in combination of two or more.

  Moreover, you may use a polymerization accelerator in addition to said photoinitiator (E) as needed. Examples of the polymerization accelerator include N, N-dialkylaminobenzoic acid alkyl esters such as N, N-dimethylaminobenzoic acid ethyl ester; 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, 2-mercaptobenzimidazole, and the like. And mercapto compounds such as aliphatic polyfunctional mercapto compounds. These polymerization accelerators can be used alone or in combination of two or more.

  The blending amount of the polymerization initiator (E) is preferably in the range of 0.01 to 30 parts by mass, more preferably in the range of 0.1 to 15 parts by mass with respect to 100 parts by mass of the total solid content in the color resist composition. The range of 0.5 to 10 parts by mass is more preferable. Moreover, also when using a polymerization accelerator, it is preferable to make it the sum total of a polymerization initiator (E) and a polymerization accelerator become these ranges.

  Furthermore, a sensitizing dye may be used to improve the polymerization sensitivity. The sensitizing dye is appropriately selected according to the wavelength of light used for polymerization, and examples thereof include xanthene dyes, coumarin dyes, 3-ketocoumarin dyes, and dyes having a dialkylaminobenzene skeleton.

  Among the sensitizing dyes, those having an amino group are preferable, and those having an amino group and a phenyl group are more preferable. Specifically, 4,4′-dimethylaminobenzophenone, 4,4′-diethylaminobenzophenone, 2-aminobenzophenone, 4-aminobenzophenone, 4,4′-diaminobenzophenone, 3,3′-diaminobenzophenone, 3, Benzophenone compounds such as 4-diaminobenzophenone; 2- (p-dimethylaminophenyl) benzoxazole, 2- (p-diethylaminophenyl) benzoxazole, 2- (p-dimethylaminophenyl) benzo [4,5] benzoxazole 2- (p-dimethylaminophenyl) benzo [6,7] benzoxazole, 2,5-bis (p-diethylaminophenyl) -1,3,4-oxazole, 2- (p-dimethylaminophenyl) benzothiazole 2- (p-diethylaminophenyl) Nyl) benzothiazole, 2- (p-dimethylaminophenyl) benzimidazole, 2- (p-diethylaminophenyl) benzimidazole, 2,5-bis (p-diethylaminophenyl) -1,3,4-thiadiazole, (p -Dimethylaminophenyl) pyridine, (p-diethylaminophenyl) pyridine, (p-dimethylaminophenyl) quinoline, (p-diethylaminophenyl) quinoline, (p-dimethylaminophenyl) pyrimidine, (p-diethylaminophenyl) pyrimidine, etc. Examples thereof include a p-dialkylaminophenyl group-containing compound. Of these, 4,4'-dialkylaminobenzophenone is most preferred. These sensitizing dyes can be used alone or in combination of two or more.

  The blending amount of the photosensitizer is preferably 0.01 to 30 parts by mass, more preferably 0.1 to 15 parts by mass with respect to 100 parts by mass of the total solid content in the color resist composition. More preferably, the range is 5 to 10 parts by mass.

  Furthermore, the color resist composition of the present invention is an organic solvent, a polymerization inhibitor, an antistatic agent, an antifoaming agent, a viscosity modifier, light resistance, within a range that does not impair the effects of the present invention, depending on purposes such as use and characteristics. Additives such as a stabilizer stabilizer, a heat-resistant stabilizer, and an antioxidant can be blended.

