KR20180115714A - Random copolymer, resist composition, color filter and method for producing random copolymer - Google Patents

Abstract

A random copolymer (a fluorine-based surfactant) which can obtain a smooth color resist layer and which can inhibit the generation of foreign matter derived from a coloring agent such as a pigment in the color resist layer and can provide a resist composition excellent in developability, A resist composition, and a color filter. Specifically, a polymerizable monomer (a1) having a fluorinated alkyl group having 1 to 6 carbon atoms in which fluorine atoms are directly bonded and a polymerizable unsaturated group and a random polymerizable monomer (a2) having a skeleton of a crosslinked ring hydrocarbon and a polymerizable monomer having a polymerizable unsaturated group And a ratio (Mw / Mn) of a weight average molecular weight (Mw) to a number average molecular weight (Mn) of 1.0 to 1.8, and is a resist composition and a color filter using the copolymer.

Description

Random copolymer, resist composition, color filter and method for producing random copolymer

The present invention relates to a random copolymer (fluorochemical surfactant) which can obtain a smooth color resist layer, suppress the generation of foreign matter derived from a coloring agent such as a pigment in the color resist layer, A resist composition using the same, and a color filter. The present invention also relates to a method for producing the random copolymer.

BACKGROUND ART Conventionally, various surfactants, such as hydrocarbons, silicones, and fluorine-based surfactants, have been used for the purpose of improving the homogeneity and smoothness of a coating film (coating film) obtained in various coating fields. Among them, fluorine-based surfactants are widely used because of their high ability of lowering the surface tension and having less contamination after coating (coating).

Among the above-mentioned fluorine-based surfactants, surfactants using perfluoroalkyl groups having 8 or more carbon atoms are excellent in the performance as a leveling agent due to their surface tension lowering ability. However, surfactants having a perfluoroalkyl group having 8 or more carbon atoms A surfactant using a perfluoroalkyl group having a carbon atom number of less than 8 has been proposed since it produces a compound such as perfluorooctanesulfonic acid or the like which is likely to accumulate in the environment or in a living body. 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 has been proposed (see, for example, Patent Document 1) .

In addition, in the above-mentioned coating field, particularly in a composition (color resist composition) for producing a color filter, a performance is required which is hard to discolor the coating film (difficult to be stained with water) even when exposed to an alkaline aqueous solution used as a developing solution. In order to obtain a resist composition having such a performance, a fluorine-based surfactant, which is a block copolymer having a polymer segment of a polymerizable monomer having a fluorinated alkyl group of 1 to 6 carbon atoms and a polymer segment of a polymerizable monomer having a skeleton of a crosslinked ring hydrocarbon, (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 by an alkaline aqueous solution is insufficient.

In addition, a desired color is also required when forming a colored coating film layer such as a coating film (color resist pattern) of a color resist composition. In order to obtain a coating film layer having a desired color, for example, a color resist pattern having a hue excellent in color, CI Pigment Red 254 and the like (coloring agent) are used. However, the above C.I. Pigments such as Pigment Red 254 are easy to sublimate and have a property that crystals tend to grow due to their intermolecular interaction. Therefore, in the heating process for forming a color filter, pigments such as pigment The molecules are crystallized and coagulated on the surface of the coating film, and foreign matter is generated. When such a foreign matter is generated, light scattering due to the particles and non-uniformity of the pigment dispersion occur, and as a result, it becomes difficult to obtain the desired color.

Japanese Patent Application Laid-Open No. 2013-6928 International Publication No. 2015/137229 pamphlet

A problem to be solved by the present invention is to provide a copolymer in which a smooth color resist layer can be obtained and occurrence of foreign matter derived from the colorant in the color resist layer can be suppressed and a resist composition excellent in developability can be obtained An activator), a resist composition using the same, and a color filter. In addition, a problem to be solved by the present invention is to provide a process for producing the above fluoropolymer (a random copolymer of living radical polymerization).

As a result of intensive studies, the present inventors have found that a polymerizable monomer having a polymerizable monomer having a fluorinated alkyl group and a polymerizable unsaturated group and a polymerizable monomer having a skeleton of a crosslinked ring hydrocarbon such as a polymerizable monomer having an adamantane ring and a polymerizable unsaturated group and a polymerizable monomer having a polymerizable unsaturated group (Mw) / (Mn) of the weight average molecular weight (Mw) to the number average molecular weight (Mn) of the random copolymer is 1.0 to 1.8 , It is possible to obtain a resist composition which is less susceptible to generation of foreign matter in the coating film even when a colorant which is easy to sublimate or crystallize is used. The resist composition is also excellent in developing property. By using these compositions A color filter having a desired color can be obtained, and so on, and thus the present invention has been accomplished.

That is, the present invention relates to a polymerizable monomer composition comprising a polymerizable monomer (a1) having a fluorinated alkyl group having 1 to 6 carbon atoms in which fluorine atoms are directly bonded and a polymerizable unsaturated group, and a polymerizable monomer (a2) having a skeleton of a crosslinked ring hydrocarbon and a polymerizable monomer And a ratio (Mw / Mn) of a weight average molecular weight (Mw) to a number average molecular weight (Mn) of 1.0 to 1.8.

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

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

(A1) having a fluorinated alkyl group having 1 to 6 carbon atoms to which a fluorine atom is directly bonded and a polymerizable monomer having a polymerizable unsaturated group and a polymerizable monomer (a2) having a skeleton of a crosslinked ring hydrocarbon and a polymerizable unsaturated group, , And a living radical polymerization is carried out under the coexistence of the polymerizable monomer (a1) and the polymerizable monomer (a2).

The present invention can provide a random copolymer which can obtain a smooth color resist layer, suppress the generation of foreign matter derived from the coloring agent in the color resist layer, and can provide a resist composition excellent in developing property, and a process for producing the same have. Further, the present invention can provide a resist composition for obtaining a desired color coat layer and a color filter having a desired color coat layer.

Further, the random copolymer of the present invention can be suitably used for a color resist composition, as well as for forming a coating layer on the surface of an article such as a composition for forming a black matrix, It may be used suitably for a composition or the like.

1 is a chart of an IR spectrum of the random copolymer (1) obtained in Example 1;
2 is a chart of the ¹³ C-NMR spectrum of the random copolymer (1) obtained in Example 1. Fig.
3 is a chart of GPC of the random copolymer (1) obtained in Example 1. Fig.

The present invention relates to a random copolymer (a1) comprising a polymerizable monomer (a1) having a fluorinated alkyl group having 1 to 6 carbon atoms directly bonded with a fluorine atom and a polymerizable unsaturated group and a polymerizable monomer (a2) having a skeleton of a crosslinked ring hydrocarbon and a polymerizable unsaturated group (Mw / Mn) of the weight average molecular weight (Mw) to the number average molecular weight (Mn) is 1.0 to 1.8. The present invention also provides a random copolymer.

The polymerizable monomer (a1) having a fluorinated alkyl group and a polymerizable unsaturated group having 1 to 6 carbon atoms in which the fluorine atoms are directly bonded is not particularly limited as far as the compound has the fluorinated alkyl group and the polymerizable unsaturated group in the molecule.

Here, the fluorinated alkyl group having 1 to 6 carbon atoms in which the fluorine atoms are directly bonded is a perfluoroalkyl group having 1 to 6 carbon atoms in which fluorine atoms are directly bonded, or a partially fluorinated alkyl group in which a part of hydrogen atoms are fluorine atoms. Of these fluorinated alkyl groups, perfluoroalkyl groups are preferred because the resulting polymer has a high effect as a surfactant. The number of carbon atoms to which a fluorine atom is bonded directly is more preferable, and the number of carbon atoms to which a fluorine atom is directly bonded is particularly preferably from 4 to 6. [

Examples of the polymerizable unsaturated group of the polymerizable monomer (a1) include a (meth) acryloyl group, a vinyl group and a maleimide group. Among them, it is easy to obtain the raw materials, and when the resist composition or the coating composition is produced by using the obtained random copolymer, it is easy to control the compatibility of the random copolymer with respect to the compounding ingredients in the composition And (meth) acryloyl group is preferable since polymerization reactivity is good. As specific examples having (meth) acryloyl groups, for example, monomers represented by the following general formula (1) can be preferably exemplified. The polymerizable monomer (a1) may be used singly or in combination of two or more.

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' X represents any one of groups represented by the following formulas (X-1) to (X-10), Rf represents a group represented by the following formula (Rf-1) to (Rf-4).

N in the formulas (X-1), (X-3), (X-4), (X-5), (X-6) and (X-7) represents an integer of 1 to 8. M in the formulas (X-8), (X-9) and (X-10) represents an integer of 1 to 8 and n represents an integer of 0 to 8. Rf "in the formulas (X-6) and (X-7) represents any one of groups represented by the following formulas (Rf-1) to (Rf-4)

[N in the formulas (Rf-1) and (Rf-2) represents an integer of 1 to 6) N in the formula (Rf-3) represents an integer of 2 to 6. And n in the formula (Rf-4) represents an integer of 4 to 6.)

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

The polymerizable monomer (a2) has a crosslinked ring hydrocarbon skeleton 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 sometimes referred to as a block layer) is localized on the surface. The random copolymer of the present invention has a high glass transition temperature (Tg) 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 layer formed in the method of manufacturing a color filter described later has a block layer having a high hardness due to the presence of the skeleton of the crosslinked ring hydrocarbon. This block layer having a high hardness prevents the colorant such as pigment in the coating layer from being deposited (sublimed) on the outermost surface, and the skeleton of the crosslinked ring hydrocarbon in the block layer is dispersed in the pigment layer And as a result, the inventors presume that the formation of foreign matters derived from a coloring agent such as a pigment is suppressed.

Examples of the skeleton of the crosslinked ring hydrocarbon include adamantane ring, perhydroindenylene ring, decalin ring, perhydrofluorene ring, perhydroanthracene ring, perhydrophenanthrene ring, dicyclopentane ring, dicyclopentane ring , Perhydro-acenaphthene ring, perhydrophenylene ring, norbornane ring, norbornene ring and the like. Of these, adamantane, dicyclopentane, norbornane, and norbornene rings are preferable because a block layer having a high Tg can be formed by the outermost surface of the coating film and the generation of foreign matter derived from the pigment can be suppressed , And adamantanemethane is more preferable.

Hereinafter, the 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 adamantane ring and (meth) acryloyl group include the compounds represented by the following formulas (a2-1) and (a2-2).

(Wherein 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, and an acid anhydride group. Among them, a hydroxyl group is preferable since a random copolymer having good compatibility with a compounding component in a composition can be obtained when a resist composition or a coating composition is produced using the obtained random copolymer.

The bonding position of the organic group having a reactive functional group represented by -XL in the general formula (a2-1) and Y may be bonded to any carbon atom in the adamantanemember, and two or more . The hydrogen atom bonded to the carbon atom constituting the adamantanemember may be partially or entirely substituted with a fluorine atom, an alkyl group, or the like. In the general formula (a2-1), X and Y are a divalent organic group or a single bond. Examples of the divalent organic group include a methylene group, a propyl group, an isopropylidene group and the like having 1 to 8 carbon atoms Alkylene group.

In the compound represented by the above formula (a2-2), the (meth) acryloyl group may be bonded to any carbon atom in the adamantyl group. The hydrogen atom bonded to the carbon atom constituting the adamantane structure in the general formula (a2-1) may be partially or entirely 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, for example, the following compounds.

More specific examples of the polymerizable monomer represented by the general formula (a2-2) include, for example, the following compounds.

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

Hereinafter, the polymerizable monomer having a dicyclopentanecane 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).

(Wherein R represents a hydrogen atom, a methyl group or CF ₃ )

In the compound represented by the above formula (a2-3), the (meth) acryloyl group may be bonded to any carbon atom in the dicyclopentanemal ring. The hydrogen atom bonded to the carbon atom constituting the dicyclopentanecane ring in the general formula (a2-3) may be partially or entirely 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, for example, the following compounds.

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

Hereinafter, the 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).

(Wherein R represents a hydrogen atom, a methyl group or CF ₃ )

In the compound represented by the formula (a2-4), the (meth) acryloyl group may be bonded to any carbon atom in the dicyclopentane ring. The hydrogen atom bonded to the carbon atom constituting the dicyclopentane ring in the general formula (a2-3) may be partially or entirely 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, for example, the following compounds.

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

Hereinafter, the norbornane ring and the polymerizable monomer having 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).

(Wherein R represents a hydrogen atom, a methyl group or CF ₃ )

In the compound represented by the formula (a2-5), the (meth) acryloyl group may be bonded to any carbon atom in the norbornane ring. The hydrogen atom bonded to the carbon atom constituting the norbornane ring in the general formula (a2-5) may be partially or entirely 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, for example, the following compounds.

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

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

The polymerizable monomer having a norbornene ring and a (meth) acryloyl group includes, for example, a compound represented by the following formula (a2-6).

(Wherein R represents a hydrogen atom, a methyl group or CF ₃ )

In the compound represented by the formula (a2-6), the (meth) acryloyl group may be bonded to any carbon atom in the norbornene ring. The hydrogen atom bonded to the carbon atom constituting the norbornene ring in the general formula (a2-6) may be partially or entirely 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, for example, the following compounds.

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

The present invention relates to a random copolymer (a1) comprising a polymerizable monomer (a1) having a fluorinated alkyl group having 1 to 6 carbon atoms directly bonded with a fluorine atom and a polymerizable unsaturated group and a polymerizable monomer (a2) having a skeleton of a crosslinked ring hydrocarbon and a polymerizable unsaturated group (Mw / Mn) of the weight average molecular weight (Mw) to the number average molecular weight (Mn) is 1.0 to 1.8. The present invention also provides a random copolymer. Here, when the ratio (Mw / Mn) exceeds 1.8, a solid coating film surface can not be formed, which is not preferable. The ratio (Mw / Mn) is more preferably in the range of 1.0 to 1.7, and 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 in the range of 500 to 200,000, more preferably in the range of 1,000 to 150,000, since a stiffer coat film surface is obtained and a random copolymer having good leveling property is obtained. More preferably in the range of 1,500 to 100,000.

The number average molecular weight (Mn) of the random copolymer of the present invention is preferably in the range of 300 to 120,000, and more preferably in the range of 500 to 80,000, since the random copolymer obtains a stiffer coat film surface and has a good leveling property , And more preferably in the range of 800 to 60,000.

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

[Conditions for measuring GPC]

Measurement apparatus: "HLC-8220 GPC" manufactured by Tosoh Corporation,

Column: " HHR-H " (6.0 mm ID x 4 cm) manufactured by Tosoh Corporation, TSK-GEL GMHHR-N (7.8 mm ID x 30 cm) manufactured by Tosoh Corporation, TSK-GEL GMHHR-N "(7.8 mm ID × 30 cm) manufactured by Tosoh Corporation, TSK-GEL GMHHR-N (7.8 mm ID x 30 cm)

Detector: ELSD (ELSD2000 manufactured by Alltech Japan)

Data processing: "GPC-8020 Model II Data Analysis Version 4.30" manufactured by Tosoh Corporation

Measurement conditions: column temperature 40 ℃

      Developing solvent Tetrahydrofuran (THF)

      Flow rate 1.0 ml / min

Sample: A tetrahydrofuran solution of 1.0% by mass in terms of resin solid matter was filtered with a microfilter (5 μl).

Standard samples: 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".

(Monodisperse polystyrene)

Quot; A-500 " manufactured by Tosoh Corporation

&Quot; A-1000 " manufactured by Tosoh Corporation

Quot; A-2500 " manufactured by Tosoh Corporation

Quot; A-5000 " manufactured by Tosoh Corporation

Quot; F-1 " manufactured by Tosoh Corporation

Quot; F-2 " manufactured by Tosoh Corporation

Quot; F-4 " manufactured by Tosoh Corporation

Quot; F-10 " manufactured by Tosoh Corporation

Quot; F-20 " manufactured by Tosoh Corporation

Quot; F-40 " manufactured by Tosoh Corporation

Quot; F-80 " manufactured by Tosoh Corporation

Quot; F-128 " manufactured by Tosoh Corporation

Quot; F-288 " manufactured by Tosoh Corporation

Quot; F-550 " manufactured by Tosoh Corporation

The content of fluorine atoms in the random copolymer of the present invention is preferably in the range of 4 to 40 mass%, more preferably in the range of 5 to 35 mass%, and more preferably in the range of 5 to 35 mass%, since it is a random copolymer which exhibits less uniformity of coating and exhibits good leveling property By mass, more preferably from 6 to 30% by mass. The content of fluorine atoms can be measured by combustion ion chromatography.

