TWI709576B - Color resist composition, color filter and manufacturing method of color resist composition - Google Patents

Abstract

To provide a random copolymer (fluorine-based resist composition) that can obtain a smooth color resist layer, can suppress the generation of foreign matter originating from pigments and other colorants in the color resist layer, and has excellent developability. Surfactant), resist composition and color filter using it. Specifically, it is a random copolymer, a resist composition using the same, and a color filter. The random copolymer is a random copolymer of a polymerizable monomer (a1) and a polymerizable monomer (a2), And the ratio of weight average molecular weight (Mw) to number average molecular weight (Mn) (Mw/Mn) is 1.0~1.8, the polymerizable monomer (a1) has a carbon atom number of 1~6 directly bonded to fluorine atom A fluorinated alkyl group and a polymerizable unsaturated group, and the polymerizable monomer (a2) has a bridged cyclic hydrocarbon skeleton and a polymerizable unsaturated group.

Description

Color resist composition, color filter and manufacturing method of color resist composition

The present invention relates to a random copolymer of a resist composition that can obtain a smooth color resist layer, can suppress the generation of foreign matter derived from pigments and other colorants in the color resist layer, and has excellent developability (Fluorine-based surfactant), resist composition and color filter using it. In addition, the present invention relates to a method for producing the aforementioned random copolymer.

In the past, in various coating fields, in order to improve the homogeneity and smoothness of the obtained coating film, various surfactants called leveling agents such as hydrocarbon-based, silicone-based, and fluorine-based surfactants have been used. Among them, fluorine-based surfactants are widely used due to their high surface tension reduction ability and less pollution after coating.

Among the above-mentioned fluorine-based surfactants, surfactants that use perfluoroalkyl groups with 8 or more carbon atoms have excellent performance as a leveling agent derived from their surface tension reduction ability, but those with 8 or more carbon atoms Surfactants based on perfluoroalkyls can generate compounds that have concerns about environmental and living body accumulation, such as perfluorooctane sulfonic acid. Therefore, surfactants using perfluoroalkyls with less than 8 carbon atoms have been proposed. As such a surfactant, for example, a random copolymer produced by living radical polymerization of a monomer having a fluorinated alkyl group with carbon atoms of 6 or less and a non-fluorine-based monomer in the coexistence (such as , Refer to Patent Document 1).

In addition, in the above-mentioned coating field, especially for the composition (color resist composition) used to manufacture color filters, it is required that the coating film is difficult to change color even if it is placed in an alkaline aqueous solution used as a developer ( Hard to produce water stains) performance. In order to obtain a resist composition with such properties, the following fluorine-based surfactants are proposed as block copolymers, which have the polymerizability of a fluorinated alkyl group having 1 to 6 carbon atoms A polymer segment of a monomer; a polymer segment of a polymerizable monomer having a skeleton of a bridged cyclic hydrocarbon (for example, refer to Patent Document 2). However, the resist composition containing the fluorine-based surfactant disclosed in Patent Document 2 has the problem of insufficient developability due to an alkaline aqueous solution.

In addition, when forming a colored coating layer such as a coating film (color resist pattern) of the color resist composition, a desired hue is also required. In order to obtain a coating layer with a desired hue, such as a color resist pattern with a hue with excellent brightness, pigments (colorants) such as C.I. Pigment Red 254 with excellent brightness are used. However, the aforementioned CI Pigment Red 254 and other pigments are easy to sublime, and crystals are easy to grow due to their intermolecular interaction. Therefore, in the heating step when forming the color filter, the pigment molecules sublimated from the coating film will be on the coating film. The surface is crystallized and agglomerated to cause foreign matter. If such foreign matter is generated, light scattering caused by the particles or uneven dispersion of the pigment will result. As a result, it will become difficult to obtain the desired hue.

[Prior Technical Literature]

[Patent Literature]

[Patent Document 1] JP 2013-6928 A

[Patent Document 2] International Publication No. 2015/137229 Specification

The problem to be solved by the present invention is to provide a resist composition that can obtain a smooth color resist layer, can suppress the generation of foreign matter originating from the coloring agent in the color resist layer, and has excellent developability. Copolymer (fluorine-based surfactant), resist composition and color filter using it. In addition, the problem to be solved by the present invention is to provide a method for producing the above-mentioned fluoropolymer (living radical polymerization random copolymer).

The inventors of the present invention conducted intensive studies and found the following: by using a polymerizable monomer having a fluorinated alkyl group and a polymerizable unsaturated group, and a polymerizable monomer having an adamantane ring and a polymerizable unsaturated group Such as polymerizable monomers having a bridged cyclic hydrocarbon backbone and polymerizable unsaturated groups, a random copolymer that can be used as a surfactant can be obtained; by adding the random copolymer, the weight average molecular weight (Mw) Random copolymers whose ratio to number average molecular weight (Mn) [(Mw)/(Mn)] are in the range of 1.0~1.8 can be obtained even if a coloring agent that is easy to sublime or crystallize is used, it is difficult to apply in the coating film A resist composition that generates foreign matter; the resist composition is also excellent in developability; and by using these compositions, a color filter with a desired hue can be obtained, thereby completing the present invention.

That is, the present invention provides a random copolymer characterized in that it is a random copolymer of a polymerizable monomer (a1) and a polymerizable monomer (a2), and has a weight average molecular weight (Mw) and a number average molecular weight ( The ratio (Mw/Mn) of Mn) is 1.0 to 1.8. The polymerizable monomer (a1) has a fluorinated alkyl group having 1 to 6 carbon atoms directly bonded to a fluorine atom and a polymerizable unsaturated group. The polymerizable monomer (a2) has a bridged cyclic hydrocarbon skeleton and a polymerizable unsaturated group.

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

In addition, the present invention provides a color filter characterized in that a coating film layer of the above-mentioned resist composition is formed on a substrate.

In addition, the present invention provides a method for producing a random copolymer, which is characterized in that the polymerizable monomer (a1) and the polymerizable monomer (a2) are combined with the polymerizable monomer (a1) and the polymerizable monomer (a2). Living radical polymerization is carried out in the coexistence of the polymerizable monomer (a1) having a fluorinated alkyl group having 1 to 6 carbon atoms directly bonded to a fluorine atom and a polymerizable unsaturated group, and the polymerizable monomer (a1) a2) Having a bridged cyclic hydrocarbon skeleton and a polymerizable unsaturated group.

The present invention can provide a random copolymer of a resist composition that can obtain a smooth color resist layer, can also suppress the generation of foreign matter originating from the coloring agent in the color resist layer, and has excellent developability. Manufacturing method. In addition, the present invention can provide a resist composition that can obtain a coating layer of a desired hue and a color filter having a coating layer of a desired hue.

In addition, the random copolymer of the present invention can be preferably used not only in color resist compositions, but also in compositions used to form black matrices, and used in the housings of electronic devices, etc. The composition of the coating layer formed on the surface.

Fig. 1 is a line graph of the IR spectrum of the random copolymer (1) obtained in Example 1.

2 is a line chart of the ¹³ C-NMR spectrum of the random copolymer (1) obtained in Example 1.

Fig. 3 is a GPC graph of the random copolymer (1) obtained in Example 1.

The present invention provides a random copolymer characterized in that it is a random copolymer of a polymerizable monomer (a1) and a polymerizable monomer (a2), and has a weight average molecular weight (Mw) and a number average molecular weight (Mn) The ratio (Mw/Mn) is 1.0 to 1.8. The polymerizable monomer (a1) has a fluorinated alkyl group with 1 to 6 carbon atoms directly bonded to a fluorine atom and a polymerizable unsaturated group. The monomer (a2) has a bridged cyclic hydrocarbon skeleton and a polymerizable unsaturated group.

As the above-mentioned polymerizable monomer (a1) having a fluorinated alkyl group having 1 to 6 carbon atoms directly bonded to a fluorine atom and a polymerizable unsaturated group, as long as it has the above-mentioned fluorinated alkyl group in the molecule and polymerized Compounds with a sexually unsaturated group can be used without particular restrictions.

Here, a fluorinated alkyl group with 1 to 6 carbon atoms directly bonded to a fluorine atom is a perfluoroalkyl group with 1 to 6 carbon atoms directly bonded to a fluorine atom, or a part of the hydrogen atom is set as Partially fluorinated alkyl groups of fluorine atoms. Among these fluorinated alkyl groups, a perfluoroalkyl group is preferable in terms of the high effect of the obtained polymer as a surfactant. Furthermore, the more carbon atoms directly bonded to fluorine atoms, the better, and the number of carbon atoms directly bonded to fluorine atoms is particularly preferably 4-6.

As a polymerizable unsaturated group which the said polymerizable monomer (a1) has, (meth)acryloyl group, a vinyl group, a maleimide group etc. are mentioned, for example. Among them, it is easy to obtain raw materials; when using the obtained random copolymer to manufacture a resist composition or a coating composition, it is easy to control the compatibility of the random copolymer with the blending components in the composition; and In terms of good polymerization reactivity, a (meth)acryloyl group is preferred. As a specific example having this (meth)acryloyl group, for example, a monomer represented by the following general formula (1) can be preferably exemplified. Also, the above-mentioned polymerizability Monomer (a1) may use only 1 type, and may use 2 or more types together.

[In the above general formula (1), R ¹ represents a hydrogen atom, a fluorine atom, a methyl group, a cyano group, a phenyl group, a benzyl group, or -C _n H _2n -Rf' (n represents an integer from 1 to 8, and Rf' represents Any one of the following formulas (Rf-1)~(Rf-4)), X represents any one of the following formulas (X-1)~(X-10), Rf represents the following formula (Rf -1)~(Rf-4) any group. ]

-OC _n H _2n- (X-1)

-OCH ₂ CH ₂ OCH _2- (X-2)

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

-C _n F _2n+1 (Rf-1)

-C _n F _2n H (Rf-2)

-C _n F _2n-1 (Rf-3)

-C _n F _2n-3 (Rf-4)

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

Furthermore, in the present invention, the so-called "(meth)acrylate" refers to one or both of methacrylate and acrylate, and the so-called "(meth)acrylic acid" refers to methacrylic acid and acrylate One or both of acrylic.

The polymerizable monomer (a2) has a bridged cyclic 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, the layer containing the random copolymer (hereinafter, sometimes referred to as a block layer) will be concentrated于surface. The random copolymer of the present invention has a high glass transition temperature (Tg) due to the presence of the bridged cyclic hydrocarbon skeleton. As a result, the barrier layer becomes a strong layer. That is, the coating film layer formed in the following color filter manufacturing method has a high-hardness barrier layer due to the presence of the skeleton of the bridged cyclic hydrocarbon. The inventors speculated that the barrier layer with high hardness prevents the precipitation of colorants such as pigments in the coating layer (Sublimation) to the outermost surface. In addition, the skeleton of the bridged cyclic hydrocarbon in the barrier layer has some influence on the pigment dispersed in the coating layer below the barrier layer. As a result, it suppresses the colorant derived from the pigment The formation of foreign bodies.

烷(norbornane)環、降莰烯環等。其中，就於塗膜最表面可形成Tg更高之阻擋層，並且可抑制源自顏料之異物產生之方面而言，較佳為金剛烷環、二環戊烷環、降

烷環、降莰烯環，更佳為金剛烷環。 Examples of the skeleton of the bridged cyclic hydrocarbon include: adamantane ring, perhydroindene ring, decahydronaphthalene ring, perhydropyridine ring, perhydroanthracene ring, perhydrophenanthrene ring, dicyclopentane ring, and bicyclic ring. Pentene ring, perhydroacenaphthylene ring, perhydrogen ring, drop

Alkane (norbornane) ring, norbornene ring, etc. Among them, in terms of forming a barrier layer with a higher Tg on the outermost surface of the coating film and suppressing the generation of foreign matter originating from the pigment, the adamantane ring, the dicyclopentane ring, and the lower

The alkane ring and norbornene ring are more preferably an adamantane ring.

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

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

(In the formula, L represents a reactive functional group, X and Y represent a divalent organic group or a single bond, and R represents a hydrogen atom, a methyl group or CF ₃ )

As said reactive functional group, a hydroxyl group, an isocyanate group, an epoxy group, a carboxyl group, a carboxylic acid halide group, an acid anhydride group etc. are mentioned, for example. Among them, it is preferable to obtain a random copolymer having good compatibility with the blending component in the composition when the obtained random copolymer is used to produce a resist composition or a coating composition. For hydroxyl.

The bonding position of the organic group with the above reactive functional group and Y represented by -XL in the above general formula (a2-1) can be bonded to any carbon atom in the adamantane ring, and -XL may also have 2 or more. Furthermore, a part or all of the hydrogen atoms bonded to the carbon atoms constituting the adamantane ring may be substituted with fluorine atoms, alkyl groups, or the like. In addition, X and Y in the general formula (a2-1) are divalent organic groups or single bonds. Examples of the divalent organic groups include carbon atoms such as methylene, propyl, and isopropylidene. The number 1~8 alkylene group.

In addition, in the compound represented by the above formula (a2-2), the (meth)acryloyl group may be bonded to any carbon atom in the adamantane ring. In addition, a part or all of the hydrogen atoms bonded to the carbon atoms constituting the adamantane structure in the general formula (a2-1) may be substituted with fluorine atoms, alkyl groups, or the like.

As more specific examples of the polymerizable monomer represented by the above general formula (a2-1), for example, the compounds shown below can be cited.

In addition, as a more specific example of the polymerizable monomer represented by the general formula (a2-2), for example, the compounds shown below can be cited.

Among the polymerizable monomers having an adamantane ring and a (meth)acrylic acid group, the obtained random copolymer can be used to produce a resist composition with good compatibility with the blending components in the composition. In terms of random copolymers, the compound represented by the above formula (a2-2) is preferred, and the compound represented by the above formula (a2-2-1) is more preferred.

Hereinafter, the polymerizable monomer having a dicyclopentane ring and a polymerizable unsaturated group that 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 compounds represented by the following formula (a2-3).

(In the formula, R represents a hydrogen atom, a methyl group or CF ₃ )

In addition, in the compound represented by the above formula (a2-3), the (meth)acryloyl group may Bonded to any carbon atom in the dicyclopentane ring. In addition, a part or all of the hydrogen atoms bonded to the carbon atoms constituting the dicyclopentane ring in the general formula (a2-3) may be substituted with fluorine atoms, alkyl groups, or the like.

As more specific examples of the polymerizable monomer represented by the above general formula (a2-3), for example, the compounds shown below can be cited.

Among the polymerizable monomers having a dicyclopentane ring and a (meth)acrylic acid group, in terms of obtaining a resist composition with a high Tg of the coating film, the above-mentioned formula (a2-3-2 ) Represents the compound.

Hereinafter, the polymerizable monomer having a dicyclopentene ring and a polymerizable unsaturated group that 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 compounds represented by the following formula (a2-4).

(In the formula, R represents a hydrogen atom, a methyl group or CF ₃ )

In addition, in the compound represented by the above formula (a2-4), the (meth)acryloyl group may be bonded to any carbon atom in the dicyclopentene ring. In addition, part or all of the hydrogen atoms bonded to the carbon atoms constituting the dicyclopentene ring in the general formula (a2-3) may be substituted with fluorine atoms, alkyl groups, or the like.

As more specific examples of the polymerizable monomer represented by the above general formula (a2-4), for example, the compounds shown below can be cited.

Among the polymerizable monomers having a dicyclopentene ring and a (meth)acryloyl group, in terms of obtaining a high Tg resist composition of the coating film, the above-mentioned formula (a2-4-2 ) Represents the compound.

烷環與聚合性不飽和基之聚合性單體進行說明。 Hereinafter, the present invention can be preferably used as the polymerizable monomer (a2) has a decrease

The polymerizable monomer of an alkane ring and a polymerizable unsaturated group will be described.

烷環與(甲基)丙烯醯基之聚合性單體，例如可列舉下述式(a2-5)表示之化合物等。 As the above has a drop

Examples of the polymerizable monomer of an alkane ring and a (meth)acryloyl group include compounds represented by the following formula (a2-5).

(In the formula, R represents a hydrogen atom, a methyl group or CF ₃ )

烷環中之任意碳原子。又，上述通式(a2-5)中之鍵結於構成降

烷環之碳原子之氫原子亦可其一部分或全部被取代為氟原子、烷基等。 In addition, in the compound represented by the above formula (a2-5), the (meth)acryloyl group may be bonded to

Any carbon atom in the alkane ring. Moreover, the bond in the above general formula (a2-5) is

A part or all of the hydrogen atoms of the carbon atoms of the alkane ring may be substituted with fluorine atoms, alkyl groups, and the like.

As more specific examples of the polymerizable monomer represented by the above general formula (a2-5), for example, the compounds shown below can be cited.

烷環與(甲基)丙烯醯基之聚合性單體中，就可獲得塗膜之Tg高之阻劑組成物之方面而言，較佳為上述式(a2-5-2)表示之化合物。 With drop

Among the polymerizable monomers of alkane ring and (meth)acryloyl group, the compound represented by the above formula (a2-5-2) is preferred in terms of obtaining a high Tg resist composition of the coating film .

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

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

(In the formula, R represents a hydrogen atom, a methyl group or CF ₃ )

In addition, in the compound represented by the above formula (a2-6), the (meth)acryloyl group may be bonded to any carbon atom in the norbornene ring. In addition, part or all of the hydrogen atoms bonded to the carbon atoms constituting the norbornene ring in the general formula (a2-6) may be substituted with fluorine atoms, alkyl groups, or the like.

As more specific examples of the polymerizable monomer represented by the above general formula (a2-6), for example, the compounds shown below can be cited.

Among the polymerizable monomers having a norbornene ring and a (meth)acrylic acid group, the above-mentioned formula (a2-6-2) is preferred in terms of obtaining a high Tg resist composition of the coating film Represents the compound.