In addition, in order to impart coating suitability to the color resist composition of the present invention, an organic solvent may be added to adjust the viscosity. Examples of the organic solvent that can be used here include the alkali-soluble resin (A), the polymerizable compound (B), the colorant (C), the fluorosurfactant (D), and the photopolymerization initiator (E). Those having good solubility in components are preferred. Examples of the organic solvent include alcohol solvents such as methyl alcohol, ethyl alcohol, N-propyl alcohol, and i-propyl alcohol; cellosolv solvents such as methoxy alcohol and ethoxy alcohol; carbs such as methoxyethoxyethanol and ethoxyethoxyethanol. Toll solvents; ester solvents such as ethyl acetate, butyl acetate, methyl methoxypropionate, ethyl ethoxypropionate, and ethyl lactate; ketone solvents such as acetone, methyl isobutyl ketone, cyclohexanone; methoxyethyl acetate, ethoxyethyl acetate, ethyl Cellosolve acetate solvents such as cellosolve acetate; Carbitol acetates such as methoxyethoxyethyl acetate and ethoxyethoxyethyl acetate Solvents; ether solvents such as diethyl ether, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether and tetrahydrofuran; aprotic amide solvents such as N, N-dimethylformamide, N, N-dimethylacetamide and N-methylpyrrolidone; and γ-butyrolactone Examples include lactone solvents; unsaturated hydrocarbon solvents such as benzene, toluene, xylene, and naphthalene; and organic solvents such as saturated hydrocarbon solvents such as N-heptane, N-hexane, and N-octane. Among these solvents, cellosolve acetate solvents such as methoxyethyl acetate, ethoxyethyl acetate, and ethyl cellosolve acetate; carbitol acetate solvents such as methoxyethoxyethyl acetate and ethoxyethoxyethyl acetate; ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, propylene Ether solvents such as glycol diethyl ether; aprotic amide solvents such as N, N-dimethylacetamide; ester solvents such as methyl methoxypropionate, ethyl ethoxypropionate and ethyl lactate are particularly preferably used. Particularly preferably, N, N-dimethylacetamide, MBA (3-methoxybutyl acetate, CH ₃ CH (OCH ₃ ) CH ₂ CH ₂ OCOCH ₃ ), PGMEA (propylene glycol monomethyl ether acetate, CH ₃ OCH ₂ CH (CH ₃ ) OCOCH ₃ ), DMDG (diethylene glycol dimethyl ether, H ₃ COC ₂ H ₄ OCH ₃ ), or a mixture thereof can be used. Moreover, in the color resist composition of this invention, it is preferable to adjust solid content concentration to 10-70 mass% using these organic solvents.

  Moreover, it is preferable to select an organic solvent as appropriate depending on the method of applying the color resist composition of the present invention. For example, when a coating film is formed by a spin coater, a slit-and-spin coater, a slit die coater, or the like, for example, Japanese Patent Application Laid-Open Nos. 2003-330187, 2004-246340, and 2004-346218. As disclosed in Japanese Patent Laid-Open No. 2004-354601, etc., it is preferable to use a solvent having different physical properties such as boiling point by appropriately mixing them. Moreover, when forming a pixel by the inkjet method, it is preferable to use a high boiling point solvent as disclosed, for example, in JP-A-2009-7560.

  Examples of active energy rays for curing the color resist composition of the present invention include active energy rays such as light, electron beam, and radiation. Specific energy sources or curing devices include, for example, germicidal lamps, ultraviolet fluorescent lamps, carbon arcs, xenon lamps, high pressure mercury lamps for copying, medium or high pressure mercury lamps, ultrahigh pressure mercury lamps, electrodeless lamps, metal halide lamps, natural light, etc. Or an electron beam using a scanning type or curtain type electron beam accelerator. In addition, when making it harden | cure with an electron beam, the mixing | blending of the said polymerization initiator (E) to the color resist composition of this invention is unnecessary.

  Among these active energy rays, ultraviolet rays are particularly preferable. Further, it is preferable to irradiate in an inert gas atmosphere such as nitrogen gas since the surface curability of the coating film is improved. Further, if necessary, heat may be used as an energy source and heat treatment may be performed after curing with active energy rays.

  The coating method of the color resist composition of the present invention varies depending on the application. For example, gravure coater, roll coater, comma coater, knife coater, curtain coater, shower coater, spin coater, slit coater, slit and spin coater, slit Examples of the coating method include a die coater, dipping, screen printing, spraying, applicator, and bar coater.

The color resist composition of the present invention is useful for color filters (RGB pixel portions and black matrix portions) used in liquid crystal display devices. In addition, the color filter of this invention can be produced by forming a colored pattern through the following processes.
(1) The color resist composition of the present invention is applied on a substrate.
(2) The applied color resist composition is dried (prebaked).
(3) Exposure to a desired pattern using a photomask.
(4) Development processing is performed using an alkali developer.
(5) Wash (rinse) with distilled water and dry.

  Said drying (prebaking) can be performed by heating at a temperature range of 50-140 degreeC with a hotplate, oven, etc. for 10 to 300 seconds. Especially, it is preferable to heat for 30 to 180 second in the temperature range of 70-130 degreeC, and it is more preferable to heat for 30-90 second in the temperature range of 80-120 degreeC. Moreover, in order to dry more completely, you may vacuum-dry before drying (prebaking).

