JP6908020B2 - Random copolymer, resist composition, color filter and method for producing random copolymer - Google Patents

Description

INDUSTRIAL APPLICABILITY The present invention provides a random copolymer (a resist composition capable of obtaining a smooth color resist layer, suppressing the generation of foreign substances derived from a colorant such as a pigment in the color resist layer, and having excellent developability. Fluorine-based surfactant), a resist composition using the same, and a color filter. The present invention also relates to a method for producing the random copolymer.

Conventionally, in various coating fields, various surfactants called leveling agents such as hydrocarbon-based, silicone-based, and fluorine-based surfactants have been used for the purpose of improving the homogeneity and smoothness of the obtained coating film. .. Among them, fluorine-based surfactants are widely used because of their high ability to reduce surface tension and less contamination after coating.

Among the fluorine-based surfactants, a surfactant that utilizes a perfluoroalkyl group having 8 or more carbon atoms is excellent in performance as a leveling agent due to its ability to reduce surface tension, but the carbon atom number is 8 The above-mentioned surfactant having a perfluoroalkyl group uses a perfluoroalkyl group having a carbon atom number smaller than 8 in order to generate a compound such as perfluorooctanesulfonic acid that may be accumulated in the environment and the living body. Surfactants have been proposed. As such a surfactant, for example, a random copolymer produced by living radical polymerization of a monomer having a fluorinated alkyl group having 6 or less carbon atoms and a non-fluorinated monomer in the coexistence. Polymers have been proposed (see, for example, Patent Document 1).

Further, in the above-mentioned coating field, particularly in a composition for producing a color filter (color resist composition), the coating film is less likely to be discolored (difficult to stain with water) even when exposed to an alkaline aqueous solution used as a developing solution. Performance is required. In order to obtain a resist composition having such performance, a polymerizable single amount having a polymer segment of a polymerizable monomer having a fluorinated alkyl group having 1 to 6 carbon atoms and a skeleton of a bridging ring hydrocarbon. A fluorine-based surfactant which is a block copolymer having a polymer segment of the body has been proposed (see, for example, Patent Document 2). However, the resist composition containing the fluorine-based surfactant disclosed in Patent Document 2 has a problem that the developability with an alkaline aqueous solution is not sufficient.

In addition, when forming a colored coating film layer such as a coating film (color resist pattern) of a color resist composition, a desired hue is also required. In order to obtain a coating film layer having a desired hue, for example, a color resist pattern having a hue excellent in lightness, C.I. I. Pigment Red 254 and other pigments (colorants) are used. However, the C.I. I. Pigment Red 254 and other pigments have the property of being easily sublimated and of crystal growth due to their intermolecular interactions. Therefore, pigment molecules sublimated from the coating film in the heating step when forming a color filter are applied to the coating film. Crystallization and agglomeration occur on the surface, and foreign matter is generated. When such a foreign substance is generated, light scattering by particles and non-uniformity of pigment dispersion occur, and as a result, it becomes difficult to obtain the desired hue.

Japanese Unexamined Patent Publication No. 2013-6928 International Publication No. 2015/137229 Pamphlet

The problem to be solved by the present invention is that a smooth color resist layer can be obtained, the generation of foreign substances derived from the colorant in the color resist layer can be suppressed, and a resist composition having excellent developability can be obtained. It is to provide a coalescence (fluorine-based surfactant), a resist composition using this, and a color filter. Another object to be solved by the present invention is to provide a method for producing the fluorine-containing polymer (random copolymer of living radical polymerization).

As a result of diligent research, the present inventors have bridged a polymerizable monomer having a fluorinated alkyl group and a polymerizable unsaturated group with a polymerizable monomer having an adamantan ring and a polymerizable unsaturated group. By using a polymerizable monomer having a ring hydrocarbon skeleton and a polymerizable unsaturated group, a random copolymer that can be used as a surfactant can be obtained. Sublimation and crystallization by adding a random copolymer in which the ratio [(Mw) / (Mn)] of the average molecular weight (Mw) to the number average molecular weight (Mn) is in the range of 1.0 to 1.8. It is desirable to obtain a resist composition in which foreign substances are less likely to be generated in the coating film even if a colorant that is easily peeled off is used, and that the resist composition is also excellent in developability. We have found that a color filter having a hue can be obtained, and have completed the present invention.

That is, in the present invention, the skeleton of the crosslinked ring hydrocarbon and the polymerizable monomer (a1) having a fluorinated alkyl group having 1 to 6 carbon atoms directly bonded to the fluorine atom and a polymerizable unsaturated group. It is a random copolymer of a polymerizable monomer (a2) having a polymerizable unsaturated group and a weight average molecular weight (Mw) and a number average molecular weight (Mn) of 1 (Mw / Mn). It provides a random copolymer characterized by being .0 to 1.8.

The present invention also provides a resist composition containing the random copolymer (A), a colorant (B), an alkali-soluble resin (C), and a polymerizable compound (D). Is.

The present invention also provides a color filter characterized in that a coating film layer of the resist composition is formed on a substrate.

Further, in the present invention, the skeleton of a crosslinked ring hydrocarbon and a polymerizable monomer (a1) having a fluorinated alkyl group having 1 to 6 carbon atoms to which a fluorine atom is directly bonded and a polymerizable unsaturated group. A polymerizable monomer (a2) having a polymerizable unsaturated group and a polymerizable monomer (a2) is subjected to living radical polymerization in the coexistence of the polymerizable monomer (a1) and the polymerizable monomer (a2). It provides a method for producing a random copolymer.

The present invention provides a random copolymer and a method for producing the same, which can obtain a smooth color resist layer, suppress the generation of foreign substances derived from a colorant in the color resist layer, and obtain a resist composition having excellent developability. Can be provided. Further, the present invention can provide a resist composition capable of obtaining a coating film layer having a desired hue and a color filter having a coating film layer having a desired hue.

Further, the random copolymer of the present invention can be suitably used for a color resist composition, and also forms a coating film layer on the surface of an article such as a composition for forming a black matrix or a housing of an electronic device or the like. It can also be suitably used for a composition or the like.

FIG. 1 is a chart diagram of the IR spectrum of the random copolymer (1) obtained in Example 1. ^{FIG. 2 is a chart of the 13} C-NMR spectrum of the random copolymer (1) obtained in Example 1. FIG. 3 is a chart diagram of the GPC of the random copolymer (1) obtained in Example 1.

In the present invention, a polymerizable monomer (a1) having a fluorinated alkyl group having 1 to 6 carbon atoms to which a fluorine atom is directly bonded and a polymerizable unsaturated group is polymerized with the skeleton of a bridging ring hydrocarbon. It is a random copolymer with a polymerizable monomer (a2) having a sex unsaturated group, and the ratio (Mw / Mn) of the weight average molecular weight (Mw) to the number average molecular weight (Mn) is 1.0. Provided is a random copolymer characterized by being ~ 1.8.

The polymerizable monomer (a1) having a fluorinated alkyl group having 1 to 6 carbon atoms directly bonded to the fluorine atom and a polymerizable unsaturated group is polymerized with the fluorinated alkyl group in the molecule. Any compound having a sex unsaturated group can be used without particular limitation.

Here, the fluorinated alkyl group having 1 to 6 carbon atoms directly bonded to the fluorine atom is a part of the perfluoroalkyl group or hydrogen atom having 1 to 6 carbon atoms directly bonded to the fluorine atom. It is a partially fluorinated alkyl group with a fluorine atom. Among these fluorinated alkyl groups, a perfluoroalkyl group is preferable because the obtained polymer is highly effective as a surfactant. Further, the larger the number of carbon atoms to which the fluorine atom is directly bonded is preferable, and the number of carbon atoms to which the fluorine atom is directly bonded is particularly preferably 4 to 6.

Examples of the polymerizable unsaturated group contained in the polymerizable monomer (a1) include a (meth) acryloyl group, a vinyl group, a maleimide group, and the like. Among these, the raw materials are easily available, and when the resist composition or coating composition is produced using the obtained random copolymer, the compatibility of the random copolymer with the compounding components in the composition is controlled. A (meth) acryloyl group is preferable because it is easy to carry out and has good polymerization reactivity. As a specific example having this (meth) acryloyl group, for example, a monomer represented by the following general formula (1) can be preferably exemplified. Further, the polymerizable monomer (a1) may be used alone or in combination of two or more.

〔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−４）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−４）のいずれか１つの基を表す。〕

In [the above general formula (1), ^{R 1} represents a hydrogen atom, a fluorine atom, a methyl group, a cyano group, a phenyl group, an integer of benzyl group or _-C n _H 2n -Rf '(n is 1 to 8, Rf 'Represents any one group of the following formulas (Rf-1) to (Rf-4)), and X represents any one group of the following formulas (X-1) to (X-10). , And Rf represents any one group of the following formulas (Rf-1) to (Rf-4). ]

〔上記式（Ｘ−１）、（Ｘ−３）、（Ｘ−４）、（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−４）のいずれか１つの基を表す。〕

[N in the above formulas (X-1), (X-3), (X-4), (X-5), (X-6) and (X-7) represents an integer of 1 to 8. In the above formulas (X-8), (X-9) and (X-10), m represents an integer of 1 to 8 and n represents an integer of 0 to 8. Rf'' in the above formulas (X-6) and (X-7) represents any one group of the following formulas (Rf-1) to (Rf-4). ]

〔上記式（Ｒｆ−１）及び（Ｒｆ−２）中のｎは１〜６の整数を表す。上記式（Ｒｆ−３）中のｎは２〜６の整数を表す。上記式（Ｒｆ−４）中のｎは４〜６の整数を表す。〕

[N in the above equations (Rf-1) and (Rf-2) represents an integer of 1 to 6. N in the above equation (Rf-3) represents an integer of 2 to 6. N in the above equation (Rf-4) represents an integer of 4 to 6. ]

In the present invention, "(meth) acrylate" means one or both of methacrylate and acrylate, and "(meth) acrylic acid" means one or both of methacrylic acid and acrylic acid.

The polymerizable monomer (a2) has a skeleton of a crosslinked ring hydrocarbon and a polymerizable unsaturated group. On the outermost surface of the coating film layer obtained by using the resist composition containing the random copolymer of the present invention, a layer containing the random copolymer (hereinafter, may be referred to as a block layer) is unevenly distributed on the surface. do. In the random copolymer of the present invention, the glass transition temperature (Tg) is high due to the presence of the skeleton of the crosslinked ring hydrocarbon, and as a result, the block layer becomes a hard layer. That is, the coating film layer formed in the method for producing a color filter described later has a block layer having high hardness due to the presence of the skeleton of the bridging ring hydrocarbon. This high-hardness block layer prevents colorants such as pigments in the coating film layer from precipitating (sublimating) on the outermost surface, and the skeleton of the bridging ring hydrocarbon in the block layer is the coating film layer underneath. The inventors speculate that it has some effect on the pigments dispersed in the pigment, and as a result, suppresses the formation of foreign substances derived from colorants such as pigments.

Examples of the skeleton of the crosslinked hydrocarbon include an adamantane ring, a perhydroindene ring, a decalin ring, a perhydrofluorene ring, a perhydroanthracene ring, a perhydrophenanthrene ring, a dicyclopentane ring, a dicyclopentene ring, and a perhydro. Examples thereof include an anthracene ring, a perhydrophenanthrene ring, a norbornane ring, and a norbornene ring. Of these, the adamantane ring, dicyclopentane ring, norbornane ring, and norbornene ring are preferable, and the adamantane ring is more preferable, because a block layer having a high Tg can be formed on the outermost surface of the coating film and the generation of foreign substances derived from the pigment can be suppressed.

Hereinafter, a polymerizable monomer having an adamantane ring and a polymerizable unsaturated group, which can be preferably used as the polymerizable monomer (a2) in the present invention, will be described.

Examples of the polymerizable monomer having an adamantane ring and a (meth) acryloyl group include compounds represented by the following formulas (a2-1) and (a2-2).

（式中、Ｌは反応性官能基を表し、Ｘ及びＹは２価の有機基又は単結合を表し、Ｒは水素原子、メチル基又はＣＦ_３を表す。）

(In the formula, L represents a reactive functional group, X and Y represent a divalent organic group or a single bond, and R represents a hydrogen atom, a methyl group or CF _3. )

Examples of the reactive functional group include a hydroxyl group, an isocyanate group, an epoxy group, a carboxyl group, a carboxylic acid halide group, an acid anhydride group and the like. Above all, when a resist composition or a coating composition is produced using the obtained random copolymer, a hydroxyl group is preferable because a random copolymer having good compatibility with the compounding components in the composition can be obtained.

The bonding positions of the organic group having the reactive functional group represented by -XL in the general formula (a2-1) and Y may be bonded to any carbon atom in the adamantane ring. , -XL may have two or more. Further, the hydrogen atom bonded to the carbon atom constituting the adamantane ring may be partially or wholly substituted with a fluorine atom, an alkyl group or the like. Further, X and Y in the above general formula (a2-1) are divalent organic groups or single bonds, and the divalent organic group includes carbon atoms such as a methylene group, a propyl group and an isopropylidene group. The number 1 to 8 alkylene groups can be mentioned.

Further, in the compound represented by the above formula (a2-2), the (meth) acryloyl group may be bonded to any carbon atom in the adamantane ring. Further, the hydrogen atom bonded to the carbon atom constituting the adamantane structure in the above general formula (a2-1) may be partially or wholly substituted with a fluorine atom, an alkyl group or the like.

More specific examples of the polymerizable monomer represented by the general formula (a2-1) include compounds represented by the following.

Further, as a more specific example of the polymerizable monomer represented by the general formula (a2-2), for example, a compound represented by the following can be mentioned.

Among the polymerizable monomers having an adamantan ring and a (meth) acryloyl group, when a resist composition is produced using the obtained random copolymer, random with good compatibility with the compounding components in the composition. Since a copolymer can be obtained, the compound represented by the formula (a2-2) is preferable, and the compound represented by the formula (a2-2-1) is more preferable.

Hereinafter, a polymerizable monomer having a dicyclopentane ring and a polymerizable unsaturated group, which can be preferably used as the polymerizable monomer (a2) in the present invention, will be described.

Examples of the polymerizable monomer having a dicyclopentane ring and a (meth) acryloyl group include a compound represented by the following formula (a2-3).

（式中、Ｒは水素原子、メチル基又はＣＦ_３を表す。）

(In the formula, R represents a hydrogen atom, a methyl group or CF _3. )

Further, in the compound represented by the above formula (a2-3), the (meth) acryloyl group may be bonded to any carbon atom in the dicyclopentane ring. Further, the hydrogen atom bonded to the carbon atom constituting the dicyclopentane ring in the above general formula (a2-3) may be partially or wholly substituted with a fluorine atom, an alkyl group or the like. ..

More specific examples of the polymerizable monomer represented by the general formula (a2-3) include compounds represented by the following.

Among the polymerizable monomers having a dicyclopentane ring and a (meth) acryloyl group, the compound represented by the above formula (a2-3-2) is preferable because a resist composition having a high Tg of the coating film can be obtained. ..

Hereinafter, a polymerizable monomer having a dicyclopentene ring and a polymerizable unsaturated group, which can be preferably used as the polymerizable monomer (a2) in the present invention, will be described.

Examples of the polymerizable monomer having a dicyclopentene ring and a (meth) acryloyl group include a compound represented by the following formula (a2-4).

（式中、Ｒは水素原子、メチル基又はＣＦ_３を表す。）

(In the formula, R represents a hydrogen atom, a methyl group or CF _3. )

Further, in the compound represented by the above formula (a2-4), the (meth) acryloyl group may be bonded to any carbon atom in the dicyclopentene ring. Further, the hydrogen atom bonded to the carbon atom constituting the dicyclopentene ring in the above general formula (a2-3) may be partially or wholly substituted with a fluorine atom, an alkyl group or the like.

More specific examples of the polymerizable monomer represented by the general formula (a2-4) include compounds represented by the following.

Among the polymerizable monomers having a dicyclopentene ring and a (meth) acryloyl group, the compound represented by the above formula (a2-4-2) is preferable because a resist composition having a high Tg of the coating film can be obtained.

Hereinafter, a polymerizable monomer having a norbornane ring and a polymerizable unsaturated group, which can be preferably used as the polymerizable monomer (a2) in the present invention, will be described.

Examples of the polymerizable monomer having a norbornane ring and a (meth) acryloyl group include a compound represented by the following formula (a2-5).

（式中、Ｒは水素原子、メチル基又はＣＦ_３を表す。）

(In the formula, R represents a hydrogen atom, a methyl group or CF _3. )

Further, in the compound represented by the above formula (a2-5), the (meth) acryloyl group may be bonded to any carbon atom in the norbornane ring. Further, the hydrogen atom bonded to the carbon atom constituting the norbornane ring in the above general formula (a2-5) may be partially or wholly substituted with a fluorine atom, an alkyl group or the like.

More specific examples of the polymerizable monomer represented by the general formula (a2-5) include compounds represented by the following.

Among the polymerizable monomers having a norbornane ring and a (meth) acryloyl group, the compound represented by the above formula (a2-5-2) is preferable because a resist composition having a high Tg of the coating film can be obtained.

Hereinafter, a polymerizable monomer having a norbornene ring and a polymerizable unsaturated group, which can be preferably used as the polymerizable monomer (a2) in the present invention, will be described.

Examples of the polymerizable monomer having a norbornene ring and a (meth) acryloyl group include a compound represented by the following formula (a2-6).

（式中、Ｒは水素原子、メチル基又はＣＦ_３を表す。）

(In the formula, R represents a hydrogen atom, a methyl group or CF _3. )

Further, in the compound represented by the above formula (a2-6), the (meth) acryloyl group may be bonded to any carbon atom in the norbornene ring. Further, the hydrogen atom bonded to the carbon atom constituting the norbornene ring in the above general formula (a2-6) may be partially or wholly substituted with a fluorine atom, an alkyl group or the like.

More specific examples of the polymerizable monomer represented by the general formula (a2-6) include compounds represented by the following.

Among the polymerizable monomers having a norbornene ring and a (meth) acryloyl group, the compound represented by the above formula (a2-6-2) is preferable because a resist composition having a high Tg of the coating film can be obtained.

In the present invention, a polymerizable monomer (a1) having a fluorinated alkyl group having 1 to 6 carbon atoms to which a fluorine atom is directly bonded and a polymerizable unsaturated group, and a skeleton and a polymerizable ring hydrocarbon skeleton are polymerizable. It is a random copolymer with a polymerizable monomer (a2) having an unsaturated group, and the ratio (Mw / Mn) of the weight average molecular weight (Mw) to the number average molecular weight (Mn) is 1.0 to 1. Provided is a random copolymer characterized by being 1.8. Here, if the ratio (Mw / Mn) exceeds 1.8, a solid coating film surface cannot be formed, which is not preferable. The ratio (Mw / Mn) is more preferably in the range of 1.0 to 1.7, and even more preferably in the range of 1.0 to 1.5.

The weight average molecular weight (Mw) of the random copolymer of the present invention is preferably 500 to 200,000 because a more solid coating film surface can be obtained and the random copolymer has good leveling properties. , 1,000 to 150,000, more preferably 1,500 to 100,000.

Further, the number average molecular weight (Mn) of the random copolymer of the present invention is 300 to 120,000 because a more solid coating film surface can be obtained and the random copolymer has good leveling property. Is preferable, the range of 500 to 80,000 is more preferable, and the range of 800 to 60,000 is even more preferable.

Here, the number average molecular weight (Mn) and the weight average molecular weight (Mw) are values converted into polystyrene based on gel permeation chromatography (hereinafter abbreviated as “GPC”) measurement. The measurement conditions of GPC are as follows.

[GPC measurement conditions]
Measuring device: "HLC-8220 GPC" manufactured by Tosoh Corporation,
Column: Tosoh Co., Ltd. guard column "HHR-H" (6.0 mm I.D. x 4 cm) + Tosoh Co., Ltd. "TSK-GEL GMHHR-N" (7.8 mm I.D. x 30 cm) + Tosoh Co., Ltd. "TSK-GEL GMHHR-N" (7.8 mm I.D. x 30 cm) + Tosoh Co., Ltd. "TSK-GEL GMHHR-N" (7.8 mm I.D. x 30 cm) + Tosoh Co., Ltd. "TSK-" GEL GMHHR-N "(7.8 mm ID x 30 cm)
Detector: ELSD ("ELSD2000" manufactured by Oltec Japan Co., Ltd.)
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 velocity 1.0 ml / min Sample: A solution of 1.0 mass% tetrahydrofuran in terms of resin solid content filtered through a microfilter (5 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".

(Unidispersed 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

The fluorine atom content in the random copolymer of the present invention is preferably in the range of 4 to 40% by mass, preferably 5 to 35% by mass, because it is a random copolymer that exhibits good leveling properties with little coating unevenness. The range of% is more preferable, and the range of 6 to 30% by mass is further preferable. The fluorine atom content can be measured by combustion ion chromatography.

In the present invention, the random copolymer of the polymerizable monomer (a1) and the polymerizable monomer (a2) is a polymerizable monomer with the polymerizable monomer (a1) as long as the effects of the present invention are not impaired. It may have a structure derived from a polymerizable monomer (a3) other than the quanta (a2).