In the present invention, the random copolymer of the polymerizable monomer (a1) and the polymerizable monomer (a2) may be copolymerized with the polymerizable monomer (a1) and the polymerizable monomer (a2) within a range that does not impair the effect of the present invention Or may have a structure derived from a monomer (a3).

Examples of the polymerizable monomer (a3) include a monomer (a3-1) having an oxyalkylene group and a monomer (a3-2) having an alkyl group. Examples of the polymerizable unsaturated group contained in the polymerizable monomer (a3) include a (meth) acryloyl group, a vinyl group and a maleimide group. The polymerizable monomer (a1) and the polymerizable monomer (a2 ) Is a (meth) acryloyl group, it is preferable that the polymerizable unsaturated (meth) acryloyl group possessed by the polymerizable monomer (a3) has a good copolymerization.

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

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

Y ¹ and Y ² in the general formula (a3-1) are alkylene groups, but these alkylene groups include those having a substituent. ^{-O- (Y 1 O) n- (} Y 2 O) Specific examples of m- part, be repeating units wherein p is 1 and m is 0, and Y ¹ is ethylene glycol residues, the repeating unit number p is 1 Propylene glycol residues in which m is 0 and Y ¹ is propylene, a butylene glycol residue in which the number of repeating units p is 1 and m is 0 and Y ¹ is butylene, the number of repeating units p is an integer of 2 or more and q Is 0, and Y ¹ is ethylene, a polypropylene glycol residue in which the number of repeating units p is an integer of 2 or more and q is 0 and Y ¹ is propylene, the number of repeating units p and q is an integer of 1 or more And a residue of a polyalkylene glycol such as a copolymer of ethylene oxide and propylene oxide in which Y ¹ or Y ² is ethylene and the other is propylene.

The polymerization degree of the polyalkylene glycol in the monomer (a3-1) having an oxyalkylene group, that is, the sum of p and q in the general formula (a3-1) is preferably in the range of 1 to 100, more preferably in the range of 2 to 80 More preferably in the range of 3 to 50, The repeating unit containing Y ¹ and the repeating unit containing Y ² may be arranged in a random phase or in a block phase.

R ³ in the 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 an alkylene glycol such as polyethylene glycol, polypropylene glycol or polybutylene glycol, and when R ³ has 1 to 6 carbon atoms, (Meth) acrylic acid ester of an alkylene glycol mono (meth) acrylic ester is encapsulated by an alkyl group having 1 to 6 carbon atoms.

Among the monomer (a3-1) having an oxyalkylene group, a monomer having a poly (oxyalkylene) group composed of a plurality of oxyalkylene groups is preferable, and specific examples thereof include polypropylene glycol mono (meth) acrylate, 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, polyethyleneglycol · polytetramethylene glycol mono (meth) acrylate, poly (propylene glycol · tetramethylene glycol) Polypropylene glycol · polytetramethylene glycol mono (meth) acrylate, Polypropylene glycol · polybutylene glycol mono (meth) acrylate, poly (ethylene glycol · butylene glycol) mono (meth) acrylate, polyethylene glycol · propylene glycol · butylene glycol Polybutylene glycol mono (meth) acrylate, poly (tetraethylene glycol-butylene glycol) mono (meth) acrylate, polytetraethylene glycol-polybutylene glycol mono (meth) acrylate, polybutylene glycol mono (Meth) acrylate, poly (ethylene glycol · trimethylene glycol) mono (meth) acrylate, polyethylene glycol · polytrimethylene glycol mono (meth) acrylate, poly (propylene glycol · trimethylene glycol) , Polypropylene glycol · polytrimethylene glycol mono (meth) acrylate, poly (trimethylene glycol · tetramethylene glycol) mono ( Poly (butylene glycol · trimethylene glycol) mono (meth) acrylate, polybutylene glycol · polytrimethylene glycol mono (meth) acrylate, polytrimethylene glycol · polytetramethylene glycol mono ) Acrylate, and the like. "Poly (ethylene glycol-propylene glycol)" means a random copolymer of ethylene glycol and propylene glycol, and "polyethylene glycol-polypropylene glycol" means a block copolymer of ethylene glycol and propylene glycol do. Other things are the same. When the monomer (a3-1) having an oxyalkylene group is used in the method for producing a fluorine-containing polymer of the present invention, a fluorine-containing polymer having good compatibility with other components in the resist composition or coating composition is obtained, Propylene glycol mono (meth) acrylate, polyethylene glycol mono (meth) acrylate, and polyethylene glycol · polypropylene glycol mono (meth) acrylate.

Examples of commercially available monomer (a3-1) having an oxyalkylene group include "NK ester M-20G", "NK ester M-40G" and "NK ester" manufactured by Shin Nakamura Kagaku Kogyo Co., NK Ester AMP-20G "," NK Ester AMP-60G "," NK Ester AM-90G "," NK Ester AMP-10G " Blenda PE-90 "," Blenda PE-200 "," Blenda PE-350 "," Blenda PME-100 "," Blenda PME-200 "," Blenda PME- Blender PM-4000, Blenda PP-1000, Blenda PP-500, Blenda PP-800, Blenda 70PEP-350B, Blenda 55PET-800, Blenda 10PPB-500B, Blenda NKH-5050, Blenda AP-400, and Blenda AE-350. These oxyalkylene group-containing monomer (a3-1) may be used alone or in combination of two or more.

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

(Wherein R ⁴ is a hydrogen atom or a methyl group and R ⁵ is an alkyl group having a straight, branched or cyclic structure having 1 to 18 carbon atoms)

In the general formula (a3-2), R ⁵ is a linear, branched or cyclic alkyl group having 1 to 18 carbon atoms. The alkyl group may have a substituent such as an aliphatic or aromatic 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 Alkyl esters having 1 to 18 carbon atoms of (meth) acrylic acid such as ethylhexyl (meth) acrylate, decyl (meth) acrylate, dodecyl (meth) acrylate and stearyl (meth) acrylate; (Meth) acrylate, dicyclopentanyloxylethyl (meth) acrylate, isobornyloxylethyl (meth) acrylate, isobornyl (meth) acrylate, adamantyl (A2) having 1 to 18 carbon atoms of (meth) acrylic acid such as dicyclopentanyl (meth) acrylate and dicyclopentenyl (meth) acrylate. These monomer (a3-2) having an alkyl group may be used alone or in combination of two or more.

When the polymerizable monomer (a3) is used together with the polymerizable monomer (a1) and the polymerizable monomer (a2), the amount of the polymerizable monomer (a3) is preferably from 1 to 100 parts by mass based on 100 parts by mass of the total of the monomer (a1) It is preferable that a random copolymer capable of suppressing generation of foreign matter derived from a coloring agent such as a pigment and exhibiting various effects due to the monomer (a3) can be obtained, and more preferably 1 to 50 parts by mass desirable.

The random copolymer of the present invention can be produced, for example, by copolymerizing a polymerizable monomer (a1) having a fluorinated alkyl group having 1 to 6 carbon atoms with a fluorine atom directly bonded thereto and a polymerizable monomer having a polymerizable unsaturated group The polymerizable monomer (a2) can be obtained by living radical polymerization in the presence of the polymerizable monomer (a1) and the polymerizable monomer (a2).

In the living radical polymerization, a dormant species in which an active polymerization terminal is protected by an atom or an atomic group generates a radical in a reversible manner and reacts with the monomer to proceed a growth reaction. Examples of such living radical polymerization include atom transfer radical polymerization (ATRP), reversible addition-cleavable radical polymerization (RAFT), radical polymerization through nitroxide (NMP), radical polymerization using organic tellurium . No particular limitation is imposed on which of these methods is used, but the above ATRP is preferable because of ease of control and the like. ATRP is polymerized using an organic halide, a halogenated sulfonyl compound or the like as a catalyst as a catalyst, a metal complex comprising a transition metal compound and a ligand.

As the polymerization initiator used in the ATRP, an organic halogenated compound may be used. Specific examples thereof include 1-phenylethyl chloride and 1-phenylethyl bromide, chloroform, carbon tetrachloride, 2-chloropropionitrile,?,? '- dichloro xylene,?,?' - dibromohydrin, hexakis (E.g., 2-chloropropionic acid, 2-bromopropionic acid, 2-chloroisobutyric acid, 2-bromoisobutyric acid, etc.) of 2-halogenated carboxylic acid having 1 to 6 carbon atoms Alkyl esters having a number of 1 to 6, and the like. Further, more specific examples of the alkyl ester having 1 to 6 carbon atoms in the 2-halogenated carboxylic acid having 1 to 6 carbon atoms include methyl 2-chloropropionate, ethyl 2-chloropropionate, methyl 2-bromopropionate , Ethyl 2-bromoisobutyrate, and the like.

The transition metal compound used in the ATRP is represented by M ^{n +} X _n . Transition metal M ^{n + is, 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 +, can be selected from the group consisting of Ag ⁺ and Ag ^{+ 2.} X represents a halogen atom, an alkoxyl group having 1 to 6 carbon atoms, (SO ₄ ) _1/2 , (PO ₄ ) _1/3 , (HPO ₄ ) _1/2 , (H ₂ PO ₄ ) Plate, hexafluorophosphate, methanesulfonate, arylsulfonate (preferably benzene sulfonate or toluene sulfonate), SeR ¹ , CN and R ² COO. Here, R ¹ represents an alkyl group having 1 to 20 (preferably 1 to 10) carbon atoms in the aryl, straight-chain or branched chain, and R ² denotes a hydrogen atom, (Preferably a methyl group) having 1 to 6 carbon atoms in the straight chain or branched chain, which may be substituted one to three times with fluorine or chlorine. Also, n represents a formal charge on the metal, and is an integer of 0 to 7.

The transition metal complex is not particularly limited but is preferably a transition metal complex of group 7, 8, 9, 10 or 11, more preferably a transition metal complex of 0 valent copper, monovalent copper, divalent ruthenium, Nickel complexes of nickel and silver.

Examples of the compound having a ligand capable of coordinating with the transition metal include compounds having a ligand containing at least one nitrogen atom, oxygen atom, phosphorus atom or sulfur atom capable of coordinating with a transition metal through a sigma bond, a compound having a ligand containing two or more carbon atoms capable of coordinating through a π bond, and a compound having a ligand capable of coordinating with a transition metal through a μ-bond or an η-bond.

Specific examples of the compound having the above-mentioned ligand include, for example, 2,2'-bipyridyl and its derivatives when the central metal is copper, 1,10-phenanthroline and its derivatives, tetramethylethylenediamine, pentamethyl And polyamines such as diethylenetriamine, hexamethyltris (2-aminoethyl) amine, and the like. Examples of divalent ruthenium complexes include dichlorotris (triphenylphosphine) ruthenium, dichlorotris (tributylphosphine) ruthenium, dichloro (cyclooctadiene) ruthenium, dichlorobenzene ruthenium, dichloro p-cymene ruthenium, Ruthenium, cis-dichlorobis (2,2'-bipyridine) ruthenium, dichlorotris (1,10-phenanthroline) ruthenium and carbonylchlorohydrid tris (triphenylphosphine) ruthenium . Examples of the divalent iron complexes include bistriphenylphosphine complexes and triazacyclononane complexes.

In the living radical polymerization, a solvent is preferably used. Examples of the solvent to be 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-based solvents such as dichloromethane and dichloroethane; Aromatic solvents such as toluene and xylene; Ketone solvents such as methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone; Alcohol solvents such as methanol, ethanol and isopropanol; And aprotic polar solvents such as dimethylformamide and dimethylsulfoxide. These solvents may be used alone or in combination of two or more.

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

In the method for producing a random copolymer of the present invention, the ratio (reaction ratio) of the polymerizable monomer (a1) to the polymerizable monomer (a2) is preferably such that the polymerizable monomer (a2 ) Is preferably added in an amount of from 50 to 900 parts by mass, a leveling property is good and a random copolymer having a high pigment sublimation inhibition effect can be obtained, and the polymerizable monomer (a2) is contained in an amount of 100 to 800 mass parts per 100 parts by mass of the polymerizable monomer The addition is more preferable.

The polymerization temperature in the living radical polymerization is preferably in the range of room temperature to 120 캜.

In addition, when the random copolymer of the present invention is produced by the method for producing a random copolymer of the present invention, the metal attributed to the transition metal compound may remain in the random copolymer. Therefore, when a random copolymer is used for a semiconductor such as a photoresist composition in which a problem occurs when the metal remains, it is preferable to remove the residual metal using activated alumina or the like after the polymerization reaction.

The present invention relates to a random copolymer (hereinafter sometimes referred to as " random copolymer (A) ") of the present invention, a colorant (B), an alkali- And a resist composition comprising the same. The resist composition can be produced, for example, by copolymerizing a polymerizable monomer (a1) having a fluorinated alkyl group of 1 to 6 carbon atoms in which fluorine atoms are directly bonded and a polymerizable monomer having a polymerizable unsaturated group and a polymerizable monomer (a2) is subjected to living radical polymerization in the presence of a polymerizable monomer (a1) and a polymerizable monomer (a2) to obtain a living radical polymerization random copolymer (A); and a step of mixing the random copolymer (A) (B), an alkali-soluble resin (C), and a polymerizable compound (D). The step of obtaining the random copolymer (A) corresponds to the method of producing the random copolymer of the present invention.

The colorant (B) may be a pigment or a dye, and the pigment may be an organic pigment or an inorganic pigment. As the organic pigments, pigments of various colors such as red pigment, green pigment, blue pigment, yellow pigment, purple pigment and orange pigment may be used. Examples of the chemical structure of the organic pigment include quinacridone, perylene, pyrrolo pyrrole, anthraquinone, phthalocyanine, indanthrene, halogenated phthalocyanine, tetrachloroisoindolinone, , Benzidine yellow series, azo series, azabenzimidazolone series, isoindolinone series, and dioxazine series. In the following, " C.I. " means a color index (CI., Published by The Society of Dyers and Colourists).

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

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

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

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

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

As the orange pigment, for example, C.I. Pigment Orange 1, C.I. Pigment Orange 2, C.I. Pigment Orange 5, C.I. Pigment Orange 13, C.I. Pigment Orange 16, C.I. Pigment Orange 17, C.I. Pigment Orange 19, C.I. Pigment Orange 20, C.I. Pigment Orange 21, C.I. Pigment Orange 22, C.I. Pigment Orange 23, C.I. Pigment Orange 24, C.I. Pigment Orange 34, C.I. Pigment Orange 36, C.I. Pigment Orange 38, C.I. Pigment Orange 39, C.I. Pigment Orange 43, C.I. Pigment Orange 46, C.I. Pigment Orange 48, C.I. Pigment Orange 49, C.I.C.I. Pigment Orange 51, C.I. Pigment Orange 55, C.I. Pigment Orange 59, Pigment Orange 61, C.I. Pigment Orange 62, C.I. Pigment Orange 64, C.I. Pigment Orange 65, C.I. Pigment Orange 67, C.I. Pigment Orange 68, C.I. Pigment Orange 69, C.I. Pigment Orange 70, C.I. Pigment Orange 71, C.I. Pigment Orange 72, C.I. Pigment Orange 73, C.I. Pigment Orange 74, C.I. Pigment Orange 75, C.I. Pigment Orange 77, C.I. Pigment Orange 78, C.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, green and blue pigments And for the purpose of improving the color reproducibility, the above organic pigments of yellow, purple, orange or the like may be used as the color adjustment.

Examples of the inorganic pigments include barium sulfate, lead sulfate, titanium oxide, yellow lead, spinach, and chromium oxide.

Examples of the dye used in the present invention include dyes represented by the following formula (b1)

And dyestuff dyes and the like represented by the following general formula (1) can be preferably exemplified.

As the xanthene dyes, for example, C.I. Acid Red 51, 52, 87, 92, 289, 388, C.I. Acid Violet 9, 30, C.I. Basic Red 8, C.I. Modern tread 27, rose bengal B, sulfolodamine G, rhodamine 6G, zeolite dyes described in Japanese Patent Application Laid-Open Nos. 2010-032999 and 2011-138094, and the like.