  In the above development processing, unexposed uncured portions are eluted in an alkaline developer, leaving only the photocured cured portions. Any alkali developer can be used without particular limitation as long as it dissolves uncured portions and does not dissolve cured portions that become the RGB pixel portions and black matrix portions. Specific alkali developers include, for example, sodium hydroxide, potassium hydroxide, sodium carbonate, sodium bicarbonate, sodium oxalate, sodium metasuccinate, aqueous ammonia, ethylamine, diethylamine, dimethylethanolamine, tetramethylammonium hydroxy And aqueous solutions of alkaline compounds such as chodo, tetraethylammonium hydroxide, choline, pyrrole, piperidine, 1,8-diazabicyclo- [5,4,0] -7-undecene. The alkali concentration of the alkali developer is preferably 0.001 to 10% by mass, and more preferably 0.01 to 1% by mass. The development temperature is usually 20 ° C. to 30 ° C., and the development time is preferably in the range of 20 to 90 seconds.

  After the development processing, post-baking processing can be performed as necessary. Post-baking is a heat treatment after development to complete the curing, and is usually heated in a temperature range of 200 to 250 ° C. The post-baking treatment can be performed continuously or batchwise by using a heating means such as a hot plate, a convection oven (hot air circulation dryer), a high-frequency heater or the like so that the layer after development is in the above-described condition.

  A substrate in which a transparent electrode such as ITO is formed on the pixel of the color filter produced as described above is used as a substrate for sandwiching a liquid crystal layer together with another substrate, and a liquid crystal display device combining a backlight, a polarizing plate, and a liquid crystal layer can do.

  The liquid crystal display device using the color filter of the present invention includes, for example, a liquid crystal television, a personal computer, a liquid crystal projector, a portable game machine, a mobile phone, a personal digital assistant (PDA), a digital audio player, a digital camera, and a digital video camera. It can be used in a wide range as an image display unit for car navigation and the like.

  Furthermore, the color resist composition of the present invention can also be used for the production of color filters for solid-state imaging devices such as CCD image sensors and CMOS image sensors, and organic EL display devices.

  Hereinafter, the present invention will be described in more detail with reference to specific examples. The molecular weight of the produced fluorosurfactant was measured under the following conditions.

[GPC measurement conditions]
Measuring device: “HLC-8220 GPC” manufactured by Tosoh Corporation
Column: Guard column “HHR-H” manufactured by Tosoh Corporation (6.0 mm ID × 4 cm)
+ "TSK-GEL GMHHR-N" (7.8 mm ID x 30 cm) manufactured by Tosoh Corporation
+ "TSK-GEL GMHHR-N" (7.8 mm ID x 30 cm) manufactured by Tosoh Corporation
+ "TSK-GEL GMHHR-N" (7.8 mm ID x 30 cm) manufactured by Tosoh Corporation
+ "TSK-GEL GMHHR-N" (7.8 mm ID x 30 cm) manufactured by Tosoh Corporation
Detector: ELSD ("ELSD2000" manufactured by Oltec)
Data processing: “GPC-8020 Model II data analysis version 4.30” manufactured by Tosoh Corporation
Measurement conditions: Column temperature 40 ° C
Developing solvent Tetrahydrofuran (THF)
Flow rate 1.0 ml / min Sample: A 1.0% by mass tetrahydrofuran solution filtered in terms of resin solids through a microfilter (100 μl).
Standard sample: The following monodisperse polystyrene having a known molecular weight was used in accordance with the measurement manual of “GPC-8020 Model II Data Analysis Version 4.30”.

(Monodispersed polystyrene)
“A-500” manufactured by Tosoh Corporation
"A-1000" manufactured by Tosoh Corporation
"A-2500" manufactured by Tosoh Corporation
"A-5000" manufactured by Tosoh Corporation
“F-1” manufactured by Tosoh Corporation
"F-2" manufactured by Tosoh Corporation
“F-4” manufactured by Tosoh Corporation
“F-10” manufactured by Tosoh Corporation
“F-20” manufactured by Tosoh Corporation
“F-40” manufactured by Tosoh Corporation
“F-80” manufactured by Tosoh Corporation
“F-128” manufactured by Tosoh Corporation
“F-288” manufactured by Tosoh Corporation
“F-550” manufactured by Tosoh Corporation