Examples of the polymerizable monomer (a3) include a monomer having an oxyalkylene group (a3-1) and a monomer having an alkyl group (a3-2). Here, examples of the polymerizable unsaturated group contained in the polymerizable monomer (a3) include a (meth) acryloyl group, a vinyl group, a maleimide group, and the like, and the polymerizable monomer (a1) and polymerization When the polymerizable unsaturated group of the sex monomer (a2) is a (meth) acryloyl group, the copolymerizability is good, and therefore the polymerizable unsaturated group of the polymerizable monomer (a3) has. The group is also preferably a (meth) acryloyl group.

Examples of the monomer having an oxyalkylene group (a3-1) include a monomer represented by the following general formula (a3-1).

（式中、Ｒ^２は水素原子又はメチル基であり、Ｙ^１Ｘ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との合計は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。）

(In the formula, R ² is a hydrogen atom or a methyl group, Y ¹ X and Y ² are independent alkylene groups, respectively, p and q are 0 or an integer of 1 or more, respectively, and p and q The total is 1 or more, and R ³ is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.)

^{Y 1} and Y ² in the above general formula (a3-1) are alkylene groups, and the alkylene groups include those having a substituent. As a specific example of the −O− (Y ¹ O) n− (Y ² O) m− moiety, an ethylene glycol residue in which the number of repetition units p is 1, m is 0, and Y ^{1 is ethylene, repetition.} A propylene glycol residue having a unit number p of 1 and m being 0 and Y ¹ being propylene, a butylene glycol residue having a repeating unit number p of 1 and m being 0 and Y ^{1 being butylene, repeating.} A polyethylene glycol residue in which the number of units p is an integer of 2 or more and q is 0 and Y ¹ is ethylene, and the number of repetitions p is an integer of 2 or more and q is 0 and Y ¹ is propylene. Polyalkylene residues such as ethylene oxide and propylene oxide copolymer residues in which the polypropylene glycol residue, the number of repeating units p and q are both integers of 1 or more, and Y ¹ or Y ^{2 is ethylene and the other is propylene.} Glycol residues can be mentioned.

The degree of polymerization of the polyalkylene glycol in the monomer (a3-1) having an oxyalkylene group, that is, the total of p and q in the general formula (a3-1) is preferably in the range of 1 to 100, 2 Those in the range of ~ 80 are more preferable, and those in the range of 3 to 50 are more preferable. The ^{repeating unit including Y 1} and the repeating unit including Y ² may be arranged randomly or in a block shape.

^{R 3} in the above general formula (a3-1) is hydrogen or an alkyl group having 1 to 6 carbon atoms. When R ³ is hydrogen, the monomer is a mono (meth) acrylic acid ester of alkylene glycol such as polyethylene glycol, polypropylene glycol, polybutylene glycol, and when R ³ has 1 to 6 carbon atoms, it is an alkylene. The non-(meth) acrylic acid ester of the mono (meth) acrylic acid ester of glycol is sealed with an alkyl group having 1 to 6 carbon atoms.

Among the monomers having an oxyalkylene group (a3-1), a monomer having a poly (oxyalkylene) group composed of a plurality of oxyalkylene groups is preferable, and a specific example is polypropylene glycol mono (meth). ) Acrylic, polyethylene glycol mono (meth) acrylate, polytrimethylene glycol mono (meth) acrylate, polytetramethylene glycol mono (meth) acrylate, 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 / tetramethylene glycol) mono (meth) acrylate, polypropylene Glycol / polytetramethylene glycol mono (meth) acrylate, poly (propylene glycol / butylene glycol) mono (meth) acrylate, polypropylene glycol / polybutylene glycol mono (meth) acrylate, poly (ethylene glycol / butylene glycol) mono (meth) Acrylic, 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) Acrylic, poly (ethylene glycol / trimethylene glycol) mono (meth) acrylate, polyethylene glycol / polytrimethylethylene glycol mono (meth) acrylate, poly (propylene glycol / trimethylene glycol) mono (meth) acrylate, polypropylene glycol / polytri Methylene glycol mono (meth) acrylate, poly (trimethylethylene glycol / tetramethylene glycol) mono (meth) acrylate, polytrimethylethylene glycol / polytetramethylene glycol mono (meth) acrylate, poly (butylene glycol / trimethylene glycol) mono ( Examples thereof include meta) acrylate, polybutylene glycol and polytrimethylene glycol mono (meth) acrylate. In addition, "poly (ethylene glycol / propylene glycol)" means a random copolymer of ethylene glycol and propylene glycol, and "polyethylene glycol / polypropylene glycol" is a block copolymer of ethylene glycol and propylene glycol. means. The same is true for other things. When a monomer having an oxyalkylene group (a3-1) is used in the method for producing a fluorine-containing polymer of the present invention, the compatibility with other components in the resist composition and the coating composition becomes good. Polypropylene glycol mono (meth) acrylate, polyethylene glycol mono (meth) acrylate, and polyethylene glycol / polypropylene glycol mono (meth) acrylate are preferable because a fluorine-containing polymer can be obtained.

Examples of commercially available products of the monomer (a3-1) having an oxyalkylene group include "NK ester M-20G", "NK ester M-40G" and "NK ester" manufactured by Shin-Nakamura Chemical Industry Co., Ltd. "M-90G", "NK Ester M-230G", "NK Ester AM-90G", "NK Ester AMP-10G", "NK Ester AMP-20G", "NK Ester AMP-60G", manufactured by Nichiyu Co., Ltd. "Blemmer PE-90", "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", "Blemmer 55PET-800", "Blemmer 50 POEP-800B", "Blemmer 10PPB-500B", "Blemmer 10PPB-500B" Examples thereof include "Blemmer NKH-5050", "Blemmer AP-400", and "Blemmer AE-350". These monomers having an oxyalkylene group (a3-1) can be used alone or in combination of two or more.

Examples of the monomer having an alkyl group (a3-2) include a monomer represented by the following general formula (a3-2).

（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.)

^{In addition, R 5} in the above general formula (a3-2) is an alkyl group having a linear, branched or ring structure having 1 to 18 carbon atoms, and this alkyl group is an aliphatic or aromatic group. It may have a substituent such as a hydrocarbon group or a hydroxyl group. Specific examples of the monomer (a3-2) having an alkyl group include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, octyl (meth) acrylate, and 2 -Alkyl esters of (meth) acrylic acids such as ethylhexyl (meth) acrylates, decyl (meth) acrylates, dodecyl (meth) acrylates, and stearyl (meth) acrylates having 1 to 18 carbon atoms; dicyclopentanyloxyl ethyl ( Meta) acrylate, isobornyloxylethyl (meth) acrylate, isobornyl (meth) acrylate, adamantyl (meth) acrylate, dimethyl adamantyl (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentenyl (meth) acrylate, etc. Examples thereof include bridging cyclic alkyl esters other than the above (a2) having 1 to 18 carbon atoms of the (meth) acrylic acid. These alkyl group-containing monomers (a3-2) can be used alone or in combination of two or more.

When the polymerizable monomer (a3) is used in combination with the polymerizable monomer (a1) and the polymerizable monomer (a2), the amount used is the monomer (a1) and the monomer (a2). 1 to 100 parts by mass with respect to 100 parts by mass in total suppresses the leveling property and the generation of foreign substances derived from a colorant such as a pigment, and can also exhibit various effects caused by the monomer (a3). It is preferable because a random copolymer can be obtained, and more preferably 1 to 50 parts by mass.

The random copolymer of the present invention, for example, bridges with a polymerizable monomer (a1) having a fluorinated alkyl group having 1 to 6 carbon atoms directly bonded to a fluorine atom and a polymerizable unsaturated group. A polymerizable monomer (a2) having a ring hydrocarbon skeleton and a polymerizable unsaturated group is subjected to living radical polymerization in the coexistence of the polymerizable monomer (a1) and the polymerizable monomer (a2). Therefore, it can be preferably obtained.

In the living radical polymerization, the growth reaction proceeds when the Dormant species whose active polymerization terminal is protected by an atom or an atomic group reversibly generates radicals and reacts with the monomer. Examples of such living radical polymerization include atom transfer radical polymerization (ATRP), reversible addition-cleavage radical polymerization (RAFT), nitroxide-mediated radical polymerization (NMP), and radical polymerization using organic tellurium (TERP). Can be mentioned. Which of these methods is used is not particularly limited, but the ATRP is preferable from the viewpoint of ease of control and the like. ATRP is polymerized using an organic halide, a sulfonyl halide compound or the like as an initiator, and a metal complex composed of a transition metal compound and a ligand as a catalyst.

An organic halogenated compound can be used as the polymerization initiator used in the ATRP. Specifically, 1-phenylethyl chloride and 1-phenylethyl bromide, chloroform, carbon tetrachloride, 2-chloropropionitrile, α, α'-dichloroxylene, α, α'-dibromoxylene, hexakis (α-). Bromomethyl) benzene, a 2-halogenated carboxylic acid having 1 to 6 carbon atoms (for example, 2-chloropropionic acid, 2-bromopropionic acid, 2-chloroisobutyric acid, 2-bromoisobutyric acid, etc.) having 1 to 6 carbon atoms. Examples thereof include alkyl esters. Further, more specific examples of the alkyl ester having 1 to 6 carbon atoms of the 2-halogenated carboxylic acid having 1 to 6 carbon atoms include, for example, methyl 2-chloropropionate, ethyl 2-chloropropionate, and the like. Examples thereof include methyl 2-bromopropionate and ethyl 2-bromoisobutyrate.

The transition metal compound used in the ATRP is represented by ^{M n +} X _n. The transition metals M ^{n +} are Cu ⁺ , Cu ²⁺ , Fe ²⁺ , Fe ³⁺ , Ru ²⁺ , Ru ³⁺ , Cr ²⁺ , Cr ³⁺ , Mo ⁰ , Mo ⁺ , Mo ²⁺ , Mo ³⁺ , W ²⁺ , W ³⁺ , Rh ³⁺ , Rh ⁴⁺ , Co ⁺ , Co ²⁺ , Re ²⁺ , Re ³⁺ , Ni ⁰ , Ni ⁺ , Mn ³⁺ , Mn ⁴⁺ , V ²⁺ , V ³⁺ , Zn ⁺ , Zn ²⁺ , Au ⁺ , Au ²⁺ , Ag ⁺ And can be selected from the group consisting of ^{Ag 2+.} Further, X is a halogen atom, an alkoxyl group having 1 to 6 carbon atoms, (S0 ₄ ) _1/2 , (P0 ₄ ) _1/3 , (HP0 ₄ ) _1/2 , (H ₂ P0 ₄ ), and a triflate. , Hexafluorophosphate, methane sulfonate, aryl sulfonate (preferably benzene sulfonate or toluene sulfonate), SeR ¹ , CN and R ² COO. Here, R ¹ represents an aryl, linear or branched alkyl group having 1 to 20 carbon atoms (preferably 1 to 10 carbon atoms), and R ² is a hydrogen atom or halogen and 1 to 5 carbon atoms. It represents a linear or branched alkyl group having 1 to 6 carbon atoms (preferably a methyl group) which may be substituted with fluorine or chlorine 1 to 6 times (preferably 1 to 3 times). Further, n represents a formal charge on the metal and is an integer of 0-7.

The transition metal complex is not particularly limited, but preferably, the transition metal complex of groups 7, 8, 9, 10, and 11 is preferable, and more preferably, 0-valent copper, monovalent copper, and divalent ruthenium. Examples include divalent iron or divalent nickel complexes.

Examples of the compound having a ligand capable of coordinating with the transition metal include a ligand containing one or more nitrogen atom, oxygen atom, phosphorus atom or sulfur atom capable of coordinating with the transition metal via a σ bond. A compound having a ligand having two or more carbon atoms that can be coordinated with a transition metal via a π bond, and a compound having a ligand having a ligand capable of coordinating with a transition metal via a μ bond or an η bond. Can be mentioned.

Specific examples of the compound having the above-mentioned ligand include 2,2'-bipyridyl and its derivatives, 1,10-phenanthroline and its derivatives, tetramethylethylenediamine, pentamethyldiethylenetriamine, and hexa, when the central metal is copper. Examples thereof include a complex with a ligand such as a polyamine such as methyltris (2-aminoethyl) amine. Examples of the divalent ruthenium complex include dichlorotris (triphenylphosphine) ruthenium, dichlorotris (tributylphosphine) ruthenium, dichloro (cyclooctadiene) ruthenium, dichlorobenzene ruthenium, dichlorop-simenruthenium, and dichloro (norbornadiene) ruthenium. Examples thereof include cis-dichlorobis (2,2'-bipyridine) ruthenium, dichlorotris (1,10-phenanthroline) ruthenium, and carbonylchlorohydridotris (triphenylphosphine) ruthenium. Further, examples of the divalent iron complex include a bistriphenylphosphine complex and a triazacyclononane complex.

Further, in the above-mentioned living radical polymerization, it is preferable to use a solvent. Examples of the solvent used include ester solvents such as ethyl acetate, butyl acetate and propylene glycol monomethyl ether acetate; ether solvents such as diisopropyl ether, dimethoxyethane and diethylene glycol dimethyl ether; halogen solvents such as dichloromethane and dichloroethane; toluene and Aromatic solvents such as xylene; ketone solvents such as methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone; alcohol solvents such as methanol, ethanol and isopropanol; aprotonic polar solvents such as dimethylformamide and dimethyl sulfoxide. In addition, these solvents can be used alone or in combination of two or more.

In the method for producing a random copolymer of the present invention, a polymerizable monomer (a1) is present in the presence of a polymerization initiator, a transition metal compound, a compound having a ligand capable of coordinating with the transition metal, and a solvent. ) And the polymerizable monomer (a2) are preferably subjected to living radical polymerization.

In the method for producing a random copolymer of the present invention, the ratio (reaction ratio) of the polymerizable monomer (a1) and the polymerizable monomer (a2) to be used is 100 parts by mass of the polymerizable monomer (a1). On the other hand, 50 to 900 parts by mass of the polymerizable monomer (a2) is preferable because a random copolymer having good leveling property and a high effect of suppressing pigment sublimation can be obtained. 100 to 800 parts by mass of the polymerizable monomer (a2) is more preferable with respect to parts by mass.

The polymerization temperature during living radical polymerization is preferably in the range of room temperature to 120 ° C.

Further, when the random copolymer of the present invention is produced by the method for producing a random copolymer of the present invention, a metal due to the transition metal compound may remain in the random copolymer. Therefore, when a random copolymer is used by the production method of the present invention for semiconductor applications such as photoresist compositions that cause problems when metals remain, it is possible to remove the residual metal using activated alumina or the like after the polymerization reaction. preferable.

The present invention is polymerizable with the random copolymer of the present invention (hereinafter, this may be referred to as "random copolymer (A)"), the colorant (B), and the alkali-soluble resin (C). Provided is a resist composition characterized by containing the compound (D). The resist composition comprises, for example, a polymerizable monomer (a1) having a fluorinated alkyl group having 1 to 6 carbon atoms directly bonded to the fluorine atom and a polymerizable unsaturated group, and a bridging ring hydrocarbon. Living radical polymerization of a polymerizable monomer (a2) having a skeleton and a polymerizable unsaturated group in the coexistence of a polymerizable monomer (a1) and a polymerizable monomer (a2) Includes a step of obtaining a random copolymer (A) of radical polymerization and a step of mixing the random copolymer (A), a colorant (B), an alkali-soluble resin (C), and a polymerizable compound (D). It can be preferably provided by a method for producing a resist composition, which is characterized by the above. The step of obtaining the random copolymer (A) is a step corresponding to the method for producing a random copolymer of the present invention.

Examples of the colorant (B) include pigments and dyes, and the pigments may be organic pigments or inorganic pigments. As the organic pigment, pigments having various hues such as red pigment, green pigment, blue pigment, yellow pigment, purple pigment, and orange pigment can be used. The chemical structures of organic pigments include, for example, quinacridone, perylene, pyrrolo-pyrrole, anthraquinone, phthalocyanine, indanslen, halogenated phthalocyanine, tetrachloroisoindolenone, and Hansa yellow. Benzidine yellow type, azo type, aventuimidazolone type, isoindolinone type, dioxazine type, and the like can be mentioned. The following "CI" means a color index (CI; published by The Society of Dyers and Colorists).

Examples of the red pigment include C.I. I. Pigment Red 1, C.I. I. Pigment Red 2, C.I. I. Pigment Red 3, C.I. I. Pigment Red 4, C.I. I. Pigment Red 5, C.I. I. Pigment Red 6, C.I. I. Pigment Red 7, C.I. I. Pigment Red 8, C.I. I. Pigment Red 9, C.I. I. Pigment Red 12, C.I. I. Pigment Red 14, C.I. I. Pigment Red 15, C.I. I. Pigment Red 16, C.I. I. Pigment Red 17, C.I. I. Pigment Red 21, C.I. I. Pigment Red 22, C.I. I. Pigment Red 23, C.I. I. Pigment Red 31, C.I. I. Pigment Red 32, C.I. I. Pigment Red 37, C.I. I. Pigment Red 38, C.I. I. Pigment Red 41, C.I. I. Pigment Red 47, C.I. I. Pigment Red 48, C.I. I. Pigment Red 48: 1, C.I. I. Pigment Red 48: 2, C.I. I. Pigment Red 48: 3, C.I. I. Pigment Red 48: 4, C.I. I. Pigment Red 49, C.I. I. Pigment Red 49: 1, C.I. I. Pigment Red 49: 2, C.I. I. Pigment Red 50: 1, C.I. I. Pigment Red 52: 1, C.I. I. Pigment Red 52: 2, C.I. I. Pigment Red 53, C.I. I. Pigment Red 53: 1, C.I. I. Pigment Red 53: 2, C.I. I. Pigment Red 53: 3, C.I. I. Pigment Red 57, C.I. I. Pigment Red 57: 1, C.I. I. Pigment Red 57: 2, C.I. I. Pigment Red 58: 4, C.I. I. Pigment Red 60, C.I. I. Pigment Red 63, C.I. I. Pigment Red 63: 1, C.I. I. Pigment Red 63: 2, C.I. I. Pigment Red 64, C.I. I. Pigment Red 64: 1, C.I. I. Pigment Red 68, C.I. I. Pigment Red 69, C.I. I. Pigment Red 81, C.I. I. Pigment Red 81: 1, C.I. I. Pigment Red 81: 2, C.I. I. Pigment Red 81: 3, C.I. I. Pigment Red 81: 4, C.I. I. Pigment Red 83, C.I. I. Pigment Red 88, C.I. I. Pigment Red 90: 1, C.I. I. Pigment Red 97, C.I. I. Pigment Red 101, C.I. I. Pigment Red 101: 1, C.I. I. Pigment Red 104, C.I. I. Pigment Red 108, C.I. I. Pigment Red 108: 1, C.I. I. Pigment Red 109, C.I. I. Pigment Red 112, C.I. I. Pigment Red 113, C.I. I. Pigment Red 114, C.I. I. Pigment Red 122, C.I. I. Pigment Red 123, C.I. I. Pigment Red 144, C.I. I. Pigment Red 146, C.I. I. Pigment Red 147, C.I. I. Pigment Red 149, C.I. I. Pigment Red 151, C.I. I. Pigment Red 166, C.I. I. Pigment Red 168, C.I. I. Pigment Red 169, C.I. I. Pigment Red 170, C.I. I. Pigment Red 172, C.I. I. Pigment Red 173, C.I. I. Pigment Red 174, C.I. I. Pigment Red 175, C.I. I. Pigment Red 176, C.I. I. Pigment Red 177, C.I. I. Pigment Red 178, C.I. I. Pigment Red 179, C.I. I. Pigment Red 180, C.I. I. Pigment Red 181 and C.I. I. Pigment Red 184, C.I. I. Pigment Red 185, C.I. I. Pigment Red 187, C.I. I. Pigment Red 188, C.I. I. Pigment Red 190, C.I. I. Pigment Red 192, C.I. I. Pigment Red 193, C.I. I. Pigment Red 194, C.I. I. Pigment Red 200, C.I. I. Pigment Red 202, C.I. I. Pigment Red 206, C.I. I. Pigment Red 207, C.I. I. Pigment Red 208, C.I. I. Pigment Red 209, C.I. I. Pigment Red 210, C.I. I. Pigment Red 213, C.I. I. Pigment Red 214, C.I. I. Pigment Red 215, C.I. I. Pigment Red 216, C.I. I. Pigment Red 217, C.I. I. Pigment Red 220, C.I. I. Pigment Red 221 and C.I. I. Pigment Red 223, C.I. I. Pigment Red 224, C.I. I. Pigment Red 226, C.I. I. Pigment Red 227, C.I. I. Pigment Red 228, C.I. I. Pigment Red 230, C.I. I. Pigment Red 231 and C.I. I. Pigment Red 232, C.I. I. Pigment Red 233, C.I. I. Pigment Red 235, C.I. I. Pigment Red 236, C.I. I. Pigment Red 237, C.I. I. Pigment Red 238, C.I. I. Pigment Red 239, C.I. I. Gument Red 240, C.I. I. Pigment Red 242, C.I. I. Pigment Red 243, C.I. I. Pigment Red 245, C.I. I. Pigment Red 247, C.I. I. Pigment Red 249, C.I. I. Pigment Red 250, C.I. I. Pigment Red 251 and C.I. I. Pigment Red 253, C.I. I. Pigment Red 254, C.I. I. Pigment Red 255, C.I. I. Pigment Red 256, C.I. I. Pigment Red 257, C.I. I. Pigment Red 258, C.I. I. Pigment Red 259, C.I. I. Pigment Red 260, C.I. I. Pigment Red 262, C.I. I. Pigment Red 263, C.I. I. Pigment Red 264, C.I. I. Pigment Red 265, C.I. I. Pigment Red 266, C.I. I. Pigment Red 267, C.I. I. Pigment Red 268, C.I. I. Pigment Red 269, C.I. I. Pigment Red 270, C.I. I. Pigment Red 271, C.I. I. Pigment Red 272, C.I. I. Pigment Red 273, C.I. I. Pigment Red 274, C.I. I. Pigment Red 275, C.I. I. Pigment Red 276 and the like.