Among the aforementioned zeta-based dyes, the following formula (b2)

: Wherein R ¹ to R ⁴ each independently represent a hydrogen atom, -R ⁸ or a monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms, and the hydrogen atom contained in the aromatic hydrocarbon group is halogen ^{atoms, -R 8, -OH, -OR 8} , -SO 3 -, -SO 3 H, -SO 3 - M +, -CO 2 H, -CO 2 R 8, -SO 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 ₂ NR ⁹ R ¹⁰ .

m represents an integer of 0 to 5; When m is an integer of 2 or more, plural R ⁵ 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 may be substituted with -OH or a halogen atom, -CH ₂ - included in the saturated aliphatic hydrocarbon group may be substituted with -O-, -CO-, -NH- or -NR ⁸ -, and R ⁹ and R ¹⁰ may be bonded to each other to form a 3- Or may form a heterocyclic ring of 10-membered ring.]

Is preferred as the dye.

Examples of the monovalent aromatic hydrocarbon group represented by R ¹ to R ⁴ in the formula (b2) having 6 to 10 carbon atoms include a phenyl group, a toluyl group, a xylyl group, a mesyl group, a propylphenyl group and a butylphenyl group. .

The formula (b2) groups of 6 to 10 carbon atoms, a monovalent aromatic hydrocarbon in the, as a substituent, -SO ₃ - M ⁺ and consisting of ^{_{-SO 2 NR 9 R 10 -,}} -SO 3 H, -SO 3 , And more preferably at least one member selected from the group consisting of -SO ₃ ^- M ⁺ and -SO ₂ NR ⁹ R ¹⁰ . In this case, -SO ₃ ^- M ⁺ is preferably -SO ₃ ^{- +} N (R ¹¹ ) ₄ . When R ¹ to R ⁴ are these groups, the resist composition can be expected to give a coating layer having less generation of foreign matter and having 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, an isobutyl group, An alkyl group having from 1 to 20 carbon atoms such as a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a pentyl group, an isopentyl group, a neopentyl group, a hexyl group, a heptyl group, an octyl group, a 2-ethylhexyl group, And cycloalkyl groups having 3 to 20 carbon atoms such as cyclopropyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group and 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 described 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, and a phenylbutyl group.

M ⁺ is, for example, ⁺ N (R ¹¹ ) ₄ , Na ⁺ or K ⁺ , preferably ⁺ N (R ¹¹ ) ₄ . As the ⁺ N (R ¹¹ ) ₄ , for example, at least two of the four R ^{11 s} are preferably monovalent saturated hydrocarbon groups having 5 to 20 carbon atoms. The total number of carbon atoms of the four R < ¹¹ > s is preferably from 20 to 80, more preferably from 20 to 60. [ When R < ¹¹ > is one of these groups, the resist composition of the present invention can be expected to form a colored coating film or pattern with few foreign matters.

Among the aforementioned zeta-based dyes, the following formula (b3)

: Wherein 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 hydrogen atom contained in the aromatic hydrocarbon group is - SO ₃ ^-, -SO ₃ - or may be substituted by _{^{M a +, -SO 3 H,}} -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 of 0 to 5; When m1 is 2 or more integer, a plurality of R ²⁵ are the same or different.

M ^{a +} represents ⁺ N (R ²⁷ ) ₄ , Na ⁺ or K ⁺ .

R ²⁵ is, -SO ₃ - shows a 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 each independently represent a monovalent saturated hydrocarbon group or benzyl group having 1 to 20 carbon atoms.

Is more preferable.

Examples of the monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms in R ²¹ to R ²⁴ in the formula (b3) include groups similar to those of the aromatic hydrocarbon group in R ¹ to R ⁴ have. Among them, R ²¹ and R ²³ are hydrogen atoms, and R ²² and R ²⁴ are monovalent aromatic hydrocarbon groups each having 6 to 10 carbon atoms, and the hydrogen atom contained in the aromatic hydrocarbon group is -SO ³ -, - SO ³ M ^{a +} , -SO ₃ H, -SO ₃ R ^26, or -SO ₂ NHR ²⁶ . 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 atom contained in the aromatic hydrocarbon group is -SO ₃ ^- M ⁺ or it is preferably substituted by -SO ₂ NHR ^26. 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 pattern excellent in heat resistance.

Examples of the monovalent saturated hydrocarbon group having 1 to 20 carbon atoms in R ²⁶ and R ²⁷ in the formula (b3) include groups similar to those of the saturated hydrocarbon groups in R ⁸ to R ¹¹ .

It is preferable that each of -R ²⁶ in R ²¹ to R ²⁴ in the formula (b3) is independently a hydrogen atom, a methyl group or an ethyl group.

Examples of -SO ³ R ^26, and -SO ₂ NHR ²⁶ R ²⁶ in the above formula (b3), is from 3 to 20 carbon atoms, a branched chain alkyl group are preferred, and more of the carbon atoms of 6 to 12 branched chain alkyl group And more preferred is a 2-ethylhexyl group. When R ²⁶ is a group of these, the resist composition containing the compound (b3) is expected to be capable of forming a colored coating film or pattern with less foreign matter.

Ma ⁺ is ⁺ N (R ²⁷ ) ₄ , Na ⁺ or K ⁺ , preferably ⁺ N (R ²⁷ ) ₄ . As the ⁺ N (R ²⁷ ) ₄ , it is preferable that at least two of the four R ^{27 s} are monovalent saturated hydrocarbon groups having 5 to 20 carbon atoms. The total number of carbon atoms of four R < ²⁷ > is preferably 20 to 80, more preferably 20 to 60. [ It is expected that the resist composition containing the compound (b3) wherein R ²⁷ is a group thereof can form a coat layer or a pattern with less foreign matter.

Examples of the preferred zetaene dyes usable in the present invention include dyes containing a compound represented by the formula (b4) to formula (b21) as a main component. In the following formulas, Ra represents a 2-ethylhexyl group.

Of the compounds which are the main components of the xanthene dyes, C.I. Sulfonamides of Acid Red 289 or C.I. Quaternary ammonium salts of Acid Red 289 are preferred. Examples of such a compound include compounds represented by formulas (b4) to (b11), (b16) and (b17).

The compound represented by the above formula (b1) can be obtained by, for example, chlorinating a coloring matter or a dyeing intermediate having -SO ₃ H by a conventional method and then dissolving the coloring matter or dyeing intermediate having -SO ₂ Cl with R ⁸ -NH ₂ Lt; / RTI > with an amine represented by the formula < RTI ID = 0.0 > Also, the dye prepared by the method described in the upper left column to the lower left column of Japanese Patent Laid-Open Publication No. 3-78702 can be produced by chlorination and reacting with the amine 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 zanthene-based dye may 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 specific examples thereof include color Compounds classified as dyes in the index (published by The Society of Dyers and Colourists), and various dyes described in dyeing notes (Shika Sensha).

As other dyes, for example, C.I. 14, 15, 23, 24, 38, 62, 63, 68, 82, 94, 98, 99, and 20; solvent yellow 4 (hereinafter, the description of CI. Solvent yellow is omitted. C.I. Solvent Red 45, 49, 125, 130; C.I. Solvent Orange 2, 7, 11, 15, 26, 56; C.I. Solvent dyes,

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, 112, 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, 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, 277, 280, 281, 195, 308, 312, 315, 316, 339, 341, 345, 346, 349, 266, 268, 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; C.I. Acid dyes,

C.I. Direct Yellow 2, 33, 34, 35, 38, 39, 43, 47, 50, 54, 58, 68, 69, 70, 71, 86, 93, 94, 95, 98, 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, 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. Direct Violet 47, 52, 54, 59, 60, 65, 66, 79, 80, 81, 82, 84, 89, 90, 93, 95, 96, 103, 104; C.I. Direct dyes,

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

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

On the other hand, the colorant (B) to be used for forming the black matrix (BM) is not particularly limited as long as it is black. Examples thereof include pigments such as carbon black, metal oxides and composite metal compounds composed of two or more metal oxides . Further, it may be a combination of two or more organic pigments selected from pigments having hue of red, blue, green, blue, yellow, cyan and magenta and black by mixing.

Examples of the carbon black include lamp black, acetylene black, thermal black, channel black, and furnace black. Examples of the metal oxide include titanium black obtained by oxidation of titanium or reduction of titanium dioxide. Usually, titanium black is represented by Ti _m O _{2 m -1} (m is a number of 1 or more). As the metal oxide, metal oxides such as copper, iron, chromium, manganese, and cobalt can also be used. Examples of the composite metal compound composed of two or more metal oxides include oxides of copper-chromium, oxides of copper-chromium-manganese, oxides of copper-iron-manganese, and oxides of cobalt-iron- .

Examples of commercial products of the above carbon black include MA7, MA8, MA11, MA100, MA100R, MA220, MA230, MA600, # 5, # 10, # 20, # 25, # 30, # 32, # 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 Printex 3, Printex 3OP, Printex 30, Printex 30OP, Printex 40, Printex 45, Printex 55, Printex 60, Printex 75, Printex 80, Printex 85, Printex 90, Printex A, Printex L, Printex G, Printex P Color Black FW2, Colorl Black FW2, Colorl Black FW18, Colorl Black FW18, Colorl Black FW1, Colorl Black FW1, Colorl Black FW2, Colorl Black FW18, Colorl Black FW18, Colorl Black FW200, Colorl Black S160, Colorl Black S170, Monarch120, Monarch280, Monarch460, Monarch800, Monarch880, Monarch900, Monarch1000, Monarch1100, Monarch1300, Monarch1400, Monarch4630, REGAL99, REGAL99R, REGAL415, REGAL415R, REGAL250, REGAL250R, REGAL330, REGAL400R, REGAL55R0, REGAL660R, BLACK PEARLS480, PEARLS130, VULCAN XC72R and ELFTEX-8 manufactured by Nissan Chemical Industries, Ltd. and RAVEN11, RAVEN14, RAVEN15, RAVEN16, RAVEN22RAVEN30, RAVEN35, RAVEN40, RAVEN410, RAVEN420, RAVEN450, RAVEN500, RAVEN780, RAVEN850, RAVEN890H, RAVEN1000, RAVEN1020, RAVEN1040, RAVEN1060U, RAVEN1080U , RAVEN1170, RAVEN1190U, RAVEN1250, RAVEN1500, RAVEN2000, RAVEN2500U, RAVEN3500, RAVEN5000, RAVEN5250, RAVEN5750, RAVEN7000.

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

Examples of the method for producing the titanium black include a method in which a mixture of titanium dioxide and titanium metal disclosed in Japanese Patent Application Laid-Open No. 49-5432 is heated and reduced in a reducing atmosphere, A method of reducing ultrafine titanium dioxide obtained by high-temperature hydrolysis of titanium in a reducing atmosphere containing hydrogen, titanium dioxide or titanium hydroxide described in Japanese Patent Application Laid-Open Nos. 60-65069 and 61-201610 A method of high-temperature reduction in the presence of ammonia, a method of attaching a vanadium compound to titanium dioxide or titanium hydroxide described in Japanese Patent Application Laid-Open No. 61-201610, and high-temperature reduction in the presence of ammonia. Examples of commercial products of titanium black include titanium blacks 10S, 12S, 13R, 13M and 13M-C manufactured by Mitsubishi Materials Corporation.

As a combination in which two or more organic pigments are mixed and made black by mixing, there can be mentioned black pigments in which pigments of three colors of red, green and blue are mixed. Examples of the usable coloring materials for preparing the black pigment include Victorian pure blue (CI42595), aramine O (CI41000), catilon brilliant flavin (basic 13), rhodamine 6GCP (CI45160), rhodamine B (CI 45170), Saffronine OK 70: 100 (CI50240), ErioGlausin X (CI42080), No.120 / Rionol Yellow (CI21090), Rionol Yellow GRO (CI21090) Yellow 8GF (CI21105), Benzidine Yellow 4T-564D (CI21095), Simuler Fast Red 4015 (CI12355), Lionol Red 7B4401 (CI15850), Fastgreen Blue TGR-L (CI74160) SM (CI 26150), Rionol Blue ES (CI Pigment Blue 15: 6), Riolongen Red GD (CI Pigment Red 168), Lionol Green 2YS (CI Pigment Green 36) and the like.

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

When carbon black is used as the black pigment, the average primary particle diameter is preferably in the range of 0.01 to 0.08 mu m, and more preferably in the range of 0.02 to 0.05 mu m because the developing property is good. The amount of dibutylphthalic acid (hereinafter abbreviated as " DBP ") of the carbon black to be used is preferably in the range of 40 to 100 cm 3/100 g and is preferably in the range of 50 to 80 cm 3 / The range is more preferable. The specific surface area of the carbon black to be used according to the BET method is preferably in the range of 50 to 120 m < 2 > / g and more preferably in the range of 60 to 95 m < 2 >

Unlike organic pigments and the like, carbon black exists in a state called a structure in which primary particles are fused, and fine pores are formed on the surface of the particles by post treatment. Therefore, in general, in order to exhibit the shape of the carbon black, the DBP absorption (JIS K6221) and the specific surface area (JIS K6217) according to the BET method are determined in addition to the average particle diameter of the primary particles obtained by the same method as the organic pigment It is preferable to measure it as an index of the structure or pore volume.

Among the colorants (B), a coating film layer having good productivity, high color density and excellent durability can be obtained, so that the effect of the present invention that the pigment is preferable and the occurrence of foreign matters derived from the colorant can be suppressed to the maximum CI Pigment Red 177, C.I. Pigment Red 207, C.I. Pigment Red 254, C.I. Pigment Green 7, C.I. Pigment Green 36, C.I. Pigment Green 58, C.I. Pigment Green 59, C.I. Pigment Yellow 83, C.I. Pigment Yellow 93, C.I. Pigment Yellow 109, C.I. Pigment Yellow 110, C.I. Pigment Yellow 129, C.I. Pigment Yellow 138, C.I. Pigment Yellow 139, C.I. Pigment Yellow 150, C.I. Pigment Yellow 154, C.I. Pigment Yellow 180, C.I. Pigment Yellow 185, C.I. Pigment Blue 15: 1, C.I. Pigment Blue 15: 2, C.I. Pigment Blue 15: 6 and C.I. Pigment Violet 23 is more preferable.

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

The amount of the colorant (B) to be blended is preferably in the range of 10 to 80 parts by mass, more preferably in the range of 15 to 65 parts by mass based on 100 parts by mass of the total of the alkali-soluble resin (C) and the polymerizable compound (D) And more preferably in the range of the mass part.

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

The alkali-soluble resin (C) will be described in more detail, for example, by the following resins.

An alkali-soluble resin (C1) obtained by polymerizing a (meth) acrylic polymerizable monomer having an acidic group as an essential component.

(C2) obtained by reacting a polymer having no acidic group obtained by polymerizing a (meth) acrylic polymerizable monomer having a reactive group as an essential component with a compound having an acid group and a reactive group having reactivity with the reactive group, .

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

Epoxy (meth) acrylate resins having carboxyl groups (C4).

Hereinafter, (C1) to (C4) will be described in detail.

Examples of the alkali-soluble resin (C1) include a (meth) acrylic polymerizable monomer having an alkali-soluble resin or a sulfonic acid group obtained by polymerizing a (meth) acrylic polymerizable monomer having a carboxyl group as an essential component, And an alkali-soluble resin obtained by polymerization as a polymerization initiator. Among them, 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, cinnamic acid, 2- (meth) acryloyloxyethylsuccinic acid, 2- (Meth) acryloyloxyethyl adipic acid, 2- (meth) acryloyloxyethyl maleic acid, 2- (meth) acryloyloxyethylhexahydrophthalic acid, 2- (Meth) acryloyloxypropyl succinic acid, 2- (meth) acryloyloxypropyl adipic acid, 2- (meth) acryloyloxypropyl maleic acid, 2- (Meth) acryloyloxybutyl succinic acid, 2- (meth) acryloyloxybutyl adipic acid, 2- (meth) acryloyloxypropyl phthalic acid, 2- Polymerizable monomers such as oxybutylmaleic acid, 2- (meth) acryloyloxybutylhydrophthalic acid, and 2- (meth) acryloyloxybutylphthalic acid;

Polymerizable monomers in which lactones such as? -Caprolactone,? -Propiolactone,? -Butyrolactone, and? -Valerolactone are added to acrylic acid; And polymeric monomers in which succinic acid, maleic acid, phthalic acid, or acid anhydrides thereof are added to hydroxyalkyl (meth) acrylate. These (meth) acrylic polymerizable monomers having a carboxyl group may be used singly or in combination of two or more. Among (meth) acrylic polymerizable monomers having a carboxyl group, (meth) acrylic acid and 2- (meth) acryloyloxyethyl succinic acid are preferred.