The present invention provides a random copolymer characterized in that it is a random copolymer of a polymerizable monomer (a1) and a polymerizable monomer (a2), and has a weight average molecular weight (Mw) and a number average molecular weight (Mn) The ratio (Mw/Mn) is 1.0 to 1.8. The polymerizable monomer (a1) has a fluorinated alkyl group with 1 to 6 carbon atoms directly bonded to a fluorine atom and a polymerizable unsaturated group. The polymerizable monomer (a2) has a bridged cyclic hydrocarbon skeleton and a polymerizable unsaturated group. Here, if the ratio (Mw/Mn) exceeds 1.8, a strong coating film surface cannot be formed, which is not preferable. The ratio (Mw/Mn) is more preferably in the range of 1.0 to 1.7, and still more preferably in the range of 1.0 to 1.5.

Regarding the weight average molecular weight (Mw) of the random copolymer of the present invention, it is preferably 500 to 200,000 in terms of obtaining a stronger coating film surface and having good leveling properties. , More preferably in the range of 1,000 to 150,000, still more preferably in the range of 1,500 to 100,000.

In addition, regarding the number average molecular weight (Mn) of the random copolymer of the present invention, it is preferably 300 in terms of obtaining a stronger coating film surface and having good leveling properties. ~120,000, more preferably in the range of 500 to 80,000, further preferably in the range of 800 to 60,000.

Here, the number average molecular weight (Mn) and the weight average molecular weight (Mw) are measured based on gel permeation chromatography (hereinafter referred to as "GPC") and converted into polystyrene. Furthermore, the measurement conditions of GPC are as follows.

[GPC measurement conditions]

Measuring device: "HLC-8220 GPC" manufactured by Tosoh Co., Ltd.,

Column: Protection column "HHR-H" (6.0mmI.D.×4cm) manufactured by Tosoh Co., Ltd. + "TSK-GEL GMHHR-N" (7.8mmI.D.×30cm) manufactured by Tosoh Co., Ltd. +"TSK-GEL GMHHR-N" (7.8mmI.D.×30cm) made by Tosoh Co., Ltd.+"TSK-GEL GMHHR-N" (7.8mmI.D.×30cm) made by Tosoh Co., Ltd.+Tosoh "TSK-GEL GMHHR-N" manufactured by Co., Ltd. (7.8mmI.D.×30cm)

Detector: ELSD ("ELSD2000" manufactured by Alltech Japan Co., Ltd.)

Data processing: "GPC-8020 Model II Data Analysis Version 4.30" manufactured by Tosoh Co., Ltd.

Sample: obtained by filtering a 1.0% by mass tetrahydrofuran solution (5 μl) in terms of resin solid content using a microfilter.

Standard sample: According to the measurement guide of "GPC-8020 Model II Data Analysis Version 4.30", the following monodisperse polystyrene with known molecular weight is used.

(Monodisperse polystyrene)

"A-500" manufactured by Tosoh Co., Ltd.

"A-1000" manufactured by Tosoh Co., Ltd.

"A-2500" manufactured by Tosoh Co., Ltd.

"A-5000" manufactured by Tosoh Co., Ltd.

"F-1" manufactured by Tosoh Co., Ltd.

"F-2" manufactured by Tosoh Co., Ltd.

"F-4" manufactured by Tosoh Co., Ltd.

"F-10" manufactured by Tosoh Co., Ltd.

"F-20" manufactured by Tosoh Co., Ltd.

"F-40" manufactured by Tosoh Co., Ltd.

"F-80" manufactured by Tosoh Co., Ltd.

"F-128" manufactured by Tosoh Co., Ltd.

"F-288" manufactured by Tosoh Co., Ltd.

"F-550" manufactured by Tosoh Co., Ltd.

Regarding the fluorine atom content in the random copolymer of the present invention, it is preferably in the range of 4-40% by mass in terms of a random copolymer with less uneven coating and good leveling properties. , More preferably in the range of 5 to 35% by mass, still more preferably in the range of 6 to 30% by mass. Furthermore, the fluorine atom content rate can be measured by combustion ion chromatography.

In the present invention, the random copolymer of polymerizable monomer (a1) and polymerizable monomer (a2) may have polymerizable monomer (a1) and polymerizable monomer (a2) within a range that does not impair the effects of the present invention. The structure other than) is derived from the polymerizable monomer (a3).

As said polymerizable monomer (a3), the monomer (a3-1) which has an oxyalkylene group, the monomer (a3-2) which has an alkyl group, etc. are mentioned, for example. Here, examples of the polymerizable unsaturated group possessed by the polymerizable monomer (a3) include (meth)acrylic acid groups, vinyl groups, maleimide groups, etc. However, the above-mentioned polymerizable unsaturated groups When the polymerizable unsaturated group possessed by the monomer (a1) and the polymerizable monomer (a2) is a (meth)acryloyl group, the above-mentioned polymerizable monomer is preferred in terms of better copolymerizability The polymerizable unsaturated group possessed by the body (a3) is also a (meth)acryloyl group.

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

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

The Y ¹ and Y ² in the above general formula (a3-1) are alkylene groups, but the alkylene groups also include those having substituents. Specific examples of the -O-(Y ¹ O)n-(Y ² O)m- moiety include: the number of repeating units p is 1, m is 0, and Y ¹ is an ethylene glycol residue The number of repeating units p is 1 and m is 0, and Y ¹ is a propylene glycol residue of propylene; the number of repeating units p is 1 and m is 0, and Y ¹ is a butanediol residue of butylene; repeats The number of units p is an integer of 2 or more and q is 0, and Y ¹ is an ethylene glycol residue; the number of repeating units p is an integer of 2 or more and q is 0, and Y ¹ is an ethylene glycol residue Polypropylene glycol residue; the number of repeating units p and q are both integers greater than 1, and Y ¹ or Y ² is ethylene and the other is the residue of a copolymer of ethylene oxide and propylene oxide The residues of polyalkylene glycol such as groups.

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

R ³ in the above general formula (a3-1) is hydrogen or an alkyl group having 1 to 6 carbon atoms. When R ³ is hydrogen, the monomer becomes a mono(meth)acrylate of alkylene glycols such as polyethylene glycol, polypropylene glycol, and polybutylene glycol, and R ³ is a carbon number of 1 to 6 In this case, the end of the (meth)acrylate which is not the mono(meth)acrylate of the alkylene glycol is terminated by an alkyl group having 1 to 6 carbon atoms.

Among the above-mentioned monomers (a3-1) having an oxyalkylene group, a monomer having a poly(oxyalkylene) group composed of a plurality of oxyalkylene groups is preferred. Specific examples include: poly(oxyalkylene) Propylene glycol mono(meth)acrylate, polyethylene glycol mono(meth)acrylate, poly 1,3-propylene glycol mono(meth)acrylate, poly 1,4-butanediol mono(meth)acrylate , Poly(ethylene glycol‧propylene glycol) mono(meth)acrylate, polyethylene glycol‧polypropylene glycol mono(meth)acrylate, poly(ethylene glycol‧1,4-butanediol)mono(methyl) )Acrylate, polyethylene glycol‧poly1,4-butanediol mono(meth)acrylate, poly(propylene glycol‧1,4-butanediol)mono(meth)acrylate, polypropylene glycol‧poly1 ,4-Butanediol mono(meth)acrylate, poly(propylene glycol‧butanediol) mono(meth)acrylate, polypropylene glycol‧polybutylene glycol mono(meth)acrylate, poly(ethylene glycol) ‧Butylene glycol) mono(meth)acrylate, polyethylene glycol‧Polybutylene glycol mono(meth)acrylate, poly(tetraethylene glycol‧butanediol) mono(meth)acrylate, poly Tetraethylene glycol‧polybutylene glycol mono(meth)acrylate, polybutylene glycol mono(meth)acrylate, poly(ethylene glycol‧1,3-propanediol)mono(meth)acrylate, poly Ethylene glycol‧poly1,3-propylene glycol mono(meth)acrylate, poly(propylene glycol‧1,3-propylene glycol) mono(meth)acrylate, polypropylene glycol‧poly1,3-propylene glycol mono(meth) Acrylate, poly(1,3-propanediol‧1,4-butanediol) mono(meth)acrylate, poly1,3-propanediol‧poly1,4-butanediol mono(meth)acrylate, Poly(butylene glycol‧1,3-propylene glycol) mono(meth)acrylate, polybutylene glycol‧poly1,3-propylene glycol mono(meth)acrylate, etc. Furthermore, "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. The others are the same. In the production method of the fluoropolymer of the present invention, when the monomer (a3-1) having an oxyalkylene group is used, it can be combined with other components in the resist composition or coating composition. In terms of fluoropolymers with good compatibility, polypropylene glycol mono(meth)acrylate, polyethylene glycol mono(meth)acrylate, polyethylene glycol‧polypropylene glycol mono(methyl) )Acrylate.

Moreover, as a commercially available product of the monomer (a3-1) having an oxyalkylene group, for example, "NK ESTER M-20G", "NK ESTER M-40G" manufactured by Shin Nakamura Chemical Industry Co., Ltd., "NK ESTER M-90G", "NK ESTER M-230G", "NK ESTER AM-90G", "NK ESTER AMP-10G", "NK ESTER AMP-20G", "NK ESTER AMP-60G"; NOF "Blemmer PE-90", "Blemmer PE-200", "Blemmer PE-350", "Blemmer PME-100", "Blemmer PME-200", "Blemmer PME-400", "Blemmer PME" manufactured by Co., Ltd. -4000", "Blemmer PP-1000", "Blemmer PP-500", "Blemmer PP-800", "Blemmer 70PEP-350B", "Blemmer 55PET-800", "Blemmer 50POEP-800B", "Blemmer 10PPB- 500B", "Blemmer NKH-5050", "Blemmer AP-400", "Blemmer AE-350", etc. These oxyalkylene-containing monomers (a3-1) may be used alone or in combination of two or more kinds.

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

(In the formula, R ⁴ is a hydrogen atom or a methyl group, R ⁵ is a linear, branched or cyclic alkyl group with 1 to 18 carbon atoms)

Furthermore, R ⁵ in the above general formula (a3-2) is a linear, branched or cyclic alkyl group with 1 to 18 carbon atoms, and the alkyl group may have an aliphatic or aromatic Substituents such as hydrocarbon groups and hydroxyl groups. Specific examples of the monomer (a3-2) having an alkyl group include: methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate Ester, octyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, decyl (meth)acrylate, dodecyl (meth)acrylate, stearyl (meth)acrylate, etc. (Meth) acrylic acid alkyl esters with 1 to 18 carbon atoms; (meth) biscyclopentyloxy ethyl acrylate, (meth) acrylate isobornyloxy ethyl, (meth) acrylate iso Camphenyl ester, adamantyl (meth)acrylate, dimethyladamantyl (meth)acrylate, dicyclopentyl (meth)acrylate, dicyclopentenyl (meth)acrylate, etc. (meth) ) Bridged cyclic alkyl esters of acrylic acid other than the above (a2) with 1 to 18 carbon atoms. These monomers (a3-2) having an alkyl group may be used singly or in combination of two or more kinds.

When the polymerizable monomer (a3) is used in combination with the above-mentioned polymerizable monomer (a1) and polymerizable monomer (a2), regarding the amount of use, the leveling property and the suppression of coloring derived from pigments In terms of random copolymers that produce foreign matter in the agent and can also exhibit various effects derived from the monomer (a3), it is preferably 100 mass relative to the total of the monomer (a1) and the monomer (a2) Parts, 1-100 parts by mass, more preferably 1-50 parts by mass.

The random copolymer of the present invention can be preferably obtained, for example, by combining the polymerizable monomer (a1) and the polymerizable monomer (a2) in the polymerizable monomer (a1) and the polymerizable monomer (a2). ) In the coexistence of living radical polymerization, the polymerizable monomer (a1) has a fluorinated alkyl group having 1 to 6 carbon atoms directly bonded to a fluorine atom and a polymerizable unsaturated group, the polymerizable monomer (a2) It has a bridged cyclic hydrocarbon skeleton and a polymerizable unsaturated group.

In the above-mentioned living radical polymerization, a dormant substance whose living polymerization terminal is protected by an atom or an atom group reversibly generates free radicals and reacts with the monomer, whereby the growth reaction proceeds. As examples of such living radical polymerization, atom transfer radical polymerization (ATRP), Reversible addition-cracking radical polymerization (RAFT), radical polymerization via nitroxide radicals (NMP), radical polymerization using organic tellurium (TERP), etc. Among these, there is no particular restriction on which method is used, and in terms of ease of control, etc., the above-mentioned ATRP is preferred. ATRP uses organic halides or halogenated sulfonyl compounds as initiators, and uses metal complexes composed of transition metal compounds and ligands as catalysts for polymerization.

The polymerization initiator used in the ATRP can be an organic halogenated compound. Specifically, examples include: 1-phenethyl chloride and 1-phenethyl bromide, chloroform, carbon tetrachloride, 2-chloropropionitrile, α,α'-dichloroxylene, α,α'-di Bromoxylene, hexa(α-bromomethyl)benzene, 2-halogenated carboxylic acids with 1 to 6 carbon atoms (e.g. 2-chloropropionic acid, 2-bromopropionic acid, 2-chloroisobutyric acid, 2-bromo Isobutyric acid, etc.) alkyl esters with 1 to 6 carbon atoms. Furthermore, as more specific examples of the alkyl ester of 2-halogenated carboxylic acid having 1 to 6 carbon atoms and having 1 to 6 carbon atoms, for example, methyl 2-chloropropionate and ethyl 2-chloropropionate can be cited. , 2-bromopropionic acid methyl ester, 2-bromoisobutyric acid ethyl ester, etc.

The transition metal compound used in the ATRP is represented by M ^{n +} X _n . M ⁿ⁺ as a transition metal can be selected from Cu ⁺ , Cu ²⁺ , Fe ²⁺ , Fe ³⁺ , Ru ²⁺ , Ru ³⁺ , Cr ²⁺ , Cr ³⁺ , Mo ⁰ , Mo ⁺ , Mo ²⁺ , Mo ³⁺ , W ²⁺ , W ³⁺ , Rh ³⁺ , Rh ⁴⁺ , Co ⁺ , Co ²⁺ , Re ²⁺ , Re ³⁺ , Ni ⁰ , Ni ⁺ , Mn ³⁺ , Mn ⁴⁺ , V ²⁺ , V ³⁺ , Zn ⁺ , Zn ²⁺ , Au ⁺ , Au ²⁺ , Ag ⁺ and Ag ²⁺ . Further, X may be selected from a halogen atom, an alkoxy group of 1 to 6 carbon _{atoms, (SO 4) 1/2, (} PO 4) 1/3, (HPO 4) 1/2, (H 2 PO 4) , Trifluoromethanesulfonate, hexafluorophosphate, methanesulfonate, arylsulfonate (preferably benzenesulfonate or toluenesulfonate), Ser ¹ , CN and R ² COO. Here, R ¹ represents an aryl group, a linear or branched alkyl group having 1 to 20 carbon atoms (preferably 1 to 10 carbon atoms), and R ² represents a hydrogen atom, which may be substituted with 1 to 1 halogen. 5 times (preferably 1 to 3 times substituted by fluorine or chlorine) linear or branched alkyl group with 1 to 6 carbon atoms (preferably methyl). Furthermore, n represents the formal charge on the metal and is an integer of 0-7.

The transition metal complexes are not particularly limited. Preferred ones include transition metal complexes of groups 7, 8, 9, 10, and 11, and further preferred ones include: 0-valent A complex of copper, monovalent copper, divalent ruthenium, divalent iron or divalent nickel.

Examples of the above-mentioned compound having a ligand capable of coordinately bonding with a transition metal include: having a nitrogen atom, an oxygen atom, a phosphorus atom, or a sulfur atom that can coordinate with the transition metal via a σ bond Compounds with ligands, compounds with ligands containing 2 or more carbon atoms that can be coordinated to transition metals via π bonds, and coordination that can coordinate with transition metals via mu bonds or η bonds Based compound.

As a specific example of the compound having a ligand, for example, in the case where the central metal is copper, examples include: 2,2'-bipyridine and its derivatives, 1,10-phenanthroline and its derivatives, tetramethyl Complexes of ethylenediamine, pentamethyldiethylenetriamine, hexamethyltris(2-aminoethyl)amine and polyamines. In addition, as divalent ruthenium complexes, dichlorotris(triphenylphosphine)ruthenium, dichlorotris(tributylphosphine)ruthenium, dichloro(cyclooctadiene)ruthenium, dichlorobenzene ruthenium , Dichloro p-phenylene ruthenium, dichloro (norbornadiene) ruthenium, cis-dichlorobis(2,2'-bipyridine) ruthenium, dichlorotris(1,10-phenanthroline) ruthenium, carbonyl chloride Hydrogen tris (triphenylphosphine) ruthenium and the like. Further examples of the bivalent iron complex include bistriphenylphosphine complexes, triazacyclononane complexes, and the like.

In addition, in the above-mentioned living radical polymerization, it is preferable to use a solvent. As the solvent used, for example, ester solvents such as ethyl acetate, butyl acetate, and propylene glycol monomethyl ether acetate; diisopropyl ether, dimethoxyethane, diethylene glycol dimethyl ether, etc. Ether solvents; halogen 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; methanol, Alcohol solvents such as ethanol and isopropanol; two Aprotic polar solvents such as methylformamide and dimethyl sulfide. Moreover, these solvents may be used individually, and 2 or more types may be used together.

In the method for producing the random copolymer of the present invention, it is preferable to use a polymerization initiator, a transition metal compound, a compound having a ligand capable of coordinate bonding with the transition metal, and a solvent. The polymerizable monomer (a1) and the polymerizable monomer (a2) undergo living radical polymerization.

In the production method of the random copolymer of the present invention, as the use ratio (reaction ratio) of the polymerizable monomer (a1) to the polymerizable monomer (a2), a good leveling property and a high pigment sublimation inhibitory effect can be obtained In terms of the random copolymer, it is preferable to use 50 to 900 parts by mass of the polymerizable monomer (a2) relative to 100 parts by mass of the polymerizable monomer (a1), and more preferably relative to the polymerizable monomer ( a1) 100 parts by mass, using 100 to 800 parts by mass of the polymerizable monomer (a2).