Examples of the green pigment include C.I. I. Pigment Green 1, C.I. I. Pigment Green 2, C.I. I. Pigment Green 4, C.I. I. Pigment Green 7, C.I. I. Pigment Green 8, C.I. I. Pigment Green 10, C.I. I. Pigment Green 13, C.I. I. Pigment Green 14, C.I. I. Pigment Green 15, C.I. I. Pigment Green 17, C.I. I. Pigment Green 18, C.I. I. Pigment Green 19, C.I. I. Pigment Green 26, C.I. I. Pigment Green 36, C.I. I. Pigment Green 45, C.I. I. Pigment Green 48, C.I. I. Pigment Green 50, C.I. I. Pigment Green 51, C.I. I. Pigment Green 54, C.I. I. Pigment Green 55, C.I. I. Pigment Green 58, C.I. I. Pigment Green 59 and the like.

Examples of the blue pigment include C.I. I. Pigment Blue 1, C.I. I. Pigment Blue 1: 2, C.I. I. Pigment Blue 9, C.I. I. Pigment Blue 14, C.I. I. Pigment Blue 15, C.I. I. Pigment Blue 15: 1, C.I. I. Pigment Blue 15: 2, C.I. I. Pigment Blue 15: 3, C.I. I. Pigment Blue 15: 4, C.I. I. Pigment Blue 15: 6, C.I. I. Pigment Blue 16, C.I. I. Pigment Blue 17, C.I. I. Pigment Blue 19, C.I. I. Pigment Blue 22, C.I. I. Pigment Blue 25, C.I. I. Pigment Blue 27, C.I. I. Pigment Blue 28, C.I. I. Pigment Blue 29, C.I. I. Pigment Blue 33, C.I. I. Pigment Blue 35, C.I. I. Pigment Blue 36, C.I. I. Pigment Blue 56, C.I. I. Pigment Blue 56: 1, C.I. I. Pigment Blue 60, C.I. I. Pigment Blue 61, C.I. I. Pigment Blue 61: 1, C.I. I. Pigment Blue 62, C.I. I. Pigment Blue 63, C.I. I. Pigment Blue 64, C.I. I. Pigment Blue 66, C.I. I. Pigment Blue 67, C.I. I. Pigment Blue 68, C.I. I. Pigment Blue 71, C.I. I. Pigment Blue 72, C.I. I. Pigment Blue 73, C.I. I. Pigment Blue 74, C.I. I. Pigment Blue 75, C.I. I. Pigment Blue 76, C.I. I. Pigment Blue 78, C.I. I. Pigment Blue 79 and the like.

Examples of the yellow pigment include C.I. I. Pigment Yellow 1, C.I. I. Pigment Yellow 1: 1, C.I. I. Pigment Yellow 2, C.I. I. Pigment Yellow 3, C.I. I. Pigment Yellow 4, C.I. I. Pigment Yellow 5, C.I. I. Pigment Yellow 6, C.I. I. Pigment Yellow 9, C.I. I. Pigment Yellow 10, C.I. I. Pigment Yellow 12, C.I. I. Pigment Yellow 13, C.I. I. Pigment Yellow 14, C.I. I. Pigment Yellow 16, C.I. I. Pigment Yellow 17, C.I. I. Pigment Yellow 20, C.I. I. Pigment Yellow 24, C.I. I. Pigment Yellow 31, C.I. I. Pigment Yellow 32, C.I. I. Pigment Yellow 34, C.I. I. Pigment Yellow 35, C.I. I. Pigment Yellow 35: 1, C.I. I. Pigment Yellow 36, C.I. I. Pigment Yellow 36: 1, C.I. I. Pigment Yellow 37, C.I. I. Pigment Yellow 37: 1, C.I. I. Pigment Yellow 40, C.I. I. Pigment Yellow 41, C.I. I. Pigment Yellow 42, C.I. I. Pigment Yellow 43, C.I. I. Pigment Yellow 48, C.I. I. Pigment Yellow 53, C.I. I. Pigment Yellow 55, C.I. I. Pigment Yellow 61, C.I. I. Pigment Yellow 62, C.I. I. Pigment Yellow 62: 1, C.I. I. Pigment Yellow 63, C.I. I. Pigment Yellow 65, C.I. I. Pigment Yellow 73, C.I. I. Pigment Yellow 74, C.I. I. Pigment Yellow 75, C.I. I. Pigment Yellow 81, C.I. I. Pigment Yellow 83, C.I. I. Pigment Yellow 86, C.I. I. Pigment Yellow 87, C.I. I. Pigment Yellow 93, C.I. I. Pigment Yellow 94, C.I. I. Pigment Yellow 95, C.I. I. Pigment Yellow 97, C.I. I. Pigment Yellow 100, C.I. I. Pigment Yellow 101, C.I. I. Pigment Yellow 104, C.I. I. Pigment Yellow 105, C.I. I. Pigment Yellow 108, C.I. I. Pigment Yellow 109, C.I. I. Pigment Yellow 110, C.I. I. Pigment Yellow 111, C.I. I. Pigment Yellow 116, C.I. I. Pigment Yellow 117, C.I. I. Pigment Yellow 119, C.I. I. Pigment Yellow 120, C.I. I. Pigment Yellow 125, C.I. I. Pigment Yellow 126, C.I. I. Pigment Yellow 127, C.I. I. Pigment Yellow 127: 1, C.I. I. Pigment Yellow 128, C.I. I. Pigment Yellow 129, C.I. I. Pigment Yellow 133, C.I. I. Pigment Yellow 134, C.I. I. Pigment Yellow 136, C.I. I. Pigment Yellow 137, C.I. I. Pigment Yellow 138, C.I. I. Pigment Yellow 139, C.I. I. Pigment Yellow 142, C.I. I. Pigment Yellow 147, C.I. I. Pigment Yellow 148, C.I. I. Pigment Yellow 150, C.I. I. Pigment Yellow 151, C.I. I. Pigment Yellow 153, C.I. I. Pigment Yellow 154, C.I. I. Pigment Yellow 155, C.I. I. Pigment Yellow 157, C.I. I. Pigment Yellow 158, C.I. I. Pigment Yellow 159, C.I. I. Pigment Yellow 160, C.I. I. Pigment Yellow 161 and C.I. I. Pigment Yellow 162, C.I. I. Pigment Yellow 163, C.I. I. Pigment Yellow 164, C.I. I. Pigment Yellow 165, C.I. I. Pigment Yellow 166, C.I. I. Pigment Yellow 167, C.I. I. Pigment Yellow 168, C.I. I. Pigment Yellow 169, C.I. I. Pigment Yellow 170, C.I. I. Pigment Yellow 172, C.I. I. Pigment Yellow 173, C.I. I. Pigment Yellow 174, C.I. I. Pigment Yellow 175, C.I. I. Pigment Yellow 176, C.I. I. Pigment Yellow 180, C.I. I. Pigment Yellow 181 and C.I. I. Pigment Yellow 182, C.I. I. Pigment Yellow 183, C.I. I. Pigment Yellow 184, C.I. I. Pigment Yellow 185, C.I. I. Pigment Yellow 188, C.I. I. Pigment Yellow 189, C.I. I. Pigment Yellow 190, C.I. I. Pigment Yellow 191 and C.I. I. Pigment Yellow 191: 1, C.I. I. Pigment Yellow 192, C.I. I. Pigment Yellow 193, C.I. I. Pigment Yellow 194, C.I. I. Pigment Yellow 195, C.I. I. Pigment Yellow 196, C.I. I. Pigment Yellow 197, C.I. I. Pigment Yellow 198, C.I. I. Pigment Yellow 199, C.I. I. Pigment Yellow 200, C.I. I. Pigment Yellow 202, C.I. I. Pigment Yellow 203, C.I. I. Pigment Yellow 204, C.I. I. Pigment Yellow 205, C.I. I. Pigment Yellow 206, C.I. I. Pigment Yellow 207, C.I. I. Pigment Yellow 208 and the like.

Examples of the purple pigment include C.I. I. Pigment Violet 1, C.I. I. Pigment Violet 1: 1, C.I. I. Pigment Violet 2, C.I. I. Pigment Violet 2: 2, C.I. I. Pigment Violet 3, C.I. I. Pigment Violet 3: 1, C.I. I. Pigment Violet 3: 3, C.I. I. Pigment Violet 5, 5: 1, C.I. I. Pigment Violet 14, C.I. I. Pigment Violet 15, C.I. I. Pigment Violet 16, C.I. I. Pigment Violet 19, C.I. I. Pigment Violet 23, C.I. I. Pigment Violet 25, C.I. I. Pigment Violet 27, C.I. I. Pigment Violet 29, Pigment Violet 30, C.I. I. Pigment Violet 31, C.I. I. Pigment Violet 32, C.I. I. Pigment Violet 37, C.I. I. Pigment Violet 39, Pigment Violet 40, C.I. I. Pigment Violet 42, C.I. I. Pigment Violet 44, C.I. I. Pigment Violet 47, C.I. I. Pigment Violet 49, C.I. I. Pigment Violet 50 and the like.

Examples of the orange pigment include C.I. I. Pigment Orange 1, C.I. I. Pigment Orange 2, C.I. I. Pigment Orange 5, C.I. I. Pigment Orange 13, C.I. I. Pigment Orange 16, C.I. I. Pigment Orange 17, C.I. I. Pigment Orange 19, C.I. I. Pigment Orange 20, C.I. I. Pigment Orange 21, C.I. I. Pigment Orange 22, C.I. I. Pigment Orange 23, C.I. I. Pigment Orange 24, C.I. I. Pigment Orange 34, C.I. I. Pigment Orange 36, C.I. I. Pigment Orange 38, C.I. I. Pigment Orange 39, C.I. I. Pigment Orange 43, C.I. I. Pigment Orange 46, C.I. I. Pigment Orange 48, C.I. I. Pigment Orange 49, C.I. I. C. I. Pigment Orange 51, C.I. I. Pigment Orange 55, C.I. I. Pigment Orange 59, Pigment Orange 61, C.I. I. Pigment Orange 62, C.I. I. Pigment Orange 64, C.I. I. Pigment Orange 65, C.I. I. Pigment Orange 67, C.I. I. Pigment Orange 68, C.I. I. Pigment Orange 69, C.I. I. Pigment Orange 70, C.I. I. Pigment Orange 71, C.I. I. Pigment Orange 72, C.I. I. Pigment Orange 73, C.I. I. Pigment Orange 74, C.I. I. Pigment Orange 75, C.I. I. Pigment Orange 77, C.I. I. Pigment Orange 78, C.I. I. Pigment Orange 79 and the like.

Since each pixel of the three primary colors of the color filter used in the liquid crystal display device and the organic EL display device is red (R), green (G), and blue (B), the red pigment, the green pigment, and the blue pigment are the main components. Therefore, for the purpose of improving color reproducibility, the 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, red iron oxide, and chromium oxide.

Examples of the dye used in the present invention include the following (b1).

A salt represented by, a xanthene dye, or the like can be preferably exemplified.

Examples of the xanthene dye include C.I. I. Acid Red 51, 52, 87, 92, 289, 388, C.I. I. Acid Violet 9, 30, C.I. I. Basic Red 8, C.I. I. Examples thereof include Modant Red 27, Rose Bengal B, Sulforhodamine G, Rhodamine 6G, and xanthene dyes described in JP-A-2010-032999 and JP-A-2011-13894.

Among the xanthene dyes, the following formula (b2)

[In the formula (1), R ^{1 to} R ⁴ independently represent a hydrogen atom, −R ⁸ or a monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms, and the aromatic hydrocarbon group can be used as the aromatic hydrocarbon group. hydrogen atoms contained is a halogen _{^{atom, -R 8, -OH, -OR 8}} , -SO 3 -, - SO 3 H, -SO 3 - M +, -CO 2 H, -CO 2 R 8, -SO _It may be replaced with 3 R ⁸ or -SO ₂ NR ⁹ R ^10.
R ^{5 _{is, -OH, -SO 3 -, -}} SO 3 H, -SO 3 - M +, -CO 2 H, -CO 2 - M +, -CO 2 R 8, -SO 3 R 8 or -SO Represents ₂ NR ⁹ R ^10.
m represents an integer from 0 to 5. When m is an integer of 2 or more, the plurality of R ^5s are the same or different.
R ⁶ and R ⁷ each independently represent an alkyl group having 1 to 6 carbon atoms.
M ⁺ represents ⁺ N (R ¹¹ ) ₄ , Na ⁺ or K ⁺ .
X represents a halogen atom.
a represents an integer of 0 or 1.
R ⁸ represents a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms, and the hydrogen atom contained in the saturated hydrocarbon group may be substituted with a halogen atom.
R ¹¹ independently represents a hydrogen atom, a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms, or an aralkyl group having 7 to 10 carbon atoms.
R ⁹ and R ¹⁰ each independently represent a hydrogen atom or a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms, and the hydrogen atom contained in the saturated hydrocarbon group is -OH or a halogen atom. may be substituted, _-CH 2 contained in the saturated aliphatic hydrocarbon group - is, -O -, - CO -, - NH- or -NR ⁸ - may have I placed conversion in, ^{R 9} And R ¹⁰ may be bonded to each other to form a 3- to 10-membered heterocycle containing a nitrogen atom. ]

A dye containing the compound represented by (1) as a main component is preferable.

^{Examples of the monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms in R 1 to} R ⁴ in the formula (b2) include a phenyl group, a toluyl group, a xsilyl group, a mesityl group, a propylphenyl group and a butyl group. Examples include a phenyl group.

The monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms in the above formula (b2) has -SO _{3- , -SO 3} H, -SO ₃ ^- M ⁺ and -SO ₂ NR ⁹ R as substituents. ^{It is preferable to have at least one selected from the group consisting of 10,} and more preferably to have at least one selected from the group consisting of -SO ₃ ^- M ⁺ and -SO ₂ NR ⁹ R ^10. preferable. In this case, as −SO ₃ ⁻ M ⁺ , −SO ₃ ^{− +} N (R ¹¹ ) ₄ is preferable. When R ^{1 to} R ⁴ are these groups, it can be expected that the resist composition can obtain a coating film layer having less foreign matter generated and excellent heat resistance.

^{Examples of the monovalent saturated hydrocarbon group having 1 to 20 carbon atoms in R 8 to} R ¹¹ in the formula (b2) include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group and an isobutyl group. Alkyl group having 1 to 20 carbon atoms such as pentyl group, isopentyl group, neopentyl group, hexyl group, heptyl group, octyl group, 2-ethylhexyl group, nonyl group, decyl group, dodecyl group, hexadecyl group, icosyl group; cyclopropyl Examples thereof include a cycloalkyl group having 3 to 20 carbon atoms such as a group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group and a tricyclodecyl group.

^{Examples of the alkyl group having 1 to 6 carbon atoms in R 6} and R ⁷ in the formula (b2) include those having 1 to 6 carbon atoms among the alkyl groups listed above.

^{Examples of the aralkyl group having 7 to 10 carbon atoms in R 11} in the formula (b2) include a benzyl group, a phenylethyl group, a phenylbutyl group and the like.

The M ⁺ is, for example, ⁺ N (R ¹¹ ) ₄ , Na ⁺ or K ⁺ , preferably ⁺ N (R ¹¹ ) ₄ . The ⁺ a N ^(R _{11) 4,} for example, of the four ^{R 11,} it is preferred that at least two of a monovalent saturated hydrocarbon group having 5 to 20 carbon atoms. The total number of carbon atoms of the four ^{R 11} is preferably 20 to 80, 20 to 60 is more preferable. When R ¹¹ is these groups, the resist composition of the present invention can be expected to form a colored coating film or a pattern with few foreign substances.

Further, among the xanthene dyes, the following formula (b3)

[In the formula (b3), R ^{21 to} R ²⁴ each independently represent a hydrogen atom, -R ^26, or a monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms, and the aromatic hydrocarbon group can be used as the aromatic hydrocarbon group. hydrogen atoms contained _{^{in, -SO 3 -, - SO 3}} - M a +, -SO 3 H, optionally substituted by -SO ^{3 R 26} or _-SO 2 ^{NHR 26.}
X represents a halogen atom.
a1 represents an integer of 0 or 1.
m1 represents an integer from 0 to 5. When m1 is an integer of 2 or more, the plurality of R ^25s are the same or different.
Ma ⁺ represents ⁺ N (R ²⁷ ) ₄ , Na ⁺ or K ⁺ .
R ²⁵ _is, -SO 3 ^_-, - representing the M a +, -SO ₃ H or _SO 2 ^{NHR 26 -} _SO ^3.
R ²⁶ represents a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms.
R ²⁷ independently represents a monovalent saturated hydrocarbon group or benzyl group having 1 to 20 carbon atoms. ]

The dye represented by is more preferable.

The monovalent aromatic hydrocarbon groups having 6 to 10 carbon atoms in ^{R 21 to} R ²⁴ in the formula (b3) are the same as those listed as the aromatic hydrocarbon groups in ^{R 1 to} R ^{4, for example.} The basis of is mentioned. Among them, R ²¹ and R ²³ are hydrogen atoms, R ²² and R ²⁴ are monovalent aromatic hydrocarbon groups having 6 to 10 carbon atoms, and the hydrogen atoms contained in the aromatic hydrocarbon groups are-. _{^{SO 3 -, - SO 3- M}} +, -SO 3 H, it is preferable that may be substituted by -SO ^{3 R 26} or _-SO 2 ^{NHR 26.} Further, R ²¹ and R ²³ are hydrogen atoms, and R ²² and R ²⁴ are monovalent aromatic hydrocarbon groups having 6 to 10 carbon atoms, and the hydrogen atoms contained in the aromatic hydrocarbon groups are Those substituted with −SO ₃ ⁻ M ⁺ or −SO ₂ NHR ^{26 are preferred.} When R ^{21 to} R ²⁴ are these groups, it is expected that the resist composition containing the compound (b-2-3) can form a colored coating film or a pattern having excellent heat resistance.

The monovalent saturated hydrocarbon groups having 1 to 20 carbon atoms in ^{R 26} and R ²⁷ in the formula (b3) are the same as those listed as the saturated hydrocarbon groups in ^{R 8 to} R ^{11, for example.} The group etc. can be mentioned.

It is preferable that -R ^{26 in R 21 to} R ²⁴ in the formula (b3) is a hydrogen atom, a methyl group or an ethyl group, respectively.

Formula (b3) as ^{R 26} in ^-SO 3 ^{R 26} and _-SO 2 ^{NHR 26} in the preferred branched alkyl group having 3 to 20 carbon atoms, branched chain having 6 to 12 carbon atoms Alkyl groups are more preferred, and 2-ethylhexyl groups are even more preferred. When R ²⁶ is these groups, it is expected that the resist composition containing the compound (b3) can form a colored coating film or a pattern with less generation of foreign substances.

The Ma ⁺ is ⁺ N (R ²⁷ ) ₄ , Na ⁺ or K ⁺ , preferably ⁺ N (R ²⁷ ) ₄ . The ⁺ a N ^(R _{27) 4,} among the four ^{R 27,} it is preferred that at least two of a monovalent saturated hydrocarbon group having 5 to 20 carbon atoms. The total number of carbon atoms of the four ^{R 27} is preferably 20 to 80, 20 to 60 is more preferable. It is expected that the resist composition containing the compound (b3) in which R ²⁷ is a group thereof can form a coating film layer or a pattern in which a small amount of foreign matter is generated.

Preferred xanthene dyes that can be used in the present invention include, for example, dyes containing compounds represented by the formulas (b4) to (b21) as main components. In the following formula, Ra represents a 2-ethylhexyl group.

Among the compounds that are the main components of xanthene dyes, C.I. I. Sulfonamides of Acid Red 289 or C.I. I. A quaternary ammonium salt of Acid Red 289 is preferred. Examples of such compounds include compounds represented by formulas (b4) to (b11), formulas (b16) and formulas (b17).

The compound represented by the formula (b1) is, for example, -SO 3 _H and chlorination by a conventional method the dye or dye intermediate having a dye or dye intermediate having a -SO 2 _Cl obtained with R ⁸ - It can be produced by reacting with an amine represented by NH _2. Further, the dye produced by the method described in the upper right column to the lower left column on page 3 of JP-A-3-78702 can also be produced by reacting with an amine after chlorination in the same manner as described above.

As the dye (b2) used in the present invention, other dyes other than the salt represented by the formula (b1) and the xanthene dye can also be used. Examples of the other dyes include oil-soluble dyes, acid dyes, dyes such as amine salts of acid dyes and sulfonamide derivatives of acid dyes, and specifically, for example, Color Index (The Society of Dyeers). Examples thereof include compounds classified as dyes by and Colorists (published by and Colorists) and various dyes described in dyeing notes (color dyeing company).