Examples of the (meth) acrylic polymerizable monomer having a sulfonic acid group include (meth) acrylic acid 2-sulfoethyl, (meth) acrylic acid 2-sulfopropyl, 2-hydroxy- Propanesulfonic acid, 2- (meth) acrylamide-2-methylpropanesulfonic acid, and salts thereof.

When the alkali-soluble resin (C1) is prepared, other polymerizable monomers may be used in combination within a range not to impair the effect of the present invention. Examples of other monomers include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, butyl (meth) Acrylates such as benzyl (meth) acrylate, phenyl (meth) acrylate, cyclohexyl (meth) acrylate, phenoxyethyl (meth) acrylate, phenoxymethyl (Meth) acrylate such as isobornyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, glycerol mono (meth) acrylate and tetrahydrofurfuryl (meth) acrylate;

(Meth) acrylate such as 2-hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate and 4-hydroxybutyl (meth) acrylate, glycerol mono (Meth) acrylic acid esters having a hydroxyl group;

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;

A macromonomer such as polymethyl (meth) acrylate macromonomer, polystyrene macromonomer, poly 2-hydroxyethyl (meth) acrylate macromonomer, polyethylene glycol macromonomer, polypropylene glycol macromonomer and polycaprolactone macromonomer . The other polymerizable monomers may be used alone or in combination of two or more.

Among these other polymerizable monomers, styrene, methyl (meth) acrylate, cyclohexyl (meth) acrylate, benzyl (meth) acrylate, 4- hydroxybutyl (meth) acrylate, 2- Acrylate, hydroxypropyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, N-cyclohexylmaleimide, N-benzylmaleimide and N-phenylmaleimide And is preferable in that heat resistance is not easily damaged.

The amount of these other polymerizable monomers to be used is preferably 95% by mass or less, more preferably 85% by mass or less, of the total (all) polymerizable monomer components.

Specific examples of the alkali-soluble resin (C1) include a copolymer of (meth) acrylic acid with at least one member selected from the group consisting of methyl (meth) acrylate, benzyl (meth) acrylate, butyl (meth) acrylate, isobutyl (Meth) acrylates such as 2-hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate and the like ) Copolymer with a hydroxyl group-containing polymerizable monomer such as acrylate;

(Meth) acrylic acid esters such as methyl (meth) acrylate, benzyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, and 2-hydroxyethyl methacrylate ≪ / RTI >

A copolymer of (meth) acrylic acid and styrene; Copolymers of (meth) acrylic acid with styrene and? -Methylstyrene; And copolymers of (meth) acrylic acid and cyclohexylmaleimide. Among the alkali-soluble resin (C1), an alkali-soluble resin using benzyl (meth) acrylate is preferable because a resist composition excellent in 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, more preferably in the range of 40 to 300 mgKOH / g Do. The weight average molecular weight (Mw) of the alkali-soluble resin (C1) as measured by GPC in terms of polystyrene is preferably in the range of 2,000 to 100,000, more preferably 3,000 to 80,000, and more preferably 4,000 to 50,000 More preferable.

In the present invention, an alkali-soluble resin (C1-1) obtained by adding an epoxy group-containing unsaturated compound to a carboxyl group of a carboxyl-containing alkali-soluble resin obtained by polymerizing a (meth) acrylic polymerizable monomer having a carboxyl group as an essential component .

Examples of the epoxy group-containing unsaturated compound include glycidyl (meth) acrylate, allyl glycidyl ether, glycidyl-α-ethyl acrylate, crotonyl glycidyl ether, (3,5-dimethyl-4-glycidyl) benzyl acrylamide, and 4-hydroxybutyl (meth) acrylate glycidyl ether. Further, an unsaturated compound containing an alicyclic epoxy group is preferable because it can improve the heat resistance and improve the dispersibility when the pigment is used as the colorant (B).

Examples of the alicyclic epoxy group of the alicyclic epoxy group-containing unsaturated compound include 2,3-epoxycyclopentyl group, 3,4-epoxycyclohexyl group, 7,8-epoxy [tricyclo [5.2.1.0] decy 2-yl] group and the like. As the ethylenic 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.

In order to add the epoxy group-containing unsaturated compound to the carboxyl group portion of the alkali-soluble resin containing the carboxyl group, a known method can be used. For example, when a carboxyl group-containing alkali-soluble resin and an epoxy group-containing unsaturated compound are reacted with a tertiary amine such as triethylamine or benzylmethylamine; Quaternary ammonium salts such as dodecyltrimethylammonium chloride, tetramethylammonium chloride, tetraethylammonium chloride, tetrabutylammonium chloride and benzyltriethylammonium chloride; An epoxy group-containing unsaturated compound can be added to the carboxyl group of the resin by reacting in an organic solvent in the presence of a catalyst such as pyridine or triphenylphosphine at a reaction temperature of 50 to 150 DEG C for several hours to several hours.

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, more preferably in the range of 40 to 300 mgKOH / g More preferable. The weight average molecular weight of the alkali-soluble resin (C1-1) measured by GPC in terms of polystyrene is preferably in the range of 2,000 to 100,000, more preferably in the range of 3,000 to 80,000, further preferably in the range of 4,000 to 50,000 Do.

Among the alkali-soluble resins (C1), an 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 Bis (2-propyl) -2,2 '- [oxybis (methylene)] bis-2-propenoate, di Propane, di (n-butyl) -2,2 '- [oxybis (methylene)] bis-2-propenoate, di (isobutyl) -2,2' (T-butyl) -2,2 '- [oxybis (methylene)] bis-2-propenoate, di (t-amyl) -2,2' - [ Di (stearyl) -2,2 '- [oxybis (methylene)] bis-2-propenoate, di (lauryl) -2,2' Di (2-ethylhexyl) -2,2'- [oxybis (methylene)] bis-2-propenoate, di (1-methoxy Ethyl) -2,2 '- [oxybis (methylene)] bis-2-propenoate, di Bis (methylene)] bis-2-propenoate, dibenzyl-2,2 '- [oxybis (methylene)] bis- Propylene glycol di (t-butylcyclohexyl) -2,2'- [oxybis (methylene)] bis-2-propenoate, (Dicyclopentadienyl) -2,2 '- [oxybis (methylene)] bis-2-propenoate, bis Di (isobornyl) -2,2 '- [oxybis (methylene)] bis (tricyclodecanyl) -2,2' - [oxybis (2-methyl-2-adamantyl) -2,2 '- [bis (2-methylphenyl) Oxybis (methylene)] bis-2-propenoate. Among these, dimethyl-2,2 '- [oxybis (methylene)] bis-2-propenoate, diethyl-2,2' - [oxybis (methylene)] bis- Bis [2-propenyl] hexyl-2,2 '- [oxybis (methylene)] bis-2-propenoate and dibenzyl-2,2' - [oxybis (methylene)] bis-2-propenoate. These ether dimers may be used singly or in combination of two or more.

When an ether dimer is used as a raw material of the alkali-soluble resin (C1-2), the proportion of the ether dimer in the polymerizable monomer can be controlled by controlling the ratio of the ether dimer in the polymerizable monomer to the alkali- It is preferably in the range of 2 to 60 mass%, more preferably in the range of 5 to 55 mass%, and more preferably in the range of 5 to 50 mass%, based on the mass of the prepolymerizable monomer.

On the other hand, when a (meth) acrylate ester having an alicyclic structure such as an adamantyl group is used as a raw material of the alkali-soluble resin (C1-2), the ratio of the (meth) Is preferably 0.5 to 60% by mass, more preferably 1 to 55% by mass, based on the mass of the prepolymerizable monomer, so that a resist composition having good background contamination suitability can be obtained. , More preferably from 5 to 50 mass%.

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 employed. In particular, a solution polymerization method is preferable. Further, the polymerization temperature and the polymerization concentration (polymerization concentration = [total mass of polymerizable monomer / total mass of polymerizable monomer + mass of solvent] x 100) are determined depending on the kind and ratio of the polymerizable monomer to be used, It depends on the molecular weight of the soluble resin. The polymerization temperature is preferably in the range of 40 to 150 占 폚, and more preferably in the range of 60 to 130 占 폚. 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 which is used in ordinary radical polymerization reaction. Specific examples thereof include 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; Esters such as ethyl acetate, butyl acetate, propylene glycol monomethyl ether acetate and 3-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. These solvents may be used alone or in combination of two or more.

When the polymerizable monomer is polymerized, 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-butyl peroxyisopropyl carbonate, t- Organic peroxides such as peroxy-2-ethylhexanoate, t-butylperoxy-2-ethylhexanoate and the like; Azo compounds such as 2,2'-azobis (isobutyronitrile), 1,1'-azobis (cyclohexanecarbonitrile), 2,2'-azobis (2,4-dimethylvaleronitrile) '-Azobis (2-methylpropionate), and the like. These polymerization initiators may be used alone or in combination of two or more. The amount of these polymerization initiators to be used may be set appropriately depending on the combination of the monomers to be used, the reaction conditions, the molecular weight of the target alkali-soluble resin (C1), and the like. Is preferably in the range of 0.1 to 15 mass%, more preferably in the range of 0.5 to 10 mass%, with respect to the prepolymerizable monomer component, because several thousands to several tens of thousands of alkali-soluble resins are obtained.

In order to adjust the molecular weight, a chain transfer agent may be added. Examples of the chain transfer agent include mercapane chain transfer agents such as n-dodecyl mercaptan, mercaptoacetic acid and methyl mercaptoacetate; -methylstyrene dimer, and the like. Of these, n-dodecyl mercaptan and mercaptoacetic acid, which have a high chain transfer effect and can reduce the polymerizable monomers remaining in the reaction system and are easily available, are preferable. The amount of the chain transfer agent to be used is not particularly limited, but may be appropriately selected depending on the combination of the monomers to be used, the reaction conditions, the molecular weight of the desired monomer, and the like. Resin is obtained, it is preferably in the range of 0.1 to 15 mass%, more preferably in the range of 0.5 to 10 mass% with respect to the total monomer.

The alkali-soluble resin (C2) is obtained by reacting a polymer having no acidic group obtained by polymerizing a (meth) acrylic polymerizable monomer having a reactive group as an essential component with a compound having an acid group and a reactive group to the reactive group . As the alkali-soluble resin (C2), for example, the following alkali-soluble resins may be mentioned.

A polymerizable monomer having a hydroxyl group such as 2-hydroxyethyl (meth) acrylate is obtained as an essential component, and then an acid anhydride such as succinic anhydride, tetrahydrophthalic anhydride or maleic anhydride is added to obtain an alkali soluble Suzy.

A polymerizable monomer having an epoxy group such as glycidyl (meth) acrylate as an essential component, and then adding a compound having an acid group and an amino group such as N-methylaminobenzoic acid or N- Alkali soluble resin.

· A polymerizable monomer having an isocyanate group such as 2-isocyanatoethyl (meth) acrylate is obtained as an essential component, and then a compound having a hydroxyl group and an acid group such as 2-hydroxybutyric acid is added to obtain an alkali-soluble resin .

The weight average molecular weight of the alkali-soluble resin (C2) is preferably in the range of 1,000 to 200,000, more preferably in the range of 2,000 to 50,000, in terms of polystyrene as measured by GPC, because a coating film having good coating film formation and excellent heat resistance is obtained. And more preferably in the range of 2,000 to 30,000. If necessary, the alkali-soluble resin (C2) may also be obtained by using a polymerizable monomer used for preparing the alkali-soluble resin (C1) in combination.

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

Examples of the epoxy group-containing (meth) acrylate include glycidyl (meth) acrylate, 3,4-epoxybutyl (meth) acrylate, (3,4-epoxycyclohexyl) , 4-hydroxybutyl (meth) acrylate glycidyl ether, and the like. Among them, glycidyl (meth) acrylate is preferable. These epoxy group-containing (meth) acrylates may be used alone or in combination of two or more.

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

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

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

(Meth) acrylate, n-propyl (meth) acrylate, n-butyl (meth) acrylate, (Meth) acrylate, neopentyl (meth) acrylate, isoamyl (meth) acrylate, hexyl (meth) acrylate, 2-ethylhexyl , Cyclohexyl (meth) acrylate, dicyclohexyl (meth) acrylate, isobornyl (meth) acrylate, isobornyl (meth) acrylate, (Meth) acrylic acid propanediol, (meth) acrylic acid propargyl, phenyl (meth) acrylate, naphthyl (meth) acrylate, anthracenyl (meth) acrylate, anthraninomethylacrylate, (Meth) acrylic acid salicylate, (meth) acrylic acid furyl, (meth) acrylic acid furfuryl, (meth) (Meth) acrylate, benzyl (meth) acrylate, phenethyl (meth) acrylate, cresyl (meth) acrylate, 1,1,1-trifluoroethyl Perfluoro-n-propyl (meth) acrylate, perfluoro-isopropyl (meth) acrylate, triphenylmethyl (meth) acrylate, cumyl (meth) acrylate, (Meth) acrylic acid esters such as (N, N-dimethylamino) propyl, 2-hydroxyethyl (meth) acrylate and 2-hydroxypropyl (meth) acrylate;

(Meth) acrylic acid amide, N, N-dimethyl amide, N, N-diethyl amide, N, N-dipropyl amide, (Meth) acrylic amides such as di-i-propyl amide and anthracenyl amide (meth) acrylate; Vinylidene chloride, vinylidene chloride, vinylidene fluoride, N-vinylpyrrolidone, vinylpyridine, and vinyl acetate; (meth) acrylonitrile, (meth) acrylonitrile, acrolein, vinyl chloride, vinylidene chloride, vinyl fluoride, vinylidene fluoride,

Unsaturated dicarboxylic acid diesters such as diethyl citraconate, diethyl maleate, diethyl fumarate and diethyl itaconate; Monomaleimides such as N-phenylmaleimide, N-cyclohexylmaleimide, N-laurylmaleimide and N- (4-hydroxyphenyl) maleimide; And N- (meth) acryloyl phthalimide.

Of the above-mentioned other polymerizable monomers, at least one of styrene, benzyl (meth) acrylate and monomaleimide is preferably used because heat resistance and mechanical strength of the cured product of the color resist composition of the present invention can be improved. Styrene, benzyl (meth) acrylate and monomaleimide is preferably 1 to 70 mol%, more preferably 3 to 50 mol% based on the total amount of the other polymerizable monomers.

The copolymerization reaction of the epoxy group-containing (meth) acrylate with the other polymerizable monomer may be carried out by a known polymerization method such as a solution polymerization method using a radical polymerization initiator. The solvent to be used is not particularly limited as long as it is inert to radical polymerization, and an organic solvent which is generally used can be used.

As the copolymer of the epoxy group-containing (meth) acrylate and the other polymerizable monomer, 5 to 90 mol% of a repeating unit derived from an epoxy group-containing (meth) acrylate and 10 to 90 mol% of a repeating unit derived from another radically polymerizable monomer To 95 mol%, more preferably from 20 to 80 mol% of the former and from 80 to 20 mol% of the latter, more preferably from 30 to 70 mol% of the former and from 70 to 30 mol% of the latter Do.

The alkali-soluble resin (C3) is a copolymer of an unsaturated monocarboxylic acid (polymerizable component) and an acid anhydride of a polycarboxylic acid (an alkali-soluble component ). ≪ / RTI >

Examples of the unsaturated monocarboxylic acid include (meth) acrylic acid, crotonic acid, o-, m-, p-vinylbenzoic acid, the α-position is a haloalkyl group, an alkoxyl group, a halogen atom, a nitro group, And monocarboxylic acids such as substituted (meth) acrylic acid. Among these, (meth) acrylic acid is preferable. These unsaturated monocarboxylic acids may be used singly or in combination of two or more. By using the unsaturated monocarboxylic acid, the alkali-soluble resin (A3) can be given polymerizability.

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

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

The acid anhydride of the polycarboxylic acid is preferably added in an amount of 10 to 100 mol%, more preferably 20 to 90 mol%, of the hydroxyl group formed by adding an unsaturated monocarboxylic acid to the epoxy group of the copolymer , And more preferably 30 to 80 mol%.

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

The epoxy (meth) acrylate resin (C4) can be prepared by, for example, adding an?,? - unsaturated monocarboxylic acid or an?,? - unsaturated monocarboxylic acid ester having a carboxyl group in the ester moiety to an epoxy resin, Lt; / RTI > with an anhydride.