(Synthesis Example 1)
In a glass flask equipped with a stirrer, a thermometer, a condenser, and a dropping device, 150 parts by mass of methyl isobutyl ketone (hereinafter abbreviated as “MIBK”) is placed, and stirred at 90 ° C. in a nitrogen gas stream. 3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorohexylethyl acrylate (hereinafter abbreviated as "monomer (d1-1-1)") .) 35 parts by mass, a mixed solution of 65 parts by mass of poly (ethylene glycol / tetramethylene glycol) monomethacrylate (hereinafter abbreviated as “monomer (d2-1)”) and 40 parts by mass of MIBK, and a polymerization initiator As a mixture, 8 parts by mass of t-butylperoxy-2-ethylhexanoate and 10 parts by mass of MIBK were simultaneously added dropwise over 2 hours. After completion of the dropwise addition, the reaction was continued for 10 hours, and then the solvent was distilled off to obtain a fluorinated surfactant (1).

(Synthesis Examples 2 to 8)
Fluorosurfactants (1) to (8) were obtained in the same manner as in Synthesis Example 1 except that the raw materials and amounts used and the polymerization time shown in Table 1 were changed.

The abbreviations in Table 1 represent the following, and the numbers in parentheses represent the amount used (parts by mass).
d1-1-1: 3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorohexylethyl acrylate d1-1-2: 3,3,4 4,5,5,6,6,7,7,8,8,9,9,10,10,10-heptadecafluorooctylethyl acrylate d2-1: poly (ethylene glycol tetramethylene glycol) monomethacrylate d2 -2: Poly (propylene glycol / tetramethylene glycol) monomethacrylate d2-3: Propylene glycol / polybutylene glycol monomethacrylate "
BMA: Butyl methacrylate EHA: 2-ethylhexyl acrylate

Preparation Example 1 Preparation of Pigment Dispersion Solution A high-speed disperser charged with 200 parts by mass of zirconia beads having a diameter of 0.5 mm was used as a coloring agent. I. 8 parts by mass of Pigment Red 254, 2.5 parts by mass of a polyester-based dispersant (“Ajisper PB-814” manufactured by Ajinomoto Fine Techno Co., Ltd.), and methacrylic acid / benzyl methacrylate = 13/87 (mass ratio) as an alkali-soluble resin 25 parts by mass of a copolymer (acid value 84, number average molecular weight 9,500) propylene glycol monomethyl ether acetate (hereinafter abbreviated as “PGMEA”) solution (non-volatile content 39.7% by mass) as a solvent, PGMEA 64 .5 parts by mass was charged and dispersed at 2000 rpm for 8 hours to obtain a red pigment dispersion.

Example 1
For 100 parts by mass of the red pigment dispersion obtained in Preparation Example 1 above, 7 parts by mass of dipentaerythritol hexaacrylate as a polymerizable compound, a photopolymerization initiator (BASF Japan Ltd. “Irgacure 369”; 2-benzyl- 0.3 part by mass of 2-dimethylamino-1- (4-morpholinophenyl) -butanone-1) was added and mixed. The mixture was mixed with 0.5% by mass of the fluorosurfactant (1) obtained in Synthesis Example 1 based on the non-volatile content contained in the composition, and then mixed with a filter having a pore size of 1.0 μm. Filtration was performed to prepare a color resist composition.

(Examples 2 to 5)
A color resist composition was prepared in the same manner except that the fluorosurfactant (1) used in Example 1 was changed to the fluorosurfactants (2) to (5) obtained in Synthesis Examples 2 to 5. Prepared.

(Comparative Example 1)
A color resist composition was prepared in the same manner as in Example 1 except that no fluorine-based surfactant was added.

(Comparative Examples 2 to 4)
A color resist composition was prepared in the same manner except that the fluorosurfactant (1) used in Example 1 was changed to the fluorosurfactants (6) to (8) obtained in Synthesis Examples 6 to 8. Prepared.

  Using the color resist composition obtained above, the defoaming property of the composition, the surface smoothness of the coating film, and the pigment aggregation on the coating film surface were evaluated. In addition, the bioaccumulation safety of the fluorosurfactant used in each color resist composition was also evaluated.

(Evaluation of bioaccumulation safety)
The bioaccumulation safety of each fluorosurfactant was evaluated according to the following criteria.
○: It does not contain a perfluoroalkyl group having 8 or more carbon atoms, has a low possibility of accumulating in a living body, and is highly safe.
X: It contains a perfluoroalkyl group having 8 or more carbon atoms, has a high possibility of accumulating in a living body, and has low safety.