Examples of the other dye include C.I. I. Solvent Yellow 4 (Hereinafter, the description of CI Solvent Yellow is omitted and only the number is described), 14, 15, 23, 24, 38, 62, 63, 68, 82, 94, 98, 99. ,; C.I. I. Solvent Red 45, 49, 125, 130; C.I. I. Solvent Orange 2, 7, 11, 15, 26, 56; etc. I. Solvent dye,

C. I. Acid Yellow 1, 3, 7, 9, 11, 17, 23, 25, 29, 34, 36, 38, 40, 42, 54, 65, 72, 73, 76, 79, 98, 99, 111, 112, 113, 114, 116, 119, 123, 128, 134, 135, 138, 139, 140, 144, 150, 155, 157, 160, 161, 163, 168, 169, 172, 177, 178, 179, 184, 190, 193, 196, 197, 199, 202, 203, 204, 205, 207, 212, 214, 220, 221 228, 230, 232, 235, 238, 240, 242, 243, 251;

C. I. Acid Red 1, 4, 8, 14, 17, 18, 26, 27, 29, 31, 34, 35, 37, 42, 44, 50, 51, 52, 57, 66, 73, 80, 87, 88, 91, 92, 94, 97, 103, 111, 114, 129, 133, 134, 138, 143, 145, 150, 151, 158, 176, 182, 183, 198, 206, 211, 215, 216, 217, 227, 228, 249, 252, 257, 258, 260, 261, 266, 268, 270, 274, 277, 280, 281, 195, 308, 312, 315, 316, 339, 341, 345, 346, 349, 382, 383, 394, 401, 412, 417, 418, 422, 426;

C. I. Acid Orange 6, 7, 8, 10, 12, 26, 50, 51, 52, 56, 62, 63, 64, 74, 75, 94, 95, 107, 108, 169, 173;

C. I. Acid Violet 6B, 7, 9, 17, 19; etc. I. Acid dye,

C. I. Direct Yellow 2, 33, 34, 35, 38, 39, 43, 47, 50, 54, 58, 68, 69, 70, 71, 86, 93, 94, 95, 98, 102, 108, 109, 129, 136, 138, 141;

C. I. Direct Red 79, 82, 83, 84, 91, 92, 96, 97, 98, 99, 105, 106, 107, 172, 173, 176, 177, 179, 181, 182, 184, 204, 207, 211, 213, 218, 220, 221, 222, 232, 233, 234, 241, 243, 246, 250;

C. I. Direct Orange 34, 39, 41, 46, 50, 52, 56, 57, 61, 64, 65, 68, 70, 96, 97, 106, 107; C.I. I. Direct Violet 47, 52, 54, 59, 60, 65, 66, 79, 80, 81, 82, 84, 89, 90, 93, 95, 96, 103, 104; etc. I. Direct dye,

C. I. Modant Yellow 5, 8, 10, 16, 20, 26, 30, 31, 33, 42, 43, 45, 56, 61, 62, 65;

C. I. Modant Red 1, 2, 3, 4, 9, 11, 12, 14, 17, 18, 19, 22, 23, 24, 25, 26, 30, 32, 33, 36, 37, 38, 39, 41 , 43, 45, 46, 48, 53, 56, 63, 71, 74, 85, 86, 88, 90, 94, 95;

C. I. Modant Orange 3, 4, 5, 8, 12, 13, 14, 20, 21, 23, 24, 28, 29, 32, 34, 35, 36, 37, 42, 43, 47, 48;

C. I. Modant Violet 1, 2, 4, 5, 7, 14, 22, 24, 30, 31, 32, 37, 40, 41, 44, 45, 47, 48, 53, 58; etc. I. Examples include modern dyes.

On the other hand, the colorant (B) used to form the black matrix (BM) is not particularly limited as long as it is black, but for example, carbon black, a metal oxide, or two or more kinds of metal oxides. Pigments such as composite metal compounds composed of are preferable. Further, a combination of two or more kinds of organic pigments selected from pigments having hues of red, blue, green, purple, yellow, cyan and magenta and making them black by mixing may be used.

Examples of the carbon black include lamp black, acetylene black, thermal black, channel black, furnace black and the like. Examples of the metal oxide include titanium black obtained by oxidizing titanium or reducing titanium dioxide. Usually, titanium _{black, Ti m O 2m-1 (} m is a number of 1 or more) is expressed by. Further, examples of the metal oxide include metal oxides such as copper, iron, chromium, manganese and cobalt. Further, examples of the composite metal compound composed of two or more kinds of metal oxides include copper-chromium oxide, copper-chromium-manganese oxide, copper-iron-manganese oxide or cobalt-iron-manganese. Oxides and the like can be mentioned.

Examples of commercially available carbon black products 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 Etc., Printex3, Printex3OP, Printex30, Printex30OP, Printex40, Printex45, Printex55, Printex60, Printex75, Printex80, Printex85, Printex90, PrintexA , Printex V, PrintexG, SpecialBlack550, SpecialBlack 350, SpecialBlack250, SpecialBlack100, SpecialBlack6, SpecialBlack5, SpecialBlack4, Color Black FW1, Color Black FW2, Color Black FW2V, Color Black FW18, Color Black FW18, Color Black FW200, Color Black S160, Color Black S170, Monarch 120, Monarch 280, Monarch 460, Monarch 800, Monarch 880, Monarch 900, Monarch 1000, Monarch 1100, Monarch 1300, Monarch 1400, Monarch 1300, Monarch 1400, Monarch 4630, REGAL99, REGAL REGAL66 0R, BLACK PEARLS480, PEARLS130, VULCAN XC72R, ELFTEX-8, etc., RAVEN11, RAVEN14, RAVEN15, RAVEN16, RAVEN22RAVEN30, RAVEN35, RAVEN40, RAVEN410, RAVEN4 RAVEN1000, RAVEN1020, RAVEN1040, RAVEN1060U, RAVEN1080U, RAVEN1170, RAVEN1190U, RAVEN1250, RAVEN1500, RAVEN2000, RAVEN2500U, RAVEN3500, RAVEN5000, RAVEN5250, RAVEN5750, RAVEN7000, etc.

Among the above carbon blacks, it is preferable to use carbon black coated with a resin as having a high optical density and a high surface resistivity required for the black matrix of the color filter. The resin-coated carbon black is, for example, 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 No.

Further, as a method for producing the titanium black, a method of heating and reducing a mixture of titanium dioxide and metallic titanium described in JP-A-49-5432 in a reducing atmosphere, and a method described in JP-A-57-205322. A method for 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, a method of adhering a vanadium compound to titanium dioxide or titanium hydroxide described in JP-A-61-201610, and reducing the temperature at a high temperature in the presence of ammonia. Examples of commercially available titanium black products include titanium black 10S, 12S, 13R, 13M, 13M-C manufactured by Mitsubishi Materials Corporation.

Examples of the combination in which two or more kinds of organic pigments are mixed to obtain black by mixing colors include a black pigment in which three color pigments of red, green, and blue are mixed. Coloring materials that can be mixed and used to prepare black pigments include Victoria Pure Blue (CI 42595), Auramine O (CI 41000), Cachiron Brilliant Flavin (Basic 13), and Rhodamine 6 GCP (C). I. 45160), Rhodamine B (CI 45170), Safranin OK70: 100 (CI 50240), Eriograusin X (CI 42080), No. 120 / Lionol Yellow (CI21090), Lionol Yellow GRO (CI21090), Simler First Yellow 8GF (CI21105), Benzidine Yellow 4T-564D (CI21095), Simler First Red 4015 (CI 12355), Lionol Red 7B4401 (CI 15850), First Gen Blue TGR-L (CI 74160), Lionol Blue SM (CI 26150), Examples thereof include Lionol Blue ES (CI Pigment Blue 15: 6), Lionogen Red GD (CI Pigment Red 168), Lionol Green 2YS (CI Pigment Green 36) and the like.

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

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 its 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.

Further, unlike organic pigments and the like, carbon black exists in a state called a structure in which primary particles are fused, and may form fine pores on the particle surface by post-treatment. Therefore, in order to represent the particle shape of carbon black, in general, in addition to the average particle size of the primary particles obtained by the same method as the organic pigment, the DBP absorption amount (JIS K6221) and the specific surface area by the BET method ( It is preferable to measure JIS K6217) and use it as an index of the structure and the amount of pores.

Among the colorants (B), pigments are preferable because a coating film layer having good productivity, a high color density, and excellent durability can be obtained, and it is possible to suppress the generation of foreign substances derived from the colorant. Since the effect of the present invention can be maximized, C.I. I. Pigment Red 177, C.I. I. Pigment Red 207, C.I. I. Pigment Red 254, C.I. I. Pigment Green 7, C.I. I. Pigment Green 36, C.I. I. Pigment Green 58, C.I. I. Pigment Green 59, C.I. I. Pigment Yellow 83, C.I. I. Pigment Yellow 93, C.I. I. Pigment Yellow 109, C.I. I. Pigment Yellow 110, C.I. I. Pigment Yellow 129, C.I. I. Pigment Yellow 138, C.I. I. Pigment Yellow 139, C.I. I. Pigment Yellow 150, C.I. I. Pigment Yellow 154, C.I. I. Pigment Yellow 180, C.I. I. Pigment Yellow 185, C.I. I. Pigment Blue 15: 1, C.I. I. Pigment Blue 15: 2, C.I. I. Pigment Blue 15: 6 and C.I. I. More preferably, one or more pigments selected from the group consisting of Pigment Violet 23.

The colorant (B) can be used alone or in combination of two or more.

The blending amount of the colorant (B) may be in the range of 10 to 80 parts by mass on a mass basis with respect to a total of 100 parts by mass of the alkali-soluble resin (C) and the polymerizable compound (D) described later. It is preferably in the range of 15 to 65 parts by mass, more preferably.

The alkali-soluble resin (C) used in the present invention is soluble in an alkaline developer. The alkali-soluble resin (C) is preferably a resin having at least one acidic group selected from the group of a carboxyl group, a phenolic hydroxyl group and a sulfonic acid group, or a salt thereof.

More specifically, the alkali-soluble resin (C) will be described, for example, the following resins and the like.
An alkali-soluble resin (C1) obtained by polymerizing a (meth) acrylic polymerizable monomer having an acidic group as an essential component.
-A polymer having no acidic group obtained by polymerizing a (meth) acrylic polymerizable monomer having a reactive group as an essential component, and a reactive group having reactivity with the reactive group. An alkali-soluble resin (C2) obtained by reacting a compound having an acid group with an alkali-soluble resin (C2).
-An unsaturated monocarboxylic acid is added to at least a part of the epoxy group of the copolymer of the epoxy group-containing (meth) acrylate and another polymerizable monomer, and the copolymer is further unsaturated. An alkali-soluble resin (C3) obtained by adding an acid anhydride of a polycarboxylic acid to at least a part of the hydroxyl groups generated by the addition reaction of the monocarboxylic acid.
-Epoxy (meth) acrylate resin (C4) having a carboxyl group
The above (C1) to (C4) will be described in detail below.

The alkali-soluble resin (C1) includes, for example, an alkali-soluble resin obtained by polymerizing a (meth) acrylic polymerizable monomer having a carboxyl group as an essential component or a (meth) acrylic having a sulfonic acid group. Examples thereof include an alkali-soluble resin obtained by polymerizing a polymerizable monomer as an essential component. Of these, an alkali-soluble resin obtained by polymerizing a (meth) acrylic polymerizable monomer having a carboxyl group as an essential component is preferable.

Examples of the (meth) acrylic polymerizable monomer having a carboxyl group include (meth) acrylic acid, maleic acid, crotonic acid, itaconic acid, fumaric acid, silicic acid, and 2- (meth) acryloyloxyethyl. Succinic acid, 2- (meth) acryloyloxyethyl adiponic acid, 2- (meth) acryloyloxyethyl maleic acid, 2- (meth) acryloyloxyethyl hexahydrophthalic acid, 2- (meth) acryloyloxyethylphthalic acid, 2 -(Meta) acryloyloxypropyl succinic acid, 2- (meth) acryloyloxypropyladipic acid, 2- (meth) acryloyloxypropylmaleic acid, 2- (meth) acryloyloxypropylhydrophthalic acid, 2- (meth) acryloyl Oxypropylphthalic acid, 2- (meth) acryloyloxybutylsuccinic acid, 2- (meth) acryloyloxybutyladipic acid, 2- (meth) acryloyloxybutylmaleic acid, 2- (meth) acryloyloxybutylhydrophthalic acid, Polymerizable monomer such as 2- (meth) acryloyloxybutylphthalic acid;

Polymerizable monomer in which lactones such as ε-caprolactone, β-propiolactone, γ-butyrolactone, and δ-valerolactone are added to acrylic acid; hydroxyalkyl (meth) acrylate with succinic acid, maleic acid, phthalic acid, Alternatively, a polymerizable monomer to which these acid anhydrides are added can be mentioned. These (meth) acrylic polymerizable monomers having a carboxyl group may be used alone or in combination of two or more. Among the (meth) acrylic polymerizable monomers having a carboxyl group, (meth) acrylic acid and 2- (meth) acryloyloxyethyl succinic acid are preferable.

Examples of the (meth) acrylic polymerizable monomer having a sulfonic acid group include -2-sulfoethyl (meth) acrylate, -2-sulfopropyl (meth) acrylate, and 2-hydroxy-3- (meth). ) Acrylic acid propanesulfonic acid, 2- (meth) acrylamide-2-methylpropanesulfonic acid, salts thereof and the like can be mentioned.

When preparing the alkali-soluble resin (C1), other polymerizable monomers may be used in combination as long as the effects of the present invention are not impaired. Examples of other monomers include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, and 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) acrylate , Gglycerol mono (meth) acrylate, tetrahydrofurfuryl (meth) acrylate and other (meth) acrylic acid esters;

Hydroxyalkyl (meth) acrylates such as 2-hydroxyethyl (meth) acrylates, hydroxypropyl (meth) acrylates and 4-hydroxybutyl (meth) acrylates, (meth) acrylic acid esters having hydroxyl groups such as glycerol mono (meth) acrylates. ;

Aromatic vinyl compounds such as styrene and derivatives thereof; vinyl compounds such as N-vinylpyrrolidone; N-substituted maleimides such as N-cyclohexylmaleimide, N-phenylmaleimide, and N-benzylmaleimide;

Examples thereof include polymethyl (meth) acrylate macromonomers, polystyrene macromonomers, poly2-hydroxyethyl (meth) acrylate macromonomers, polyethylene glycol macromonomers, polypropylene glycol macromonomers, and macromonomers such as polycaprolactone macromonomers. The other polymerizable monomers may be used alone or in combination of two or more.

Among the above other polymerizable monomers, styrene, methyl (meth) acrylate, cyclohexyl (meth) acrylate, benzyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, and hydroxy Ppropyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, N-cyclohexylmaleimide, N-benzylmaleimide, and N-phenylmaleimide are preferable because they have good transparency and do not easily impair heat resistance.

The amount of these other polymerizable monomers used is preferably 95% by mass or less, more preferably 85% by mass or less, based on the total polymerizable monomer component.

Specific examples of the alkali-soluble resin (C1) include (meth) acrylic acid, methyl (meth) acrylate, benzyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, and cyclohexyl (meth) acrylate. , Cyclohexyl maleimide and other hydroxyl-free polymerizable monomers, and hydroxyl group-containing polymerizable monomers such as 2-hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate and 4-hydroxybutyl (meth) acrylate. Copolymer;

Copolymers of (meth) acrylic acid with (meth) acrylic acid esters such as methyl (meth) acrylate, benzyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, and 2-hydroxyethyl methacrylate;

Examples thereof include a copolymer of (meth) acrylic acid and styrene; a copolymer of (meth) acrylic acid, styrene and α-methylstyrene; and a copolymer of (meth) acrylic acid and cyclohexyl maleimide. Among the alkali-soluble resins (C1), an alkali-soluble resin using benzyl (meth) acrylate is preferable because a resist composition having excellent pigment dispersibility can be obtained.

The acid value of the alkali-soluble resin (C1) is preferably in the range of 10 to 500 mgKOH / g, more preferably in the range of 30 to 350 mgKOH / g, and even more preferably in the range of 40 to 300 mgKOH / g. The polystyrene-equivalent weight average molecular weight (Mw) of the alkali-soluble resin (C1) measured by GPC is preferably in the range of 2,000 to 100,000, more preferably in the range of 3,000 to 80,000. The range of 4,000 to 50,000 is even more preferred.

In the present invention, an alkali obtained by polymerizing a (meth) acrylic polymerizable monomer having a carboxyl group as an essential component and adding an epoxy group-containing unsaturated compound to the carboxyl group of the carboxyl group-containing alkali-soluble resin. Soluble resin (C1-1) 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, glycidyl ether (iso) crotonic acid, and N- (3,5-dimethyl). Examples thereof include -4-glycidyl) benzylacrylamide and 4-hydroxybutyl (meth) acrylate glycidyl ether. In addition, an alicyclic epoxy group-containing unsaturated compound is preferable because it can improve heat resistance and dispersibility when a pigment is used as the colorant (B).

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

A known method can be used to add the epoxy group-containing unsaturated compound to the carboxyl group portion of the alkali-soluble resin containing a carboxyl group. For example, a carboxyl group-containing alkali-soluble resin and an epoxy group-containing unsaturated compound are mixed with a tertiary amine such as triethylamine or benzylmethylamine; dodecyltrimethylammonium chloride, tetramethylammonium chloride, tetraethylammonium chloride, tetrabutylammonium chloride, benzyltriethyl. A quaternary ammonium salt such as ammonium chloride; an epoxy group on the carboxyl group of the resin by reacting in an organic solvent at a reaction temperature of 50 to 150 ° C. for several hours to several tens of hours in the presence of a catalyst such as pyridine or triphenylphosphine. The contained unsaturated compound can be added.

The acid value of the alkali-soluble resin (C1-1) is preferably in the range of 10 to 500 mgKOH / g, more preferably in the range of 30 to 350 mgKOH / g, and even more preferably in the range of 40 to 300 mgKOH / g. The polystyrene-equivalent weight average molecular weight of the alkali-soluble resin (C1-1) measured by GPC is preferably in the range of 2,000 to 100,000, more preferably in the range of 3,000 to 80,000, and 4, The range of 000 to 50,000 is more preferred.

Further, among the alkali-soluble resins (C1), the alkali-soluble resin (C1-2) obtained by using a (meth) acrylic acid ester having an alicyclic structure such as an ether dimer or an adamantyl group as a polymerizable monomer. Is more preferable.

Examples of the ether dimer include dimethyl-2,2'-[oxybis (methylene)] bis-2-propenoate, diethyl-2,2'-[oxybis (methylene)] bis-2-propenoate, and 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, di (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-butylcyclohexyl) -2,2'-[oxybis (methylene)] bis-2-propenoate, di (dicyclopentadienyl) -2,2'- [Oxybis (methylene)] bis-2-propenoate, di (tricyclodecanyl) -2,2'-[oxybis (methylene)] bis-2-propenoate, di (isobornyl) -2,2'-[oxybis (methylene) 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 can be mentioned. 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 an ether dimer is used as a raw material for the alkali-soluble resin (C1-2), the ratio of the ether dimer in the polymerizable monomer suppresses gelation to obtain a low molecular weight alkali-soluble resin, and the transparency and transparency are improved. Since the resin composition has excellent heat resistance, the range of 2 to 60% by mass, more preferably 5 to 55% by mass, and 5 to 50% by mass of the mass of the total polymerizable monomer is preferable. More preferred.

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 (C1-2), the proportion of the (meth) acrylic acid ester used is the colorant (B). ), The dispersibility of the pigment can be improved, and a resist composition having good ground stain suitability can be obtained. Therefore, the range of 0.5 to 60% by mass of the mass of the total polymerizable monomer is preferable. , 1-55% by mass is more preferred, and 5-50% by mass is even more preferred.

The method for producing the alkali-soluble resin (C1) used in the present invention is not particularly limited, and various conventionally known methods can be adopted, but the solution polymerization method is particularly preferable. The polymerization temperature and the polymerization concentration (polymerization concentration = [total mass of the polymerizable monomer / (total mass of the polymerizable monomer + mass of the solvent)] × 100) are determined by the type of the polymerizable monomer used. It depends on the ratio and the target molecular weight of the alkali-soluble resin. The polymerization temperature is preferably in the range of 40 to 150 ° C, more preferably in the range of 60 to 130 ° C. 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- Esters such as methoxybutyl 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 Can be mentioned. These solvents may be used alone or in combination of two or more.

When polymerizing the polymerizable monomer, a polymerization initiator may be used, if necessary. Examples of the polymerization initiator include cumene hydroperoxide, diisopropylbenzene hydroperoxide, di-t-butyl peroxide, lauroyl peroxide, benzoyl peroxide, t-butylperoxyisopropyl carbonate, and t-amylperoxy-2. Organic peroxides such as -ethylhexanoate, t-butylperoxy-2-ethylhexanoate; 2,2'-azobis (isobutyronitrile), 1,1'-azobis (cyclohexanecarbonitrile), Examples thereof include azo compounds such as 2,2'-azobis (2,4-dimethylvaleronitrile) and dimethyl 2,2'-azobis (2-methylpropionate). These polymerization initiators may be used alone or in combination of two or more. The amount of these polymerization initiators used may be appropriately set according to the combination of the monomers used, the reaction conditions, the target molecular weight of the alkali-soluble resin (C1), and the like, and is not particularly limited, but gels. Since an alkali-soluble resin having a weight average molecular weight of several thousand to several tens of thousands can be obtained without any problem, the range of 0.1 to 15% by mass is preferable with respect to the total polymerizable monomer component, and 0.5 to 10% by mass is preferable. The range of is more preferable.