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

In addition, when the random copolymer of the present invention is produced by the method of producing the random copolymer of the present invention, the metal derived from the transition metal compound may remain in the random copolymer. Therefore, when a random copolymer is used by the manufacturing method of the present invention for semiconductor applications such as photoresist compositions that cause problems if the metal remains, it is preferable to use activated alumina or the like to remove the residue after the polymerization reaction. Metal removal.

The present invention provides a resist composition characterized by containing: the random copolymer of the present invention (hereinafter, sometimes referred to as "random copolymer (A)"), coloring agent (B), and alkali-soluble resin (C) and polymerizable compound (D). The resist composition can be preferably provided by, for example, a method of manufacturing a resist composition. The method of manufacturing the resist composition is characterized by containing the following Step: Live radical polymerization of polymerizable monomer (a1) and polymerizable monomer (a2) in the coexistence of polymerizable monomer (a1) and polymerizable monomer (a2) to obtain living radical polymerization The random copolymer (A), the polymerizable monomer (a1) has a fluorinated alkyl group having 1 to 6 carbon atoms directly bonded to a fluorine atom and a polymerizable unsaturated group, the polymerizable monomer ( a2) Having a bridged cyclic hydrocarbon skeleton and a polymerizable unsaturated group; this random copolymer (A), colorant (B), alkali-soluble resin (C), and polymerizable compound (D) are mixed. The above-mentioned step of obtaining the random copolymer (A) corresponds to the step of the method for producing the random copolymer of the present invention.

系等。再者，下述之「C.I.」意指色指數(C.I.；The Society of Dyers and Colourists公司發行)。 The colorant (B) may be a pigment or a dye, and the pigment may be an organic pigment or an inorganic pigment. The above-mentioned organic pigments can use pigments of various hues such as red pigments, green pigments, blue pigments, yellow pigments, purple pigments, and orange pigments. In addition, as the chemical structure of organic pigments, for example, quinacridone series, perylene series, pyrrolopyrrole series, anthraquinone series, phthalocyanine series, indanthrene series, halogenated phthalocyanine series, Tetrachloroisoindolinone series, Hansa yellow series, benzidine yellow series, azo series, benzimidazolone series, isoindolinone series, two

Department etc. Furthermore, the following "CI" means color index (CI; issued by The Society of Dyers and Colourists).

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

Examples of the above-mentioned green pigments include: CI Pigment Green 1, CI Pigment Green 2, CI Pigment Green 4, CI Pigment Green 7, CI Pigment Green 8, CI Pigment Green 10, CI Pigment Green 13, CI Pigment Green 14, CI Pigment Green 15, CI Pigment Green 17, CI Pigment Green 18, CI Pigment Green 19, CI Pigment Green 26, CI Pigment Green 36, CI Pigment Green 45, CI Pigment Green 48, CI Pigment Green 50, CI Pigment Green 51, CI Pigment Green 54, CI Pigment Green 55, CI Pigment Green 58, CI Pigment Green 59, etc.

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

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

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

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

The pixels of the three primary colors of the color filters used in liquid crystal display devices and organic EL display devices are red (R), green (G), and blue (B), so the above-mentioned red pigments, green pigments and blue pigments can also be used It is a main component and uses organic pigments of the above-mentioned yellow, purple, and orange colors for the purpose of improving color reproducibility for hue adjustment.

Moreover, as said inorganic pigment, barium sulfate, lead sulfate, titanium oxide, yellow plum, iron plum, chromium oxide, etc. are mentioned, for example.

As the dye used in the present invention, for example, the following (b1) can be preferably exemplified

Said salt or dibenzopyran dyes, etc.

Examples of the dibenzopyran-based dye include: CI Acid Red 51, 52, 87, 92, 289, 388, CI Acid Violet 9, 30, CI Basic Red 8, CI Mordant Red 27 , Rose Bengal B, sulforhodamine G, Rose Bengal 6G, Japanese Patent Laid-Open No. 2010-032999 or Japanese Patent Laid-Open No. 2011-138094 and other dibenzopiperan-based dyes.

Among the above-mentioned dibenzopyran-based dyes, it is preferable to combine the following formula (b2)

[In formula (1), R ¹ to R ⁴ each independently represent a hydrogen atom, -R ⁸ or a monovalent aromatic hydrocarbon group with 6 to 10 carbon atoms. The hydrogen atom contained in the aromatic hydrocarbon group may also be a halogen atom , -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 replaced.

R ⁵ represents -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 from 0 to 5. When m is an integer of 2 or more, a plurality of R ^{5 are the} same or different from each other.

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 with 1 to 20 carbon atoms, and the hydrogen atom contained in the saturated hydrocarbon group may be substituted with a halogen atom.

R ¹¹ each independently represents a hydrogen atom, a monovalent saturated hydrocarbon group with 1 to 20 carbon atoms, or an aralkyl group with 7 to 10 carbon atoms.

R ⁹ and R ¹⁰ each independently represent a hydrogen atom or a monovalent saturated hydrocarbon group with 1 to 20 carbon atoms. The hydrogen atom contained in the saturated hydrocarbon group may be substituted with -OH or halogen atoms. The saturated aliphatic hydrocarbon group contains The -CH ₂ -can also be substituted by -O-, -CO-, -NH- or -NR ⁸ -, R ⁹ and R ¹⁰ can also be bonded to each other to form a 3- to 10-membered heterocyclic ring containing a nitrogen atom ].

The indicated compound is used as the main component of the dye.

Examples of the monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms in R ¹ to R ⁴ in the above formula (b2) include: phenyl, tolyl, xylyl, 2,4,6- Mesityl, propylphenyl and butylphenyl etc.

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

Examples of monovalent saturated hydrocarbon groups with 1 to 20 carbon atoms in R ⁸ to R ¹¹ in the above formula (b2) include methyl, ethyl, propyl, isopropyl, butyl, and isobutyl. , Pentyl, isopentyl, neopentyl, hexyl, heptyl, octyl, 2-ethylhexyl, nonyl, decyl, dodecyl, hexadecyl, eicosyl, etc. carbon number 1 ~20 alkyl groups; cyclopropyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, tricyclodecyl and other cycloalkyl groups with 3 to 20 carbon atoms.

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

Examples of the aralkyl group having 7 to 10 carbon atoms in R ¹¹ in the above formula (b2) include benzyl, phenethyl, and phenbutyl.

The above-mentioned M ^{+ is,} for example, ⁺ N(R ¹¹ ) ₄ , Na ⁺ or K ⁺ , preferably ⁺ N(R ¹¹ ) ₄ . As the above-mentioned ⁺ N(R ¹¹ ) ₄ , for example, it is preferable that at least two of the four R ¹¹ are monovalent saturated hydrocarbon groups having 5 to 20 carbon atoms. In addition, the total carbon number of the four R ¹¹ is preferably 20 to 80, more preferably 20 to 60. If R ^{11 is} such a group, the resist composition of the present invention can be expected to form a colored coating film or pattern with less foreign matter.

Moreover, among the above-mentioned dibenzopyran dyes, the following formula (b3) is more preferable

[In formula (b3), R ²¹ ~ R ²⁴ each independently represent a hydrogen atom, -R ²⁶ or a monovalent aromatic hydrocarbon group with 6 to 10 carbon atoms, and the hydrogen atom contained in the aromatic hydrocarbon group may also be passed through -SO ₃ -, -SO ₃ ^- Ma ⁺ , -SO ₃ H, -SO ₃ R ²⁶ or -SO ₂ NHR ^{26 are} substituted.

X represents a halogen atom.

a1 represents an integer of 0 or 1.

m1 represents an integer from 0 to 5. When m1 is an integer of 2 or more, a plurality of R ^{25 are the} same or different from each other.

Ma ⁺ represents ⁺ N(R ²⁷ ) ₄ , Na ⁺ or K ⁺ .

R ²⁵ represents -SO ₃ -, -SO ₃ ^- Ma ⁺ , -SO ₃ H, or SO ₂ NHR ²⁶ .

R ²⁶ represents a monovalent saturated hydrocarbon group with 1 to 20 carbon atoms.

R ²⁷ each independently represents a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms or a benzyl group. ]

The dye represented.

Examples of the monovalent aromatic hydrocarbon groups having 6 to 10 carbon atoms in R ²¹ to R ²⁴ in the above formula (b3) include the same groups as those listed as the aromatic hydrocarbon groups in R ¹ to R ⁴ . Among them, it is preferable that R ²¹ and R ²³ are hydrogen atoms, and R ²² and R ²⁴ are monovalent aromatic hydrocarbon groups with 6 to 10 carbon atoms, and the hydrogen atoms contained in the aromatic hydrocarbon groups may be through -SO ^3- , -SO ^3- M ⁺ , -SO ₃ H, -SO ₃ R ²⁶ or -SO ₂ NHR ²⁶ replacement. More preferably, R ²¹ and R ²³ are hydrogen atoms, and R ²² and R ²⁴ are monovalent aromatic hydrocarbon groups with 6 to 10 carbon atoms, and the hydrogen atoms contained in the aromatic hydrocarbon groups are through -SO ₃ ^- M ⁺ Or -SO ₂ NHR ²⁶ replacement. If 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 with excellent heat resistance.

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

-R ²⁶ in R ²¹ to R ²⁴ in the above formula (b3) is preferably a hydrogen atom, a methyl group or an ethyl group independently.

As in the above formula (b3) -SO ³ R ²⁶ and -SO ₂ NHR ²⁶ in the R ^26, preferably a carbon atom number of a branched chain alkyl of 3 to 20, more preferably 6 to 12 carbon atoms, the The branched alkyl group is more preferably 2-ethylhexyl. If R ^{26 is} such a group, it is expected that the resist composition containing the compound (b3) can form a colored coating film or pattern with less foreign matter generation.

The aforementioned Ma ⁺ is ⁺ N(R ²⁷ ) ₄ , Na ⁺ or K ⁺ , preferably ⁺ N(R ²⁷ ) ₄ . As the above-mentioned ⁺ N(R ²⁷ ) ₄ , it is preferable that at least two of the four R ²⁷ are monovalent saturated hydrocarbon groups having 5 to 20 carbon atoms. In addition, the total number of carbon atoms of 4 R ²⁷ is preferably 20 to 80, more preferably 20 to 60. It is expected that the resist composition containing the compound (b3) in which R ^{27 is} these groups can form a coating layer or pattern with less foreign matter generation.

As preferred dibenzopyran-based dyes that can be used in the present invention, for example, dyes in which compounds represented by formulas (b4) to (b21) are used as main components, etc. can be cited. In addition, in the following formula, Ra represents 2-ethylhexyl.

Among the compounds that become the main component of dibenzopiperan dyes, the sulfonamide of C.I. Acid Red 289 or the quaternary ammonium salt of C.I. Acid Red 289 is preferred. Examples of such compounds include compounds represented by formula (b4) to formula (b11), formula (b16), and formula (b17).

The compound represented by the above formula (b1) can be produced, for example, by chlorinating a pigment or pigment intermediate having -SO ₃ H by convention to obtain a pigment or pigment intermediate having -SO ₂ Cl It reacts with the amine represented by R ⁸ -NH ₂ . In addition, it can also be manufactured by the following method: in the same way as above, the dye manufactured by the method described in the upper right column to the lower left column on page 3 of JP 3-78702 A is chlorinated with an amine To react.

The dye (b2) used in the present invention may also use dyes other than the salt represented by the above formula (b1) or the dibenzopyran dye. Examples of the above-mentioned other dyes include dyes such as oil-soluble dyes, acid dyes, amine salts of acid dyes, or sulfonamide derivatives of acid dyes. Specifically, for example, color index (The Society of Dyers and Colourists) is classified as a compound of dyes, or various dyes described in Dyeing Note (Dyeing Note).

Examples of the above-mentioned other dyes include: CI Solvent Yellow 4 (hereinafter, the description of CI Solvent Yellow is omitted, and only the number is described), 14, 15, 23, 24, 38, 62, 63, 68, 82, 94, 98, 99; CI solvent red 45, 49, 125, 130; CI solvent orange 2, 7, 11, 15, 26, 56; and other CI solvent dyes, CI acid yellow 1, 3, 7, 9, 11, 17, 23, 25, 29, 34, 36, 38, 40, 42, 54, 65, 72, 73, 76, 79, 98, 99, 111, 112, 113, 114, 116, 119, 123, 128, 134, 135, 138, 139, 140, 144, 150, 155, 157, 160, 161, 163, 168, 169, 172, 177, 178, 179, 184, 190, 193, 196, 197, 199, 202, 203, 204, 205, 207, 212, 214, 220, 221, 228, 230, 232, 235, 238, 240, 242, 243, 251; CI Acid Red 1, 4, 8, 14, 17, 18, 26, 27 , 29, 31, 34, 35, 37, 42, 44, 50, 51, 52, 57, 66, 73, 80, 87, 88, 91, 92, 94, 97, 103, 111, 114, 129, 133, 134, 138, 143, 145, 150,151,158,176,182,183,198,206,211,215,216,217,227,228,249,252,257,258,260,261,266,268,270,274,277, 280, 281, 195, 308, 312, 315, 316, 339, 341, 345, 346, 349, 382, 383, 394, 401, 412, 417, 418, 422, 426; CI Acid Orange 6, 7, 8 , 10, 12, 26, 50, 51, 52, 56, 62, 63, 64, 74, 75, 94, 95, 107, 108, 169, 173; CI Acid Violet 6B, 7, 9, 17, 19; Other CI acid dyes, CI direct yellow 2, 33, 34, 35, 38, 39, 43, 47, 50, 54, 58, 68, 69, 70, 71, 86, 93, 94, 95, 98, 102, 108, 109, 129, 136, 138, 141; CI direct red 79, 82, 83, 84, 91, 92, 96, 97, 98, 99, 105, 106, 107, 172, 173, 176, 177, 179 , 181, 182, 184, 204, 207, 211, 213, 218, 220, 221, 222, 232, 233, 234, 241, 243, 246, 250; CI direct orange 34, 39, 41, 46, 50, 52, 56, 57, 61, 64, 65, 68, 70, 96, 97, 106, 107; CI direct purple 47, 52, 54, 59, 60, 65, 66, 79, 80, 81, 82, 84 , 89, 90, 93, 95, 96, 103, 104; etc. CI direct dyes, CI mordant yellow 5, 8, 10, 16, 20, 26, 30, 31, 33, 42, 43, 45, 56, 61 , 62, 65; CI mordant red 1, 2, 3, 4, 9, 11, 12, 14, 17, 18, 19, 22, 23, 24, 25, 26, 30, 32, 33, 36, 37, 38, 39, 41, 43, 45, 46, 48, 53, 56, 63, 71, 74, 85, 86, 88, 90, 94, 95; CI Mordant Orange 3, 4, 5, 8, 12, 13 , 14, 20, 21, 23, 24, 28, 29, 32, 34, 35, 36, 37, 42, 43, 47, 48; CI Mordant Violet 1, 2, 4, 5, 7, 14, 22, 24, 30, 31, 32, 37, 40, 41 , 44, 45, 47, 48, 53, 58; and other CI mordant dyes.

On the other hand, the coloring agent (B) used to form the black matrix (BM) is not particularly limited as long as it is black. For example, carbon black, metal oxide, or two or more metal oxides are preferred. The composite metal compound and other pigments. In addition, it can also be a combination of: mixing two or more organic pigments selected from pigments with hues of red, blue, green, purple, yellow, cyan, and magenta to produce by mixing colors black.

As said carbon black, lamp black, acetylene black, thermal black, chimney black, furnace black, etc. are mentioned, for example. Examples of the above-mentioned metal oxide include titanium black obtained by oxidation of titanium or reduction of titanium dioxide. Titanium black is generally represented by _2m-1 (m is a number of 1 or more of) a Ti _m O. In addition, examples of metal oxides include metal oxides such as copper, iron, chromium, manganese, and cobalt. Further, as a composite metal compound composed of two or more metal oxides, for example, copper-chromium oxide, copper-chromium-manganese oxide, copper-iron-manganese oxide, or cobalt-iron oxide -Manganese oxide, etc.

Examples of commercially available products of the above carbon black include: MA7, MA8, MA11, MA100, MA100R, MA220, MA230, MA600, #5, #10, #20, #25, #30 manufactured by Mitsubishi Chemical Corporation , #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, OIL31B, etc.; or Printex3, manufactured by Evonik Degussa Japan Co., Ltd. Printex3OP, Printex30, Printex30OP, Printex40, Printex45, Printex55, Printex60, Printex75, Printex80, Printex85, Printex90, Printex A, Print ex L, Printex G, Printex P, Printex U, Printex V, Printex G, Special Black550, Special Black 350 , Special Black250, Special Black100, Special Black6, Special Black5, Special Black4, Color Black FW1, Color Black FW2, Color Black FW2V, Color Black FW18, Color Black FW18, Color Black FW200, Color Black S160, Color Black S170; or Cabot Monarch120, Monarch280, Monarch460, Monarch800, Monarch880, Monarch900, Monarch1000, Monarch1100, Monarch1300, Monarch1400, Monarch4630, REGAL99, REGAL99R, REGAL415, REGAL415R, REGAL250, REGAL250R, REGAL330, REGAL400R, REGAL55R0, PREGAL660480R , PEARLS130, VULCAN XC72R, ELFTEX-8, etc.; or RAVEN11, RAVEN14, RAVEN15, RAVEN16, RAVEN22, RAVEN30, RAVEN35, RAVEN40, RAVEN410, RAVEN420, RAVEN450, RAVEN500, RAVEN780, RAVEN850, RAVEN890H, RAVEN1000, RAVEN104010 manufactured by Columbia Chemicals , RAVEN1060U, RAVEN1080U, RAVEN1170, RAVEN1190U, RAVEN1250, RAVEN1500, RAVEN2000, RAVEN2500U, RAVEN3500, R AVEN5000, RAVEN5250, RAVEN5750, RAVEN7000, etc.