Examples of the epoxy resin include bisphenol A type epoxy resins (commercially available products such as "jER828", "jER1001", "jER1002", "jER1004", etc. by Mitsubishi Kagaku Kogyo Co., Ltd.), bisphenol A type epoxy resins NER-1302 " (epoxy equivalent: 323, softening point: 76 占 폚) commercially available from Nippon Kayaku Co., Ltd.), bisphenol F type resin (commercially available as a commercial product), epoxy resin obtained by reacting an alcoholic hydroxyl group with epichlorohydrin Quot; jER807 ", " EP-4001 ", " EP-4002 ", " EP-4004 ", etc. manufactured by Mitsubishi Kagaku K. K. K. K. K. K.), and epoxy resin obtained by the reaction of an alcoholic hydroxyl group of a bisphenol F type epoxy resin with epichlorohydrin NER-7406 " (epoxy equivalent: 350, softening point: 66 占 폚) manufactured by Nihon Kayaku Co., Ltd.), bisphenol S type epoxy resin and biphenyl glycidyl ether (commercially available as Mitsubishi Kagaku Co., Quot; EP-1 ", manufactured by Nippon Kayaku Co., Ltd., " EP-152 ", manufactured by Mitsubishi Kagaku Kogyo K.K.), phenol novolak type epoxy resin EOCN-102S ", " EOCN-1020 ", manufactured by Nihon Kayaku K.K.) as a curing agent, , "EOCN-104S"), triglycidylisocyanurate ("TEPIC" available from Nissan Chemical Industries, Ltd.) as a commercial product, trisphenol methane type epoxy resin (commercially available from Nihon Kayaku Co., (EPPN-501, EPN-502, EPPN-503), fluorene epoxy resin (commercial product, CARDO epoxy resin "ESF-300" manufactured by Shin- Epoxy resin ("Celloxide 2021P" manufactured by Daicel Chemical Industries, Ltd., " Rocide EHPE "), a dicyclopentadiene type epoxy resin obtained by glycidylating a phenol resin by reaction of dicyclopentadiene and phenol (for example," XD-1000 "manufactured by Nihon Kayaku Co., Ltd., DIC EXA-7200 "manufactured by Nippon Kayaku Co., Ltd.," NC-3000 "and" NC-7300 "manufactured by Nihon Kayaku Co., Ltd.), an epoxy resin having a fluorene skeleton (see JP-A-4-355450 ) 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 copolymerizable epoxy resin. Examples of the copolymerizable epoxy resin include monomers having an epoxy group such as glycidyl (meth) acrylate, (meth) acryloylmethylcyclohexene oxide and vinylcyclohexene oxide, and monomers having an epoxy group such as methyl (meth) acrylate, ethyl (Meth) acrylate, butyl (meth) acrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl (meth) acrylate, (meth) acrylic acid, styrene, A copolymer obtained by copolymerizing a polymerizable monomer having no epoxy group such as (meth) acrylate,? -Methylstyrene, glycerin mono (meth) acrylate and (meth) acrylate having a polyoxyalkylene chain.

Examples of the (meth) acrylate having a polyoxyalkylene chain include polyethylenes such as diethylene glycol mono (meth) acrylate, triethylene glycol mono (meth) acrylate and tetraethylene glycol mono Glycol mono (meth) acrylate; (Meth) acrylate such as methoxyethylene glycol mono (meth) acrylate, methoxy triethylene glycol mono (meth) acrylate, methoxy tetraethylene glycol mono (meth) acrylate and the like.

The molecular weight of the copolymerizable 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 copolymerizable epoxy resin is preferably in the range of 10 to 70 mass%, more preferably in the range of 20 to 50 mass% with respect to the monomer having no epoxy group.

Examples of commercially available products of the copolymerizable epoxy resin include "CP-15", "CP-30", "CP-50", "CP-20SA", "CP- CP-50S ", " CP-50M ", and " CP-20MA ".

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

Examples of the?,? - unsaturated monocarboxylic acid include itaconic acid, crotonic acid, cinnamic acid, acrylic acid and methacrylic acid, and acrylic acid and methacrylic acid are preferable, and acrylic acid is more preferable because of its good reactivity . Examples of the?,? - unsaturated monocarboxylic acid ester having a carboxyl group in the ester moiety include acrylic acid-2-succinoyloxyethyl, acrylic acid-2-maloyloxyethyl acrylate, 2- phthaloyloxyethyl acrylate, Phthaloyloxyethyl methacrylate, 2-succinoyloxyethyl methacrylate, 2-maleoyloxyethyl methacrylate, 2-phthaloyloxyethyl methacrylate, 2-hexahydrophthaloyl methacrylate 2-phthaloyloxyethyl acrylate, and 2-phthaloyloxyethyl acrylate are preferable, and acrylic acid-2-maleoyloxyethyl acrylate and 2- More preferable. These α, β-unsaturated monocarboxylic acids and α, β-unsaturated monocarboxylic acid esters may be used singly or in combination of two or more.

The addition reaction with the α, β-unsaturated monocarboxylic acid or the ester thereof with the epoxy resin can be carried out by a known method, for example, a method of allowing the reaction at a temperature of 50 to 150 ° C. in the presence of an esterification catalyst . Examples of the esterification catalyst include tertiary amines such as triethylamine, trimethylamine, benzyldimethylamine and benzyldiethylamine; Quaternary ammonium salts such as tetramethylammonium chloride, tetraethylammonium chloride and dodecyltrimethylammonium chloride, and the like can be used.

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

Examples of the polybasic acid anhydrides added to the?,? - unsaturated carboxylic acid or the ester-added epoxy resin include maleic anhydride, succinic anhydride, itaconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, Phthalic acid, anhydrous pyromellitic acid, anhydrous trimellitic acid, benzophenonetetracarboxylic acid dianhydride, methylhexahydrophthalic anhydride, endomethylenetetrahydrophthalic anhydride, chlorinated anhydride, methyltetrahydrophthalic anhydride, biphenyltetracarboxylic acid dianhydride and the like . Of these, preferred are maleic anhydride, succinic anhydride, itaconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, pyromellitic anhydride, trimellitic anhydride and biphenyltetracarboxylic acid dianhydride, Phthalic acid and biphenyltetracarboxylic acid dianhydride are more preferable. These polybasic acid anhydrides may be used alone or in combination of two or more.

The addition reaction of the polybasic acid anhydride can be carried out by a known method and can be continuously carried out under the same conditions as the addition reaction of the?,? - unsaturated carboxylic acid or its ester. The amount of the polybasic acid anhydride to be used is preferably such that the acid value of the resulting epoxy (meth) acrylate resin is in the range of 10 to 150, and preferably in the range of 20 to 140 The amount is more preferable.

As the epoxy (meth) acrylate resin having a carboxyl group, the naphthalene-containing resin disclosed in Japanese Patent Application Laid-Open No. 6-49174; Fluorene-containing resins disclosed in JP-A-2003-89716, JP-A-2003-165830, JP-A-2005-325331, and JP-A-2001-354735; Resins described in JP-A-2005-126674, JP-A-2005-55814, JP-A-2004-295084, etc. may be mentioned. As a commercially available product, "ACA-200M" manufactured by Daicel Chemical Industries, Ltd. may be mentioned.

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 of them may be used in combination. Further, the alkali-soluble resin (C) is preferably used in combination with a pigment dispersing agent described later, because uncolored portions do not remain in the non-fired portions on the substrate and high color pixels having excellent adhesion with the substrate can be formed. Concretely, it is preferable to use a part of the alkali-soluble resin (C) together with the pigment dispersant described later in the dispersion treatment step. In this case, the alkali-soluble resin (C) is preferably used in an amount of 5 to 200 mass%, more preferably 10 to 100 mass%, based on the pigment.

As the alkali-soluble resin (C) used in the present invention, alkali-soluble resins 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 an alkali soluble resin obtained by using a polymerizable monomer having a sulfonic acid group as an acidic group as essential components Resins and the like. Examples of the polymerizable monomer having a phenolic hydroxyl group include o-hydroxystyrene, m-hydroxystyrene, p-hydroxystyrene, and the like. Also included are compounds in which at least one hydrogen atom other than a phenolic hydroxyl group and a vinyl group bonded to aromatic rings of the monomers is substituted with an alkyl group, an alkoxyl group, a halogen atom, a nitro group, a cyano group or an amide group. Examples of the polymerizable monomer having a sulfonic acid group as the acidic group include vinylsulfonic acid, styrenesulfonic acid, (meth) allylsulfonic acid, 2-hydroxy-3- (meth) allyloxypropanesulfonic acid, Methacrylic acid-2-sulfoethyl, salts thereof, and the like.

In the resist composition of the present invention, the content of the alkali-soluble resin (C) is preferably from 0.1 to 80% by mass, more preferably from 1 to 60% by mass, The range of mass% is more preferable.

As the polymerizable compound (D) used in the present invention, for example, a photopolymerizable compound having at least one ethylenic unsaturated bond can be exemplified.

Examples of the polymerizable compound (D1) having one ethylenically unsaturated bond include the compounds (c1), (c2) and (c3) described above. Among them, (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, 1,6- (Meth) acrylate, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, triethylene glycol di (Meth) acrylate, polyethylene glycol diacrylate, bis (acryloyloxyethyl) ether of bisphenol A, ethoxylated bisphenol A di (meth) acrylate, propoxylated neopentyl glycol di Neopentyl glycol di (meth) acrylate, 3-methylpentanediol di (meth) acrylate, and the like.

Examples of the polymerizable compound (D3) having three ethylenically unsaturated bonds include trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, tris (2-hydroxyethyl) iso (Meth) acrylate, pentaerythritol tri (meth) acrylate and an acid anhydride, and a reaction product of an acid anhydride, Caprolactone-modified pentaerythritol tri (meth) acrylate, caprolactone modified tris (2-hydroxyethyl) isocyanurate tri (meth) acrylate, caprolactone-modified pentaerythritol tri (meth) , A reaction product of caprolactone-modified dipentaerythritol penta (meth) acrylate and an acid anhydride, and the like.

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

Examples of the polymerizable compound (D5) having five or more ethylenic unsaturated bonds include dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (metha) acrylate, tripentaerythritol penta Acrylate, tripentaerythritol hexa (meth) acrylate, tripentaerythritol hexa (metha) acrylate, tripentaerythritol hepta (meth) acrylate, tripentaerythritol octa (metha) acrylate, dipentaerythritol penta (Meth) acrylate, caprolactone-modified pentaerythritol tetra (meth) acrylate, caprolactone-modified dipentaerythritol (meth) acrylate, caprolactone- (Meth) acrylate, caprolactone-modified dipentaerythritol hexa (meth) acrylate, caprolactone-modified tripentaerythritol Caprolactone-modified tripentaerythritol hexa (meth) acrylate, caprolactone-modified tripentaerythritol (meth) acrylate, caprolactone-modified tripentaerythritol octa (metha) acrylate, caprolactone- Caprolactone-modified tripentaerythritol hepta (meth) acrylate and acid anhydride.

As the polymerizable compound (D) used in the present invention, a photo-curable resin may also be mentioned.

The photocurable resin may be, for example, a urethane (meth) acrylate resin, an unsaturated polyester resin, an epoxy (meth) acrylate resin, a polyester (meth) acrylate resin, an acrylic Containing resin, and the like.

Examples of the urethane (meth) acrylate resin include 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) .

Examples of the aliphatic polyisocyanate compound include tetramethylene diisocyanate, pentamethylene diisocyanate, hexamethylene diisocyanate, heptamethylene diisocyanate, octamethylene diisocyanate, decamethylene diisocyanate, 2-methyl-1,5-pentane Diisocyanate, 3-methyl-1,5-pentane diisocyanate, dodecamethylene diisocyanate, 2-methylpentamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, 2,4,4-trimethylhexamethylene Examples of the diisocyanate include diisocyanate, isophorone diisocyanate, norbornane diisocyanate, hydrogenated diphenylmethane diisocyanate, hydrogenated tolylene diisocyanate, hydrogenated xylylene diisocyanate, hydrogenated tetramethyl xylylene diisocyanate, cyclohexyl diisocyanate and the like. In addition, As hyangjok poly isocyanate compound there may be mentioned tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, xylyl diisocyanate, 1,5-naphthalene diisocyanate, tri aphids diisocyanate, p- phenylene diisocyanate.

Examples of the hydroxy group-containing (meth) acrylate compound include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2- (Meth) acrylate, 1,6-hexanediol mono (meth) acrylate, neopentyl glycol mono (meth) acrylate, hydroxypivalic acid neo Mono (meth) acrylates of divalent alcohols such as pentyl glycol mono (meth) acrylate; Acrylate, trimethylolpropane di (meth) acrylate, ethoxylated trimethylolpropane (meth) acrylate, propoxylated trimethylolpropane di (meth) acrylate, glycerin di Mono or di (meth) acrylates of trihydric alcohols such as ethyl (meth) acrylate, di (meth) acryloyloxyethyl (meth) acrylate, and hydroxyethyl isocyanurate, or mono- or di (meth) acrylates containing hydroxyl groups modified with ε-caprolactone ) Acrylate; (Meth) acryloyl group having three or more functional groups such as pentaerythritol tri (meth) acrylate, ditrimethylol propane tri (meth) acrylate, dipentaerythritol penta , Or a hydroxyl group-containing polyfunctional (meth) acrylate in which the compound is further modified with? -Caprolactone; (Meth) acrylate having an oxyalkylene chain such as dipropylene glycol mono (meth) acrylate, diethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, and polyethylene glycol mono compound; (Meth) acrylate compounds having an oxyalkylene chain having a block structure such as polyethylene glycol-polypropylene glycol mono (meth) acrylate and polyoxybutylene-polyoxypropylene mono (meth) acrylate; A (meth) acrylate compound having a random oxyalkylene chain such as poly (ethylene glycol-tetramethylene glycol) mono (meth) acrylate and poly (propylene glycol-tetramethylene glycol) mono .

The reaction of the aliphatic polyisocyanate compound or aromatic polyisocyanate compound with the hydroxy group-containing (meth) acrylate compound can be carried out, for example, in the presence of an urethane-forming catalyst by a conventional method. Specific examples of the urethanization catalyst which can be used herein include amines such as pyridine, pyrrole, triethylamine, diethylamine and dibutylamine; Phosphines such as triphenylphosphine and triethylphosphine; Organotin compounds such as dibutyltin dilaurate, octyltin dilaurate, octyltin diacetate, dibutyltin diacetate, and tin octylate; And organometallic compounds such as zinc octylate.

Among these urethane (meth) acrylate resins, particularly those obtained by reacting an aliphatic polyisocyanate compound with a hydroxy group-containing (meth) acrylate compound are excellent in transparency of the cured coating film, have good sensitivity to active energy rays, It is preferable in terms of excellence.

Next, the unsaturated polyester resin can be obtained, for example, by reacting an α, β-unsaturated dibasic acid or an acid anhydride thereof, a dibasic acid other than the dibasic acid or its acid anhydride and a curing resin obtained by polycondensation of glycols . Examples of the?,? - unsaturated dibasic acid or its acid anhydride include maleic acid, maleic anhydride, fumaric acid, itaconic acid, citraconic acid, chloromaleic acid, and esters thereof.

Examples of the dibasic acids and their acid anhydrides other than the?,? - unsaturated dibasic acids or their acid anhydrides include aromatic saturated dibasic acids, aliphatic dibasic acids, alicyclic saturated dibasic acids and their 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, halogenated phthalic anhydride and esters thereof have. Examples of the 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 esters thereof . 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, triethylene glycol, tetra Ethylene glycol, 1,5-pentanediol, 1,6-hexanediol, bisphenol A, hydrogenated bisphenol A, ethylene glycol carbonate and 2,2-di- (4-hydroxypropoxydiphenyl) propane , And oxides such as ethylene oxide and propylene oxide may be used as well.

Next, examples of the epoxy vinyl ester resin include (meth) acrylic acid in the epoxy group of an epoxy resin such as bisphenol A type epoxy resin, bisphenol F type epoxy resin, phenol novolak type epoxy resin and cresol novolak type epoxy resin And the like.

Examples of the maleimide group-containing resin include a bifunctional maleimide urethane compound obtained by urethane-forming N-hydroxyethyl maleimide and isophorone diisocyanate, a bifunctional maleimide urethane compound obtained by esterifying maleimide acetic acid and polytetramethylene glycol A maleimide ester compound, a quadrivalent maleimide ester compound obtained by esterifying maleimide caproic acid and a tetraethylene oxide adduct of pentaerythritol, a polyfunctional maleimide ester compound obtained by esterifying maleimide acetic acid and a polyhydric alcohol compound . These active energy ray-curable resins may 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, dipentaerythritol hexa (meth) acrylate (Meth) acrylate such as pentaerythritol tetra (meth) acrylate and trifunctional or more polyfunctional (meth) acrylate such as pentaerythritol tetra These polymerizable compounds (D) may be used alone or in combination of two or more.