In addition, a chain transfer agent may be added for adjusting the molecular weight. Examples of the chain transfer agent include mercaptan-based chain transfer agents such as n-dodecyl mercaptan, mercaptoacetic acid, and methyl mercaptoacetate; α-methylstyrene dimer and the like, which have a high chain transfer effect and remain in the reaction system. N-dodecyl mercaptan and mercaptoacetic acid, which can reduce the amount of polymerizable monomer and are easily available, are preferable. When the chain transfer agent is used, the amount used may be appropriately set according to the combination of the monomers used, the reaction conditions, the molecular weight of the target monomer, etc., and is not particularly limited, but gelation is performed. Since an alkali-soluble resin having a weight average molecular weight of several thousand to tens of thousands can be obtained, the range of 0.1 to 15% by mass is preferable, and the range of 0.5 to 10% by mass is more preferable with respect to all the monomers. preferable.

The alkali-soluble resin (C2) has a polymer having no acidic group obtained by polymerizing a (meth) acrylic polymerizable monomer having a reactive group as an essential component, and the reactive group. It is obtained by reacting a compound having a reactive group and an acid group. Examples of the alkali-soluble resin (C2) include the following alkali-soluble resins.

-After obtaining a polymer using a polymerizable monomer having a hydroxyl group such as 2-hydroxyethyl (meth) acrylate as an essential component, an acid such as succinic anhydride, tetrahydrophthalic anhydride, maleic anhydride, etc. An alkali-soluble resin obtained by adding an anhydride.

-After obtaining a polymer using a polymerizable monomer having an epoxy group such as glycidyl (meth) acrylate as an essential component, it has an amino group and an acid group such as N-methylaminobenzoic acid and N-methylaminophenol. An alkali-soluble resin obtained by adding a compound.

-After obtaining a polymer using a polymerizable monomer having an isocyanate group such as 2-isocyanatoethyl (meth) acrylate as an essential component, a compound having a hydroxyl group and an acid group such as 2-hydroxybutyric acid is added. The resulting alkali-soluble resin.

As for the weight average molecular weight of the alkali-soluble resin (C2), the polystyrene-equivalent weight average molecular weight measured by GPC is 1,000 to 200,000 because a coating film having good coating film formation and excellent heat resistance can be obtained. The range of 2,000 to 50,000 is more preferable, and the range of 2,000 to 30,000 is even more preferable. Further, if necessary, the alkali-soluble resin (C2) may be obtained in combination with the polymerizable monomer used for preparing the alkali-soluble resin (C1).

The alkali-soluble resin (C3) is a copolymer of an epoxy group-containing (meth) acrylate and another polymerizable monomer, and is unsaturated in at least a part of the epoxy groups of the copolymer. It is obtained by adding an acid and further adding an acid anhydride of a polycarboxylic acid to at least a part of the hydroxyl groups generated by the addition reaction of the unsaturated monocarboxylic acid.

Examples of the epoxy group-containing (meth) acrylate include glycidyl (meth) acrylate, 3,4-epoxybutyl (meth) acrylate, (3,4-epoxycyclohexyl) methyl (meth) acrylate, and 4-hydroxybutyl (meth) acrylate. ) Acrylate glycidyl ether and the like can be mentioned. Of these, glycidyl (meth) acrylate is preferable. These epoxy group-containing (meth) acrylates can be used alone or in combination of two or more.

Further, as a polymerizable monomer other than the epoxy group-containing (meth) acrylate which is the raw material of the alkali-soluble resin (C3), a monomer having an alicyclic structure such as a norbornene skeleton or a dicyclopentadiene skeleton is used. , It is preferable because the heat resistance and mechanical strength of the cured product of the color resist composition of the present invention can be improved.

Further, a polymerizable monomer having no alicyclic structure may be used as a polymerizable monomer other than the epoxy group-containing (meth) acrylate. Examples of such polymerizable monomers include vinyl aromatics such as styrene, α-, o-, m-, p-alkyl, nitro, cyano, amide, and ester derivatives of styrene;

Dienes such as butadiene, 2,3-dimethylbutadiene, isoprene, chloroprene;

Methyl (meth) acrylic acid, ethyl (meth) acrylic acid, (meth) acrylic acid-n-propyl, (meth) acrylic acid-i-propyl, (meth) acrylic acid-n-butyl, (meth) acrylic acid- s-butyl, (meth) acrylate-t-butyl, (meth) acrylate pentyl, (meth) acrylate neopentyl, (meth) acrylate isoamyl, (meth) acrylate hexyl, (meth) acrylate-2- Ethylhexyl, lauryl (meth) acrylate, dodecyl (meth) acrylate, cyclopentyl (meth) acrylate, cyclohexyl (meth) acrylate, -2-methylcyclohexyl (meth) acrylate, dicyclohexyl (meth) acrylate, (meth) ) Isobolonyl acrylate, adamantyl (meth) acrylate, propagil (meth) acrylate, phenyl (meth) acrylate, naphthyl (meth) acrylate, anthrasenyl (meth) acrylate, anthraninonyl (meth) acrylate, ( Piperonyl (meth) acrylate, salicyl (meth) acrylate, frill (meth) acrylate, flufuryl (meth) acrylate, tetrahydrofuryl (meth) acrylate, pyranyl (meth) acrylate, benzyl (meth) acrylate, (meth) Penetyl acrylate, Cresyl (meth) acrylate, -1,1,1-trifluoroethyl (meth) acrylate, Perfluorethyl (meth) acrylate, Perfluoro-n-propyl (meth) acrylate , (Meta) Perfluoro-iso-propyl acrylate, Triphenylmethyl (meth) acrylate, Kumil (meth) acrylate, -3- (N, N-dimethylamino) propyl (N, N-dimethylamino) propyl, (meth) acrylate, (meth) (Meta) acrylic acid esters such as -2-hydroxyethyl acrylate and -2-hydroxypropyl (meth) acrylate;

(Meta) Acrylic Acid Amide, (Meta) Acrylic Acid N, N-Dimethylamide, (Meta) Acrylic Acid N, N-Diethylamide, (Meta) Acrylic Acid N, N-Dipropylamide, (Meta) Acrylic Acid-N , N-di-i-propylamide, (meth) acrylic acid amides such as (meth) acrylic acid anthracenylamide; (meth) acrylic acid anilide, (meth) acryloylnitrile, achlorine, vinyl chloride, vinylidene chloride, Vinyl compounds such as vinyl oxide, vinylidene fluoride, N-vinylpyrrolidone, vinylpyridine, vinyl acetate;

Unsaturated dicarboxylic acid diesters such as diethyl citraconic acid, diethyl maleate, diethyl fumarate, diethyl itaconic acid; N-phenylmaleimide, N-cyclohexylmaleimide, N-laurylmaleimide, N- (4-hydroxyphenyl) maleimide, etc. Monomaleimides; N- (meth) acryloylphthalimide and the like can be mentioned.

Among the above other polymerizable monomers, at least among styrene, benzyl (meth) acrylate and monomaleimides, 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 to use one type. The proportion of styrene, benzyl (meth) acrylate and monomaleimides used is preferably 1 to 70 mol%, more preferably 3 to 50 mol%, based on the total amount of other polymerizable monomers.

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

The copolymer of the epoxy group-containing (meth) acrylate and the other polymerizable monomer includes 5 to 90 mol% of repeating units derived from the epoxy group-containing (meth) acrylate and other radically polymerizable monomer. The repeating unit derived from 10 to 95 mol% is preferable, the former is 20 to 80 mol%, the latter is 80 to 20 mol%, and the former is 30 to 70 mol% and the latter is 70. It is more preferably composed of ~ 30 mol%.

The alkali-soluble resin (C3) contains an unsaturated monocarboxylic acid (polymerizable component) and a polycarboxylic acid in the epoxy group portion of the copolymer of the epoxy group-containing (meth) acrylate and another polymerizable monomer. It is obtained by reacting an acid with an acid anhydride (alkali-soluble component).

Examples of the unsaturated monocarboxylic acid include (meth) acrylic acid, crotonic acid, o-, m-, p-vinylbenzoic acid, and the α-position is a haloalkyl group, an alkoxyl group, a halogen atom, a nitro group, or a cyano. Examples thereof include monocarboxylic acids such as (meth) acrylic acid substituted with a group or the like. Of 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, the alkali-soluble resin (A3) can be imparted with polymerizable properties.

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

Examples of the acid anhydride of the polycarboxylic acid include acid anhydrides of dicarboxylic acids such as maleic anhydride, succinic anhydride, itaconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, and chlorendic anhydride. Examples thereof include carboxylic acid anhydrides having three or more carboxyl groups such as trimellitic anhydride, pyromellitic anhydride, benzophenone tetracarboxylic acid anhydride, and biphenyltetracarboxylic acid anhydride. Among these, tetrahydrophthalic anhydride and succinic anhydride are preferable. The acid anhydrides of these polycarboxylic acids may be used alone or in combination of two or more. By using the acid anhydride of this polycarboxylic acid, alkali solubility can be imparted to the alkali-soluble resin (C3).

The acid anhydride of the polycarboxylic acid is usually added to 10 to 100 mol% of the hydroxyl groups generated by adding the unsaturated monocarboxylic acid to the epoxy group of the copolymer, preferably 20 to 90. It is more preferably added to mol%, and even more preferably added to 30 to 80 mol%.

The polystyrene-equivalent weight average molecular weight (Mw) measured by gel permeation chromatography (GPC) of the alkali-soluble resin (C3) is preferably in the range of 3,000 to 100,000, preferably in the range of 5,000 to 50,000. Is more preferable. The dispersity (Mw / Mn) of the alkali-soluble resin (C3) is preferably in the range of 2.0 to 5.0.

In the epoxy (meth) acrylate resin (C4), for example, an α, β-unsaturated monocarboxylic acid or an α, β-unsaturated monocarboxylic acid ester having a carboxyl group at an ester portion is added to the epoxy resin, and further. It is obtained by reacting a polybasic acid anhydride.

Examples of the epoxy resin include bisphenol A type epoxy resins (commercially available products such as "jER828", "jER1001", "jER1002", and "jER1004" manufactured by Mitsubishi Chemical Corporation) and bisphenol A type epoxy resins having alcoholic properties. Epoxy resin obtained by the reaction of hydroxyl group and epichlorohydrin (commercially available, "NER-1302" manufactured by Nippon Kayaku Co., Ltd. (epoxy equivalent 323, softening point 76 ° C)), bisphenol F type resin (commercially available, Mitsubishi Chemical "JER807", "EP-4001", "EP-4002", "EP-4004", etc. manufactured by Co., Ltd.), an epoxy resin obtained by the reaction of the alcoholic hydroxyl group of the bisphenol F type epoxy resin with epichlorohydrin (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 (commercially available, "YX-4000" manufactured by Mitsubishi Chemical Co., Ltd. ), Phenol novolak type epoxy resin (commercially available products, "EPPN-201" manufactured by Nippon Kayaku Co., Ltd., "EP-152", "EP-154" manufactured by Mitsubishi Chemical Co., Ltd., manufactured by Dow Chemical Japan Co., Ltd. "DEN-438"), cresol novolac type epoxy resin (commercially available products, "EOCN-102S", "EOCN-1020", "EOCN-1020"), triglycidyl isocyanurate (commercially available products) , "TEPIC" manufactured by Nissan Chemical Industry Co., Ltd.), Trisphenol methane type epoxy resin ("EPPN-501", "EPN-502", "EPPN-503" manufactured by Nippon Kayaku Co., Ltd. as commercial products) , Fluorene epoxy resin (commercially available, cardo epoxy resin "ESF-300" manufactured by Nippon Steel Chemical Co., Ltd.), alicyclic epoxy resin ("Selokiside 2021P", "Selokiside EHPE" manufactured by Daicel Chemical Industry Co., Ltd.) , Dicyclopentadiene type epoxy resin made by glycidylating a phenol resin by the reaction of dicyclopentadiene and phenol (for example, "XD-1000" manufactured by Nippon Kayaku Co., Ltd., "EXA-7200" manufactured by DIC Co., Ltd., Japan "NC-3000", "NC-7300") manufactured by Yakuhin Co., Ltd., an epoxy resin having a fluorene skeleton (see Japanese Patent Application Laid-Open No. 4-355450) and the like can be used. These epoxy resins may be used alone or in combination of two or more.

Another example of the epoxy resin is a copolymerized epoxy resin. Examples of the copolymerized epoxy resin include monomers having an epoxy group such as glycidyl (meth) acrylate, (meth) acryloylmethylcyclohexene oxide, and vinylcyclohexene oxide, and methyl (meth) acrylate, ethyl (meth) acrylate, and butyl (meth). Meta) acrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl (meth) acrylate, (meth) acrylic acid, styrene, phenoxyethyl (meth) acrylate, benzyl (meth) acrylate, α-methylstyrene, glycerin mono (meth) Examples thereof include a copolymer obtained by copolymerizing an acrylate or a (meth) acrylate having a polyoxyalkylene chain with a polymerizable monomer having no epoxy group.

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 alkoxypolyethylene 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 copolymerized epoxy resin is preferably in the range of 1,000 to 200,000. The amount of the monomer having an epoxy group used as a raw material of the copolymerized 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.

Examples of commercially available copolymerized epoxy resins include "CP-15", "CP-30", "CP-50", "CP-20SA", and "CP-510SA" manufactured by NOF CORPORATION. Examples thereof include "CP-50S", "CP-50M" and "CP-20MA".

Since the epoxy resin has a good coating film formation and can prevent gelation during the addition reaction of α, β-unsaturated monocarboxylic acid, the polystyrene-equivalent weight average molecular weight measured by GPC is 200 to 200, The range of 000 is preferable, and the range of 300 to 100,000 is more preferable.

Examples of α, β-unsaturated monocarboxylic acids include itaconic acid, crotonic acid, cinnamic acid, acrylic acid, and methacrylic acid, preferably acrylic acid and methacrylic acid, and acrylic acid has good reactivity. More preferred from. Examples of the α, β-unsaturated monocarboxylic acid ester having a carboxyl group in the ester moiety include acrylic acid-2-succinoyloxyethyl, acrylic acid-2-maleinoyloxyethyl, and acrylic acid-2-phthaloyloxyethyl. -2-Hexahydrophthaloyloxyethyl acrylate, -2-succinoyloxyethyl methacrylate, -2-maleinoyloxyethyl methacrylate, -2-phthaloyloxyethyl methacrylate, -2-hexahydrophthalomethacrylate Examples thereof include yloxyethyl and -2-succinoyloxyethyl crotonate, preferably -2-maleinoyloxyethyl acrylate and -2-phthaloyloxyethyl acrylate, and -2-maleinoyloxyethyl acrylate. More preferred. These α, β-unsaturated monocarboxylic acids and α, β-unsaturated monocarboxylic acid esters can be used alone or in combination of two or more.

A known method can be used for the addition reaction between the α, β-unsaturated monocarboxylic acid or its ester and the epoxy resin. For example, a method of reacting at a temperature of 50 to 150 ° C. in the presence of an esterification catalyst is available. Can be mentioned. As the esterification catalyst, tertiary amines such as triethylamine, trimethylamine, benzyldimethylamine and benzyldiethylamine; and quaternary ammonium salts such as tetramethylammonium chloride, tetraethylammonium chloride and dodecyltrimethylammonium chloride can be used.

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

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

A known method can also be used for the addition reaction of polybasic acid anhydride, and the reaction can be continued under the same conditions as the addition reaction of α, β-unsaturated carboxylic acid or an ester thereof. The amount of the polybasic acid anhydride used is preferably such that the acid value of the produced epoxy (meth) acrylate resin is in the range of 10 to 150 because the alkali developability and the coating film formation can be improved. More preferably, the amount is in the range of 20 to 140.

Further, as an epoxy (meth) acrylate resin having a carboxyl group, a naphthalene-containing resin described in JP-A-6-49174; JP-A-2003-89716, JP-A-2003-165830, JP-A-2005-325331, Fluorene-containing resins described in JP-A-2001-354735; the resins described in JP-A-2005-126674, JP-A-2005-55514, JP-A-2004-295804, and the like can also be exemplified. Further, as a commercially available product, "ACA-200M" manufactured by Daicel Chemical Industries, Ltd. and the like can be exemplified.

As the alkali-soluble resin (C), one of the above-mentioned alkali-soluble resins (C1) to (C4) may be used alone, or two or more thereof may be used in combination. Further, when the alkali-soluble resin (C) is used in combination with a pigment dispersant described later, an undissolved substance does not remain in the non-pixel portion on the substrate, and a high-concentration color having excellent adhesion to the substrate is obtained. It is preferable because pixels can be formed. Specifically, it is preferable to use a part of the alkali-soluble resin (C) in the dispersion treatment step together with the pigment dispersant described later. In this case, the alkali-soluble resin (C) is preferably used in the range of 5 to 200% by mass, more preferably 10 to 100% by mass with respect to the pigment.

Further, as the alkali-soluble resin (C) used in the present invention, an alkali-soluble resin other than the above-mentioned alkali-soluble resins (C1) to (C4) may be used. As such a resin, for example, an alkali-soluble resin obtained by using a polymerizable monomer having a phenolic hydroxyl group as an acidic group as an essential component, or a polymerizable monomer having a sulfonic acid group as an acidic group is an essential component. Examples thereof include an alkali-soluble resin obtained by using the above. Here, examples of the polymerizable monomer having a phenolic hydroxyl group include o-hydroxystyrene, m-hydroxystyrene, p-hydroxystyrene and the like. Further, one or more hydrogen atoms other than the phenolic hydroxyl group and the 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 and an amide group. Compounds and the like can also be mentioned. Examples of the polymerizable monomer having a sulfonic acid group as an acidic group include vinyl sulfonic acid, styrene sulfonic acid, (meth) allyl sulfonic acid, 2-hydroxy-3- (meth) allyl oxypropane sulfonic acid, and the like. Examples thereof include -2-sulfoethyl (meth) acrylate, and salts thereof.

In the resist composition of the present invention, the content ratio of the alkali-soluble resin (C) 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 is preferable, and the range of 1 to 60% by mass is more preferable.

As the polymerizable compound (D) used in the present invention, for example, a photopolymerizable compound having one or more ethylenically unsaturated bonds can be exemplified.

Examples of the polymerizable compound (D1) having one ethylenically unsaturated bond include the compounds listed as (c1), (c2) and (c3). Of these, (meth) acrylic acid esters are preferable.

Examples of the polymerizable compound (D2) having two ethylenically unsaturated bonds include 1,3-butanediol di (meth) acrylate, 1,3-butanediol (meth) acrylate, and 1,6-hexanediol di. (Meta) acrylate, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, polyethylene glycol di Acrylate, bis (acryloyloxyethyl) ether of bisphenol A, ethoxylated bisphenol A di (meth) acrylate, propoxylated neopentyl glycol di (meth) acrylate, ethoxylated neopentyl glycol di (meth) acrylate, 3-methylpentane Examples thereof include diol di (meth) acrylate.

Examples of the polymerizable compound (D3) having three ethylenically unsaturated bonds include trimethylpropantri (meth) acrylate, pentaerythritol tri (meth) acrylate, and tris (2-hydroxyethyl) isocyanuratetri (meth). Acrylate, Trimethylol Propanetri (meth) Acrylate, Propoxylated Trimethylol Propanetri (Meta) Acrylate, Pentaerythritol Tri (meth) Acrylate and Acid Anhydrous Reaction, Caprolactone-Modified Pentaerythritol Tri (Meta) Acrylate, Caprolactone-modified tris (2-hydroxyethyl) isocyanurate tri (meth) acrylate, caprolactone-modified pentaerythritol tri (meth) acrylate and acid anhydride reaction product, caprolactone-modified dipentaerythritol penta (meth) acrylate and acid anhydride Examples thereof include the reactants of.

Examples of the polymerizable compound (D4) having four ethylenically unsaturated bonds include pentaerythritol tetra (meth) acrylate, tripentaerythritol tetra (meth) acrylate, and caprolactone-modified tripentaerythritol tetra (meth) acrylate. Be done.

Examples of the polymerizable compound (D5) having five or more ethylenically unsaturated bonds include dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, tripentaerythritol penta (meth) acrylate, and tripenta. Elythritol hexa (meth) acrylate, tripenta erythritol hepta (meth) acrylate, tripenta erythritol octa (meth) acrylate, dipenta erythritol penta (meth) acrylate and acid anhydride reaction product, tripenta erythritol hepta (meth) acrylate And acid anhydride caprolactone-modified trimethylol propantri (meth) acrylate, caprolactone-modified pentaerythritol tetra (meth) acrylate, caprolactone-modified dipentaerythritol penta (meth) acrylate, caprolactone-modified dipentaerythritol hexa (meth) acrylate, caprolactone-modified tri Pentaerythritol penta (meth) acrylate, caprolactone-modified tripentaerythritol hexa (meth) acrylate, caprolactone-modified tripentaerythritol hepta (meth) acrylate, caprolactone-modified tripentaerythritol octa (meth) acrylate, caprolactone-modified tripentaerythritol hepta (meth) Examples thereof include acrylate and acid anhydride.