Among the above-mentioned carbon blacks, it is preferable to use resin-coated carbon black as the black matrix of the color filter with high optical density and high surface resistivity required. Furthermore, resin-coated carbon black can be obtained, for example, by using Japanese Patent Application Publication No. 9-26571, Japanese Patent Application Publication No. 9-71733, Japanese Patent Application Publication No. 9-95625, and Japanese Patent Application Publication No. 9- 238863 The known carbon black is processed by the method described in Bulletin No. 11-60989 or JP-A No. 11-60989.

In addition, as a method of producing the above-mentioned titanium black, a method of heating a mixture of titanium dioxide and metallic titanium described in JP Sho 49-5432 A to reduce it in a reducing environment, and JP The method of reducing ultrafine titanium dioxide obtained by high-temperature hydrolysis of titanium tetrachloride in a reducing environment containing hydrogen, as described in Bulletin No. 57-205322, is described in Japanese Patent Application Publication No. 60-65069 and Japanese Patent Application Publication No. 61 -The method of high-temperature reduction of titanium dioxide or titanium hydroxide in the presence of ammonia as described in the 201610 publication, attaching a vanadium compound to the titanium dioxide or titanium hydroxide described in JP 61-201610, and performing high-temperature reduction in the presence of ammonia The method and so on. As a commercially available product of titanium black, for example, titanium black 10S, 12S, 13R, 13M, 13M-C, etc. manufactured by Mitsubishi Materials Corporation can be cited.

As a combination of mixing two or more kinds of organic pigments and mixing them to produce black, there can be mentioned: black pigments that are mixed with three colors of red, green, and blue. As color materials that can be mixed for the preparation of black pigments, include: Victoria Pure Blue (CI42595), Chrysanthemum O (CI41000), Cathilon Brilliant flavin (Alkaline 13), Rose Red 6GCP (CI45160), Rose Red B (CI45170), Safranin OK70:100 (CI50240), Erioglaucine X (CI42080), No.120/Lionol Yellow (CI 21090), Reonor Yellow GRO (CI21090), Symuler Fast Yellow 8GF (CI21105), Benzidine Yellow 4T-564D (CI21095), Smoler Fast Yellow 4015 (CI 12355), Leonor Red 7B4401 (CI15850), Fastgen Blue TGR-L (CI74160), Leonor Blue SM (CI26150), Leonor Blue ES (CI Pigment Blue 15: 6), Lionogen Red GD (CI Pigment Red 168), Leonor Green 2YS (CI Yan Material Green 36) and so on.

As other color materials that can be mixed for use in the preparation of black pigments, for example, CI Pigment Yellow 20, CI Pigment Yellow 24, CI Pigment Yellow 86, CI Pigment Yellow 93, CI Pigment Yellow 109, CI Pigment Yellow 110, CI Pigment Yellow 117, CI Pigment Yellow 125, CI Pigment Yellow 137, CI Pigment Yellow 138, CI Pigment Yellow 147, CI Pigment Yellow 148, CI Pigment Yellow 153, CI Pigment Yellow 154, CI Pigment Yellow 166, CI Pigment Orange 36, CI Pigment Orange 43, CI Pigment Orange 51, CI Pigment Orange 55, CI Pigment Orange 59, CI Pigment Orange 61, CI Pigment Red 9, CI Pigment Red 97, CI Pigment Red 122, CI Pigment Red 123, CI Pigment Red 149, CI Pigment Red 168, CI Pigment Red 177, CI Pigment Red 180, CI Pigment Red 192, CI Pigment Red 215, CI Pigment Red 216, CI Pigment Red 217, CI Pigment Red 220, CI Pigment Red 223, CI Pigment Red 224, CI Pigment Red 226, CI Pigment Red 227, CI Pigment Red 228, CI Pigment Red 240, CICI Pigment Violet 19, CI Pigment Violet 23, CI Pigment Violet 29, CI Pigment Violet 30, CI Pigment Violet 37, CI Pigment Violet 40, CI Pigment Violet 50, CI Pigment Blue 15, CI Pigment Blue 15:1, CI Pigment Blue 15:4, CI Pigment Blue 22, CI Pigment Blue 60, CI Pigment Blue 64, CI Pigment Green 7, CI Brown Pigment 23, 25, 26 and so on.

When carbon black is used as a black pigment, the average primary particle diameter is preferably in the range of 0.01 to 0.08 μm, and in terms of good developability, it is more preferably in the range of 0.02 to 0.05 μm. In addition, the absorption amount of dibutyl phthalate (hereinafter referred to as "DBP") of the carbon black used is preferably in the range of 40 to 100 cm ³ /100 g. In terms of good dispersibility and developability, More preferably, it is in the range of 50~80cm ³ /100g. Furthermore, the specific surface area based on the BET method of the carbon black used is preferably in the range of 50 to 120 m ² /g, and in terms of good dispersion stability, it is more preferably in the range of 60 to 95 m ² /g.

In addition, the particle shape of carbon black is different from that of organic pigments, and is called primary particle fusion. The state of the combined structure exists, and there are cases where fine pores are formed on the particle surface by post-processing. Therefore, in order to express the particle shape of carbon black, in general, in addition to the average particle size of the primary particles obtained by the same method as the above-mentioned organic pigments, the DBP absorption (JIS K6221) and BET based The specific surface area (JIS K6217) of the method is measured and used as an index of the structure or the amount of pores.

Among the colorants (B), in terms of obtaining a coating film layer with good productivity, high color density, and excellent durability, pigments are preferred to maximize the effects of the present invention, namely In terms of also suppressing the generation of foreign matter originating from colorants, it is more preferably selected from CI Pigment Red 177, CI Pigment Red 207, CI Pigment Red 254, CI Pigment Green 7, CI Pigment Green 36, CI Pigment Green 58, CI Pigment Green 59, CI 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 Yellow 154, CI Pigment Yellow 180, CI Pigment Yellow 185, CI Pigment Blue 15:1, CI Pigment Blue 15:2, CI Pigment Blue 15:6 and CI Pigment Violet 23 are one or more pigments.

The said coloring agent (B) may be used individually, and may use 2 or more types together.

The blending amount of the above-mentioned colorant (B) is preferably in the range of 10 to 80 parts by mass relative to the total of 100 parts by mass of the alkali-soluble resin (C) and polymerizable compound (D) described below. More preferably, it is in the range of 15 to 65 parts by mass.

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

Regarding the above-mentioned alkali-soluble resin (C), if it is more specifically described, an example Examples include the following resins.

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

‧Polymers without acidic groups obtained by polymerizing (meth)acrylic polymerizable monomers with reactive groups as essential components, and reactive groups with reactive groups that are reactive with the reactive groups Alkali-soluble resin (C2) obtained by reaction of acid-based compounds

‧For copolymers of epoxy-containing (meth)acrylates and other polymerizable monomers, unsaturated monocarboxylic acid is added to at least a part of the epoxy groups in the copolymer to further increase Alkali-soluble resin (C3) obtained by the addition reaction of an acid anhydride and at least a part of the hydroxyl group produced by the addition reaction of an unsaturated monocarboxylic acid.

‧Epoxy (meth)acrylate resin with carboxyl group (C4)

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

Examples of the alkali-soluble resin (C1) include: an alkali-soluble resin obtained by polymerizing a (meth)acrylic polymerizable monomer having a carboxyl group as an essential component; or a (methyl) ) Alkali-soluble resin obtained by polymerization of acrylic polymerizable monomer as an essential component. Among them, preferred is an alkali-soluble resin obtained by polymerizing a (meth)acrylic polymerizable monomer having a carboxyl group as an essential component.

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-(methyl) )Acrylic oxyethyl succinic acid, 2-(meth)acrylic oxyethyl adipic acid, 2-(meth)acryloxyethyl maleic acid, 2-(meth)acrylic acid Oxyethylhexahydrophthalic acid, 2-(meth)acryloxyethyl phthalic acid, 2-(meth)acryloxy Propyl succinic acid, 2-(meth)acryloxypropyl adipic acid, 2-(meth)acryloxypropyl maleic acid, 2-(meth)acryloxypropyl Hydrophthalic acid, 2-(meth)acryloxypropyl phthalic acid, 2-(meth)acryloxybutyl succinic acid, 2-(meth)acryloxybutyl Adipic acid, 2-(meth)acryloxybutyl maleic acid, 2-(meth)acryloxybutylhydrophthalic acid, 2-(meth)acryloxybutyl Polymerizable monomers such as phthalic acid; polymerizable monomers made by adding lactones such as ε-caprolactone, β-propiolactone, γ-butyrolactone, and δ-valerolactone to acrylic acid; A polymerizable monomer formed by adding succinic acid, maleic acid, phthalic acid, or these acid anhydrides to hydroxyalkyl (meth)acrylate. These carboxyl group-containing (meth)acrylic polymerizable monomers may be used alone or in combination of two or more kinds. Among the above-mentioned (meth)acrylic polymerizable monomers having a carboxyl group, (meth)acrylic acid and 2-(meth)acryloxyethyl succinic acid are preferred.

Examples of the (meth)acrylic polymerizable monomer having a sulfonic acid group include 2-sulfoethyl (meth)acrylate, 2-sulfopropyl (meth)acrylate, and 2-hydroxy- 3-(meth)acryloyloxypropanesulfonic acid, 2-(meth)acrylamide-2-methylpropanesulfonic acid or their salts, etc.

When preparing the alkali-soluble resin (C1), other polymerizable monomers may be used in combination within a range that does not impair the effects of the present invention. As other monomers, for example, methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, isopropyl (meth)acrylate, butyl (meth)acrylate, Isobutyl (meth)acrylate, benzyl (meth)acrylate, phenyl (meth)acrylate, cyclohexyl (meth)acrylate, phenoxyethyl (meth)acrylate, (meth)acrylic acid Phenoxy methyl ester, 2-ethylhexyl (meth)acrylate, isobornyl (meth)acrylate, (Meth) acrylate such as 2-hydroxyethyl (meth)acrylate, glycerol mono(meth)acrylate, tetrahydrofurfuryl (meth)acrylate; 2-hydroxyethyl (meth)acrylate, (meth)acrylate (Meth)acrylic acid esters such as hydroxyalkyl (meth)acrylate such as hydroxypropyl acrylate, 4-hydroxybutyl (meth)acrylate, glycerol mono(meth)acrylate, etc.; styrene and Aromatic vinyl compounds such as its derivatives; vinyl compounds such as N-vinylpyrrolidone; N-cyclohexyl maleimide, N-phenyl maleimide, N-benzyl N-substituted maleimides such as maleimides; polymethyl (meth)acrylate macromonomers, polystyrene macromonomers, poly(meth)acrylate 2-hydroxyethyl macromonomers Monomers, macromonomers such as polyethylene glycol macromonomers, polypropylene glycol macromonomers, polycaprolactone macromonomers, etc. As for other polymerizable monomers, only 1 type may be used, and 2 or more types may be used together.

Among the above-mentioned other polymerizable monomers, styrene, methyl (meth)acrylate, cyclohexyl (meth)acrylate, and (meth)acrylate are preferable in terms of good transparency and hardly impairing heat resistance. Benzyl acrylate, 4-hydroxybutyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, butyl (meth)acrylate, isobutyl (meth)acrylate Esters, N-cyclohexyl maleimide, N-benzyl maleimide, N-phenyl maleimide.

Regarding the usage amount of these other polymerizable monomers, it is preferably 95% by mass or less, and more preferably 85% by mass or less in all polymerizable monomer components.

As a specific example of the alkali-soluble resin (C1), for example, (meth)acrylic acid, and methyl (meth)acrylate, benzyl (meth)acrylate, butyl (meth)acrylate, (meth) Isobutyl acrylate, cyclohexyl (meth)acrylate, cyclohexyl maleic acid Amines and other non-hydroxyl polymerizable monomers, and hydroxyl-containing polymerizable monomers such as 2-hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, etc. Copolymer of (meth)acrylic acid, and methyl (meth)acrylate, benzyl (meth)acrylate, butyl (meth)acrylate, isobutyl (meth)acrylate, 2-hydroxy methacrylate Copolymers of (meth)acrylates such as ethyl ester; copolymers of (meth)acrylic acid and styrene; copolymers of (meth)acrylic acid, styrene and α-methylstyrene; (meth)acrylic acid and Copolymer of cyclohexyl maleimide, etc. Among the alkali-soluble resins (C1), it is preferable to use an alkali-soluble resin of benzyl (meth)acrylate in terms of obtaining a resist composition having excellent pigment dispersibility.

The acid value of the alkali-soluble resin (C1) is preferably in the range of 10 to 500 mgKOH/g, more preferably in the range of 30 to 350 mgKOH/g, and still more preferably in the range of 40 to 300 mgKOH/g. In addition, the weight average molecular weight (Mw) of the alkali-soluble resin (C1) 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, and still more preferably 4,000 ~50,000 range.

In the present invention, the following alkali-soluble resin (C1-1) can also be used. The alkali-soluble resin (C1-1) is made by adding an epoxy group-containing unsaturated compound to polymerize (meth)acrylic acid with a carboxyl group. It is made from the carboxyl group of the carboxyl group-containing alkali-soluble resin obtained by polymerization as an essential component.

As the above-mentioned epoxy group-containing unsaturated compound, for example, glycidyl (meth)acrylate, allyl glycidyl ether, glycidyl-α-ethyl acrylate, butenyl ring Oxypropyl ether, (iso)butenoic acid glycidyl ether, N-(3,5-dimethyl-4-epoxypropyl) Benzyl acrylamide, 4-hydroxybutyl (meth)acrylate glycidyl ether, etc. Furthermore, in terms of improving heat resistance and improving the dispersibility when using a pigment as the colorant (B), an unsaturated compound containing an alicyclic epoxy group is preferred.

Examples of the alicyclic epoxy group possessed by the above-mentioned alicyclic epoxy group-containing unsaturated compound include: 2,3-epoxycyclopentyl, 3,4-epoxycyclohexyl, 7, 8-Epoxy [tricyclo[5.2.1.0]dec-2-yl] and so on. Moreover, as an ethylenic unsaturated group, a (meth)acryloyl group is preferable. The unsaturated compound containing an alicyclic epoxy group may use only 1 type, and may use 2 or more types together.

When adding the epoxy group-containing unsaturated compound to the carboxyl part of the carboxyl-containing alkali-soluble resin, a known method can be used. For example, make alkali-soluble resins containing carboxyl groups and unsaturated compounds containing epoxy groups in tertiary amines such as triethylamine and benzylmethylamine; dodecyltrimethylammonium chloride, tetramethylammonium chloride, Tetraethylammonium chloride, tetrabutylammonium chloride, benzyltriethylammonium chloride and other quaternary ammonium salts; in the presence of pyridine, triphenylphosphine and other catalysts, and in an organic solvent, the reaction temperature The reaction is carried out at 50~150°C for several hours to tens of hours, whereby the unsaturated compound containing epoxy group can be added to the carboxyl group of the resin.

The acid value of the alkali-soluble resin (C1-1) is preferably in the range of 10 to 500 mgKOH/g, more preferably in the range of 30 to 350 mgKOH/g, and still more preferably in the range of 40 to 300 mgKOH/g. In addition, 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, and still more preferably in the range of 4,000 to 50,000 The scope.

In addition, among the above-mentioned alkali-soluble resins (C1), it is more preferable to use ether dimers or (meth)acrylates having alicyclic structures such as adamantyl groups as polymerizable monomers. Soluble resin (C1-2).

As the ether dimer, for example, 2,2'-[oxybis(methylene)]bis-2-dimethyl acrylate, 2,2'-[oxybis(methylene)] Diethyl bis-2-acrylate, 2,2'-[oxybis(methylene)] bis(n-propyl) bis-2-acrylate, 2,2'-[oxybis(methylene) )]Bis-2-acrylate di(isopropyl) ester, 2,2'-[oxybis(methylene)]bis-2-acrylate di(n-butyl) ester, 2,2'-(oxy Bis(methylene)]bis-2-acrylate di(isobutyl) ester, 2,2'-[oxybis(methylene)]bis-2-acrylate di(tertiary butyl) ester, 2,2'-[Oxybis(methylene)]bis-2-acrylate di(tertiary amyl) ester, 2,2'-[oxybis(methylene)]bis-2-acrylate (Stearyl) ester, 2,2'-[oxybis(methylene)]bis-2-acrylate di(lauryl) ester, 2,2'-[oxybis(methylene)]bis -2-Acrylate di(2-ethylhexyl) ester, 2,2'-[oxybis(methylene)]bis-2-acrylate bis(1-methoxyethyl) ester, 2,2' -[Oxybis(methylene)]bis-2-acrylic acid bis(1-ethoxyethyl) ester, 2,2'-[oxybis(methylene)]bis-2-acrylic acid dibenzyl Esters, 2,2'-[oxybis(methylene)]bis-2-diphenyl acrylate, 2,2'-[oxybis(methylene)]bis-2-dicyclohexyl acrylate Esters, 2,2'-[oxybis(methylene)]bis-2-acrylate di(tertiary butylcyclohexyl) ester, 2,2'-[oxybis(methylene)]bis- Bis(dicyclopentadienyl) acrylate, 2,2'-[oxybis(methylene)]bis-2-di(tricyclodecyl)acrylate, 2,2'-(oxy Bis(methylene)]bis-2-bis(isobornyl)acrylate, 2,2'-[oxybis(methylene)]bis-2-diadamantyl acrylate, 2,2 '-[Oxybis(methylene)]bis-2-acrylic acid bis(2-methyl-2-adamantyl) ester and the like. Among these, 2,2'-[oxybis(methylene)]bis-2-dimethyl acrylate, 2,2'-[oxybis(methylene)]bis-2- Diethyl acrylate, 2,2'-[oxybis(methylene)]bis-2-dicyclohexyl acrylate, 2,2'-[oxybis(methylene)]bis-2-acrylic acid Dibenzyl ester. These ether dimers may use only 1 type, and may use 2 or more types together.

When ether dimer is used as the raw material of alkali-soluble resin (C1-2), the ratio of the ether dimer in the polymerizable monomer becomes an alkali-soluble resin with a low molecular weight while inhibiting gelation. In terms of a resist composition with excellent transparency or heat resistance, it is preferably in the range of 2-60% by mass based on the mass of all polymerizable monomers, more preferably in the range of 5-55% by mass. Preferably, it is in the range of 5-50% by mass.