(Defoaming evaluation)
10 ml of the color resist composition was placed in a 20 ml sample tube and bubbled by shaking for 20 seconds. Thereafter, the time until 90% or more of the liquid surface area was exposed due to the disappearance of bubbles was measured, and the defoaming property was evaluated according to the following criteria.
○: Less than 60 seconds Δ: 60 seconds or more and less than 120 seconds ×: 120 seconds or more

(Preparation of coating film for evaluation)
A color resist composition was applied on a glass substrate having a size of 10 cm × 10 cm using a spin coater (“SPINNER-1H” manufactured by Kyoei Semiconductor Co., Ltd.) at a rotation speed of 3000 rpm for 30 seconds, and then a dryer (ESPEC It was dried by heating at 90 ° C. for 1 minute using “PVC-211” manufactured by Co., Ltd. After drying, ultraviolet rays were irradiated through a photomask at an irradiation intensity of 500 J / m ² using an exposure machine (“HTE-106-M07” manufactured by Hitec Corporation) equipped with a 50 kW ultra-high pressure mercury lamp. After irradiation with ultraviolet rays, development was performed with a spin developing machine for 1 minute using a 0.04 mass% potassium hydroxide aqueous solution at 25 ° C., and then the coating film was dried at 230 ° C. for 60 minutes to obtain a cured coating film.

(Evaluation of surface smoothness)
Irregularities on the surface of the coating film were observed with a fine shape measuring device (“P-16 +” manufactured by KLA Tencor), and surface smoothness was evaluated according to the following criteria.
○: The surface is smooth and unevenness is not seen.
(Triangle | delta): An unevenness | corrugation and gentle inclination are seen partially.
X: Concavities and convexities and gentle inclination are seen as a whole.

(Pigment aggregation on the coating surface)
The surface of the coating film was observed with an optical microscope, and the state of pigment aggregation was evaluated according to the following criteria. The presence or absence of color unevenness can be evaluated by the presence or absence of pigment aggregation.
○: Pigment aggregation of 0.1 μm or more is not observed.
Δ: Pigment aggregation of 0.1 μm or more is partially observed.
X: Pigment aggregation of 0.1 μm or more is observed as a whole.

  The evaluation results are shown in Table 2.

  From the evaluation results shown in Table 1, the color resist compositions of the present invention of Examples 1 to 5 have high bioaccumulation safety of the fluorosurfactant used, good antifoaming properties, and even foaming. I found that the cut was good. Moreover, it turned out that the surface smoothness of the coating film after hardening is high, and there is no pigment aggregation on the coating-film surface.

  On the other hand, the color resist composition of Comparative Example 1 that does not use a fluorosurfactant has a problem that the surface smoothness of the coating film after curing is low, pigment aggregation occurs on the coating film surface, and color unevenness occurs. I found out.

  Comparative Examples 2 to 4 are examples in which a fluorine-based surfactant using a fluorine-based monomer having a perfluoroalkyl group having 8 carbon atoms as a raw material was used, but the surface smoothness of the coating film was Although it was good and the aggregation of the pigment on the surface of the coating film was suppressed, it was found that the foaming after foaming was poor and there was a problem in the defoaming property.

Claims (5)

  A composition containing an alkali-soluble resin (A), a polymerizable compound (B), a colorant (C) and a fluorosurfactant (D), wherein the fluorosurfactant (D) is a carbon atom. A color resist composition comprising a copolymer obtained by copolymerizing a monomer (d1) having a fluorinated alkyl group of 4 to 6 and a monomer (d2) having a polyoxyalkylene chain as essential components object.   The number average molecular weight (Mn) of the fluorosurfactant (D) is in the range of 1,000 to 10,000, and the weight average molecular weight (Mw) is in the range of 2,000 to 100,000. The color resist composition according to 1.   The color resist composition according to claim 1 or 2, wherein the fluorosurfactant (D) contains 2 to 25 mass% of fluorine atoms in the surfactant.   A color filter comprising a cured coating film of the color resist composition according to claim 1.   5. A liquid crystal display device comprising: a backlight, a polarizing plate, at least two substrates, a liquid crystal layer sandwiched between the substrates, and a color filter according to claim 4 provided on at least a part of the substrate.