Further, as the polymerizable compound (D) used in the present invention, a photocurable resin can also be exemplified.

Examples of the photocurable resin include urethane (meth) acrylate resin, unsaturated polyester resin, epoxy (meth) acrylate resin, polyester (meth) acrylate resin, acrylic (meth) acrylate resin, maleimide group-containing resin and the like. ..

The urethane (meth) acrylate resin is, for example, a resin having a urethane bond and a (meth) acryloyl group obtained by reacting an aliphatic polyisocyanate compound or an aromatic polyisocyanate compound with a hydroxy group-containing (meth) acrylate compound. And so on.

Examples of the aliphatic polyisethylene compound include tetramethylene diisocyanate, pentamethylene diisocyanate, hexamethylene diisocyanate, heptamethylene diisocyanis, octamethylene diisocyanate, decamethylene diisocyanis, 2-methyl-1,5-pentanediisocyanis, and 3-methyl-. 1,5-Pentane diisocyanis, dodecamethylene diisocyanate, 2-methylpentamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanis, isophoron diisocyanis, norbornan diisocyanate, hydrogenated diphenylmethane diisocyanis , Hydrogenated tolylene diisocyanate, hydrogenated xylylene diisocyanate, hydrogenated tetramethylxamethylene diisocyanate, cyclohexamethylene diisocyanate and the like, and examples of the aromatic polyisocyanate compound include tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, and the like. Examples thereof include xylylene diisocyanate, 1,5-naphthalenedi isocyanate, trizine diisocyanate, and p-phenylenedi isocyanate.

Examples of the hydroxy group-containing (meth) acrylate compound include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, and 4-hydroxybutyl (meth) acrylate. Divalent alcohols such as 1,5-pentanediol mono (meth) acrylate, 1,6-hexanediol mono (meth) acrylate, neopentyl glycol mono (meth) acrylate, and neopentyl glycol mono (meth) acrylate of hydroxypivalate. Mono (meth) acrylate; trimethylolpropandi (meth) acrylate, ethoxylated trimethylolpropane (meth) acrylate, propoxylated trimethylolpropandi (meth) acrylate, glycerindi (meth) acrylate, bis (2- (meth)) Mono or di (meth) acrylates of trivalent alcohols such as acryloyloxyethyl) hydroxyethyl isocyanurate, or hydroxyl group-containing mono and di (meth) acrylates in which some of these alcoholic hydroxyl groups are modified with ε-caprolactone; A compound having a monofunctional hydroxyl group and a trifunctional or higher (meth) acryloyl group such as pentaerythritol tri (meth) acrylate, ditrimethylolpropantri (meth) acrylate, and dipentaerythritol penta (meth) acrylate, or a compound thereof. Further, hydroxyl group-containing polyfunctional (meth) acrylate modified with ε-caprolactone; oxy such as dipropylene glycol mono (meth) acrylate, diethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, polyethylene glycol mono (meth) acrylate, etc. (Meta) acrylate compound having an alkylene chain; (meth) acrylate compound having a block structure of an oxyalkylene chain such as polyethylene glycol-polypropylene glycol mono (meth) acrylate and polyoxybutylene-polyoxypropylene mono (meth) acrylate; poly Examples thereof include (meth) acrylate compounds having an oxyalkylene chain having a random structure such as (ethylene glycol-tetramethylene glycol) mono (meth) acrylate and poly (propylene glycol-tetramethylene glycol) mono (meth) acrylate.

The reaction of the above-mentioned aliphatic polyisocyanate compound or aromatic polyisocyanate compound with the hydroxy group-containing (meth) acrylate compound can be carried out by a conventional method, for example, in the presence of a urethanization catalyst. Specific examples of the urethanization catalysts that can be used here are amines such as pyridine, pyrrole, triethylamine, diethylamine and dibutylamine; hoffins such as triphenylphosphine and triethylphosphine; dibutyltin dilaurate, octyltin trilaurate and octyl. Organic tin compounds such as tin diacetate, dibutyltin diacetate and tin octylate; organometal compounds such as zinc octylate can be mentioned.

Among these urethane (meth) acrylate resins, those obtained by reacting an aliphatic polyisocyanate compound with a hydroxy group-containing (meth) acrylate compound have excellent transparency of the cured coating film and are sensitive to active energy rays. Is preferable from the viewpoint of good curability and excellent curability.

Next, the unsaturated polyester resin is subjected to, for example, polycondensation of α, β-unsaturated dibasic acid or an acid anhydride thereof, a dibasic acid other than the dibasic acid or the acid anhydride thereof, and glycols. Examples thereof include the obtained curable resin. Examples of α, β-unsaturated dibasic acid or acid anhydride thereof include maleic acid, maleic anhydride, fumaric acid, itaconic acid, citraconic acid, chlormaleic acid, and esters thereof.

Examples of dibasic acids other than α, β-unsaturated dibasic acid or its acid anhydride and its acid anhydride include aromatic saturated dibasic acid, aliphatic dibasic acid, alicyclic saturated dibasic acid and Examples thereof include these acid anhydrides. Examples of the aromatic saturated dibasic acid or its acid anhydride include phthalic acid, phthalic anhydride, isophthalic acid, terephthalic acid, nitrophthalic acid, tetrahydrophthalic anhydride, endomethylenetetrahydrophthalic anhydride, phthalic anhydride and phthalic anhydride. Examples thereof include these esters. Examples of aliphatic dibasic acids, alicyclic saturated dibasic acids and their acid anhydrides include oxalic acid, malonic acid, succinic acid, adipic acid, sebacic acid, azelaic acid, glutaric acid, hexahydrophthalic anhydride and Examples thereof include these esters. Examples of glycols include ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, 1,3-butanediol, 1,4-butanediol, 2-methylpropane-1,3-diol, neopentyl glycol, and triethylene glycol. Tetraethylene glycol, 1,5-pentanediol, 1,6-hexanediol, bisphenol A, hydrogenated bisphenol A, ethylene glycol carbonate, 2,2-di- (4-hydroxypropoxydiphenyl) propane and the like, and others. Similarly, oxides such as ethylene oxide and propylene oxide can be used.

Next, as the epoxy vinyl ester resin, for example, (meth) acrylic acid is reacted with the epoxy group of an epoxy resin such as bisphenol A type epoxy resin, bisphenol F type epoxy resin, phenol novolac type epoxy resin, and cresol novolac type epoxy resin. Examples thereof are those obtained by letting it.

Examples of the maleimide group-containing resin include a bifunctional maleimide urethane compound obtained by urethaneizing N-hydroxyethyl maleimide and isophorone diisocyanate, and a bifunctional maleimide ester compound obtained by esterifying maleimide acetic acid and polytetramethylene glycol. Examples thereof include a tetrafunctional maleimide ester compound obtained by esterifying maleimide caproic acid and a tetraethylene oxide adduct of pentaerythritol, and a polyfunctional maleimide ester compound obtained by esterifying maleimide acetic acid and a polyhydric alcohol compound. These active energy ray-curable resins can be used alone or in combination of two or more.

Among the polymerizable compounds (D) used in the present invention, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, and dipentaerythritol hexa (meth) are particularly excellent in the hardness of the coating film layer. ) Trifunctional or higher functional (meth) acrylates such as acrylate and pentaerythritol tetra (meth) acrylate are preferable. These polymerizable compounds (D) can be used alone or in combination of two or more.

The total content of the polymerizable compound (D) is preferably 10 to 50% by mass, more preferably 15 to 50% by mass, based on the solid content of the resist composition. When the total content of the polymerizable compound (D) is within the above range, the sensitivity, the strength and smoothness of the coating film layer, and the reliability tend to be good.

Among the polymerizable compounds (D), the content of the polymerizable compound (D5) is preferably 1 to 50% by mass, more preferably 5 to 40% by mass, and 5 to 35% by mass with respect to the solid content of the resist composition. % Is particularly preferable. When the content of the polymerizable compound (D5) is within the above range, the sensitivity, the strength and smoothness of the coating film layer, and the reliability tend to be good.

Further, among the polymerizable compounds (D), the content of the polymerizable compound (D5) is relative to the total amount of the polymerizable compounds (D1), (D2), (D3), (D4) and (D5). It is preferably 10 to 95% by mass, more preferably 20 to 90% by mass. When the content of the polymerizable compound (D5) is within the above range, the sensitivity, the strength and smoothness of the coating film layer, and the reliability tend to be good.

As described above, the method for producing the resist composition includes a step of obtaining the random copolymer (A), which is the first invention of the present invention, and the random copolymer (A), the pigment (B), and the alkali-soluble resin. It includes a step of mixing (C) and the polymerizable compound (D). When a pigment is used as the colorant (B) in the method for producing the resist composition of the present invention, the random copolymer (A), the colorant (B), the alkali-soluble resin (C), and the polymerizable compound (D) are used. ), A pigment dispersion prepared by dispersing in an organic solvent using a dispersant can be used as the colorant (B) to obtain good dispersibility and a desired hue. Therefore, it is preferable.

Examples of the dispersant include surfactants; intermediates or derivatives of pigments; resin-type dispersants such as polyamide resins, polyurethane resins, polyester resins, and acrylic resins. Among these pigment dispersants, resin-type dispersants are preferable, acrylic-based resin-type dispersants are more preferable, and an acrylic polymer having an N, N-di-substituted amino group and an acidic group in the main chain or side chain is contained. The resin type dispersant to be used is more preferable. Commercially available products of such resin-type dispersants include, for example, "BYK-160", "BYK-161", "BYK-2001" manufactured by Big Chemie, "Fuka 46" manufactured by Fcar Chemicals, and Ajinomoto Fine. Examples thereof include "Ajispar PB-814" manufactured by Techno Co., Ltd. These dispersants can be used alone or in combination of two or more.

Examples of the organic solvent used in the preparation of the pigment dispersion include acetic acid ester solvents such as propylene glycol monomethyl ether acetate and propylene glycol monoethyl ether acetate; propionate solvents such as ethoxypropionate; toluene and xylene. , Aromatic solvents such as methoxybenzene; ether solvents such as butyl cellosolve, propylene glycol monomethyl ether, diethylene glycol ethyl ether, diethylene glycol dimethyl ether; ketone solvents such as methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone; aliphatic hydrocarbon solvents such as hexane Solvents; nitrogen compound solvents such as N, N-dimethylformamide, γ-butyrolactam, N-methyl-2-pyrrolidone; lactone solvents such as γ-butyrolactone; carbamates and the like. These solvents may be used alone or in combination of two or more.

Examples of the method for preparing the pigment dispersion liquid include a method of undergoing a pigment kneading and dispersion step and a fine dispersion step, a method of performing only the fine dispersion step, and the like.

In the kneading and dispersing step, the pigment, the alkali-soluble resin (C) and, if necessary, the dispersant are mixed and kneaded. As the kneading machine, for example, a two-roll, three-roll, ball mill, tron mill, disper, kneader, conider, homogenizer, blender, single-screw or twin-screw extruder, or the like can be used as the kneader. The pigment can be dispersed in the alkali-soluble resin (C) by dispersing while applying a strong shearing force using a kneader. Further, it is preferable to reduce the particle size by a salt milling method or the like before kneading the pigment. Here, as the alkali-soluble resin, the entire amount used in the method for producing the resist composition of the present invention may be used, or a part thereof may be used.

In the fine dispersion step, an organic solvent is added to the composition containing the pigment obtained in the kneading and dispersion step, or a pigment, an alkali-soluble resin (C) solvent and, if necessary, the dispersant are mixed. Is mixed and dispersed using a disperser together with a medium for dispersing fine particles of glass, zirconia or ceramic, so that the pigment particles can be dispersed to a fine state close to the primary particles.

Examples of the organic solvent include acetic acid ester solvents such as propylene glycol monomethyl ether acetate and propylene glycol monoethyl ether acetate; propionate solvents such as ethoxypropionate; aromatic solvents such as toluene, xylene and methoxybenzene; Ether solvents such as butyl cellosolve, propylene glycol monomethyl ether, diethylene glycol ethyl ether, diethylene glycol dimethyl ether; ketone solvents such as methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone; aliphatic hydrocarbon solvents such as hexane; N, N-dimethylformamide, γ Examples thereof include nitrogen compound solvents such as −butyrolactam and N-methyl-2-pyrrolidone; lactone solvents such as γ-butylollactone; and carbamate esters. These solvents may be used alone or in combination of two or more.

The average particle size of the primary particles of the pigment is preferably 10 to 100 nm, more preferably 10 to 60 nm. The average particle size of the pigment (B) was measured with a dynamic light scattering type particle size distribution meter. For example, the Nanotrac particle size distribution measuring device "UPA-EX150" manufactured by Nikkiso Co., Ltd. , "UPA-EX250" and the like.

In the method for producing the resist composition, when the random copolymer (A), the colorant (B), the alkali-soluble resin (C), and the polymerizable compound (D) are mixed, the solid content is converted. It is preferable to mix them so as to be 0.0001 to 10 parts by mass, 5 to 80 parts by mass, 0.1 to 80 parts by mass, and 5 to 80 parts by mass, respectively, and 0.001 to 5 parts by mass and 5 to 5 parts, respectively. 70 parts by mass, 1 to 60 parts by mass, and 10 to 70 parts by mass are more preferable.

In the method for producing the resist composition, when the random copolymer (A), the colorant (B), the alkali-soluble resin (C), and the polymerizable compound (D) are mixed, various methods are used. You may use it. Specifically, for example, the mixture may be mixed using a method such as stirring using a shaker, a paint shaker, or a stirring blade, or an organic solvent may be added as needed at the time of mixing. As the organic solvent, for example, an organic solvent that can be used when preparing the pigment dispersion liquid can be used. The amount of the organic solvent used is, for example, usually 100 to 1000 parts by mass with respect to 100 parts by mass of the coating film layer forming component.

As will be described later, in order to cure the resist composition obtained by the method for producing the resist composition by irradiating it with active energy rays such as ultraviolet rays, a polymerization initiator is usually added. The polymerization initiator is mixed when the random copolymer (A), the colorant (B), the alkali-soluble resin (C) and the polymerizable compound (D) are mixed in the method for producing the resist composition of the present invention. Alternatively, (A), (B), (C) and (D) may be mixed and mixed with a obtained resist composition.

Examples of the polymerization initiator include benzophenone, acetophenone, benzoin, benzoin ethyl ether, benzoin isobutyl ether, benzylmethyl ketal, azobisisobutyronitrile, 1-hydroxycyclohexylphenyl ketone, and 2-hydroxy-2-methyl-1. -Phenyl-1-one, 1- (4'-isopropylphenyl) -2-hydroxy-2-methylpropane-1-one, 1- (4'-dodecylphenyl) -2-hydroxy-2-methylpropane-1 -On, 3,3', 4,4'-tetra (t-butylperoxycarbonyl) benzophenone, 4,4 "-diethylisophthalophen, 2,2-dimethoxy-1,2-diphenylethane-1- On, benzoin isopropyl ether, thioxanson, 2-chlorothioxanson, 2-methylthioxanson, 2-isopropylthioxanson, 2-methyl-1 [4- (methylthio) phenyl] -2-morpholinopropane-1- On, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1, bis (2,6-dimethoxybenzoyl) -2,4,4-trimethyl-pentylphosphine oxide, bis (2) , 4,6,-trimethylbenzoyl) -phenylphosphine oxide, 2,4,6-trimethylbenzoyldiphenylphosphine oxide and the like, and may be used alone or in combination of two or more. Among these, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1 is preferable, although it is relatively unaffected by the colorant (B) and exhibits high curability.

The blending amount of the polymerization initiator is in the range of 0.01 to 15 parts by mass with respect to 100 parts by mass in total of the colorant (B), the alkali-soluble resin (C) and the polymerizable compound (D). It is preferably in the range of 0.3 to 7 parts by mass, more preferably.

Further, a photosensitizer such as an amine compound or a phosphorus compound can be added to the resist composition obtained by the production method of the present invention, if necessary, to promote photopolymerization.

Further, the resist composition obtained by the production method of the present invention has an organic solvent, a polymerization inhibitor, an antistatic agent, an antifoaming agent, and a viscosity, depending on the purpose such as use and characteristics, as long as the effect of the present invention is not impaired. Additives such as a modifier, a light-resistant stabilizer, a heat-resistant stabilizer, and an antioxidant can be blended.

Examples of the organic solvent include organic solvents that can be used in the method for preparing the pigment dispersion liquid. The amount of the organic solvent used varies depending on the intended use and the desired film thickness and viscosity, but is 0.5 to 6 times the total amount of the alkali-soluble resin (C) and the polymerizable compound (D) on a mass basis. It is preferably in the range of quantity.

Examples of the polymerization inhibitor include hydroquinone, p-methoxyphenol, di-t-butyl-p-cresol, pyrogallol, t-butylcatechol, benzoquinone, and 4,4'-thiobis (3-methyl-6-t-). Butylphenol), 2,2'-methylenebis (4-methyl-6-t-butylphenol), N-nitrosophenylhydroxyamine first cerium salt and the like.

Examples of the antistatic agent include polyoxyethylene alkyl ether, polyoxyethylene alkyl phenol, polyoxyethylene alkyl amine, polyoxyethylene alkyl amide, fatty acid polyethylene glycol ester, fatty acid sorbitan ester, polyoxyethylene fatty acid sorbitan ester, and fatty acid glycerin. Examples thereof include nonionic antistatic agents such as esters and alkylpolyethyleneimine, cationic antistatic agents such as alkylamine salts, alkyl quaternary ammonium salts, and alkylimidazoline derivatives.

Examples of the defoaming agent include silicone-based defoaming agents, fluorine-based defoaming agents, nonionic surfactants, polyethers, higher alcohols, polymer-based surfactants, and the like.

Examples of the viscosity modifier include acrylic polymers and synthetic rubber latex that can be thickened by adjusting to alkalinity, urethane resins that can be thickened by associating molecules, hydroxyethyl cellulose, carboxymethyl cellulose, methyl cellulose, and polyvinyl alcohol. , Water-added castor oil, amide wax, polyethylene oxide, metal soap, dibenzylidene sorbitol and the like.

Examples of the light-resistant stabilizer include hindered amine compounds, phosphorus compounds, and cyanoacrylate compounds.

Examples of the heat-resistant stabilizer include 1,3,5-trimethyl-2,4,6-tris (3,5-di-t-butyl-4-hydroxybenzyl) benzene and 1,1,3-tris (1,1,3-tris). 2-Methyl-4-hydroxy-5-5-t-butylphenyl) butane, N, N'-hexamethylenebis (3,5-di-t-butyl-4-hydroxysilicate amide), 4,4 '-Bis (2,6-di-t-butylphenol), 2,2'-methylenebis (4-ethyl-6-t-butylphenol), pentaerythrityl-tetrakis [3- (3,5-di-t-) Butyl-4-hydroxyphenyl) propionate] and other hindered phenols; N, N'-bis (β-naphthyl) -p-phenylenediamine, N-N'-diphenyl-p-phenylenediamine, poly (2,2) , 4-trimethyl-1,2-dihydroquinoline) and other aromatic amines; sulfur compounds such as dilaurylthiodipropionate; phosphorus compounds such as tris (2,4-di-t-butylphenyl) phosphite, etc. Can be mentioned.

Examples of the antioxidant include a hindered phenol-based antioxidant, a hindered amine-based antioxidant, an organic sulfur-based antioxidant, a phosphoric acid ester-based antioxidant, and the like.

The present invention can provide a color filter. The color filter is made of, for example, a polymerizable monomer (a1) having a fluorinated alkyl group having 1 to 6 carbon atoms directly bonded to a fluorine atom and a polymerizable unsaturated group, and a bridging ring hydrocarbon. A polymerizable monomer (a2) having a skeleton and a polymerizable unsaturated group is subjected to living radical polymerization in the coexistence of the polymerizable monomer (a1) and the polymerizable monomer (a2) to contain fluorine. A step of obtaining a polymer (A), a step of mixing the fluoropolymer (A), a colorant (B), an alkali-soluble resin (C), and a polymerizable compound (D) to obtain a resist composition, and the like. It can be obtained by a method for producing a color filter, which comprises a step of forming a coating layer of a resist composition on a substrate. The step of obtaining the fluorine-containing polymer (A) is a step corresponding to the method for producing a random copolymer of the present invention.

The color filter can be manufactured, for example, by a manufacturing method including the following steps.

(1) A step of obtaining a random copolymer (A) by the method for producing a random copolymer of the present invention.
(2) A step of mixing the random copolymer (A) obtained in the above step, a colorant (B), an alkali-soluble resin (C), and a polymerizable compound (D) to obtain a resist composition. ..
(3) A step of forming a coating film layer of the resist composition on a substrate to obtain a substrate having the coating film layer.
(4) A step of drying (prebaking) the coating film layer to obtain a substrate having the dried coating film layer.
(5) A step of exposing a desired pattern on the dried coating film layer using a photomask.
(6) A step of performing a developing process using an alkaline developer.
(7) A step of washing (rinsing) with distilled water and then drying.