On the other hand, when a (meth)acrylate having an alicyclic structure such as adamantyl is used as the raw material of the alkali-soluble resin (C1-2), the ratio of the (meth)acrylate used can be In terms of obtaining a resist composition that can improve the dispersibility of the pigment when the colorant (B) is used and has good adaptability to low light, it is preferably 0.5-60 mass% of the mass of all polymerizable monomers The range is more preferably in the range of 1 to 55% by mass, and still more preferably in the range of 5 to 50% by 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 used, and the solution polymerization method is particularly preferred. Furthermore, polymerization temperature or polymerization concentration (polymerization concentration = [total mass of polymerizable monomers/(total mass of polymerizable monomers + solvent mass)]×100) depends on the type or ratio of polymerizable monomers used , The molecular weight of the alkali-soluble resin set as the target varies. The polymerization temperature is preferably in the range of 40 to 150°C, and the polymerization temperature is more preferably in the range of 60 to 130°C. In addition, the polymerization concentration is preferably in the range of 5 to 50%, and more preferably in the range of 10 to 40%.

烷、乙二醇二甲醚、二乙二醇二甲醚等醚類；丙酮、甲基乙基酮、甲基異丁基酮、環己酮等酮 類；乙酸乙酯、乙酸丁酯、丙二醇單甲醚乙酸酯、乙酸3-甲氧基丁酯等酯類；甲醇、乙醇、異丙醇、正丁醇、乙二醇單甲醚、丙二醇單甲醚等醇類；甲苯、二甲苯、乙基苯等芳香族烴類；氯仿；二甲基亞碸等。該等溶劑可僅使用1種，亦可併用2種以上。 The solvent used in the solution polymerization method can be the one used in ordinary radical polymerization reactions. Specifically, for example, tetrahydrofuran, two

Ethers such as alkane, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone; ethyl acetate, butyl acetate, Propylene glycol monomethyl ether acetate, 3-methoxybutyl acetate and other esters; methanol, ethanol, isopropanol, n-butanol, ethylene glycol monomethyl ether, propylene glycol monomethyl ether and other alcohols; toluene, two Aromatic hydrocarbons such as toluene and ethylbenzene; chloroform; dimethyl sulfide etc. These solvents may use only 1 type, and may use 2 or more types together.

When polymerizing the above-mentioned polymerizable monomer, a polymerization initiator may be used as needed. As the polymerization initiator, for example, cumene hydroperoxide, diisopropylbenzene hydroperoxide, di-tertiary butyl peroxide, laurel peroxide, benzyl peroxide, tertiary peroxide Organic peroxides such as butyl isopropyl carbonate, tertiary pentyl peroxide 2-ethylhexanoate, tertiary butyl peroxide 2-ethylhexanoate; 2,2'-azobis(iso Butyronitrile), 1,1'-azobis (cyclohexamethylene cyanide), 2,2'-azobis (2,4-dimethylvaleronitrile), dimethyl 2,2'-azobis (2-methyl propionate) and other azo compounds. Only one type of these polymerization initiators may be used, or two or more types may be used in combination. The usage amount of these polymerization initiators can be set appropriately depending on the combination of the monomers used, or reaction conditions, the molecular weight of the target alkali-soluble resin (C1), etc. It is not particularly limited and can be obtained. In terms of alkali-soluble resins that do not gel and have a weight average molecular weight of thousands to tens of thousands, it is preferably in the range of 0.1 to 15% by mass, more preferably 0.5 to 10 with respect to all polymerizable monomer components The range of mass%.

In addition, in order to adjust the molecular weight, a chain transfer agent may be added. As the chain transfer agent, for example, thiol-based chain transfer agents such as n-dodecanethiol, thioglycolic acid, and methyl thioglycolate; α-methylstyrene dimer, etc., preferably have a high chain transfer effect and can Reduce the polymerizable monomer remaining in the reaction system, and easily obtain n-dodecanethiol and thioglycolic acid. Regarding the amount of use in the case of using a chain transfer agent, as long as it is appropriately set depending on the combination of the monomers used, or the reaction conditions, the molecular weight of the target monomer, etc., it is not particularly limited. Will congeal In terms of gelling alkali-soluble resins with a weight average molecular weight of several thousands to tens of thousands, it is preferably in the range of 0.1 to 15% by mass, and more preferably in the range of 0.5 to 10% by mass relative to all monomers.

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

‧The polymerizable monomer with hydroxyl group such as 2-hydroxyethyl (meth)acrylate is used as an essential component to obtain the polymer, and then added with succinic anhydride, tetrahydrophthalic anhydride, maleic anhydride and other acid anhydrides The alkali-soluble resin.

‧Polymerizable monomers with epoxy groups such as glycidyl (meth)acrylate are used as essential components to obtain the polymer, and then N-methylaminobenzoic acid, N-methylaminophenol, etc. are added Alkali-soluble resin obtained from compounds with amine groups and acid groups.

‧After obtaining a polymer by using polymerizable monomers with isocyanate groups such as 2-isocyanatoethyl (meth)acrylate as an essential component, add 2-hydroxybutyric acid and other compounds with hydroxyl and acid groups The alkali-soluble resin.

Regarding the weight average molecular weight of the alkali-soluble resin (C2), in terms of obtaining a coating film with good coating film formation and excellent heat resistance, the weight average molecular weight measured by GPC in terms of polystyrene is preferably 1,000 The range of ~200,000 is more preferably the range of 2,000 to 50,000, and the range of 2,000 to 30,000 is still more preferable. Furthermore, if necessary, the polymerizable monomer used in the preparation of the alkali-soluble resin (C1) may be used in combination to obtain the alkali-soluble resin (C2).

The above alkali-soluble resin (C3) is for epoxy-containing (meth)propylene The copolymer of acid esters and other polymerizable monomers adds unsaturated monocarboxylic acid to at least part of the epoxy groups of the copolymer, and further makes the anhydride of polycarboxylic acid and unsaturated monocarboxylic acid At least a part of the hydroxyl group generated by the addition reaction is obtained by the addition reaction.

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

Also, regarding other polymerizable monomers other than epoxy group-containing (meth)acrylate as the raw material of the alkali-soluble resin (C3), if an alicyclic ring having a norbornene skeleton or a dicyclopentadiene skeleton is used The monomer of the formula structure can improve the heat resistance and mechanical strength of the hardened material of the color resist composition of the present invention, so it is preferred.

In addition, polymerizable monomers that do not have an alicyclic structure can also be used as polymerizable monomers other than the epoxy group-containing (meth)acrylate. Examples of such polymerizable monomers include vinyl aromatics such as styrene, α-, o-, m-, p-alkyl, nitro, cyano, amide, and ester derivatives of styrene and styrene. ; Dienes such as butadiene, 2,3-dimethylbutadiene, isoprene, chloroprene; methyl (meth)acrylate, ethyl (meth)acrylate, (meth) Acrylic acid-n-propyl ester, (meth)acrylic acid-isopropyl ester, (meth)acrylic acid-n-butyl ester, (meth)acrylic acid-second butyl ester, (meth)acrylic acid-tertiary butyl ester, (meth)acrylate Base) amyl acrylate, neopentyl (meth)acrylate, isoamyl (meth)acrylate, hexyl (meth)acrylate, (meth)propylene 2-ethylhexyl acid, lauryl (meth)acrylate, dodecyl (meth)acrylate, cyclopentyl (meth)acrylate, cyclohexyl (meth)acrylate, (meth) 2-methylcyclohexyl acrylate, dicyclohexyl (meth)acrylate, isobornyl (meth)acrylate, adamantyl (meth)acrylate, propynyl (meth)acrylate, (meth)acrylate Base) phenyl acrylate, naphthyl (meth)acrylate, anthracene (meth)acrylate, anthraquinone (meth)acrylate, sunflower (meth)acrylate, salicylate (meth)acrylate, ( Furan (meth)acrylate, furfuryl (meth)acrylate, tetrahydrofuran (meth)acrylate, pyranyl (meth)acrylate, benzyl (meth)acrylate, phenethyl (meth)acrylate, Toluene (meth)acrylate, 1,1,1-trifluoroethyl (meth)acrylate, perfluoroethyl (meth)acrylate, perfluoro-n-propyl (meth)acrylate, (methyl) ) Perfluoro-isopropyl acrylate, triphenylmethyl (meth)acrylate, cumyl (meth)acrylate, -3-(N,N-dimethylamino)acrylate (meth)acrylate (Meth)acrylates such as 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, etc.; (meth)acrylamide, (meth)acrylic acid N, N -Dimethylamide, (meth)acrylic acid N,N-diethylamide, (meth)acrylic acid N,N-dipropylamide, (meth)acrylic acid-N,N-di-iso (Meth)acrylic acid amides such as propyl amide, (meth)acrylic anthryl amide; (meth)acrylic acid aniline, (meth)acrylonitrile, acrolein, vinyl chloride, vinylidene chloride, Vinyl fluoride, vinylidene fluoride, N-vinylpyrrolidone, vinyl pyridine, vinyl acetate and other vinyl compounds; diethyl citraconic acid, diethyl maleate, diethyl fumarate, Unsaturated dicarboxylic acid diesters such as diethyl iconate; N-phenyl maleimide, N-cyclohexyl maleimide, N-lauryl maleimide Monomaleimines such as amines and N-(4-hydroxyphenyl)maleimide; N-(meth)acrylonitrile phthalimide, etc.

Among the above-mentioned other polymerizable monomers, in terms of improving the heat resistance and mechanical strength of the cured product of the color resist composition of the present invention, preferably selected from styrene, benzyl (meth)acrylate and monocis At least one of the butenediimines is used. Regarding the use ratio of styrene, benzyl (meth)acrylate and monomaleimines, based on the total amount of other polymerizable monomers, it is preferably 1 to 70 mol%, more preferably 3~50 mole%.

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

As a copolymer of the above-mentioned epoxy-containing (meth)acrylate and the above-mentioned other polymerizable monomer, it is preferably composed of a repeating unit derived from epoxy-containing (meth)acrylate of 5 to 90 mol% , It is composed of 10~95 mol% of repeating units derived from other radical polymerizable monomers, and more preferably is composed of 20~80 mol% of the former and 80~20 mol% of the latter. Preferably, it is composed of the former 30~70 mol% and the latter 70~30 mol%.

The alkali-soluble resin (C3) is obtained by combining the epoxy portion of the copolymer of the epoxy-containing (meth)acrylate and other polymerizable monomers with an unsaturated monocarboxylic acid (polymerizable component), The acid anhydride (alkali-soluble component) of polycarboxylic acid is obtained by reacting.

As the above-mentioned unsaturated monocarboxylic acid, for example, (meth)acrylic acid, crotonic acid, o-vinyl benzoic acid, m-vinyl benzoic acid, p-vinyl benzoic acid, α-position via haloalkyl, alkoxy Monocarboxylic acids such as (meth)acrylic acid substituted with groups, halogen atoms, nitro groups, or cyano groups. Among them, (meth)acrylic acid is preferred. These unsaturated monocarboxylic acids may use only 1 type, and may use 2 or more types together. By using the unsaturated monocarboxylic acid, the alkali-soluble resin (A3) Give polymerization.

The above-mentioned unsaturated monocarboxylic acid is usually preferably added to 10-100 mol% of the epoxy group of the above copolymer, more preferably added to 30-100 mol%, and further preferably added to 50~100 mole%.

Examples of the anhydrides of the above-mentioned polycarboxylic acids include maleic anhydride, succinic anhydride, itaconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, and chloro bridged anhydride. Anhydrides of carboxylic acids; 1,2,4-benzenetricarboxylic acid anhydride, 1,2,4,5-pyromellitic acid anhydride, benzophenonetetracarboxylic acid anhydride, biphenyltetracarboxylic acid anhydride, etc. Carboxylic acid with more than 3 carboxyl groups Anhydrous acid, etc. Among them, tetrahydrophthalic anhydride and succinic anhydride are preferred. The acid anhydrides of these polycarboxylic acids may use only 1 type, and may use 2 or more types together. By using the acid anhydride of the polycarboxylic acid, alkali solubility can be imparted to the alkali-soluble resin (C3).

The anhydride of the polycarboxylic acid is usually preferably added to 10-100 mol% of the hydroxyl group generated by the addition of an unsaturated monocarboxylic acid to the epoxy group possessed by the copolymer, more preferably an addition It is in the range of 20-90 mol%, more preferably in the range of 30-80 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 in the range of 5,000 to 50,000 . In addition, the dispersion degree (Mw/Mn) of the alkali-soluble resin (C3) is preferably in the range of 2.0 to 5.0.

The above-mentioned epoxy (meth)acrylate resin (C4) can be added to epoxy resin by adding α,β-unsaturated monocarboxylic acid or α,β-unsaturated monocarboxylic acid ester having a carboxyl group in the ester portion, for example, It is obtained by further reacting a polybasic acid anhydride.

As the above epoxy resin, for example, bisphenol A type epoxy resin (as Commercially available products, "jER828", "jER1001", "jER1002", "jER1004", etc. manufactured by Mitsubishi Chemical Co., Ltd.), obtained by the reaction of the alcoholic hydroxyl group of bisphenol A epoxy resin with epichlorohydrin Epoxy resin (as a commercial product, "NER-1302" (epoxy equivalent 323, softening point 76℃) manufactured by Nippon Kayaku Co., Ltd.), bisphenol F resin (as a commercial product, Mitsubishi Chemical "JER807", "EP-4001", "EP-4002", "EP-4004", etc. manufactured by Co., Ltd., obtained by the reaction of the alcoholic hydroxyl group of bisphenol F epoxy resin with epichlorohydrin Epoxy resin (as a commercially available product, "NER-7406" manufactured by Nippon Kayaku Co., Ltd. (epoxy equivalent 350, softening point 66°C)), bisphenol S type epoxy resin, biphenyl glycidyl ether (As a commercial product, "YX-4000" manufactured by Mitsubishi Chemical Co., Ltd.), phenol novolac type epoxy resin (as a commercial product, "EPPN-201" manufactured by Nippon Kayaku Co., Ltd., Mitsubishi Chemical "EP-152" and "EP-154" manufactured by Co., Ltd., "DEN-438" manufactured by Dow Chemical Japan Co., Ltd.), cresol novolac type epoxy resin (as a commercial product, Nippon Kayaku "EOCN-102S", "EOCN-1020", "EOCN-104S") manufactured by Co., Ltd., triglycidyl isocyanate (as a commercial product, "TEPIC" manufactured by Nissan Chemical Industry Co., Ltd.) , Triphenol methane type epoxy resin (as a commercial product, "EPPN-501", "EPN-502", "EPPN-503" manufactured by Nippon Kayaku Co., Ltd.), 茀 epoxy resin (as a commercial product , Phenolphthalein-based epoxy resin "ESF-300" manufactured by Nippon Steel Chemical Co., Ltd.), alicyclic epoxy resin ("Celloxide 2021P" and "Celloxide EHPE" manufactured by Daicel Chemical Industry Co., Ltd.), based on two The reaction of cyclopentadiene and phenol is a dicyclopentadiene epoxy resin obtained by epoxidizing phenolic resin (for example, "XD-1000" manufactured by Nippon Kayaku Co., Ltd., DIC Co., Ltd. "EXA-7200" manufactured by Nippon Kayaku Co., Ltd., "NC-3000" and "NC-7300" manufactured by Nippon Kayaku Co., Ltd.), epoxy resin with a skeleton (see According to Japanese Patent Laid-Open No. 4-355450) etc. These epoxy resins may use only 1 type, and may use 2 or more types together.

As other examples of epoxy resins, copolymerized epoxy resins can be cited. As a copolymerized epoxy resin, for example, glycidyl (meth)acrylate, (meth)acryloyl methyl cyclohexane, vinyl epoxy cyclohexane, etc. have epoxy groups. The monomers, and methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl (meth)acrylate, (methyl) )Acrylic acid, styrene, phenoxyethyl (meth)acrylate, benzyl (meth)acrylate, α-methylstyrene, glycerol mono(meth)acrylate, which has a polyoxyalkylene chain ( A copolymer obtained by copolymerizing polymerizable monomers without epoxy groups such as meth)acrylate.

Examples of the (meth)acrylate having a polyoxyalkylene chain include diethylene glycol mono(meth)acrylate, triethylene glycol mono(meth)acrylate, and tetraethylene glycol mono(meth)acrylate. (Meth)acrylate and other polyethylene glycol mono(meth)acrylates; methoxydiethylene glycol mono(meth)acrylate, methoxytriethylene glycol mono(meth)acrylate, methacrylate Alkoxy polyethylene glycol (meth)acrylate such as oxytetraethylene glycol mono(meth)acrylate.

The molecular weight of the aforementioned copolymerized epoxy resin is preferably in the range of 1,000 to 200,000. In addition, the amount of the monomer having epoxy group used as the raw material of the copolymerized epoxy resin is preferably in the range of 10 to 70% by mass relative to the monomer having no epoxy group, and more preferably The range of 20-50% by mass.

Examples of commercially available products of the aforementioned copolymerized epoxy resin include: "CP-15", "CP-30", "CP-50", "CP-20SA", and "CP -510SA", "CP-50S", "CP-50M", "CP-20MA", etc.

Regarding the molecular weight of the above epoxy resin, in terms of good film formation and preventing gelation during the addition reaction of α,β-unsaturated monocarboxylic acid, it is calculated as polystyrene measured by GPC The weight average molecular weight is preferably in the range of 200 to 200,000, more preferably in the range of 300 to 100,000.