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

The content of the polymerizable compound (D5) in the polymerizable compound (D) is preferably from 1 to 50 mass%, more preferably from 5 to 40 mass%, and particularly preferably from 5 to 35 mass%, based on the solid content of the resist composition, desirable. When the content of the polymerizable compound (D5) is in the above range, the sensitivity and the strength, smoothness and reliability of the coating film layer tend to be good.

The content of the polymerizable compound (D5) in the polymerizable compound (D) is preferably 10 to 95 mass% (based on the total amount of the polymerizable compounds (D1), (D2), (D3), (D4) %, More preferably from 20 to 90 mass%. When the content of the polymerizable compound (D5) is in the above range, the sensitivity, the strength, smoothness and reliability of the coating film layer tend to be good.

The method of producing the resist composition comprises the steps of obtaining the random copolymer (A) as the first invention of the present invention and the step of mixing the random copolymer (A), the pigment (B), the alkali- And a step of mixing the polymerizable compound (D). In the method for producing a resist composition of the present invention, when the pigment is used as the colorant (B), the random copolymer (A), the colorant (B), the alkali-soluble resin (C) and the polymerizable compound , It is preferable to use a pigment dispersion prepared by dispersing the pigment dispersion in an organic solvent using a dispersant as the colorant (B) because a good dispersibility is obtained and a desired color is obtained.

As the dispersing agent, for example, a surfactant; Intermediates or derivatives of pigments; And resinous dispersants such as polyamide resins, polyurethane resins, polyester resins and acrylic resins. Among these pigment dispersants, a resinous dispersant is preferable, an acrylic resin-type dispersant is more preferable, and an acrylic polymer having an N, N-disubstituted amino group and an acidic group in the main chain or side chain A resinous dispersant is more preferred. Examples of commercial products of such a resinous dispersant include BYK-160, BYK-161, BYK-2001 from BIG Chemie, Efka 46 from AFC Chemical Industries, Aji Spa PB-814 " manufactured by Techno Corporation. These dispersants may be used alone or in combination of two or more.

Examples of the organic solvent used for preparing the pigment dispersion include acetic acid ester solvents such as propylene glycol monomethyl ether acetate and propylene glycol monoethyl ether acetate; Propionate-based 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 and diethylene glycol dimethyl ether; Ketone solvents such as methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone; Aliphatic hydrocarbon solvents such as hexane; Nitrogen-based solvents such as N, N-dimethylformamide,? -Butyrolactam and N-methyl-2-pyrrolidone; lactone type solvents such as? -butyrolactone; And carbamic acid esters. These solvents may be used alone or in combination of two or more.

Examples of the method for preparing the pigment dispersion include a method in which the pigment is subjected to a kneading and dispersing step and a microdispersion step, and a method in which only a microdispersion step is carried out.

In the kneading and dispersing step, the pigment, the alkali-soluble resin (C) and, if necessary, the dispersing agent are mixed and kneaded. As a kneading machine, for example, two rolls, three rolls, a ball mill, a discussion mill, a disperser, a kneader, a coneerator, a homogenizer, a blender, a single or twin extruder, , And the pigment can be dispersed in the alkali-soluble resin (C) by dispersing the mixture while applying a strong shearing force using the kneader. It is also preferable that the particle size is made finer by a salt milling method or the like before the above-mentioned kneading of the pigment. Here, the alkali-soluble resin may be the whole amount used in the method for producing a resist composition of the present invention, or a part thereof may be used.

In the micro-dispersion step, an organic solvent is added to a composition containing the pigment obtained in the kneading and dispersing step, or a mixture of the pigment, the alkali-soluble resin (C) and, if necessary, the dispersing agent is mixed with glass, zirconia It is possible to disperse the particles of the pigment into a minute state close to the primary particles by mixing and dispersing the fine particles of the ceramics together with the dispersion medium using a dispersing machine.

Examples of the organic solvent include acetic acid ester solvents such as propylene glycol monomethyl ether acetate and propylene glycol monoethyl ether acetate; Propionate-based 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 and diethylene glycol dimethyl ether; Ketone solvents such as methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone; Aliphatic hydrocarbon solvents such as hexane; Nitrogen-based solvents such as N, N-dimethylformamide,? -Butyrolactam and N-methyl-2-pyrrolidone; lactone type solvents such as? -butyrolactone; And carbamic acid esters. These solvents may be used alone or in combination of two or more.

The average particle diameter 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) is measured with a particle size distribution meter of a dynamic light scattering type. For example, the average particle size of the pigment (B) is measured by a Nanotrac particle size distribution measuring device " UPA-EX150 & UPA-EX250 " or the like.

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 a resist composition, 0.0001 to 10 mass Preferably from 5 to 80 parts by mass, from 0.1 to 80 parts by mass, and from 5 to 80 parts by mass, and preferably from 0.001 to 5 parts by mass, from 5 to 70 parts by mass, from 1 to 60 parts by mass, More preferable.

When the random copolymer (A), the colorant (B), the alkali-soluble resin (C) and the polymerizable compound (D) are mixed in the method of producing the resist composition, various methods may be used. Concretely, for example, they may be mixed by using a shaker, a paint shaker, stirring using a stirring blade, or the like, and an organic solvent may be added as needed during mixing. As the organic solvent, for example, an organic solvent which can be used for adjusting the pigment dispersion can be used. The amount of the organic solvent to be used is, for example, generally 100 to 1000 parts by mass based on 100 parts by mass of the coating film layer forming component.

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

Examples of the polymerization initiator include benzophenone, acetophenone, benzoin, benzoin ethyl ether, benzoin isobutyl ether, benzyl methyl ketal, azobisisobutyronitrile, 1-hydroxycyclohexyl phenyl ketone, 2 (4'-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, 1- (4'-dodecylphenyl) 2-methylpropan-1-one, 3,3 ', 4,4'-tetra (t-butylperoxycarbonyl) benzophenone, 4,4'-diethylisophthalo 2-methylthioxanthone, 2-isopropylthioxanthone, 2-isopropylthioxanthone, 2-methylthioxanthone, -Methyl-1 [4- (methylthio) phenyl] -2-morpholinopropane-1-one, 2-benzyl- Bis (2,6-dimethoxybenzoyl) -2,4,4-trimethyl-pentylphosphine oxide, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, 2,4,6- And the like one trillion days diphenyl phosphine oxide, alone also may be used in combination of two or more. Of these, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1 is preferable, although it is relatively difficult to receive the influence of the colorant (B) and exhibits high curability.

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

In addition, a photosensitizer such as an amine compound or a phosphorus compound may be added to the resist composition obtained by the production method of the present invention to promote photopolymerization.

The resist composition obtained by the production method of the present invention may contain an organic solvent, a polymerization inhibitor, an antistatic agent, a defoaming agent, a viscosity adjusting agent, a light stabilizer , A heat stabilizer, an antioxidant, and the like.

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

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

Examples of the antistatic agent include polyoxyethylene alkyl ether, polyoxyethylene alkylphenol, polyoxyethylene alkylamine, polyoxyethylene alkylamide, fatty acid polyethylene glycol ester, fatty acid sorbitan ester, polyoxyethylene fatty acid sorbitan ester , Nonionic antistatic agents such as fatty acid glycerin esters and alkylpolyethyleneimines, cationic antistatic agents such as alkylamine salts, alkyl quaternary ammonium salts and alkylimidazoline derivatives, and the like.

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

As the viscosity adjusting agent, for example, an acrylic polymer or a synthetic rubber latex which can be thickened by adjusting to an alkaline state, a urethane resin capable of thickening by association of molecules, hydroxyethylcellulose, carboxymethylcellulose, methylcellulose, polyvinyl alcohol, ) Oil, amide wax, polyethylene oxide, metal soap, dibenzylidene sorbitol and the like.

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

Examples of the heat resistant stabilizer include 1,3,5-trimethyl-2,4,6-tris (3,5-di-t-butyl-4-hydroxybenzyl) benzene, 1,1,3- N, N'-hexamethylenebis (3,5-di-t-butyl-4-hydroxycinnamic acid amide), 4 , 2,2'-methylenebis (4-ethyl-6-t-butylphenol), pentaerythrityl-tetrakis [3- (3 , 5-di-t-butyl-4-hydroxyphenyl) propionate]; N, N'-diphenyl-p-phenylenediamine, poly (2,2,4-trimethyl-1,2-dihydroquinoline ); Sulfur compounds such as dilauryl thiodipropionate; Tris (2,4-di-t-butylphenyl) phosphite, and the like.

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

The present invention can provide a color filter. The color filter can be obtained, for example, by polymerizing a polymerizable monomer (a1) having a fluorinated alkyl group having 1 to 6 carbon atoms directly bonded with a fluorine atom and a polymerizable unsaturated group, a polymerizable monomer (a1) having a skeleton of a crosslinked ring hydrocarbon and a polymerizable monomer (a2) is subjected to living radical polymerization in the presence of a polymerizable monomer (a1) and a polymerizable monomer (a2) to obtain a fluoropolymer (A), and a step of mixing the fluoropolymer (A), the colorant A step of mixing a soluble resin (C) with a polymerizable compound (D) to obtain a resist composition, and a step of forming a coat layer of the resist composition on a substrate. The step of obtaining the fluorine-containing polymer (A) corresponds to the method of producing the 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 the random copolymer (A) by the process for producing the random copolymer of the present invention.

(2) A step of mixing the random copolymer (A), the colorant (B), the alkali-soluble resin (C) and the polymerizable compound (D) obtained in the above step 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 a coating film layer.

(4) A step of drying (prebaking) the coating film layer to obtain a substrate having a dried coating film layer.

(5) A step of exposing a desired pattern onto the dried coat layer using a photomask.

(6) A step of performing development processing using an alkali developing solution.

(7) Rinsing with distilled water and drying.

The substrate is not particularly limited as long as it is transparent and has appropriate strength. As the material, for example, a polyester resin such as polyethylene terephthalate; Polyolefin-based resins such as polypropylene and polyethylene; Polycarbonate resin; Acrylic resins such as polymethyl methacrylate; A sheet made of a thermoplastic resin such as polysulfone resin; Thermosetting resin sheets such as epoxy resin and unsaturated polyester resin; Or various glasses. Of these, glass and heat-resistant resin are preferable because of high heat resistance. These transparent substrates are subjected to surface treatment such as corona discharge treatment and ozone treatment, thin film formation treatment with various resins such as a silane coupling agent and urethane resin, etc., if necessary, in order to improve surface physical properties such as adhesiveness . The thickness of the transparent substrate is usually not less than 0.05 mm, preferably not less than 0.1 mm, and usually not more than 10 mm, preferably not more than 7 mm. When a thin film is formed by various resins, the film thickness is usually 0.01 탆 or more, preferably 0.05 탆 or more, usually 10 탆 or less, preferably 5 탆 or less, Mu] m.

The color filter can be usually manufactured by providing a black matrix on the above-mentioned substrate and further forming a coating film of a resist composition forming red, green, and blue pixel images. The black matrix may be formed using a light-shielding metal thin film. In the method for producing a resist composition of the present invention, the black matrix may be formed on a transparent substrate by using a resist composition obtained by using a black coloring agent as the coloring agent (B) have.

As the light-shielding metal material that can be used for forming the light-shielding metal thin film, for example, a chromium compound such as metal chromium, chromium oxide, or chromium nitride, or an alloy of nickel and tungsten may be used. Shielding metal material may be laminated on a plurality of layers. These light-shielding metal thin films are generally formed by a sputtering method.

For the metal chromium, an etchant in which ceric ammonium nitrate and perchloric acid and / or nitric acid are mixed is used, and other materials are etched using an etching solution according to the material. Finally, By peeling off with a stripping agent, a black matrix can be formed. In this case, first, a thin film of these metals or metal oxides is formed on the transparent substrate by vapor deposition or sputtering. Then, a coating film layer of the color resist composition obtained by the production method of the present invention is formed on the thin film. Then, using a photomask having a repeating pattern such as a stripe, a mosaic, or a triangle, the coating layer is exposed and developed to form an image. Thereafter, this coating film layer may be subjected to an etching treatment to form a black matrix.

A resist composition containing a coloring material of one of red, green, and blue is applied on a substrate provided with a black matrix, and after drying, a photomask is overlaid on the coating film layer, Then, a pixel image is formed by thermosetting or photo-curing to form a colored layer. The color filter image can be formed by performing this operation for each of the red, green, and blue tri-color resist compositions.

Examples of the method of supplying the resist composition to the substrate include a method of supplying the resist composition to a substrate such as 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 end spin coater, Dipping, screen printing, spraying, a method using an applicator, a bar coater, and the like.

If the thickness of the coating layer is excessively large, pattern development becomes difficult and the gap adjustment in the liquid crystal cell formation process becomes difficult. On the other hand, if the thickness is too thin, it is difficult to increase the pigment concentration, . The thickness of the coating layer is usually 0.2 to 20 占 퐉, preferably 0.5 to 10 占 퐉, and more preferably 0.8 to 5 占 퐉, as a film thickness after drying.

A resist composition is applied to a substrate to form a coating layer on the substrate, and then dried (prebaked) in the step (4). Drying (prebaking) can be performed, for example, by heating in a hot plate, an oven or the like at a temperature in the range of 50 to 140 캜 for 10 to 300 seconds. Among them, it is preferable to heat for 30 to 180 seconds in a temperature range of 70 to 130 占 폚, and more preferably for 30 to 90 seconds in a temperature range of 80 to 120 占 폚. Further, in order to perform more complete drying, vacuum drying may be performed before drying (prebaking).

After drying (prebaking), a desired pattern is exposed using a photomask in the step (5). Specifically, for example, a matrix pattern, which is a negative print, is overlaid on a dried (prebaked) coating film layer, and active energy rays such as ultraviolet rays or visible rays are irradiated through the mask pattern. At this time, if necessary, an oxygen barrier layer such as a polyvinyl alcohol layer may be formed on the coating film layer and then exposed to light, in order to prevent deterioration of sensitivity of the coating film layer formed by the resist composition with oxygen.

Examples of the active energy ray include active energy rays such as light, electron beam, and radiation. Specific examples of the energy source or curing device include a sterilizing lamp, a fluorescent lamp for ultraviolet rays, a carbon arc, a xenon lamp, a high pressure mercury lamp for copying, a medium pressure or high pressure mercury lamp, an ultra high pressure mercury lamp, an electrodeless lamp, a metal halide lamp, , Or an electron beam by a scanning type or curtain type electron beam accelerator. In addition, when curing is performed with an electron beam, the addition of the polymerization initiator to the resist composition is unnecessary.

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

After the exposure, development processing is performed in the step (6). In the above developing process, unexposed portions of unexposed light are eluted into an alkaline developing solution, leaving only the photocured cured portions. The alkali developing solution may be used without particular limitation as long as it dissolves the uncured portions and does not dissolve the respective pixel portions of RGB and the cured portions of the black matrix. Specific examples of the alkaline developer include alkali metal hydroxides such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium hydrogencarbonate, sodium silicate, sodium metasilicate, ammonia water, ethylamine, diethylamine, dimethylethanolamine, tetramethylammonium hydroxide, An aqueous solution of an alkaline compound such as ammonium hydroxide, choline, pyrrole, piperidine, and 1,8-diazabicyclo- [5,4,0] -7-undecene. The alkali concentration of the alkali developing solution is preferably 0.001 to 10 mass%, more preferably 0.01 to 1 mass%. The developing temperature is usually 20 占 폚 to 30 占 폚, and the developing time is preferably 20 to 90 seconds.

After the development processing, it is rinsed (rinsed) with distilled water in the step (7), and dried. In the case of washing and drying, a post-baking treatment can be carried out if necessary. The post-baking is a post-development heat treatment in order to make the curing to be complete, and the post baking is usually performed in a temperature range of 200 to 250 캜. The post-baking treatment can be carried out continuously or batchwise using a heating means such as a hot plate, a convection oven (hot-air circulation type drier), or a high-frequency heater so as to achieve the above conditions.

A substrate on which transparent electrodes such as ITO are formed on the pixels of the color filter manufactured as described above is used as a substrate for sandwiching the liquid crystal layer together with other substrates, and a backlight, a polarizing plate, and a liquid crystal layer are combined to form a liquid crystal display Device.