The material of the substrate is not particularly limited as long as it is transparent and has appropriate strength. Examples of the material include polyester resins such as polyethylene terephthalate; polyolefin resins such as polypropylene and polyethylene; polycarbonate resins; acrylic resins such as polymethylmethacrylate; thermoplastic resin sheets such as polysulfone resins; epoxy resins, Examples include a thermosetting resin sheet such as an unsaturated polyester resin; or various types of glass. Among these, glass and heat-resistant resin are preferable because of their high heat resistance. In order to improve the surface physical properties such as adhesiveness, these transparent substrates are subjected to surface treatment such as corona discharge treatment and ozone treatment, and thin film formation treatment with various resins such as silane coupling agent and urethane resin, if necessary. Etc. may be performed. The thickness of the transparent substrate is usually 0.05 mm or more, preferably 0.1 mm or more, and usually 10 mm or less, preferably 7 mm or less. When thin film formation treatment with various resins is performed, the film thickness is usually 0.01 μm or more, preferably 0.05 μm or more, and usually 10 μm or less, preferably 5 μm or less, more preferably 1 to 2 μm. be.

A color filter can usually be produced by providing a black matrix on the above-mentioned substrate and further forming a coating film of a resist composition that forms red, green, and blue pixel images. The black matrix may be formed by using a light-shielding metal thin film, or a resist composition obtained by using a black colorant as the colorant (B) in the method for producing a resist composition of the present invention is used. Can be formed on a transparent substrate.

As the light-shielding metal material that can be used to form the light-shielding metal thin film, for example, a chromium compound such as metallic chromium, chromium oxide, or chromium nitride, an alloy of nickel and tungsten, or the like is used, and the light-shielding metal thin film is used. , These social metal materials may be laminated in a plurality of layers. These light-shielding metal thin films are generally formed by a sputtering method.

For the metallic chromium, an etching solution obtained by mixing dicerium ammonium nitrate with perchloric acid and / or nitric acid is used, and for other materials, an etching solution suitable for the material is used for etching, and finally. A black matrix can be formed by peeling the resist composition with a special release agent. In this case, first, a thin film of these metals or metal oxides is formed on the transparent substrate by a vapor deposition method, a sputtering method, or the like. Next, a coating film layer of the color resist composition obtained by the production method of the present invention is formed on this thin film. Next, the coating film layer is exposed and developed using a photomask having a repeating pattern such as stripes, mosaics, and triangles to form an image. After that, the coating film layer can be etched to form a black matrix.

A resist composition containing a colorant of one of red, green, and blue is applied onto a substrate provided with a black matrix, dried, and then a photomask is superposed on a coating layer, and the photomask is passed through the photomask. A pixel image is formed by image exposure, development, and if necessary, heat curing or photocuring to create a colored layer. A color filter image can be formed by performing this operation on each of the three color resist compositions of red, green, and blue.

Examples of the method for supplying the resist composition to the substrate include a gravure coater, a roll coater, a comma coater, a knife coater, a curtain coater, a shower coater, a spin coater, a slit coater, a slit and spin coater, and a slit die coater. Examples include a method using dipping, screen printing, spraying, an applicator, a bar coater, and the like.

If the thickness of the coating film layer is too thick, pattern development becomes difficult and it may be difficult to adjust the gap in the liquid crystal cell formation process, while if it is too thin, it becomes difficult to increase the pigment concentration, which is desirable. Color expression may not be possible. The thickness of the coating film layer is usually in the range of 0.2 to 20 μm, preferably 0.5 to 10 μm, and more preferably 0.8 to 5 μm as the film thickness after drying.

After the resist composition is applied to the substrate to form a coating film layer on the substrate, it is dried (prebaked) in the step (4). Drying (pre-baking) can be performed, for example, by heating in a hot plate, an oven or the like in a temperature range of 50 to 140 ° C. for 10 to 300 seconds. Above all, it is preferable to heat in a temperature range of 70 to 130 ° C. for 30 to 180 seconds, and more preferably to heat in a temperature range of 80 to 120 ° C. for 30 to 90 seconds. Further, in order to perform drying more completely, vacuum drying may be performed before drying (pre-baking).

After drying (pre-baking), the desired pattern is exposed using a photomask in step (5). Specifically, for example, a negative matrix pattern is superimposed on a dried (prebaked) coating film layer, and active energy rays such as ultraviolet rays or visible light are irradiated through this mask pattern. At this time, if necessary, in order to prevent the sensitivity of the coating film layer formed by the resist composition from being lowered by oxygen, exposure may be performed after forming an oxygen blocking layer such as a polyvinyl alcohol layer on the coating film layer. good.

Examples of the active energy beam 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-pressure or high-pressure mercury lamps, ultra-high-pressure mercury lamps, electrodeless lamps, metal halide lamps, and natural light. Examples thereof include ultraviolet rays using the above as a light source, or electron beams produced by a scanning type or curtain type electron beam accelerator. When curing with an electron beam, it is not necessary to add the polymerization initiator to the resist composition.

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

After the exposure, the development process is performed in the step (6). In the above development process, the unexposed uncured portion is eluted with an alkaline developer, leaving only the photocured cured portion. The alkaline developer can be used without particular limitation as long as it dissolves the uncured portion and does not dissolve each pixel portion of RGB and the cured portion that becomes the black matrix portion. Specific examples of the alkaline developing solution include sodium hydroxide, potassium hydroxide, sodium carbonate, sodium hydrogencarbonate, sodium silicate, sodium metasilicate, aqueous ammonia, ethylamine, diethylamine, dimethylethanolamine, and tetramethylammonium hydroxy. Examples thereof include aqueous solutions of alkaline compounds such as sodium hydroxide, tetraethylammonium hydroxide, choline, pyrrole, piperidine, 1,8-diazabicyclo- [5,4,0] -7-undecene. The alkali concentration of this alkaline developer is preferably 0.001 to 10% by mass, more preferably 0.01 to 1% by mass. The developing temperature is usually 20 ° C. to 30 ° C., and the developing time is preferably in the range of 20 to 90 seconds.

After the development treatment, it is washed (rinsed) with distilled water in the step (7) and then dried. When washing and drying, post-baking treatment can be performed if necessary. Post-baking is a post-development heat treatment to complete the cure, usually in the temperature range of 200-250 ° C. The post-baking treatment can be performed on the developed layer continuously or in a batch manner by using a heating means such as a hot plate, a convection oven (hot air circulation type dryer), or a high frequency heater so as to meet the above conditions.

A substrate in which a transparent electrode such as ITO is formed on the pixels of the color filter produced as described above is used as a substrate for sandwiching a liquid crystal layer together with other substrates, and a backlight, a polarizing plate, and a liquid crystal layer are combined to form the liquid crystal of the present invention. It can be a display device.

Mixing the random copolymer (A) of the present invention, the colorant (B), and the thermoplastic resin (E) [thermoplastic resin other than the copolymer (A) and the alkaline availability resin (C)]. Can be used as a coating composition. Specifically, a polymerizable monomer (a1) having a fluorinated alkyl group having 1 to 6 carbon atoms directly bonded to the fluorine atom and a polymerizable unsaturated group, and a skeleton of a bridging ring hydrocarbon. A random copolymer by living radical polymerization of a polymerizable monomer (a2) having a polymerizable unsaturated group in the coexistence of the polymerizable monomer (a1) and the polymerizable monomer (a2). The coating composition can be obtained by a method including a step of obtaining (A) and a step of mixing the random copolymer (A), the colorant (B) and the thermoplastic resin (E).

Examples of the thermoplastic resin (E) include acrylic resin, methacrylic resin, acrylic urethane resin, acrylic silicone resin, acrylic melamine resin, acrylic modified polyolefin, acrylic modified fluororesin, aromatic polyester resin, aliphatic polyester resin, and polyamide. Examples thereof include resins, polycarbonate resins, vinyl acetate resins, ethylene-vinyl acetate resins and the like. Among the thermoplastic resins (E), an acrylic resin, a methacrylic resin, or an acrylic urethane resin is preferable because a coating composition capable of obtaining a coating layer having high strength can be obtained.

In the coating composition of the present invention, for example, the random copolymer (A), the colorant (B), and the thermoplastic resin (E) are dissolved in an organic solvent, and a shaker, a paint shaker, and a stirring blade are used. Examples thereof include a method of mixing by the method of stirring or the like used. As the organic solvent used here, for example, an organic solvent that can be used when preparing the pigment dispersion liquid can be used. The amount of the organic solvent used is, for example, usually 100 to 1000 parts by mass with respect to 100 parts by mass of the coating film layer forming component.

In the coating composition, the blending ratios when the random copolymer (A), the colorant (B), and the thermoplastic resin (E) are mixed are, for example, 0.0001 to each in terms of solid mass. It is 10 parts by mass, 5 to 80 parts by mass, and 0.1 to 80 parts by mass, preferably 0.001 to 5 parts by mass, 5 to 70 parts by mass, and 1 to 70 parts by mass.

An article with a coating film layer can be produced using the coating composition. The article with a coating film layer can be produced, for example, by forming a coating film layer of the coating composition on the article. Examples of the article include roofing materials (metal, slate, concrete, tile, cement, plastic, etc.), walls, tiles, glass plates, metals, blocks, concrete, plastics, cement, H-shaped steel, pipes, painted steel plates, and traffic lights. , Shutters, sandwich panels, tanks and other construction-related items; car body exteriors, window glass, dashboards, handles, shift levers, tires and other automobile-related items: exteriors, window glass and other aircraft-related items; Front / back sheets, housings for computers and mobile phones, various display screens such as plasma displays (PDPs) and organic EL displays, rubber rollers for OA equipment such as CDs, DVDs, Blu-ray discs, copiers and linters, copiers, etc. Electrical articles such as optical recording media such as the glass surface of the reading unit of OA equipment such as scanners: antireflection filters for display devices such as CRTs, liquid crystal displays, plasma displays, and projection televisions, spherical lenses, aspherical lenses, and Fresnel lenses. , Optical-related articles such as lens parts such as lenticular lenses.

The step of forming the coating film layer of the coating composition on the article can be performed by various methods. Specifically, for example, methods such as roll coater, electrostatic coating, bar coater, gravure coater, knife coater, dipping coating, and spray coating can be exemplified.

The thickness of the coating film layer may be appropriately selected depending on the type of the article and the intended use, but is usually 0.1 to 100 μm after drying.

After forming the coating film layer of the coating composition on the article, it is dried by various methods. The drying method may be appropriately selected according to the type of the article and the intended use. For example, a method of naturally drying by leaving it to stand and a method of forcibly drying in an atmosphere of 40 to 300 ° C. can be exemplified.

A coating composition can be obtained by mixing the random copolymer (A) of the present invention, the colorant (B), and the polymerizable compound (D). Specifically, a polymerizable monomer (a1) having a fluorinated alkyl group having 1 to 6 carbon atoms directly bonded to the fluorine atom and a polymerizable unsaturated group, and a skeleton of a bridging ring hydrocarbon. A random copolymer by living radical polymerization of a polymerizable monomer (a2) having a polymerizable unsaturated group in the coexistence of the polymerizable monomer (a1) and the polymerizable monomer (a2). The coating composition can be obtained by a method including a step of obtaining (A) and a step of mixing the random copolymer (A), the colorant (B) and the polymerizable compound (D).

In the coating composition, for example, the random copolymer (A), the colorant (B), and the polymerizable compound (D) are dissolved in an organic solvent, if necessary, and shaken, a paint shaker, and a stirring blade. A method of mixing by a method such as stirring using the above can be mentioned. As the organic solvent used here, for example, an organic solvent that can be used when preparing the pigment dispersion liquid can be used. When an organic solvent is used, the amount used is usually 100 to 1000 parts by mass with respect to 100 parts by mass of the coating film layer forming component.

When the random copolymer (A), the colorant (B), and the polymerizable compound (D) are mixed in the production of the coating composition, the blending ratio when the random copolymer (A), the colorant (B), and the polymerizable compound (D) are mixed is, for example, 0 in terms of solid mass. It is .0001 to 10 parts by mass, 5 to 80 parts by mass, and 0.1 to 80 parts by mass, and preferably, for example, 0.001 to 5 parts by mass, 5 to 70 parts by mass, and 1 to 70 parts by mass, respectively.

An article with a coating film layer can be obtained by using the coating composition. Specifically, the article with a coating film layer can be produced, for example, by forming a coating film layer of the coating composition on the article. As the article, for example, the article can be exemplified.

The step of forming the coating film layer of the coating composition on the article can be performed by various methods. Specifically, for example, methods such as roll coater, electrostatic coating, bar coater, gravure coater, knife coater, dipping coating, and spray coating can be exemplified.

The thickness of the coating film layer may be appropriately selected depending on the type of the article and the intended use, but is usually 0.1 to 100 μm after curing.

The coating film layer is cured by irradiating it with energy rays. Examples of the active energy ray include ionizing radiation such as ultraviolet rays, electron beams, α rays, β rays, and γ rays. Examples of the active energy radiation source or curing device include germicidal lamps, ultraviolet fluorescent lamps, carbon arcs, xenon lamps, high-pressure mercury lamps for copying, medium-pressure or high-pressure mercury lamps, ultra-high-pressure mercury lamps, electrodeless lamps, metal halide lamps, natural light, etc. Examples thereof include ultraviolet rays using the above as a light source, or electron beams produced by a scanning type or curtain type electron beam accelerator.

Among these, ultraviolet rays are particularly preferable, and in order to avoid curing inhibition due to oxygen or the like, it is preferable to irradiate ultraviolet rays in an atmosphere of an inert gas such as nitrogen gas. Further, if necessary, heat may be used in combination as an energy source, cured by ultraviolet rays, and then heat-treated.

Dose of the energy curable line may be any dose of the coating layer is cured, for ^example, in the range of ^{50mJ / cm 2 ~3000mJ / cm 2} .

Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples. In the example, unless otherwise specified, parts and% are based on mass. The measurement conditions for the IR spectrum, ¹³ C-NMR spectrum and GPC are as follows.

[IR spectrum measurement conditions]
Equipment: "FT / IR-6100" manufactured by JASCO Corporation
Measurement method: KBr method

[ ¹³ C-NMR spectrum measurement conditions]
Equipment: "JNM-AL400" manufactured by JEOL Ltd.
Solvent: Chloroform-d ₆

[GPC measurement conditions]
Measuring device: "HLC-8220 GPC" manufactured by Tosoh Corporation,
Column: Tosoh Co., Ltd. guard column "HHR-H" (6.0 mm I.D. x 4 cm) + Tosoh Co., Ltd. "TSK-GEL GMHHR-N" (7.8 mm I.D. x 30 cm) + Tosoh Co., Ltd. "TSK-GEL GMHHR-N" (7.8 mm I.D. x 30 cm) + Tosoh Co., Ltd. "TSK-GEL GMHHR-N" (7.8 mm I.D. x 30 cm) + Tosoh Co., Ltd. "TSK-" GEL GMHHR-N "(7.8 mm ID x 30 cm)
Detector: ELSD ("ELSD2000" manufactured by Oltec Japan Co., Ltd.)
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 velocity 1.0 ml / min Sample: A solution of 1.0 mass% tetrahydrofuran in terms of resin solid content filtered through a microfilter (5 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".

(Unidispersed 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

Reference Production Example 1 (Production of Pigment Dispersion Liquid)
C. red pigment. I. PigmentRed254 (BASF's "IRGAPHOR RED BT-CF") 10g is put in a polybin, PGMEA is 44g, DISPERBYK LPN21116 (Big Chemie Co., Ltd.) 12g, and 0.3-0.4mmΦ seple beads are added, and a paint conditioner (paint conditioner) Dispersed with Toyo Seiki Co., Ltd. for 2 hours to obtain a red pigment dispersion liquid (1).

Reference manufacturing example 2 (same as above)
C. is a yellow pigment. I. PigmentYello129 (“Irgazine Yellow L0800” manufactured by Chivas Specialty Chemicals Co., Ltd.) is placed in a polybin, 67 g of PGMEA, 23 g of DISPERBYK 161 (manufactured by Big Chemie Co., Ltd.) and Sepul beads of 0.3-0.4 mmΦ are added, and a paint conditioner is added. (Manufactured by Toyo Seiki Co., Ltd.) was dispersed for 2 hours to obtain a yellow pigment dispersion liquid (2).

Reference manufacturing example 3 (same as above)
As a yellow pigment, C.I. I. A yellow pigment dispersion (3) was obtained in the same manner as in Reference Production Example 2 except that PigmentYello 138 (“Pariotol Yellow K0961HD” manufactured by BASF) was used.

Reference manufacturing example 4 (same as above)
As a yellow pigment, C.I. I. A yellow pigment dispersion (4) was obtained in the same manner as in Reference Production Example 2 except that PigmentYello 139 (“Pariotol Yellow D1819” manufactured by BASF) was used.

Reference manufacturing example 5 (same as above)
As a yellow pigment, C.I. I. A yellow pigment dispersion (5) was obtained in the same manner as in Reference Production Example 2 except that PigmentYello150 (“E4GNGT” manufactured by LANXESS) was used.

Reference manufacturing example 6 (same as above)
As a yellow pigment, C.I. I. A yellow pigment dispersion (6) was obtained in the same manner as in Reference Production Example 2 except that PigmentYello 185 (“Pariotol Yellow D1155” manufactured by BASF) was used.

Reference Production Example 7 (Synthesis of Alkali-Soluble Resin)
100 g of propylene glycol monomethyl ether acetate was charged into a four-necked flask equipped with a stirrer, a thermometer, a cooling tube and a nitrogen introduction tube, and the internal temperature was raised to 110 ° C. while stirring under a nitrogen stream. Next, a mixture consisting of 80 g of benzyl methacrylate and 20 g of methacrylic acid, and a mixture of 46 g of propylene glycol monomethyl ether acetate, 1.5 g of t-amylperoxy-2-ethylhexanoate and 0.15 g of t-amylperbenzoate. Was added dropwise over 4 hours. After completion of the dropping, the polymerization reaction was carried out for 8 hours while maintaining the internal temperature at 110 ° C. After completion of the reaction, the mixture was diluted with propylene glycol monomethyl ether acetate to obtain a resin solution of an alkali-soluble resin having a non-volatile content of 40%. The weight average molecular weight of this resin was 17,000.

Example 1 (Production of Random Copolymer)
In a nitrogen-substituted flask, 111 g of methyl ethyl ketone, 47 g of 1-adamantyl methacrylate, and 25 g of 2- (tridecafluorohexyl) ethyl methacrylate were charged as solvents, and the temperature was raised to 60 ° C. with stirring under a nitrogen stream. Then, 5 g of 2,2'-bipyridyl, 2 g of cuprous chloride, and 3.3 g of ethyl 2-bromoisobutyrate were added, and the mixture was reacted at 60 ° C. for 23 hours under a nitrogen stream. Then, 30 g of activated alumina was added to the obtained reaction product, and the mixture was stirred. After filtering the activated alumina, the solvent was distilled off under reduced pressure to obtain a random copolymer (1). As a result of measuring the molecular weight of the random copolymer (1) by GPC, the weight average molecular weight (Mw) was 4,133, the number average molecular weight (Mn) was 3,197, and (Mw / Mn) was 1.29. rice field. The fluorine atom content of the random copolymer (1) was 20% by mass. The IR spectrum chart of the random copolymer (1) is shown in FIG. 1, the ¹³ C-NMR spectrum chart is shown in FIG. 2, and the GPC chart is shown in FIG.

A composition containing the random copolymer (1) was produced, and the smoothness of the obtained coating film layer was evaluated according to the following method. The evaluation results are shown in Table 1.

<Evaluation method of smoothness of coating film layer>
3 g of alkali-soluble resin (copolymer of benzyl methacrylate and acrylic acid) and 1.2 g of Aronix M-402 (manufactured by Toa Synthetic Chemical Co., Ltd.), which is a mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate. And 0.002 g of the random copolymer (1) in terms of solid content and 8.1 g of propylene glycol monomethyl ether acetate (PGMEA) were mixed to obtain a composition. 3 ml of this composition was dropped onto the central portion of a 10 cm × 10 cm chrome-plated glass substrate, spin-coated under the conditions of a rotation speed of 500 rpm and a rotation time of 30 seconds, and then heated and dried at 110 ° C. for 2 minutes to form a coating film layer. Created an article to have. The coating film layer was visually observed, and the smoothness of the coating film layer was evaluated according to the following criteria. The evaluation results are shown in Table 1.

<Evaluation criteria for smoothness of coating film layer>
◯: Almost no coating film unevenness is observed.
Δ: Part of the coating film unevenness is observed.
X: Many coating film unevenness is observed.

Example 2 (same as above)
In a nitrogen-substituted flask, 111 g of methyl ethyl ketone, 59 g of 1-adamantyl methacrylate, and 12 g of 2- (tridecafluorohexyl) ethyl methacrylate were charged as solvents, and the temperature was raised to 60 ° C. with stirring under a nitrogen stream. Then, 5 g of 2,2'-bipyridyl, 2 g of cuprous chloride, and 3.1 g of ethyl 2-bromoisobutyrate were added and reacted at 60 ° C. for 28 hours under a nitrogen stream. Then, 30 g of activated alumina was added to the obtained reaction product, and the mixture was stirred. After filtering the activated alumina, the solvent was distilled off under reduced pressure to obtain a random copolymer (2). As a result of measuring the molecular weight of the random copolymer by GPC, the weight average molecular weight (Mw) was 4,561, the number average molecular weight (Mn) was 3,824, and (Mw / Mn) was 1.19. The fluorine atom content of the random copolymer (2) was 10% by mass. The smoothness of the coating film layer was evaluated in the same manner as in Example 1, and the results are shown in Table 1.