As the α,β-unsaturated monocarboxylic acid, for example, itaconic acid, crotonic acid, cinnamic acid, acrylic acid, methacrylic acid, etc., are preferably acrylic acid and methacrylic acid, in terms of good reactivity , More preferably acrylic. Examples of α,β-unsaturated monocarboxylic acid esters having a carboxyl group in the ester portion include: 2-succinoxyethyl acrylate, 2-maleoxyethyl acrylate, and 2-phthalic acrylate Methoxyethyl, 2-hexahydrophthalate oxyethyl acrylate, 2-succinooxyethyl methacrylate, 2-maleoxyethyl methacrylate, 2-phthaloxyethyl methacrylate, 2-hexahydrophthaloxyethyl methacrylate, 2-succinooxyethyl methacrylate, etc., preferably They are 2-maleoxyethyl acrylate and 2-phthaloxyethyl acrylate, and more preferably 2-maleoxyethyl acrylate. These α,β-unsaturated monocarboxylic acids and α,β-unsaturated monocarboxylic acid esters may be used alone or in combination of two or more kinds.

The addition reaction of α,β-unsaturated monocarboxylic acid or its ester and epoxy resin can use known methods, for example, a method of reacting at a temperature of 50 to 150°C in the presence of an esterification catalyst . As esterification catalysts, tertiary amines such as triethylamine, trimethylamine, dimethylbenzylamine, and diethylbenzylamine can be used; tetramethylammonium chloride, tetraethylammonium chloride, dodecyltrimethyl Quaternary ammonium salts such as amine chloride, etc.

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

Examples of polybasic acid anhydrides that are further added to epoxy resins to which α, β-unsaturated carboxylic acids or their esters are added include maleic anhydride, succinic anhydride, itaconic anhydride, phthalic anhydride, and tetrahydro Phthalic anhydride, hexahydrophthalic anhydride, 1,2,4,5-pyromellitic anhydride, 1,2,4- trimellitic anhydride, benzophenonetetracarboxylic dianhydride, methylhexa Hydrogen phthalic anhydride, internal methylene tetrahydro phthalic anhydride, chloro bridged anhydride, methyl tetrahydro phthalic anhydride, biphenyl tetracarboxylic dianhydride, etc. Among them, maleic anhydride, succinic anhydride, itaconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, 1,2,4,5-benzenetetrahydrophthalic anhydride are preferred. Formic anhydride, trimellitic anhydride, biphenyltetracarboxylic dianhydride, more preferably tetrahydrophthalic anhydride and biphenyltetracarboxylic dianhydride. These polybasic acid anhydrides may use only 1 type, and may use 2 or more types together.

Regarding the addition reaction of the polybasic acid anhydride, a known method can also be used, and the reaction can be continuously performed under the same conditions as the addition reaction of the α,β-unsaturated carboxylic acid or its ester. Regarding the amount of polybasic acid anhydride used, in terms of improving alkali developability and coating film formation, it is preferable that the acid value of the produced epoxy (meth)acrylate resin is in the range of 10 to 150 The amount is more preferably an amount in the range of 20 to 140.

In addition, examples of naphthalene-containing resins described in Japanese Patent Application Laid-Open No. 6-49174; Japanese Patent Application Publication No. 2003-89716, Japanese Patent Application Publication No. 2003-165830, Japanese Patent Application Publication No. 2005-325331, Japanese Patent Application Publication No. 2001 -354735 No. 茀-containing resin; JP 2005-126674 A, JP 2005-55814, JP 2004-295084, etc. are described as epoxy (methyl) ) Acrylic resin. In addition, as a commercially available product, "ACA-200M" manufactured by Daicel Chemical Industry Co., Ltd. can also be exemplified.

The alkali-soluble resin (C) may be used alone or in combination of two or more of the alkali-soluble resins (C1) to (C4). In addition, by using the alkali-soluble resin (C) in combination with the pigment dispersant described below, it is possible to form high-density color pixels with excellent adhesion to the substrate without undissolved matter remaining in the non-pixel portion on the substrate. good. Specifically, it is preferable to use a part of the alkali-soluble resin (C) together with the following pigment dispersant in the dispersion treatment step. In this case, the alkali-soluble resin (C) is preferably used in the range of 5 to 200% by mass relative to the pigment, and more preferably used in the range of 10 to 100% by mass.

In addition, alkali-soluble resins other than the above-mentioned alkali-soluble resins (C1) to (C4) can also be used as the alkali-soluble resin (C) used in the present invention. 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 an essential component Alkali-soluble resin, etc. Here, examples of the polymerizable monomer having a phenolic hydroxyl group include ortho-hydroxystyrene, m-hydroxystyrene, and p-hydroxystyrene. In addition, one or more hydrogen atoms other than the phenolic hydroxyl group and vinyl group bonded to the aromatic ring of these monomers are substituted with alkyl groups, alkoxy groups, halogen atoms, nitro groups, cyano groups, Amido-based compounds, etc. Moreover, as a polymerizable monomer having a sulfonic acid group as an acidic group, for example, vinyl sulfonic acid, styrene sulfonic acid, (meth)propylene sulfonic acid, 2-hydroxy-3-(meth)propylene oxide Propanesulfonic acid, 2-sulfoethyl (meth)acrylate, or their salts, etc.

In the resist composition of the present invention, the content ratio of the alkali-soluble resin (C) is preferably 0.1 in the total solid components in terms of the appearance of the coating film or the adhesion to the substrate. The range of ~80% by mass, more preferably the range of 1-60% by mass.

As the polymerizable compound (D) used in the present invention, for example: A photopolymerizable compound with more than one ethylenically unsaturated bond.

As the polymerizable compound (D1) having one ethylenically unsaturated bond, for example, the compounds exemplified as (c1), (c2), and (c3) above can be cited. Among them, (meth)acrylates are preferred.

As the polymerizable compound (D2) having two ethylenically unsaturated bonds, for example, 1,3-butanediol di(meth)acrylate, 1,3-butanediol (meth)acrylate, 1,6-hexanediol di(meth)acrylate, ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate, Triethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, polyethylene glycol diacrylate, bis(acryloxyethyl) ether of bisphenol A, ethoxylate Phenol A di(meth)acrylate, propylene oxide neopentyl glycol di(meth)acrylate, ethoxylated neopentyl glycol di(meth)acrylate, 3-methylpentanediol di(meth) Acrylic etc.

As the polymerizable compound (D3) having three ethylenically unsaturated bonds, for example, trimethylolpropane tri(meth)acrylate, neopentaerythritol tri(meth)acrylate, tris(2- Hydroxyethyl) trimeric isocyanate tri(meth)acrylate, ethoxylated trimethylolpropane tri(meth)acrylate, propoxylated trimethylolpropane tri(meth)acrylate, neopentylerythritol three (Meth) acrylate and acid anhydride reactant, caprolactone modified neopentyl erythritol tri(meth)acrylate, caprolactone modified tris(2-hydroxyethyl) trimeric isocyanate tri(methyl) Acrylate and caprolactone are modified reaction products of neopentyl erythritol tri(meth)acrylate and acid anhydride, and caprolactone is modified reaction products of dineopentaerythritol penta(meth)acrylate and acid anhydride.

As the polymerizable compound (D4) having four ethylenically unsaturated bonds, for example, neopentaerythritol tetra(meth)acrylate, trineopentaerythritol tetra(meth)acrylate, Caprolactone is used to modify trineopentaerythritol tetra(meth)acrylate.

As the polymerizable compound (D5) having five or more ethylenically unsaturated bonds, for example, dineopentaerythritol penta(meth)acrylate, dineopentaerythritol hexa(meth)acrylate, three Neopentaerythritol penta(meth)acrylate, trineopentaerythritol hexa(meth)acrylate, trineopentaerythritol hepta(meth)acrylate, trineopentaerythritol octa(meth)acrylate , The reactant of pentaerythritol penta(meth)acrylate and acid anhydride; The reactant of pentaerythritol hepta(meth)acrylate and acid anhydride; Caprolactone is modified to trimethylolpropane tri(formaldehyde) Base) acrylate, caprolactone modified neopentyl erythritol tetra (meth) acrylate, caprolactone modified dineopentaerythritol penta (meth) acrylate, caprolactone modified dineopentaerythritol Hex(meth)acrylate, caprolactone modified trineopentaerythritol penta(meth)acrylate, caprolactone modified trineopentaerythritol hexa(meth)acrylate, caprolactone modified three One of neopentyl erythritol hepta (meth) acrylate, caprolactone modified trineopentaerythritol octa (meth) acrylate, caprolactone modified trineopentaerythritol hepta (meth) acrylate and acid anhydride Reactants etc.

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

Examples of the above-mentioned photocurable resin include urethane (meth)acrylate resin, unsaturated polyester resin, epoxy (meth)acrylate resin, (meth)acrylic polyester resin, (Meth)acrylate resin, maleimide group-containing resin, etc.

The above-mentioned (meth)acrylate amine ester resin includes, for example, an aliphatic polyisocyanate compound or an aromatic polyisocyanate compound and a hydroxyl group-containing (meth)acrylate compound having an amine ester bond and (meth)propylene. The resin of the base, etc.

烷二異氰酸酯、氫化二苯基甲烷二異氰酸酯、氫化甲苯二異氰酸酯、氫化苯二甲基二異氰酸酯、氫化四甲基苯二甲基二異氰酸酯、環己基二異氰酸酯等，又，作為芳香族聚異氰酸酯化合物，可列舉：甲苯二異氰酸酯、4,4'-二苯基甲烷二異氰酸酯、苯二甲基二異氰酸酯、1,5-萘二異氰酸酯、聯甲苯胺二異氰酸酯、對伸苯基二異氰酸酯等。 As said aliphatic polyisocyanate compound, for example, tetramethylene diisocyanate, pentamethylene diisocyanate, hexamethylene diisocyanate, heptamethylene diisocyanate, octamethylene diisocyanate, decamethylene diisocyanate Diisocyanate, 2-methyl-1,5-pentamethylene diisocyanate, 3-methyl-1,5-pentamethylene diisocyanate, dodecamethylene diisocyanate, 2-methyl pentamethylene diisocyanate, 2 , 2,4-trimethylhexamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, isophorone diisocyanate, drop

Alkyl diisocyanate, hydrogenated diphenylmethane diisocyanate, hydrogenated toluene diisocyanate, hydrogenated xylylene diisocyanate, hydrogenated tetramethylxylylene diisocyanate, cyclohexyl diisocyanate, etc., and as an aromatic polyisocyanate compound Examples include toluene diisocyanate, 4,4'-diphenylmethane diisocyanate, xylylene diisocyanate, 1,5-naphthalene diisocyanate, toluidine diisocyanate, paraphenylene diisocyanate, and the like.

Examples of the hydroxyl group-containing (meth)acrylate compounds include: 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 1,5-pentanediol mono(meth)acrylate, 1,6-hexanediol mono(meth)acrylate, neopentyl glycol mono(meth) Mono(meth)acrylate of dihydric alcohols such as acrylate, hydroxypivalate neopentyl glycol mono(meth)acrylate; trimethylolpropane di(meth)acrylate, ethoxylated trimethylol Propane (meth)acrylate, propylene oxide trimethylolpropane di(meth)acrylate, glycerol di(meth)acrylate, trimeric isocyanate bis(2-(meth)acryloyloxyethyl) Mono- or di(meth)acrylates of triols such as hydroxyethyl ester, or mono- and di(meth)acrylic acids containing hydroxyl groups in which part of these alcoholic hydroxyl groups has been modified by ε-caprolactone Esters; neopentyl erythritol tri (meth) acrylate, di-trimethylolpropane tri (meth) acrylate, dineopentaerythritol penta (meth) acrylate, etc. have 1 A compound of a functional hydroxyl group and a (meth)acrylic acid group with three or more functions, or a hydroxyl-containing polyfunctional (meth)acrylate in which the compound is further modified by ε-caprolactone; dipropylene glycol mono(methyl) )Acrylate, diethylene glycol mono(meth)acrylate, polypropylene glycol mono(meth)acrylate, polyethylene glycol mono(meth)acrylate, etc. (meth)acrylic acid with oxyalkylene chain Ester compound; polyethylene glycol-polypropylene glycol mono(meth)acrylate, polyoxybutylene-polyoxypropylene mono(meth)acrylate, etc. (meth)acrylic acid with block structure of oxyalkylene chain Ester compounds; poly(ethylene glycol-1,4-butanediol) mono(meth)acrylate, poly(propylene glycol-1,4-butanediol) mono(meth)acrylate, etc. have random structures (Meth)acrylate compound of oxyalkylene chain, etc.

The reaction of the aliphatic polyisocyanate compound or aromatic polyisocyanate compound and the hydroxyl group-containing (meth)acrylate compound can be carried out by a common method in the presence of an amination catalyst, for example. Regarding the amine esterification catalyst that can be used here, specifically, amines such as pyridine, pyrrole, triethylamine, diethylamine, and dibutylamine; phosphines such as triphenylphosphine and triethylphosphine ; Dibutyl tin dilaurate, octyl tin trilaurate, octyl tin diacetate, dibutyl tin diacetate, tin octoate and other organotin compounds; zinc octoate and other organometallic compounds.

Among these urethane (meth)acrylate resins, in terms of excellent transparency of the cured coating film, good sensitivity to active energy rays, and excellent curability, it is particularly preferable to combine an aliphatic polyisocyanate compound with a hydroxyl group-containing (Meth)acrylic acid ester compound reacted.

Then, the unsaturated polyester resin includes, for example, α, β-unsaturated dibasic acid or its anhydride, dibasic acid other than the dibasic acid or its anhydride, and curable resin obtained by polycondensation of diols Wait. Examples of α,β-unsaturated dibasic acid or its anhydride include maleic acid, maleic anhydride, fumaric acid, itaconic acid, citraconic acid, chloromaleic acid, and esters of these.

Examples of dibasic acids or their anhydrides other than α,β-unsaturated dibasic acids or their anhydrides include: aromatic saturated dibasic acids, aliphatic dibasic acids, alicyclic saturated dibasic acids, and the like Acid anhydride and so on. Examples of the aromatic saturated dibasic acid or its anhydride include phthalic acid, phthalic anhydride, isophthalic acid, terephthalic acid, nitrophthalic acid, and tetrahydrophthalic anhydride , Endo-methylenetetrahydrophthalic anhydride, halogenated phthalic anhydride and their esters. As the aliphatic dibasic acid, alicyclic saturated dibasic acid and the acid anhydrides thereof, for example, oxalic acid, malonic acid, succinic acid, adipic acid, sebacic acid, azelaic acid, glutaric acid, six Hydrogen phthalic anhydride and these esters, etc. Examples of glycols include ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, 1,3-butanediol, 1,4-butanediol, and 2-methylpropane-1,3-diol , Neopentyl glycol, triethylene glycol, tetraethylene glycol, 1,5-pentanediol, 1,6-hexanediol, bisphenol A, hydrogenated bisphenol A, ethylene glycol carbonate, 2,2 -Di-(4-hydroxypropoxydiphenyl)propane, etc., in addition to this, oxides such as ethylene oxide and propylene oxide can also be used in the same manner.

Then, as the epoxy vinyl ester resin, for example, bisphenol A type epoxy resin, bisphenol F type epoxy resin, phenol novolak type epoxy resin, cresol novolak type epoxy resin, etc. The epoxy group of the resin reacts with (meth)acrylic acid, etc.

Examples of resins containing maleimide groups include: bifunctional maleimide obtained by amine esterification of N-hydroxyethyl maleimide and isophorone diisocyanate Amino amine ester compound, a bifunctional maleimide compound obtained by esterifying maleiminoacetic acid and poly 1,4-butanediol, and maleimino caproic acid The 4-functional maleimide compound obtained by esterification with the tetraethylene oxide adduct of neopentylerythritol, and the most obtained by esterifying maleimide acetic acid and polyol compound Functional maleimide compound, etc. These active energy ray-curable resins may be used alone or in combination of two or more kinds.

Among the polymerizable compounds (D) used in the present invention, in terms of excellent hardness of the coating layer, trimethylolpropane tri(meth)acrylate and neopentylerythritol tri(methyl) are particularly preferred. ) Multifunctional (meth)acrylates with three or more functions, such as acrylate, dineopentaerythritol hexa(meth)acrylate, and neopentaerythritol tetra(meth)acrylate. These polymerizable compounds (D) may be used alone or in combination of two or more kinds.

Regarding the total content of the polymerizable compound (D), it is preferably 10 to 50% by mass, and more preferably 15 to 50% by mass relative to the solid content of the resist composition. If the total content of the polymerizable compound (D) is within the above-mentioned range, the sensitivity, the strength or smoothness of the coating layer, and the reliability tend to become better.

In the polymerizable compound (D), the content of the polymerizable compound (D5) relative to the solid content of the resist composition is preferably 1-50% by mass, more preferably 5-40% by mass, and particularly preferably 5~35 mass%. If the content of the polymerizable compound (D5) is within the above-mentioned range, the sensitivity, the strength or smoothness of the coating layer, and the reliability tend to become better.

In addition, in the polymerizable compound (D), the content of the polymerizable compound (D5) is preferably relative to the total amount of the polymerizable compounds (D1), (D2), (D3), (D4) and (D5) It is 10 to 95% by mass, more preferably 20 to 90% by mass. If the content of the polymerizable compound (D5) is within the above-mentioned range, the sensitivity, the strength or smoothness of the coating layer, and the reliability tend to become better.

The method for producing the above-mentioned resist composition is as described above, and includes the following steps: obtaining the random copolymer (A) as the first invention of the present invention; and the random copolymer (A), the pigment (B), and the base The soluble resin (C) and the polymerizable compound (D) are mixed. In the manufacturing method of the resist composition of the present invention, good dispersibility can be obtained, and the desired hue can be obtained. In terms of the above, it is preferable to combine the random copolymer (A), the colorant (B), the alkali-soluble resin (C) and the polymerizable compound (D) when a pigment is used as the colorant (B). When mixing, a pigment dispersion liquid prepared by dispersing in an organic solvent using a dispersant is used as the colorant (B).

Examples of the above-mentioned dispersants include: surfactants; intermediates or derivatives of pigments; resin-type dispersants such as polyamide resins, polyurethane resins, polyester resins, and acrylic resins. Among these pigment dispersants, resin-based dispersants are preferred, acrylic resin-based dispersants are more preferred, and those containing N,N-disubstituted amino groups and acidic groups in the main chain or branch are more preferred. Resin type dispersant for acrylic polymer. Commercial products of this resin-type dispersant include, for example, "BYK-160", "BYK-161", and "BYK-2001" manufactured by BYK-Chemie; "EFKA 46" manufactured by EFKA Chemicals; "Ajisper PB-814" manufactured by Ajinomoto Fine-Techno Co., Ltd. etc. These dispersants may be used alone or in combination of two or more kinds.