The random copolymer (A) of the present invention, the colorant (B) and the thermoplastic resin (E) [the thermoplastic resin other than the copolymer (A) and the alkali-soluble resin (C) have. Specifically, a polymerizable monomer (a1) having a fluorinated alkyl group having 1 to 6 carbon atoms in which fluorine atoms are directly bonded and a polymerizable unsaturated group and a polymerizable monomer (a2) having a skeleton of a crosslinked ring hydrocarbon and a polymerizable unsaturated group, (A) is obtained by living radical polymerization in the presence of a polymerizable monomer (a1) and a polymerizable monomer (a2), and a step of mixing the random copolymer (A), the colorant (B) and the thermoplastic resin (E) The coating composition can be obtained by a method including a mixing step.

Examples of the thermoplastic resin (E) include acrylic resins, methacrylic resins, acrylic urethane resins, acrylic silicone resins, acrylic melamine resins, acrylic modified polyolefins, acrylic modified fluororesins, aromatic polyester resins, aliphatic polyester resins, Polyamide resin, polycarbonate resin, vinyl acetate resin, ethylene-vinyl acetate resin and the like. Of the thermoplastic resin (E), an acrylic resin, a methacrylic resin or an acryl urethane resin is preferable because a coating composition capable of obtaining a coating film having a high strength can be obtained.

The coating composition of the present invention can be obtained by, for example, dissolving the random copolymer (A), the colorant (B) and the thermoplastic resin (E) in an organic solvent and stirring the mixture using a shaker, a paint shaker, And mixing them by a method. As the organic solvent to be used herein, for example, an organic solvent which can be used in the adjustment of the pigment dispersion can be used. The amount of the organic solvent to be used is, for example, generally 100 to 1000 parts by mass based on 100 parts by mass of the coating film layer forming component.

In the coating composition, the blending ratio when the random copolymer (A), the colorant (B) and the thermoplastic resin (E) are mixed is preferably from 0.0001 to 10 parts by mass, For example, 0.001 to 5 parts by mass, 5 to 70 parts by mass, and 1 to 70 parts by mass.

The above-mentioned coating composition can be used to produce a coated layer-attached article. The article with a coating layer can be produced, for example, by forming a coating layer of the coating composition on the article. Such articles include, for example, roofing materials (metal, slate, concrete, tile, cement, plastic, etc.), walls, tiles, glass plates, metals, blocks, concrete, plastics, cements, H- Construction related items such as shutters, sandwich panels, tanks; Automobile related products such as exterior of car body, window glass, dashboard, steering wheel, shift lever, tire, etc .: aircraft related articles such as exterior and window glass; Such as an air conditioner, a surface sheet and a back sheet for a solar cell, a casing of a computer or a mobile phone, various display screens such as a plasma display (PDP) and an organic EL display, a rubber roller for OA such as a CD, a DVD, An antireflection filter of a display device such as a CRT, a liquid crystal display, a plasma display, and a projection television, a spherical lens, an aspherical lens, an aspherical lens, An optical-related article such as a lens component such as a Fresnel lens and a lenticular lens, and the like.

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

The thickness of the coating layer may be appropriately selected depending on the kind of the article and the intended use, but is usually 0.1 to 100 占 퐉 in the thickness after drying.

After the coating layer of the coating composition is formed on the article, it is dried by various methods. The drying method may be appropriately selected depending on the kind of the article and the intended use. For example, the drying method may be natural drying by allowing it to stand or a method of forcibly drying it in an atmosphere of 40 to 300 캜.

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

The coating composition may be prepared, for example, by dissolving the random copolymer (A), the colorant (B) and the polymerizable compound (D) in an organic solvent, if necessary, and stirring with a shaker, a paint shaker, And the like. As the organic solvent to be used herein, for example, an organic solvent which can be used in the adjustment of the pigment dispersion can be used. When an organic solvent is used, its amount to be used is usually 100 to 1000 parts by mass based on 100 parts by mass of the coating film layer forming component.

When mixing the random copolymer (A), the colorant (B), and the polymerizable compound (D) in the preparation of the coating composition, the compounding ratio in the form of solids is preferably from 0.0001 to 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, respectively.

The coating composition can be used to obtain an article having a coating layer. Specifically, the article with a coating layer can be produced, for example, by forming a coating layer of the coating composition on the article. As the article, for example, the article may be mentioned.

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

The thickness of the coating layer may be appropriately selected depending on the kind of the article and the intended use, but is generally 0.1 to 100 占 퐉 in the thickness after curing.

The coating layer is cured by irradiating energy rays. Examples of the active energy ray include ionizing radiation such as ultraviolet rays, electron rays,? Rays,? Rays and? Rays. Examples of the active energy ray source or curing device include a sterilizing lamp, a fluorescent lamp for ultraviolet rays, a carbon arc, a xenon lamp, a high pressure mercury lamp for copying, a medium pressure or high pressure mercury lamp, an ultra high pressure mercury lamp, , Or an electron beam by a scanning type or curtain type electron beam accelerator.

Among these, ultraviolet rays are particularly preferable, and it is preferable to irradiate ultraviolet rays in an inert gas atmosphere such as nitrogen gas in order to avoid curing inhibition by oxygen or the like. If necessary, heat may be used as an energy source, and after curing with ultraviolet rays, heat treatment may be performed.

The irradiation amount of the energy curing wire may be an irradiation amount for curing the coating layer, and is, for example, in a range of 50 mJ / cm 2 to 3000 mJ / cm 2.

[Example]

Hereinafter, the present invention will be described in more detail by way of examples and comparative examples. Unless otherwise noted, parts and percentages are by weight. IR spectra, ¹³ C-NMR spectrum and GPC measurement conditions are as follows.

[Conditions for measuring IR spectrum]

Apparatus: "FT / IR-6100" manufactured by Nihon Bunko K.K.

Measuring method: KBr method

[Conditions for measuring ¹³ C-NMR spectrum]

Apparatus: "JNM-AL400" manufactured by Nihon Denshi Co., Ltd.

Solvent: chloroform-d ₆

[Conditions for measuring GPC]

Measurement apparatus: "HLC-8220 GPC" manufactured by Tosoh Corporation,

Column: " HHR-H " (6.0 mm ID x 4 cm) manufactured by Tosoh Corporation, " TSK- GEL GMHHR-N " (7.8 mm ID x 30 cm) manufactured by TOSOH CORPORATION, "TSK-GEL GMHHR-N" (7.8 mm ID × 30 cm) manufactured by Tosoh Corporation; "TSK-GEL GMHHR- N " (7.8 mm ID x 30 cm)

Detector: ELSD (ELSD2000 manufactured by Alltech Japan)

Data processing: "GPC-8020 Model II Data Analysis Version 4.30" manufactured by Tosoh Corporation

Measurement conditions: column temperature  40 ℃

      Developing solvent  Tetrahydrofuran (THF)

      Flow rate  1.0 ml / min

Sample: A tetrahydrofuran solution of 1.0% by mass in terms of resin solid matter was filtered with a microfilter (5 μl).

Standard samples: 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".

(Monodisperse polystyrene)

Quot; A-500 " manufactured by Tosoh Corporation

&Quot; A-1000 " manufactured by Tosoh Corporation

Quot; A-2500 " manufactured by Tosoh Corporation

Quot; A-5000 " manufactured by Tosoh Corporation

Quot; F-1 " manufactured by Tosoh Corporation

Quot; F-2 " manufactured by Tosoh Corporation

Quot; F-4 " manufactured by Tosoh Corporation

Quot; F-10 " manufactured by Tosoh Corporation

Quot; F-20 " manufactured by Tosoh Corporation

Quot; F-40 " manufactured by Tosoh Corporation

Quot; F-80 " manufactured by Tosoh Corporation

Quot; F-128 " manufactured by Tosoh Corporation

Quot; F-288 " manufactured by Tosoh Corporation

Quot; F-550 " manufactured by Tosoh Corporation

Reference Example 1 (Preparation of pigment dispersion)

10 g of a red pigment CIPigment Red 254 ("IRGAPHOR RED BT-CF" manufactured by BASF) was placed in a polybin, and 44 g of PGMEA, 12 g of DISPERBYK LPN21116 (manufactured by BICKEMI KABUSHIKI KAISHA) The beads were added and dispersed with a paint conditioner (manufactured by Toyo Seiki Co., Ltd.) for 2 hours to obtain a red pigment dispersion (1).

Reference Example 2 (homologous)

10 g of a yellow pigment CIPigment Yellow 129 ("Irvine Yellow L0800" manufactured by Ciba Specialty Chemicals) was added to a polybin, and 67 g of PGMEA, 23 g of DISPERBYK 161 (manufactured by BICKEMI K.K.) Of SEPR beads were added and dispersed with a paint conditioner (manufactured by TOYO SEIKI K.K.) for 2 hours to obtain a yellow pigment dispersion (2).

Reference Example 3 (homologous)

A yellow pigment dispersion (3) was obtained in the same manner as in Reference Production Example 2 except that C.I. Pigment Yellow 138 ("Pallitol Yellow K0961HD" manufactured by BASF) was used as a yellow pigment.

Reference Example 4 (homologous)

A yellow pigment dispersion (4) was obtained in the same manner as in Reference Production Example 2 except that C.I. Pigment Yellow 139 ("Pallitol Yellow D1819" manufactured by BASF) was used as the yellow pigment.

Reference Example 5 (homologous)

A yellow pigment dispersion (5) was obtained in the same manner as in Reference Production Example 2 except that C.I. Pigment Yellow 150 ("E4GNGT" manufactured by LANXESS Co., Ltd.) was used as a yellow pigment.

Reference Example 6 (homologous)

A yellow pigment dispersion (6) was obtained in the same manner as in Reference Production Example 2 except that C.I. Pigment Yellow 185 ("Pallitol Yellow D1155" manufactured by BASF) was used as the yellow pigment.

Reference Example 7 (Synthesis of alkali-soluble resin)

A four-necked flask equipped with a stirrer, a thermometer, a cooling tube and a nitrogen inlet tube was charged with 100 g of propylene glycol monomethyl ether acetate, and the internal temperature was elevated to 110 DEG C with stirring under a nitrogen stream. Subsequently, a mixed solution composed of 80 g of benzyl methacrylate and 20 g of methacrylic acid, 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, respectively. After completion of dropwise addition, polymerization reaction was carried out for 8 hours while keeping the inner temperature at 110 캜. After completion of the reaction, the solution was diluted with propylene glycol monomethyl ether acetate to obtain a resin solution of an alkali-soluble resin having a nonvolatile content of 40%. The weight average molecular weight of this resin was 17,000.

Example 1 (Preparation of random copolymer)

111 g of methyl ethyl ketone, 47 g of 1-adamantyl methacrylate and 25 g of 2- (tridecafluorohexyl) ethyl methacrylate as a solvent were added to a flask purged with nitrogen and stirred at 60 DEG C . Subsequently, 5 g of 2,2'-bipyridyl, 2 g of cuprous chloride and 3.3 g of ethyl 2-bromoisobutyrate were added and 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 stirred. After filtration of the activated alumina, the solvent was distilled off under reduced pressure to obtain a random copolymer (1). The molecular weight of the random copolymer (1) was measured by GPC to find that the weight average molecular weight (Mw) was 4,133, the number average molecular weight (Mn) was 3,197, and the molecular weight (Mw / Mn) was 1.29. The content of fluorine atoms in the random copolymer (1) was 20% by mass. A chart of the IR spectrum of the random copolymer (1) is shown in Fig. 1, a chart of ¹³ C-NMR spectrum is shown in Fig. 2, and a chart of GPC is shown in Fig.

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

≪ Evaluation method of smoothness of coating layer >

3 g of an alkali-soluble resin (a copolymer of benzyl methacrylate and acrylic acid), 10 g of Aronix M-402 (manufactured by Toagosei Kagaku K.K.) which is a mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate ), 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 on a central portion of a chromium-plated glass substrate of 10 cm x 10 cm, spin-coated under the conditions of a rotation number of 500 rpm and a rotation time of 30 seconds, and then heated and dried at 110 캜 for 2 minutes to obtain an article having a coating layer I wrote. The coating layer was visually observed, and the smoothness of the coating layer was evaluated according to the following criteria. The evaluation results are shown in Table 1.

≪ Criteria for Evaluation of Smoothness of Coating Layer &

?: Almost unevenness of coating film was not observed.

△: Some unevenness of coating film was observed.

X: Much unevenness of coating film was observed.

Example 2 (homology)

111 g of methyl ethyl ketone as a solvent, 59 g of 1-adamantyl methacrylate and 12 g of 2- (tridecafluorohexyl) ethyl methacrylate were fed into a nitrogen-purged flask and stirred at 60 DEG C . Subsequently, 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 stirred. After filtration of the activated alumina, the solvent was distilled off under reduced pressure to obtain a random copolymer (2). The molecular weight of the random copolymer was measured by GPC. As a result, the weight average molecular weight (Mw) was 4,561, number average molecular weight (Mn) was 3,824, and (Mw / Mn) was 1.19. The content of fluorine atoms in the random copolymer (2) was 10% by mass. The smoothness of the coating layer was evaluated in the same manner as in Example 1, and the results are shown in Table 1.

Example 3 (homology)

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

Example 4 (homologous)

111 g of methyl ethyl ketone, 47 g of isobornyl methacrylate and 25 g of 2- (tridecafluorohexyl) ethyl methacrylate as a solvent were added to a flask purged with nitrogen, and the mixture was stirred at 60 캜 It has warmed up. Subsequently, 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 in a nitrogen stream. Then, 30 g of activated alumina was added to the obtained reaction product and stirred. After filtration of the activated alumina, the solvent was distilled off under reduced pressure to obtain a random copolymer (4). The molecular weight of the random copolymer (4) was measured by GPC. As a result, the weight average molecular weight (Mw) was 9,182, the number average molecular weight (Mn) was 7,345 and (Mw / Mn) was 1.25. The content of fluorine atoms in the random copolymer (4) was 20 mass%. The smoothness of the coating layer was evaluated in the same manner as in Example 1, and the results are shown in Table 1.

Comparative Example 1 (Preparation of copolymer for comparison)

67 g of methanol, 0.961 g of 2,2'-bipyridyl and 0.305 g of cuprous chloride were added to a reaction vessel purged with nitrogen, and the mixture was stirred at room temperature for 60 minutes. Thereafter, a solution of 3.37 g of 2- (nonafluorobutyl) ethyl methacrylate, 3.33 g of 2- (tridecafluorohexyl) ethyl methacrylate, and 3.33 g of poly (1,2-oxybutylene) 13.3 g of acrylate ("Brenma 10PPB-500B" manufactured by Nichiyu Corporation; the average number of repeating oxyethylene groups: 6) and 13.3 g of polyethylene glycol monomethacrylate ("Brenma PE-200" manufactured by Nichiyu K.K.) ; Average number of repeating units of oxyethylene 4.5) and 0.6 g of ethyl 2-bromoisobutyrate were added, and the mixture was reacted at 60 DEG C for 10 hours in a nitrogen stream. Then, 30 g of activated alumina was added to the obtained reaction product and stirred. After filtration of the activated alumina, the solvent was distilled off under reduced pressure to obtain a comparative copolymer (1 ') having no crosslinked ring structure. The molecular weight of the comparative copolymer (1 ') was measured by GPC. As a result, the weight average molecular weight (Mw) was 17,000, the number average molecular weight (Mn) was 13,000, and the molecular weight (Mw / Mn) was 1.25. The fluorine atom content was 9.1% by mass. The smoothness of the coating layer was evaluated in the same manner as in Example 1, and the results are shown in Table 1.

Comparative Example 2 (Preparation of comparative control block polymer)

47.5 g of 2-propanol as a solvent and 25.6 g of 3-hydroxy-1-adamantyl methacrylate were fed into a nitrogen-purged flask, and the mixture was heated to 40 캜 while stirring under a nitrogen stream. Then, 5.3 g of 2,2'-bipyridyl and 1.9 g of cuprous chloride were added and stirred for 30 minutes while maintaining the inside of the flask at 40 ° C. Then, 3.3 g of ethyl 2-bromoisobutyrate was added and the reaction was carried out at 40 DEG C for 2 hours in 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 reaction was carried out 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 stirred. After filtration of the activated alumina, the solvent was distilled off under reduced pressure to obtain a comparative copolymer (2 '). The molecular weight of the comparative copolymer (2 ') was measured by GPC. As a result, the weight average molecular weight (Mw) was 3,100, the number average molecular weight (Mn) was 2,700, and (Mw / Mn) was 1.15. The fluorine atom content was 14.5% by mass. The smoothness of the coating layer was evaluated in the same manner as in Example 1, and the results are shown in Table 1.