Example 3 (same as above)
In a nitrogen-substituted flask, 111 g of methyl ethyl ketone, 47 g of dicyclopentanyl methacrylate, and 25 g of 2- (tridecafluorohexyl) ethyl methacrylate were charged as solvents, and the temperature was raised to 60 ° C. with stirring under a nitrogen stream. Then, 5 g of 2,2'-bipyridyl, 2 g of cuprous chloride, and 3.3 g of ethyl 2-bromoisobutyrate were added, and the mixture was reacted at 60 ° C. for 20 hours under a nitrogen stream. Then, 30 g of activated alumina was added to the obtained reaction product, and the mixture was stirred. After filtering the activated alumina, the solvent was distilled off under reduced pressure to obtain a random copolymer (3). As a result of measuring the molecular weight of the random copolymer (3) by GPC, the weight average molecular weight (Mw) was 4,219, the number average molecular weight (Mn) was 3,315, and (Mw / Mn) was 1.27. rice field. The fluorine atom content of the random copolymer (3) was 20% by mass. The smoothness of the coating film layer was evaluated in the same manner as in Example 1, and the results are shown in Table 1. The smoothness of the coating film layer was evaluated in the same manner as in Example 1, and the results are shown in Table 1.

Example 4 (same as above)
In a nitrogen-substituted flask, 111 g of methyl ethyl ketone, 47 g of isoboronyl methacrylate, and 25 g of 2- (tridecafluorohexyl) ethyl methacrylate were charged as solvents, and the temperature was raised to 60 ° C. with stirring under a nitrogen stream. Then, 4 g of 2,2'-bipyridyl, 1.5 g of cuprous chloride, and 2.1 g of ethyl 2-bromoisobutyrate were added, and the mixture was reacted at 60 ° C. for 35 hours under a nitrogen stream. Then, 30 g of activated alumina was added to the obtained reaction product, and the mixture was stirred. After filtering the activated alumina, the solvent was distilled off under reduced pressure to obtain a random copolymer (4). As a result of measuring the molecular weight of the random copolymer (4) by GPC, the weight average molecular weight (Mw) was 9,182, the number average molecular weight (Mn) was 7,345, and (Mw / Mn) was 1.25. rice field. The fluorine atom content of the random copolymer (4) was 20% by mass. The smoothness of the coating film layer was evaluated in the same manner as in Example 1, and the results are shown in Table 1.

Comparative Example 1 (Production of Copolymer for Comparative Control)
67 g of methanol, 0.961 g of 2,2'-bipyridyl and 0.305 g of cuprous chloride were charged in a nitrogen-substituted reaction vessel, and the mixture was stirred at room temperature for 60 minutes. After that, 3.37 g of 2- (nonafluorobutyl) ethyl methacrylate, 3.33 g of 2- (tridecafluorohexyl) ethyl methacrylate, and poly (1,2-oxybutylene) oxypropylene monomethacrylate (manufactured by Nichiyu Co., Ltd.). "Blemmer 10PPB-500B"; average number of repetitions of oxybutylene 6) 13.3 g and polyethylene glycol monomethacrylate ("Blemmer PE-200" manufactured by Nichiyu Co., Ltd .; average number of repetitions of oxyethylene 4.5) 20 g. 0.6 g of ethyl 2-bromoisobutyrate was added, and the mixture was reacted at 60 ° C. for 10 hours under a nitrogen stream. Then, 30 g of activated alumina was added to the obtained reaction product, and the mixture was stirred. After filtering activated alumina, the solvent was distilled off under reduced pressure to obtain a comparative control copolymer (1') having no crosslinked ring structure. As a result of measuring the molecular weight of the comparative control copolymer (1') by GPC, the weight average molecular weight (Mw) was 17,000, the number average molecular weight (Mn) was 13,000, and (Mw / Mn) was 1.25. there were. The fluorine atom content was 9.1% by mass. The smoothness of the coating film layer was evaluated in the same manner as in Example 1, and the results are shown in Table 1.

Comparative Example 2 (Production of Block Polymer for Comparative Control)
In a nitrogen-substituted flask, 47.5 g of 2-propanol and 25.6 g of 3-hydroxy-1-adamantyl methacrylate were charged as solvents, and the temperature was raised to 40 ° C. with stirring under a nitrogen stream. Next, 5.3 g of 2,2'-bipyridyl and 1.9 g of cuprous chloride were charged, and the inside of the flask was stirred for 30 minutes while keeping the temperature at 40 ° C. Then, 3.3 g of ethyl 2-bromoisobutyrate was added and reacted at 40 ° C. for 2 hours under a nitrogen stream to obtain a polymer segment containing an adamantane ring. Then, 45.9 g of 2- (tridecafluorohexyl) ethyl methacrylate was added to the reaction system containing the polymer segment, and the mixture was reacted at 40 ° C. for 5 hours to obtain a reaction product. Then, 30 g of activated alumina was added to the obtained reaction product, and the mixture was stirred. After filtering the activated alumina, the solvent was distilled off under reduced pressure to obtain a copolymer (2') for comparison and control. As a result of measuring the molecular weight of the comparative control copolymer (2') by GPC, the weight average molecular weight (Mw) was 3,100, the number average molecular weight (Mn) was 2,700, and (Mw / Mn) was 1.15. there were. The fluorine atom content was 14.5% by mass. The smoothness of the coating film layer was evaluated in the same manner as in Example 1, and the results are shown in Table 1.

Example 5 (Production of resist composition)
With respect to 5.9 g of the red pigment dispersion (1), 1.5 g of the 40 mass% resin solution of the alkali-soluble resin obtained in Reference Production Example 7 and a mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate were used. A certain Aronix M-402 (manufactured by Toa Synthetic Chemical Co., Ltd.) is 0.6 g, BASF Japan Co., Ltd. Irgacure # 369 is 0.05 g as a photopolymerization initiator, and a random copolymer (1) is converted into solid content. 0.0014 g and 2.2 g of PGMEA were added and mixed to prepare a color resist composition (1). A coating film layer is prepared using the color resist composition (1), and the ability (inhibitory property) to suppress the generation of foreign substances (foreign substances derived from pigments) in the coating film layer and the developability of the coating film layer with an alkaline solution are improved. Evaluation was performed according to the following method.

<Evaluation method for suppressing foreign substances in the coating film layer>
The color resist composition (1) was spin-coated on a 7 cm × 7 cm glass plate under the conditions of a rotation speed of 1000 rpm and a rotation time of 10 seconds, and then dried at 80 ° C. for 3 minutes to obtain an article having a dried coating film layer. .. An article having a cured coating film layer was obtained by irradiating the ^{dried coating film layer with active energy rays at 50 mJ / cm 2} using a high-pressure mercury lamp. Then, the article was heated at 270 ° C. for 1 hour, and then the coating film layer was observed with a Keyence digital microscope VHX-900 and evaluated according to the following criteria. The evaluation results are shown in Table 2.

◯: There is one or less foreign matter that can be confirmed in the coating film layer of 1 cm × 1 cm square.
Δ: An average of 2 to 9 foreign substances can be confirmed in the coating film layer of 1 cm × 1 cm square.
X: The average number of foreign substances that can be confirmed in the coating film layer of 1 cm × 1 cm square is 10 or more.

<Evaluation method of developability of coating film layer>
The color resist composition (1) was spin-coated on a 7 cm × 7 cm glass plate under the conditions of a rotation speed of 1000 rpm and a rotation time of 10 seconds, and then dried at 80 ° C. for 3 minutes to obtain an article having a dried coating film layer. .. The dried coating film layer was shower-developed (200 rpm, 45 seconds) with a 20-fold diluted aqueous solution of Semi-clean DL-A4 (an alkaline developer manufactured by Yokohama Oil & Fat Co., Ltd.), and then dried. The residual film ratio of the film was visually evaluated according to the following criteria.

◯: The residual film ratio is less than 10%.
Δ: The residual film ratio is 10 to 50%.
X: The residual film ratio is larger than 50%.

Example 6 (same as above)
To 6.2 g of the yellow pigment dispersion (2), 1.2 g of an alkali-soluble resin (copolymer of benzyl methacrylate and acrylic acid) and 0.6 g of Aronix M-402 were used as a photopolymerization initiator. Prepare the color resist composition (2) by adding 0.05 g of Irgacure # 369 manufactured by BASF Japan Co., Ltd., 0.0017 g of the random copolymer (1) in terms of solid content, and 2.2 g of PGMEA and mixing them. did. A coating film layer was prepared in the same manner as in Example 5, and the ability (inhibitory property) to suppress the generation of foreign substances (foreign substances derived from pigments) in the coating film layer and the developability of the coating film with an alkaline solution were evaluated. The evaluation results are shown in Table 2.

Example 7 (same as above)
A color resist composition (3) was prepared in the same manner as in Example 6 except that the yellow pigment dispersion liquid (3) was used instead of the yellow pigment dispersion liquid (2). A coating film layer was prepared in the same manner as in Example 5, and the ability (inhibitory property) to suppress the generation of foreign substances (foreign substances derived from pigments) in the coating film layer and the developability of the coating film with an alkaline solution were evaluated. The evaluation results are shown in Table 2.

Example 8 (same as above)
A color resist composition (4) was prepared in the same manner as in Example 6 except that the yellow pigment dispersion liquid (4) was used instead of the yellow pigment dispersion liquid (2). A coating film layer was prepared in the same manner as in Example 5, and the ability (inhibitory property) to suppress the generation of foreign substances (foreign substances derived from pigments) in the coating film layer and the developability of the coating film with an alkaline solution were evaluated. The evaluation results are shown in Table 2.

Example 9 (same as above)
A color resist composition (5) was prepared in the same manner as in Example 6 except that the yellow pigment dispersion liquid (5) was used instead of the yellow pigment dispersion liquid (2). A coating film layer was prepared in the same manner as in Example 5, and the ability (inhibitory property) to suppress the generation of foreign substances (foreign substances derived from pigments) in the coating film layer and the developability of the coating film with an alkaline solution were evaluated. The evaluation results are shown in Table 2.

Example 10 (same as above)
A color resist composition (6) was prepared in the same manner as in Example 6 except that the yellow pigment dispersion liquid (6) was used instead of the yellow pigment dispersion liquid (2). A coating film layer was prepared in the same manner as in Example 5, and the ability (inhibitory property) to suppress the generation of foreign substances (foreign substances derived from pigments) in the coating film layer and the developability of the coating film with an alkaline solution were evaluated. The evaluation results are shown in Table 2.

Example 11 (same as above)
A color resist composition (7) was prepared in the same manner as in Example 5 except that the random copolymer (2) was used instead of the random copolymer (1). A coating film layer was prepared in the same manner as in Example 5, and the ability (inhibitory property) to suppress the generation of foreign substances (foreign substances derived from pigments) in the coating film layer and the developability of the coating film with an alkaline solution were evaluated. The evaluation results are shown in Table 2.

Example 12 (same as above)
A color resist composition (8) was prepared in the same manner as in Example 5 except that the random copolymer (3) was used instead of the random copolymer (1). A coating film layer was prepared in the same manner as in Example 5, and the ability (inhibitory property) to suppress the generation of foreign substances (foreign substances derived from pigments) in the coating film layer and the developability of the coating film with an alkaline solution were evaluated. The evaluation results are shown in Table 2.

Example 13 (same as above)
A color resist composition (9) was prepared in the same manner as in Example 5 except that the random copolymer (4) was used instead of the random copolymer (1). A coating film layer was prepared in the same manner as in Example 5, and the ability (inhibitory property) to suppress the generation of foreign substances (foreign substances derived from pigments) in the coating film layer and the developability of the coating film with an alkaline solution were evaluated. The evaluation results are shown in Table 2.

Comparative Example 3 (Production of Resist Composition for Comparative Control)
A color resist composition (1') for comparison and control was prepared in the same manner as in Example 5 except that the copolymer for comparison and control (1') was used instead of the random copolymer (1). A coating film layer was prepared in the same manner as in Example 5, and the ability (inhibitory property) to suppress the generation of foreign substances (foreign substances derived from pigments) in the coating film layer and the developability of the coating film with an alkaline solution were evaluated. The evaluation results are shown in Table 3.

Comparative Example 4 (same as above)
A color resist composition (2') for comparison and control was prepared in the same manner as in Example 6 except that the copolymer for comparison and control (1') was used instead of the random copolymer (1). A coating film layer was prepared in the same manner as in Example 5, and the ability (inhibitory property) to suppress the generation of foreign substances (foreign substances derived from pigments) in the coating film layer and the developability of the coating film with an alkaline solution were evaluated. The evaluation results are shown in Table 3.

Comparative Example 5 (same as above)
Except that the yellow pigment dispersion (3) was used instead of the yellow pigment dispersion (2) and the comparative copolymer (1') was used instead of the random copolymer (1). A color resist composition (3') for comparison and control was prepared in the same manner as in Example 6. A coating film layer was prepared in the same manner as in Example 5, and the ability (inhibitory property) to suppress the generation of foreign substances (foreign substances derived from pigments) in the coating film layer and the developability of the coating film with an alkaline solution were evaluated. The evaluation results are shown in Table 3.

Comparative Example 6 (same as above)
Except that the yellow pigment dispersion (4) was used instead of the yellow pigment dispersion (2) and the comparative copolymer (1') was used instead of the random copolymer (1). A color resist composition (4') for comparison and control was prepared in the same manner as in Example 6. A coating film layer was prepared in the same manner as in Example 5, and the ability (inhibitory property) to suppress the generation of foreign substances (foreign substances derived from pigments) in the coating film layer and the developability of the coating film with an alkaline solution were evaluated. The evaluation results are shown in Table 3.

Comparative Example 7 (same as above)
Except that the yellow pigment dispersion (5) was used instead of the yellow pigment dispersion (2) and the comparative copolymer (1') was used instead of the random copolymer (1). A color resist composition (5') for comparison and control was prepared in the same manner as in Example 6. A coating film layer was prepared in the same manner as in Example 5, and the ability (inhibitory property) to suppress the generation of foreign substances (foreign substances derived from pigments) in the coating film layer and the developability of the coating film with an alkaline solution were evaluated. The evaluation results are shown in Table 3.

Comparative Example 8 (same as above)
Except that the yellow pigment dispersion (6) was used instead of the yellow pigment dispersion (2) and the comparative copolymer (1') was used instead of the random copolymer (1). A color resist composition (6') for comparison and control was prepared in the same manner as in Example 6. A coating film layer was prepared in the same manner as in Example 5, and the ability (inhibitory property) to suppress the generation of foreign substances (foreign substances derived from pigments) in the coating film layer and the developability of the coating film with an alkaline solution were evaluated. The evaluation results are shown in Table 3.

Comparative Example 9 (same as above)
A color resist composition (7') for comparison and control was prepared in the same manner as in Example 5 except that the copolymer for comparison and control (2') was used instead of the random copolymer (1). A coating film layer was prepared in the same manner as in Example 5, and the ability (inhibitory property) to suppress the generation of foreign substances (foreign substances derived from pigments) in the coating film layer and the developability of the coating film with an alkaline solution were evaluated. The evaluation results are shown in Table 4.

Comparative Example 10 (same as above)
A color resist composition (8') for comparison and control was prepared in the same manner as in Example 6 except that the copolymer for comparison and control (2') was used instead of the random copolymer (1). A coating film layer was prepared in the same manner as in Example 5, and the ability (inhibitory property) to suppress the generation of foreign substances (foreign substances derived from pigments) in the coating film layer and the developability of the coating film with an alkaline solution were evaluated. The evaluation results are shown in Table 4.

Comparative Example 11 (same as above)
Except that the yellow pigment dispersion (3) was used instead of the yellow pigment dispersion (2) and the comparative copolymer (2') was used instead of the random copolymer (1). A color resist composition (9') for comparison and control was prepared in the same manner as in Example 6. A coating film layer was prepared in the same manner as in Example 5, and the ability (inhibitory property) to suppress the generation of foreign substances (foreign substances derived from pigments) in the coating film layer and the developability of the coating film with an alkaline solution were evaluated. The evaluation results are shown in Table 4.

Comparative Example 12 (same as above)
Except that the yellow pigment dispersion (4) was used instead of the yellow pigment dispersion (2) and the comparative copolymer (2') was used instead of the random copolymer (1). A color resist composition (10') for comparison and control was prepared in the same manner as in Example 6. A coating film layer was prepared in the same manner as in Example 5, and the ability (inhibitory property) to suppress the generation of foreign substances (foreign substances derived from pigments) in the coating film layer and the developability of the coating film with an alkaline solution were evaluated. The evaluation results are shown in Table 4.

Comparative Example 13 (same as above)
Except that the yellow pigment dispersion (5) was used instead of the yellow pigment dispersion (2) and the comparative copolymer (2') was used instead of the random copolymer (1). A color resist composition (11') for comparison and control was prepared in the same manner as in Example 6. A coating film layer was prepared in the same manner as in Example 5, and the ability (inhibitory property) to suppress the generation of foreign substances (foreign substances derived from pigments) in the coating film layer and the developability of the coating film with an alkaline solution were evaluated. The evaluation results are shown in Table 4.

Comparative Example 14 (same as above)
Except that the yellow pigment dispersion (6) was used instead of the yellow pigment dispersion (2) and the comparative copolymer (2') was used instead of the random copolymer (1). A color resist composition (12') for comparison and control was prepared in the same manner as in Example 6. A coating film layer was prepared in the same manner as in Example 5, and the ability (inhibitory property) to suppress the generation of foreign substances (foreign substances derived from pigments) in the coating film layer and the developability of the coating film with an alkaline solution were evaluated. The evaluation results are shown in Table 4.

Claims (8)

A color resist composition containing a random copolymer (A), a colorant (B), an alkali-soluble resin (C), and a polymerizable compound (D).
The random copolymer (A) has a bridging ring with a polymerizable monomer (a1) having a fluorinated alkyl group having 1 to 6 carbon atoms to which a fluorine atom is directly bonded and a polymerizable unsaturated group. It is a random copolymer of a polymerizable monomer (a2) having a hydrocarbon skeleton and a polymerizable unsaturated group, and is a ratio of a weight average molecular weight (Mw) to a number average molecular weight (Mn) (Mw /). A color resist composition having Mn) of 1.0 to 1.8. The color resist composition according to claim 1, wherein the skeleton of the bridging ring hydrocarbon contained in the polymerizable monomer (a2) is an adamantane ring, a dicyclopentane ring, a dicyclopentene ring, a norbornane ring or a norbornene ring. The color resist composition according to claim 1, wherein the skeleton of the crosslinked ring hydrocarbon contained in the polymerizable monomer (a2) is an adamantane ring. The color resist composition according to claim 1, wherein the polymerizable unsaturated group of the polymerizable monomer (a1) and the polymerizable unsaturated group of the polymerizable monomer (a2) are (meth) acryloyl groups, respectively. .. The color resist composition according to claim 1, wherein the polymerizable monomer (a1) is a monomer represented by the following general formula (1).

[In the above 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 and Rf. 'Represents any one group of the following formulas (Rf-1) to (Rf-4)), and X represents any one group of the following formulas (X-1) to (X-10). , And Rf represents any one group of the following formulas (Rf-1) to (Rf-4). ]

[N in the above formulas (X-1), (X-3), (X-4), (X-5), (X-6) and (X-7) represents an integer of 1 to 8. In the above formulas (X-8), (X-9) and (X-10), m represents an integer of 1 to 8 and n represents an integer of 0 to 8. Rf'' in the above formulas (X-6) and (X-7) represents any one group of the following formulas (Rf-1) to (Rf-4). ]

[N in the above equations (Rf-1) and (Rf-2) represents an integer of 1 to 6. N in the above equation (Rf-3) represents an integer of 2 to 6. N in the above equation (Rf-4) represents an integer of 4 to 6. ] The color resist composition according to claim 1, wherein the ratio (Mw / Mn) of the weight average molecular weight (Mw) to the number average molecular weight (Mn) is 1.0 to 1.5. The colorant (B) is C.I. I. Pigment Red 177, C.I. I. Pigment Red 207, C.I. I. Pigment Red 254, C.I. I. Pigment Green 7, C.I. I. Pigment Green 36, C.I. I. Pigment Green 58, C.I. I. Pigment Green 59, C.I. I. Pigment Yellow 83, C.I. I. Pigment Yellow 93, C.I. I. Pigment Yellow 109, C.I. I. Pigment Yellow 110, C.I. I. Pigment Yellow 129, C.I. I. Pigment Yellow 138, C.I. I. Pigment Yellow 139, C.I. I. Pigment Yellow 150, C.I. I. Pigment Yellow 154, C.I. I. Pigment Yellow 180, C.I. I. Pigment Yellow 185, C.I. I. Pigment Blue 15: 1, C.I. I. Pigment Blue 15: 2, C.I. I. Pigment Blue 15: 6 and C.I. I. The color resist composition according to any one of claims 1 to 6, which is one or more pigments selected from the group consisting of Pigment Violet 23. A color filter characterized in that a coating film layer of the resist composition according to any one of claims 1 to 7 is formed on a substrate.

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