As the organic solvent used in the preparation of the pigment dispersion, for example, acetate-based solvents such as propylene glycol monomethyl ether acetate and propylene glycol monoethyl ether acetate; and propionate-based solvents such as ethoxy propionate Solvents; aromatic solvents such as toluene, xylene, and methoxybenzene; ether solvents such as butyl siloxol, propylene glycol monomethyl ether, diethylene glycol ethyl ether, and diethylene glycol dimethyl ether; methyl ethyl Ketone solvents such as ketone, methyl isobutyl ketone, cyclohexanone; aliphatic hydrocarbon solvents such as hexane; N,N-dimethylformamide, γ-butyrolactamide, N-methyl-2 -Nitrogen compound solvents such as pyrrolidone; lactone solvents such as γ-butyrolactone; carbamates, etc. These solvents may be used alone or in combination of two or more kinds.

As a method of preparing the above-mentioned pigment dispersion, for example, the The method of kneading the dispersion step and the micro-dispersing step, the method of performing only the micro-dispersing step, etc.

In the above-mentioned kneading and dispersing step, the pigment, the alkali-soluble resin (C), and the above-mentioned dispersant as necessary are mixed and kneaded. The machinery used for kneading can be, for example, a two-roller, a three-roller, a ball mill, a tumbler screen, a disperser, a kneader, a two-way kneader, a homogenizer, a mixer, a single-shaft or twin-shaft extruder, etc. , Using these kneaders to disperse while applying a strong shear force, whereby the pigment can be dispersed in the alkali-soluble resin (C). Furthermore, it is preferable to refine the particle size by a salt milling method or the like before the pigment is kneaded as described above. Here, the above-mentioned alkali-soluble resin may use all the amounts used in the manufacturing method of the resist composition of this invention, and may use a part.

In the above-mentioned micro-dispersion step, a dispersion medium and a dispersing machine of fine particles of glass, zirconia or ceramic are used, and an organic solvent is added to the composition containing the pigment obtained in the above-mentioned kneading and dispersion step, or the pigment , Alkali-soluble resin (C) solvent and if necessary the above-mentioned dispersant are mixed and dispersed, whereby the pigment particles can be dispersed to a tiny state close to primary particles.

Examples of the above-mentioned organic solvents include: acetate solvents such as propylene glycol monomethyl ether acetate and propylene glycol monoethyl ether acetate; propionate solvents such as ethoxy propionate; toluene, xylene, and methoxy Benzene and other aromatic solvents; butyl siloxol, propylene glycol monomethyl ether, diethylene glycol ethyl ether, diethylene glycol dimethyl ether and other ether solvents; methyl ethyl ketone, methyl isobutyl ketone, Ketone solvents such as cyclohexanone; aliphatic hydrocarbon solvents such as hexane; nitrogen compound solvents such as N,N-dimethylformamide, γ-butyrolactone, and N-methyl-2-pyrrolidone ; Lactone solvents such as γ-butyrolactone; urethanes, etc. These solvents may be used alone or in combination of two or more kinds.

The average particle size of the primary particles of the above-mentioned pigments is preferably 10~100nm, more preferably It is 10~60nm. Furthermore, the average particle size of the pigment (B) is measured by a dynamic light scattering particle size distribution meter. For example, the Nanotrac particle size distribution measuring device "UPA-EX150" manufactured by Nikkiso Co., Ltd. can be used. "UPA-EX250" and other measurements.

In the manufacturing method of the above-mentioned resist composition, it is preferable to use a solid substance when mixing the random copolymer (A), the colorant (B), the alkali-soluble resin (C) and the polymerizable compound (D) The ingredients are converted into 0.0001 to 10 parts by mass, 5 to 80 parts by mass, 0.1 to 80 parts by mass, and 5 to 80 parts by mass, respectively. It is more preferably 0.001 to 5 parts by mass, 5 to 70 parts by mass, 1~60 parts by mass, 10~70 parts by mass.

In the manufacturing method of the above-mentioned resist composition, various methods can be used when mixing the random copolymer (A), the colorant (B), the alkali-soluble resin (C), and the polymerizable compound (D). Specifically, for example, it is sufficient to use a shaker, a paint shaker, or a stirring method using a stirring blade for mixing, and an organic solvent may be added as necessary during mixing. The organic solvent can be, for example, an organic solvent that can be used in the adjustment of the above-mentioned pigment dispersion. Regarding the usage amount of the organic solvent, for example, it is usually 100 to 1000 parts by mass relative to 100 parts by mass of the coating film layer forming components.

As described below, the resist composition obtained in the above-mentioned resist composition manufacturing method is usually blended with a polymerization initiator in order to be cured by irradiating active energy rays such as ultraviolet rays. The polymerization initiator can be used in the production method of the resist composition of the present invention when mixing the random copolymer (A), the colorant (B), the alkali-soluble resin (C) and the polymerizable compound (D) It can be mixed, and it can also be mixed in the resist composition obtained by mixing (A), (B), (C), and (D).

As the polymerization initiator, for example, benzophenone, acetophenone, benzoin, benzoin ethyl ether, benzoin isobutyl ether, biphenyl dimethyl acetal, azobisisobutyronitrile, 1 -Hydroxycyclohexylphenyl ketone, 2-hydroxy-2-methyl-1-phenyl-1-one, 1-(4'-isopropylphenyl)-2-hydroxy-2-methylpropan-1 -Ketone, 1-(4'-dodecylphenyl)-2-hydroxy-2-methylpropan-1-one, 3,3',4,4'-tetra(tertiary butyl peroxide) ) Benzophenone, 4,4"-diethyl isophthalophenone, 2,2-dimethoxy-1,2-diphenylethane-1-one, benzoin isopropyl ether, Thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, 2-isopropylthioxanthone, 2-methyl-1[4-(methylthio)phenyl]-2-morpholine Propan-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinylphenyl)-butanone-1, bis(2,6-dimethoxybenzyl) )-2,4,4-trimethyl-pentylphosphine oxide, bis(2,4,6,-trimethylbenzyl)-phenylphosphine oxide, 2,4,6-trimethylbenzene Formyl diphenyl phosphine oxide, etc., can be used alone or in combination of two or more. Among these, it is relatively hard to be affected by the colorant (B) and exhibits high curability. Preferably, it is 2-benzyl-2-dimethylamino-1-(4-morpholinylphenyl)-butanone-1.

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

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

Furthermore, the resist composition obtained in the manufacturing method of the present invention may be blended with organic solvents, polymerization inhibitors, antistatic agents, defoamers, and viscosity adjustments within a range that does not impair the effects of the present invention, depending on the purpose, characteristics, etc. Additives such as agents, light stabilizers, heat stabilizers, antioxidants, etc.

Examples of the above-mentioned organic solvent include: preparation of the above-mentioned pigment dispersion Organic solvents that can be used in the method, etc. Regarding the amount of organic solvent used, it depends on the application or the target film thickness or viscosity, but it is preferably calculated on a mass basis relative to the total of the alkali-soluble resin (C) and polymerizable compound (D) The range of 0.5~6 times the amount.

Examples of the above-mentioned polymerization inhibitor include hydroquinone, p-methoxyphenol, di-tertiary butyl-p-cresol, pyrogallol, tertiary butylcatechol, benzoquinone, 4 ,4'-thiobis(3-methyl-6-tertiary butylphenol), 2,2'-methylene bis(4-methyl-6-tertiary butylphenol), N-nitroso The first cerium salt of phenylhydroxylamine and so on.

Examples of the antistatic agent include: polyoxyethylene alkyl ether, polyoxyethylene alkyl phenol, polyoxyethylene alkyl amine, polyoxyethylene alkyl amide, polyethylene glycol fatty acid ester, and sorbitol anhydride Nonionic antistatic agents such as fatty acid esters, polyoxyethylene sorbitan fatty acid esters, fatty acid glycerides, alkyl polyethylene imines, alkyl amine salts, alkyl quaternary ammonium salts, alkyl imidazolines Cationic antistatic agents such as derivatives.

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

As the aforementioned viscosity modifier, for example, acrylic polymer or synthetic rubber latex that can be thickened by adjusting to alkali, urethane resin that can be thickened by molecular association, hydroxyethyl cellulose, Carboxymethyl cellulose, methyl cellulose, polyvinyl alcohol, hydrogenated castor oil, amide wax, oxidized polyethylene, metal alkaloids, dibenzylidene sorbitol, etc.

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

As said heat-resistant stabilizer, for example, 1,3,5-trimethyl-2,4,6-tris(3,5-di-tertiarybutyl-4-hydroxybenzyl)benzene, 1,1 ,3-Tris(2-methyl-4-hydroxy -5-5-tertiary butyl phenyl) butane, N,N'-hexamethylene bis(3,5-di-tertiary butyl-4-hydroxycinnamic acid amide), 4,4' -Bis(2,6-di-tertiary butylphenol), 2,2'-methylene bis(4-ethyl-6-tertiary butylphenol), pentaerythritol-tetra[3-(3, 5-di-tertiary butyl-4-hydroxyphenyl) propionate] and other hindered phenols; N,N'-bis(β-naphthyl)-p-phenylenediamine, N-N'-diphenyl -Aromatic amines such as p-phenylenediamine and poly(2,2,4-trimethyl-1,2-dihydroquinoline); sulfur compounds such as dilauryl thiodipropionate; tris(2,4 -Phosphorus compounds such as di-tertiary butyl phenyl) phosphite.

Examples of the antioxidants include hindered phenol antioxidants, hindered amine antioxidants, organic sulfur antioxidants, and phosphoric ester antioxidants.

The present invention can provide a color filter. The color filter can be obtained by, for example, the following color filter manufacturing method, the manufacturing method including: polymerizable monomer (a1) and polymerizable monomer (a2) in the polymerizable monomer (a1) and polymerizable The step of carrying out living radical polymerization under the coexistence of the monomer (a2) to obtain a fluoropolymer (A), the polymerizable monomer (a1) having 1 to 6 carbon atoms directly bonded to fluorine atoms The fluorinated alkyl group and the polymerizable unsaturated group, the polymerizable monomer (a2) has the backbone of the bridged cyclic hydrocarbon and the polymerizable unsaturated group; and the fluoropolymer (A) and the colorant (B) , The step of mixing the alkali-soluble resin (C) and the polymerizable compound (D) to obtain the resist composition; the step of forming the coating layer of the resist composition on the substrate. The step of obtaining the fluoropolymer (A) corresponds to the step of the method for producing the random copolymer of the present invention.

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

(1) The step of obtaining a random copolymer (A) using the method for producing a random copolymer of the present invention.

(2) Combine the random copolymer (A), colorant (B), alkali-soluble The step of mixing the resin (C) and the polymerizable compound (D) to obtain a resist composition.

(3) A step of forming the coating film layer of the above-mentioned resist composition on a substrate to obtain a substrate having a coating film layer.

(4) The step of drying (pre-baking) the above-mentioned coating layer to obtain a substrate with a dried coating layer.

(5) The step of exposing the desired pattern by using a photomask on the above-mentioned dried coating film layer.

(6) A step of performing development treatment using an alkaline developer.

(7) After washing (rinsing) with distilled water, a step of drying is performed.

The material of the above-mentioned substrate is not particularly limited as long as it is transparent and has moderate strength. Examples of materials include polyester resins such as polyethylene terephthalate; polyolefin resins such as polypropylene and polyethylene; polycarbonate resins; acrylic resins such as polymethyl methacrylate; Thermoplastic resin sheets such as resins; thermosetting resin sheets such as epoxy resins and unsaturated polyester resins; various glasses, etc. Among them, in terms of high heat resistance, glass and heat-resistant resin are preferred. For these transparent substrates, in order to improve surface properties such as adhesiveness, surface treatments such as corona discharge treatment, ozone treatment, and thin film formation treatments using various resins such as silane coupling agents or urethane resins may be performed as needed. The thickness of the transparent substrate is usually 0.05 mm or more, preferably 0.1 mm or more, and usually 10 mm or less, preferably 7 mm or less. In addition, in the case of performing thin film formation treatment using various resins, the film thickness is usually 0.01 μm or more, preferably 0.05 μm or more, and usually 10 μm or less, preferably 5 μm or less, and more preferably 1~ 2μm range.

The color filter can usually be manufactured by forming a coating film of a resist composition that forms the image of each pixel of red, green, and blue due to the black matrix provided on the above-mentioned substrate. Above black The matrix can also be formed using a light-shielding metal thin film. In the method of manufacturing the resist composition of the present invention, the resist composition obtained by using a black coloring agent as the colorant (B) can be used to form the resist composition on a transparent substrate.

As the light-shielding metal material that can be used to form the above-mentioned light-shielding metal film, for example, chromium compounds such as metallic chromium, chromium oxide, chromium nitride, or an alloy of nickel and tungsten can be used. It is composed of multiple layers. These light-shielding metal films are usually formed by sputtering.

For the above metal chromium, use an etching solution made by mixing cerium ammonium nitrate with perchloric acid and/or nitric acid. For other materials, use an etching solution corresponding to the material for etching, and finally use a special stripper to perform the resist composition Peel off, thereby forming a black matrix. In this case, the thin films of these metals or metal oxides are first formed on the transparent substrate by evaporation or sputtering. Then, a coating film layer of the color resist composition obtained by the manufacturing method of the present invention is formed on the film. Then, using a photomask with repeating patterns such as stripes, mosaics, triangles, etc., the coating layer is exposed and developed to form an image. After that, the coating layer can be etched to form a black matrix.

On a substrate with a black matrix, apply a resist composition containing a color material of one of red, green, and blue, and after drying, overlay a photomask on the coating layer, and perform the image through the photomask The image is exposed, developed, and thermally or photo-cured as necessary to form a pixel image to produce a colored layer. This operation is performed separately for the three-color resist composition of red, green, and blue, thereby forming a color filter image.

As a method of supplying the above-mentioned resist composition to the substrate, for example, the use of a gravure coater, a roll coater, a chipped wheel coater, a knife coater, a curtain coater, Spraying machine, spin coater, slit coater, slit-spin coater, slit die nozzle coater, dipping, screen printing, spray, applicator, bar coater, etc. Methods etc.

Regarding the thickness of the coating layer, if it is too thick, pattern development becomes difficult, and the gap adjustment in the liquid crystal cell formation step becomes difficult. On the other hand, if it is too thin, it is difficult to increase the pigment concentration, and the desired color appearance becomes It's impossible. Regarding the thickness of the coating film layer, as the film thickness after drying, it is usually in the range of 0.2 to 20 μm, preferably 0.5 to 10 μm, and more preferably 0.8 to 5 μm.

After coating the resist composition on the substrate and forming the coating film layer on the substrate, it is dried (pre-baked) in step (4). Drying (pre-baking) can be performed by heating for 10 to 300 seconds in a temperature range of 50 to 140° C. using a hot plate, oven, etc., for example. Among them, it is preferable to perform heating in a temperature range of 70 to 130°C for 30 to 180 seconds, and it is more preferable to perform heating in a temperature range of 80 to 120°C for 30 to 90 seconds. Moreover, in order to dry more completely, you may perform vacuum drying before drying (pre-baking).

After drying (pre-baking), use a photomask in step (5) to expose the desired pattern. Specifically, for example, a negative matrix pattern is superimposed on a dried (pre-baked) 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, in order to prevent the sensitivity of the coating film layer formed of the resist composition from decreasing due to oxygen, an oxygen blocking layer such as a polyvinyl alcohol layer is formed on the coating film layer and then exposed.

Examples of the above-mentioned active energy rays include active energy rays such as light, electron beams, and radiation. Specific energy sources or curing devices include, for example, germicidal lamps, ultraviolet fluorescent lamps, carbon arcs, xenon lamps, high-pressure mercury lamps for photocopying, medium or high pressure mercury lamps, ultra-high pressure mercury lamps, electrodeless lamps, and metal halide lamps. Lights, ultraviolet rays that use natural light as the light source, or Use scanning type, curtain type electron beam accelerator, etc. Furthermore, in the case of curing with an electron beam, it is not necessary to blend the above-mentioned resist composition with the above-mentioned polymerization initiator.

Among the above-mentioned active energy rays, ultraviolet rays are particularly preferred. In addition, if irradiated in an inert gas atmosphere such as nitrogen, the surface hardenability of the coating film is improved, which is preferable. In addition, if necessary, heat may be used as an energy source and used in combination, and after curing with active energy rays, heat treatment may be performed.

After exposure, the development process is carried out in step (6). In the above development process, the unexposed, unhardened part is eluted into the alkaline developing solution, and only the hardened part that has been photohardened remains. The alkaline developer can be used without particular limitation as long as it dissolves the unhardened part and does not dissolve the hardened part of each pixel part of RGB and the black matrix part. As a specific alkaline developer, for example, sodium hydroxide, potassium hydroxide, sodium carbonate, sodium bicarbonate, sodium silicate, sodium metasilicate, ammonia, ethylamine, diethylamine, dimethylethanolamine can be cited. , Tetramethylammonium hydroxide, tetraethylammonium hydroxide, choline, pyrrole, piperidine, 1,8-diazabicyclo-[5,4,0]-7-undecene and other basic compounds Aqueous solution. The alkali concentration of the alkaline developer is preferably 0.001 to 10% by mass, more preferably 0.01 to 1% by mass. In addition, the development temperature is usually 20°C to 30°C, and the development time is preferably in the range of 20 to 90 seconds.

After the development treatment, in step (7), it is washed (rinsed) with distilled water, and then dried. When washing and drying, post-baking can be carried out as needed. Post-baking is the heat treatment after development to complete the hardening, usually in the temperature range of 200~250℃. The post-baking treatment is performed in a continuous or batch manner using heating means such as a heating plate, a convection oven (hot air circulation type dryer), a high-frequency heater, and the like for the layer after development to meet the above conditions.