[Table 1]

Example 5 (Preparation of resist composition)

To 5.9 g of the red pigment dispersion (1), 1.5 g of a 40% by mass resin solution of the alkali-soluble resin obtained in Reference Production Example 7, 1.5 g of a mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate 0.6 g of Aronix M-402 (manufactured by Toagosei Chemical Industry Co., Ltd.), 0.05 g of Irgacure # 369 manufactured by BASF Japan Co., Ltd. as a photopolymerization initiator, 0.0014 g of the random copolymer (1) and 2.2 g of PGMEA were added and mixed to prepare a color resist composition (1). The ability to form a coating layer using the color resist composition (1), to inhibit the generation of foreign matter (foreign matter originating from the pigment) in the coating layer (inhibitory property), and to develop the coating layer with the alkali solution, I appreciated.

≪ Evaluation method of inhibiting property of foreign matter in coating layer >

The color resist composition (1) was spin-coated on a 7 cm x 7 cm glass plate under the conditions of the number of revolutions of 1000 rpm and the rotation time of 10 seconds, and dried at 80 캜 for 3 minutes to obtain an article having a dried coating layer. A dry film layer was irradiated with an active energy ray at 50 mJ / cm 2 using a high-pressure mercury lamp to obtain an article having a coating layer cured. Thereafter, the article was heated at 270 DEG C for 1 hour, and then the coating film layer was observed with a Giannez digital microscope VHX-900 and evaluated according to the following criteria. The evaluation results are shown in Table 2.

?: 1 or less foreign matter that can be identified in a coating layer of 1 cm x 1 cm in all directions.

?: An average of 2 to 9 foreign objects can be identified in a coating layer of 1 cm x 1 cm on all sides.

X: An average of 10 or more foreign particles that can be identified in a coating layer of 1 cm x 1 cm on all sides.

≪ Evaluation method of developability of coating layer >

The color resist composition (1) was spin-coated on a 7 cm x 7 cm glass plate under the conditions of the number of revolutions of 1000 rpm and the rotation time of 10 seconds, and dried at 80 캜 for 3 minutes to obtain an article having a dried coating layer. The dried coating film layer was subjected to a shower phenomenon (200 rpm, 45 seconds) using a 20-fold diluted aqueous solution of Semiclin DL-A4 (an alkaline developer manufactured by Yokohama Yushi Kogyo K.K.), and the residual film ratio Was evaluated according to the following criteria.

?: Remaining film ratio is smaller than 10%.

?: Residual film ratio is 10 to 50%.

X: Remaining film ratio is larger than 50%.

Example 6 (homology)

1.2 g of an alkali-soluble resin (a copolymer of benzyl methacrylate and acrylic acid), 0.6 g of ARONIX M-402, and 0.6 g of an alkali-soluble resin were mixed with 6.2 g of the yellow pigment dispersion (2) 0.05 g of Jay Cakir # 369, 0.0017 g of the random copolymer (1) in terms of solid content, and 2.2 g of PGMEA were added and mixed to prepare a color resist composition (2). A coating layer was prepared in the same manner as in Example 5 to evaluate the ability (inhibitory property) of suppressing the generation of foreign matter (foreign matter derived from the pigment) in the coating layer and the developability of the coating film with an alkali solution. The evaluation results are shown in Table 2.

Example 7 (homology)

A color resist composition (3) was prepared in the same manner as in Example 6 except that the yellow pigment dispersion (3) was used instead of the yellow pigment dispersion (2). A coating layer was prepared in the same manner as in Example 5 to evaluate the ability (inhibitory property) of suppressing the generation of foreign matter (foreign matter derived from the pigment) in the coating layer and the developability of the coating film with an alkali solution. The evaluation results are shown in Table 2.

Example 8 (homology)

A color resist composition (4) was prepared in the same manner as in Example 6 except that the yellow pigment dispersion (4) was used instead of the yellow pigment dispersion (2). A coating layer was prepared in the same manner as in Example 5 to evaluate the ability (inhibitory property) of suppressing the generation of foreign matter (foreign matter derived from the pigment) in the coating layer and the developability of the coating film with an alkali solution. The evaluation results are shown in Table 2.

Example 9 (homology)

A color resist composition (5) was prepared in the same manner as in Example 6 except that the yellow pigment dispersion (5) was used instead of the yellow pigment dispersion (2). A coating layer was prepared in the same manner as in Example 5 to evaluate the ability (inhibitory property) of suppressing the generation of foreign matter (foreign matter derived from the pigment) in the coating layer and the developability of the coating film with an alkali solution. The evaluation results are shown in Table 2.

Example 10 (homology)

A color resist composition (6) was prepared in the same manner as in Example 6 except that the yellow pigment dispersion (6) was used instead of the yellow pigment dispersion (2). A coating layer was prepared in the same manner as in Example 5 to evaluate the ability (inhibitory property) of suppressing the generation of foreign matter (foreign matter derived from the pigment) in the coating layer and the developability of the coating film with an alkali solution. The evaluation results are shown in Table 2.

Example 11 (homology)

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 layer was prepared in the same manner as in Example 5 to evaluate the ability (inhibitory property) of suppressing the generation of foreign matter (foreign matter derived from the pigment) in the coating layer and the developability of the coating film with an alkali solution. The evaluation results are shown in Table 2.

Example 12 (homology)

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 layer was prepared in the same manner as in Example 5 to evaluate the ability (inhibitory property) of suppressing the generation of foreign matter (foreign matter derived from the pigment) in the coating layer and the developability of the coating film with an alkali solution. The evaluation results are shown in Table 2.

Example 13 (homologous)

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 layer was prepared in the same manner as in Example 5 to evaluate the ability (inhibitory property) of suppressing the generation of foreign matter (foreign matter derived from the pigment) in the coating layer and the developability of the coating film with an alkali solution. The evaluation results are shown in Table 2.

[Table 2]

Comparative Example 3 (Preparation of resist composition for comparison)

A comparative control color resist composition (1 ') was prepared in the same manner as in Example 5 except that the copolymer (1') for comparison control was used instead of the random copolymer (1). A coating layer was prepared in the same manner as in Example 5 to evaluate the ability (inhibitory property) of suppressing the generation of foreign matter (foreign matter derived from the pigment) in the coating layer and the developability of the coating film with an alkali solution. The evaluation results are shown in Table 3.

Comparative Example 4 (homologous)

A comparative control color resist composition (2 ') was prepared in the same manner as in Example 6 except that the copolymer (1') for comparison control was used instead of the random copolymer (1). A coating layer was prepared in the same manner as in Example 5 to evaluate the ability (inhibitory property) of suppressing the generation of foreign matter (foreign matter derived from the pigment) in the coating layer and the developability of the coating film with an alkali solution. The evaluation results are shown in Table 3.

Comparative Example 5 (homology)

A yellow pigment dispersion 3 was used instead of the yellow pigment dispersion 2 and the copolymer 1 'for comparison and comparison was used in place of the random copolymer 1 in the same manner as in Example 6 To prepare a comparative color resist composition (3 '). A coating layer was prepared in the same manner as in Example 5 to evaluate the ability (inhibitory property) of suppressing the generation of foreign matter (foreign matter derived from the pigment) in the coating layer and the developability of the coating film with an alkali solution. The evaluation results are shown in Table 3.

Comparative Example 6 (homology)

The procedure of Example 6 was repeated except that the yellow pigment dispersion (4) was used in place of the yellow pigment dispersion (2) and the copolymer (1 ') for comparison control was used in place of the random copolymer (1) To prepare a comparative color resist composition (4 '). A coating layer was prepared in the same manner as in Example 5 to evaluate the ability (inhibitory property) of suppressing the generation of foreign matter (foreign matter derived from the pigment) in the coating layer and the developability of the coating film with an alkali solution. The evaluation results are shown in Table 3.

Comparative Example 7 (homology)

A yellow pigment dispersion 5 was used instead of the yellow pigment dispersion 2 and the copolymer 1 'for comparison and comparison was used in place of the random copolymer 1 in the same manner as in Example 6 To prepare a comparative color resist composition (5 '). A coating layer was prepared in the same manner as in Example 5 to evaluate the ability (inhibitory property) of suppressing the generation of foreign matter (foreign matter derived from the pigment) in the coating layer and the developability of the coating film with an alkali solution. The evaluation results are shown in Table 3.

Comparative Example 8 (homology)

The procedure of Example 6 was repeated except that the yellow pigment dispersion 6 was used in place of the yellow pigment dispersion 2 and the copolymer (1 ') for comparison control was used in place of the random copolymer (1) To prepare a comparative color resist composition (6 '). A coating layer was prepared in the same manner as in Example 5 to evaluate the ability (inhibitory property) of suppressing the generation of foreign matter (foreign matter derived from the pigment) in the coating layer and the developability of the coating film with an alkali solution. The evaluation results are shown in Table 3.

Comparative Example 9 (homology)

A comparative control color resist composition (7 ') was prepared in the same manner as in Example 5 except that the copolymer (2') for comparison control was used instead of the random copolymer (1). A coating layer was prepared in the same manner as in Example 5 to evaluate the ability (inhibitory property) of suppressing the generation of foreign matter (foreign matter derived from the pigment) in the coating layer and the developability of the coating film with an alkali solution. The evaluation results are shown in Table 4.

Comparative Example 10 (homology)

A comparative control color resist composition (8 ') was prepared in the same manner as in Example 6 except that the copolymer (2') for comparison control was used instead of the random copolymer (1). A coating layer was prepared in the same manner as in Example 5 to evaluate the ability (inhibitory property) of suppressing the generation of foreign matter (foreign matter derived from the pigment) in the coating layer and the developability of the coating film with an alkali solution. The evaluation results are shown in Table 4.

Comparative Example 11 (homology)

A yellow pigment dispersion 3 was used in place of the yellow pigment dispersion 2 and the copolymer 2 'for comparison control was used instead of the random copolymer 1 in the same manner as in Example 6 To prepare a comparative color resist composition (9 '). A coating layer was prepared in the same manner as in Example 5 to evaluate the ability (inhibitory property) of suppressing the generation of foreign matter (foreign matter derived from the pigment) in the coating layer and the developability of the coating film with an alkali solution. The evaluation results are shown in Table 4.

Comparative Example 12 (homology)

The procedure of Example 6 was repeated except that yellow pigment dispersion (4) was used in place of yellow pigment dispersion (2) and copolymer (2 ') was used instead of random copolymer (1) To prepare a comparative color resist composition (10 '). A coating layer was prepared in the same manner as in Example 5 to evaluate the ability (inhibitory property) of suppressing the generation of foreign matter (foreign matter derived from the pigment) in the coating layer and the developability of the coating film with an alkali solution. The evaluation results are shown in Table 4.

Comparative Example 13 (homologous)

The procedure of Example 6 was repeated except that the yellow pigment dispersion 5 was used in place of the yellow pigment dispersion 2 and the copolymer (2 ') for comparison control was used in place of the random copolymer (1) To prepare a comparative color resist composition (11 '). A coating layer was prepared in the same manner as in Example 5 to evaluate the ability (inhibitory property) of suppressing the generation of foreign matter (foreign matter derived from the pigment) in the coating layer and the developability of the coating film with an alkali solution. The evaluation results are shown in Table 4.

Comparative Example 14 (homologous)

The procedure of Example 6 was repeated except that the yellow pigment dispersion 6 was used in place of the yellow pigment dispersion 2 and the copolymer (2 ') for comparison control was used in place of the random copolymer (1) Thereby preparing a comparative color resist composition (12 '). A coating layer was prepared in the same manner as in Example 5 to evaluate the ability (inhibitory property) of suppressing the generation of foreign matter (foreign matter derived from the pigment) in the coating layer and the developability of the coating film with an alkali solution. The evaluation results are shown in Table 4.

[Table 3]

[Table 4]

Claims (15)

A random copolymer of a polymerizable monomer (a1) having a fluorinated alkyl group having 1 to 6 carbon atoms directly bonded with a fluorine atom and a polymerizable unsaturated group and a polymerizable monomer (a2) having a skeleton of a crosslinked ring hydrocarbon and a polymerizable 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 1.8. The method according to claim 1,
Wherein the skeleton of the crosslinked ring hydrocarbon of the polymerizable monomer (a2) is an adamantane ring, a dicyclopentane ring, a dicyclopentane ring, a norbornane ring or a norbornene ring. The method according to claim 1,
Wherein the skeleton of the crosslinked ring hydrocarbon of the polymerizable monomer (a2) is an adamantane ring. The method according to claim 1,
Wherein the polymerizable monomer (a1) is a monomer represented by the following 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' X represents any one of groups represented by the following formulas (X-1) to (X-10), Rf represents a group represented by the following formula (Rf-1) to (Rf-4).

N in the formulas (X-1), (X-3), (X-4), (X-5), (X-6) and (X-7) represents an integer of 1 to 8. M in the formulas (X-8), (X-9) and (X-10) represents an integer of 1 to 8 and n represents an integer of 0 to 8. Rf "in the formulas (X-6) and (X-7) represents any one of groups represented by the following formulas (Rf-1) to (Rf-4)

[N in the formulas (Rf-1) and (Rf-2) represents an integer of 1 to 6) N in the formula (Rf-3) represents an integer of 2 to 6. And n in the formula (Rf-4) represents an integer of 4 to 6.) The method 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. A resist composition comprising the random copolymer (A), the colorant (B), the alkali-soluble resin (C) and the polymerizable compound (D) according to any one of claims 1 to 5. The method according to claim 6,
Wherein the colorant (B) is at least one selected from the group consisting of CI Pigment Red 177, CI Pigment Red 207, CI Pigment Red 254, CI Pigment Green 7, CI Pigment Green 36, CI Pigment Green 58, Pigment Yellow 83, CI Pigment Yellow 93, CI Pigment Yellow 109, CI Pigment Yellow 110, CI Pigment Yellow 129, CI Pigment Yellow 138, CI Pigment Yellow 139, CI Pigment Yellow 150, CI Pigment CI Pigment Blue 15: 2, CI Pigment Blue 15: 6 and CI Pigment Blue 15: 1, CI Pigment Blue 15: 2, CI Pigment Blue 15: 6 and CI Pigment Blue 18 At least one pigment. A color filter characterized in that a coating film layer of the resist composition according to claim 6 is formed on a substrate. A polymerizable monomer (a1) having a fluorinated alkyl group having 1 to 6 carbon atoms directly bonded with a fluorine atom and a polymerizable unsaturated group and a polymerizable monomer (a2) having a skeleton of a crosslinked ring hydrocarbon and a polymerizable unsaturated group, wherein the living radical polymerization is carried out in the presence of the polymerizable monomer (a1) and the polymerizable monomer (a2). 10. The method of claim 9,
Wherein the skeleton of the crosslinked ring hydrocarbon of the polymerizable monomer (a2) is an adamantane ring, a dicyclopentane ring, a dicyclopentane ring, a norbornane ring, or a norbornene ring. 10. The method of claim 9,
Wherein the skeleton of the crosslinked ring hydrocarbon of the polymerizable monomer (a2) is an adamantane ring. 10. The method of claim 9,
Wherein the polymerizable monomer (a1) is a monomer represented by the following 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' X represents any one of groups represented by the following formulas (X-1) to (X-10), Rf represents a group represented by the following formula (Rf-1) to (Rf-4).

N in the formulas (X-1), (X-3), (X-5), (X-6) and (X-7) represents an integer of 1 to 8. M in the formulas (X-8), (X-9) and (X-10) represents an integer of 1 to 8 and n represents an integer of 0 to 8. Rf "in the formulas (X-6) and (X-7) represents any one of groups represented by the following formulas (Rf-1) to (Rf-4)

[N in the formulas (Rf-1) and (Rf-2) represents an integer of 1 to 6) N in the formula (Rf-3) represents an integer of 2 to 6. And n in the formula (Rf-4) represents an integer of 4 to 6.) 10. The method of claim 9,
Wherein the living radical polymerization is an atom transfer radical polymerization. 10. The method of claim 9,
A method for producing a random copolymer in which the polymerizable monomer (a1) and the polymerizable monomer (a2) are subjected to atomic transfer radical polymerization in the presence of a polymerization initiator, a transition metal compound, a compound having a ligand capable of coordinating bonding with the transition metal, . 10. The method of claim 9,
Wherein the polymerizable monomer (a2) is used in an amount of 50 to 900 parts by mass based on 100 parts by mass of the polymerizable monomer (a1).

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