The substrate with transparent electrodes such as ITO formed on the pixels of the color filter fabricated in the above-mentioned manner is used as the substrate for sandwiching the liquid crystal layer with other substrates, and the backlight device, polarizing plate, and liquid crystal layer are combined to form the liquid crystal display of the present invention Device.

By mixing the random copolymer (A), colorant (B), and thermoplastic resin (E) of the present invention [thermoplastic resin other than the above-mentioned copolymer (A) and alkali-soluble resin (C)], Can be made into coating composition. Specifically, the coating composition described above can be obtained by a method comprising: polymerizing a fluorinated alkyl group having 1 to 6 carbon atoms directly bonded to a fluorine atom and a polymerizable unsaturated group The monomer (a1) and the polymerizable monomer (a2) with the backbone of the bridged cyclic hydrocarbon and the polymerizable unsaturated group carry out active free radicals in the coexistence of the polymerizable monomer (a1) and the polymerizable monomer (a2) A step of polymerization to obtain a random copolymer (A); and a step of mixing the random copolymer (A), colorant (B), and thermoplastic resin (E).

As the above-mentioned thermoplastic resin (E), for example, acrylic resin, methacrylic resin, urethane acrylate resin, acrylic polysiloxane resin, acrylic melamine resin, acrylic modified polyolefin, acrylic modified fluororesin, Aromatic polyester resin, aliphatic polyester resin, polyamide resin, polycarbonate resin, vinyl acetate resin, ethylene-vinyl acetate resin, etc. Among the thermoplastic resins (E), acrylic resins, methacrylic resins, or urethane acrylate resins are preferred in terms of obtaining a coating composition capable of obtaining a coating film layer with high strength.

Regarding the coating composition of the present invention, for example, the following method can be cited: the random copolymer (A), the colorant (B), and the thermoplastic resin (E) are dissolved in an organic solvent, and the coating composition is shaken by a shaker. Mixing by means of machine, using agitating blades, etc. As the organic solvent used here, for example, the organic solvent that can be used in the adjustment of the above-mentioned pigment dispersion can be used. Agent. The usage amount of the organic solvent is, for example, 100 to 1000 parts by mass relative to 100 parts by mass of the coating film layer forming components.

In the above-mentioned coating composition, the blending ratio when mixing the random copolymer (A), the coloring agent (B), and the thermoplastic resin (E) is, for example, 0.0001 to each in terms of solid content conversion. 10 parts by mass, 5 to 80 parts by mass, 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.

The above-mentioned coating composition can be used to manufacture an article with a coating film layer. The article with a coating film layer can be manufactured by forming the coating film layer of this coating composition on an article, for example. Examples of the above-mentioned articles include roofing materials (metal, slate, concrete, tiles, cement, plastic, etc.), walls, tiles, glass plates, metals, bearing blocks, concrete, plastics, cement, H-shaped steel, pipes Construction related items such as tubes, painted steel plates, signals, baffles, sandwich panels, grooves, etc.; car body exteriors, window glass, instrument panels, handles, gear levers, tires and other automotive related items: exteriors, window glass, etc. Aircraft-related items; air conditioners, front/back sheets for solar cells, computer or mobile phone casings, plasma displays (PDP) or organic EL displays and other display screens, CD or DVD or Blu-ray discs, photocopiers or printers, etc. Electrical related articles such as optical recording media such as rubber rollers for office automation equipment, the glass surface of the reading section of office automation equipment such as photocopiers or scanners: anti-reflection filtering of display devices such as CRT, liquid crystal display, plasma display, and projection TV Optical-related items such as lens parts such as optical devices, spherical lenses, aspheric lenses, Fresnel lenses, biconvex lenses, etc.

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

The thickness of the coating layer can be appropriately selected depending on the type of the article or the purpose of use, and it is usually 0.1-100μm as 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 type of the article or the purpose of use. For example, it can be exemplified: a method of natural drying by leaving it; or a method of forced drying in an environment of 40 to 300°C.

The random copolymer (A) of the present invention, the coloring agent (B), and the polymerizable compound (D) are mixed to form a coating composition. Specifically, the coating composition described above can be obtained by a method comprising: polymerizing a fluorinated alkyl group having 1 to 6 carbon atoms directly bonded to a fluorine atom and a polymerizable unsaturated group The monomer (a1) and the polymerizable monomer (a2) with the backbone of the bridged cyclic hydrocarbon and the polymerizable unsaturated group carry out active free radicals in the coexistence of the polymerizable monomer (a1) and the polymerizable monomer (a2) A step of polymerization to obtain a random copolymer (A); and a step of mixing the random copolymer (A), colorant (B), and polymerizable compound (D).

Regarding the coating composition, for example, the following method can be cited: the random copolymer (A), the colorant (B), and the polymerizable compound (D) are dissolved in an organic solvent as necessary, and the coating is shaken by a shaker. Mixing by means of machine, using agitating blades, etc. As the organic solvent used here, for example, an organic solvent that can be used in the adjustment of the above-mentioned pigment dispersion liquid can be used. In the case of using an organic solvent, the usage amount is, for example, 100 to 1000 parts by mass relative to 100 parts by mass of the coating film layer forming components.

When manufacturing the coating composition, the blending ratio when mixing the random copolymer (A), the coloring agent (B), and the polymerizable compound (D) is based on the solid content The conversion amount is, for example, 0.0001 to 10 parts by mass, 5 to 80 parts by mass, and 0.1 to 80 parts by mass, and preferably, for example, 0.001 to 5 parts by mass, 5 to 70 parts by mass, and 1 to 70 parts by mass, respectively.

By using the above coating composition, an article with a coating film layer can be obtained. Specifically, an article with a coating film layer can be manufactured by forming the coating film layer of the coating composition on the article, for example. As said article, the article mentioned above can be illustrated, for example.

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

The thickness of the coating layer can be appropriately selected depending on the type of the article or the purpose of use, and it is usually 0.1-100μm as the thickness after curing.

The above-mentioned coating layer is cured by irradiating energy rays. Examples of active energy rays include ionizing radiation such as ultraviolet rays, electron beams, α rays, β rays, and γ rays. Examples of active energy ray sources or curing devices include: germicidal lamps, ultraviolet fluorescent lamps, carbon arcs, xenon lamps, high-pressure mercury lamps for photocopying, medium or high pressure mercury lamps, ultra-high pressure mercury lamps, electrodeless lamps, and metal halides Lamps, ultraviolet rays using natural light as the light source, or electron beams using scanning or curtain electron beam accelerators.

Among them, ultraviolet light is particularly preferred. In order to avoid curing inhibition caused by oxygen or the like, it is preferred to irradiate ultraviolet rays under an inert gas environment such as nitrogen. Furthermore, if necessary, heat may be used as an energy source and used in combination, and after curing with ultraviolet rays, heat treatment may be performed.

The irradiation amount of the energy hardening rays only needs to be the irradiation amount at which the coating film layer is hardened, for example, in the range of 50 mJ/cm ² to 3000 mJ/cm ² .

[Example]

Examples and comparative examples are listed below to describe the present invention in further detail. In the examples, unless otherwise specified, parts and% are based on quality. The measurement conditions of IR spectrum, ¹³ C-NMR spectrum and GPC are as follows.

[IR spectrum measurement conditions]

Device: "FT/IR-6100" manufactured by JASCO Corporation

Measurement method: KBr method

[ ¹³ C-NMR spectrum measurement conditions]

Device: "JNM-AL400" manufactured by JEOL Ltd.

Solvent: chloroform-d ₆

[GPC measurement conditions]

Measuring device: "HLC-8220 GPC" manufactured by Tosoh Co., Ltd.,

Column: Protection column "HHR-H" (6.0mmI.D.×4cm) manufactured by Tosoh Co., Ltd. + "TSK-GEL GMHHR-N" (7.8mmI.D.×30cm) manufactured by Tosoh Co., Ltd. +"TSK-GEL GMHHR-N" (7.8mmI.D.×30cm) made by Tosoh Co., Ltd.+"TSK-GEL GMHHR-N" (7.8mmI.D.×30cm) made by Tosoh Co., Ltd.+Tosoh "TSK-GEL GMHHR-N" manufactured by Co., Ltd. (7.8mmI.D.×30cm)

Detector: ELSD ("ELSD2000" manufactured by Alltech Japan Co., Ltd.)

Data processing: "GPC-8020 Model II Data Analysis Version 4.30" manufactured by Tosoh Co., Ltd.

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

Standard sample: According to the measurement guide of "GPC-8020 Model II Data Analysis Version 4.30", the following monodisperse polystyrene with known molecular weight is used.

(Monodisperse polystyrene)

"A-500" manufactured by Tosoh Co., Ltd.

"A-1000" manufactured by Tosoh Co., Ltd.

"A-2500" manufactured by Tosoh Co., Ltd.

"A-5000" manufactured by Tosoh Co., Ltd.

"F-1" manufactured by Tosoh Co., Ltd.

"F-2" manufactured by Tosoh Co., Ltd.

"F-4" manufactured by Tosoh Co., Ltd.

"F-10" manufactured by Tosoh Co., Ltd.

"F-20" manufactured by Tosoh Co., Ltd.

"F-40" manufactured by Tosoh Co., Ltd.

"F-80" manufactured by Tosoh Co., Ltd.

"F-128" manufactured by Tosoh Co., Ltd.

"F-288" manufactured by Tosoh Co., Ltd.

"F-550" manufactured by Tosoh Co., Ltd.

Reference manufacturing example 1 (manufacturing of pigment dispersion)

Put 10g of C.I.Pigment Red254 ("IRGAPHOR RED BT-CF" manufactured by BASF Corporation) as a red pigment into a polyethylene bottle, and add PGMEA 44g, DISPERBYK 12 g of LPN21116 (manufactured by BYK-Chemie Co., Ltd.) and Sepul Beads of 0.3-0.4 mmΦ were dispersed using a paint conditioner (manufactured by Toyo Seiki Co., Ltd.) for 2 hours to obtain a red pigment dispersion (1).

Reference manufacturing example 2 (same as above)

Put 10 g of CIPigment Yellow129 ("Irgazin Yellow L0800" manufactured by Ciba Specialty Chemicals) as a yellow pigment into a polyethylene bottle, and add 67 g of PGMEA, 23 g of DISPERBYK 161 (manufactured by BYK-Chemie Co., Ltd.), and 0.3- Sepul Beads of 0.4mmΦ were dispersed for 2 hours using a paint conditioner (manufactured by Toyo Seiki Co., Ltd.) to obtain a yellow pigment dispersion (2).

Reference manufacturing example 3 (same as above)

Except using C.I. Pigment Yellow 138 ("Paliotol Yellow K0961HD" manufactured by BASF Corporation) as the yellow pigment, a yellow pigment dispersion liquid (3) was obtained in the same manner as in Reference Manufacturing Example 2.

Reference manufacturing example 4 (same as above)

Except for using C.I. Pigment Yellow139 ("Paliotol Yellow D1819" manufactured by BASF Corporation) as the yellow pigment, a yellow pigment dispersion (4) was obtained in the same manner as in Reference Manufacturing Example 2.

Reference manufacturing example 5 (same as above)

Except using C.I. Pigment Yellow 150 ("E4GNGT" manufactured by Lanxess Corporation) as the yellow pigment, a yellow pigment dispersion (5) was obtained in the same manner as in Reference Manufacturing Example 2.

Reference manufacturing example 6 (same as above)

Use C.I.Pigment Yellow185 ("Paliotol Yellow D1155" made by BASF) As the yellow pigment, except for this, a yellow pigment dispersion liquid (6) was obtained in the same manner as in Reference Production Example 2.

Reference Manufacturing Example 7 (Synthesis of alkali-soluble resin)

100 g of propylene glycol monomethyl ether acetate was added to a four-necked flask equipped with a stirrer, a thermometer, a cooling tube, and a nitrogen introduction tube, and the internal temperature was raised to 110° C. while stirring under nitrogen flow. Next, a mixed liquid 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 tertiary amyl peroxy 2-ethylhexanoate, and peroxybenzoic acid The mixture composed of 0.15 g of tertiary amyl ester was dropped over 4 hours. After the dripping, the polymerization reaction was carried out for 8 hours while maintaining the internal temperature at 110°C. After the reaction, it is diluted with propylene glycol monomethyl ether acetate to obtain a resin solution of an alkali-soluble resin with a non-volatile content of 40%. The weight average molecular weight of this resin is 17,000.

Example 1 (Manufacturing of Random Copolymer)

To a flask replaced with nitrogen, 111 g of methyl ethyl ketone, 47 g of 1-adamantyl methacrylate, and 25 g of 2-(tridecafluorohexyl) ethyl methacrylate were added as solvents, and proceeded under nitrogen flow. The temperature was raised to 60°C while stirring. Then, 5 g of 2,2'-bipyridine, 2 g of cuprous chloride, and 3.3 g of ethyl 2-bromoisobutyrate were added, and the reaction was carried out at 60° C. for 23 hours under a nitrogen stream. Then, 30 g of activated alumina was added to the obtained reactant and stirred. After filtering the activated alumina, the solvent was distilled off under reduced pressure to obtain a random copolymer (1). The results obtained by measuring the molecular weight of the random copolymer (1) by GPC were that the weight average molecular weight (Mw) was 4,133, the number average molecular weight (Mn) was 3,197, and (Mw/Mn) was 1.29. In addition, the fluorine atom content of the random copolymer (1) is 20% by mass. The line diagram of the IR spectrum of the random copolymer (1) is shown in FIG. 1, the line diagram of the ¹³ C-NMR spectrum is shown in FIG. 2, and the line diagram of GPC is shown in FIG. 3.

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

<The evaluation method of the smoothness of the coating layer>

Combine 3g of alkali-soluble resin (copolymer of benzyl methacrylate and acrylic acid), a mixture of dineopentaerythritol pentaerythritol pentaacrylate acid and dineopentaerythritol hexaacrylate acid, namely ARONIX M-402 (Toya Synthetic Chemical Co., Ltd. Company make) 1.2 g, random copolymer (1) 0.002 g in solid content conversion, and 8.1 g of propylene glycol monomethyl ether acetate (PGMEA) were mixed to obtain a composition. Drop 3ml of the composition onto the central part of a 10cm×10cm chrome-plated glass substrate, spin-coated at 500 rpm and 30 seconds, and then heat and dry at 110°C for 2 minutes to produce a coating film Layer of items. The coating film layer was visually observed, and the smoothness of the coating film layer was evaluated based on the following criteria. The evaluation results are shown in Table 1.

<Evaluation criteria for smoothness of coating layer>

○: Almost no unevenness in the coating film is observed.

△: Partial coating film unevenness is observed.

×: A large amount of unevenness in the coating film is observed.

Example 2 (same as above)

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

Example 3 (same as above)

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

Example 4 (same as above)

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

Comparative example 1 (manufacturing of copolymer for comparison and control)

67 g of methanol, 0.961 g of 2,2'-bipyridine, and 0.305 g of cuprous chloride were added to the reaction vessel replaced with nitrogen, and the mixture was stirred at room temperature for 60 minutes. Thereafter, 3.37 g of 2-(nonafluorobutyl) ethyl methacrylate, 3.33 g of 2-(tridecafluorohexyl) ethyl methacrylate, and poly(1,2-oxybutene) propylene glycol monomethyl Acrylate ("Blemmer 10PPB-500B" manufactured by NOF Corporation; oxybutylene) average repeat number 6) 13.3g, polyethylene glycol monomethacrylate ("Blemmer PE manufactured by NOF Corporation" -200"; the average repetition number of oxyethylene 4.5) 20 g, 2-bromoisobutyrate ethyl 0.6 g, reacted at 60°C for 10 hours under a nitrogen stream. Then, 30 g of activated alumina was added to the obtained reactant and stirred. After filtering the activated alumina, the solvent was distilled off under reduced pressure to obtain a comparative copolymer (1') that does not have a bridged ring structure. As a result of measuring the molecular weight of the comparative copolymer (1') by GPC, the weight average molecular weight (Mw) was 17,000, the number average molecular weight (Mn) was 13,000, and (Mw/Mn) was 1.25. In addition, the fluorine atom content was 9.1% by mass. The smoothness of the coating film layer was evaluated in the same manner as in Example 1, and the results are shown in Table 1.

Comparative Example 2 (Manufacture of block polymer for comparison and control)

Add 47.5 g of 2-propanol and 3 methacrylic acid as a solvent to a flask replaced by nitrogen -25.6 g of hydroxy-1-adamantyl ester, heated to 40°C while stirring under nitrogen flow. Then, 5.3 g of 2,2'-bipyridine and 1.9 g of cuprous chloride were added, and the flask was 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 performed at 40°C for 2 hours under a nitrogen stream to obtain a polymer segment containing an adamantane ring. Then, 45.9 g of 2-(tridecafluorohexyl)ethyl methacrylate was added to the reaction system containing the polymer segment, and reacted at 40°C for 5 hours to obtain a reactant. Then, 30 g of activated alumina was added to the obtained reactant and stirred. After filtering the activated alumina, the solvent was distilled off under reduced pressure to obtain a comparative copolymer (2'). The result of measuring the molecular weight of the comparative copolymer (2') by GPC was that the weight average molecular weight (Mw) was 3,100, the number average molecular weight (Mn) was 2,700, and (Mw/Mn) was 1.15. In addition, the fluorine atom content was 14.5% by mass. The smoothness of the coating film layer was evaluated in the same manner as in Example 1, and the results are shown in Table 1.

Example 5 (manufacturing of resist composition)

With respect to 5.9 g of the red pigment dispersion (1), 1.5 g of the 40% by mass resin solution of the alkali-soluble resin obtained in Reference Production Example 7, dineopentaerythritol pentaacrylate acid and dineopentaerythritol hexadecyl A mixture of acrylate acids, 0.6 g of ARONIX M-402 (manufactured by Toa Synthetic Chemical Co., Ltd.), Irgacure #369 manufactured by BASF Japan Co., Ltd. as a photopolymerization initiator 0.05 g, random copolymer (1) The solid content is converted to 0.0014g, and PGMEA 2.2 g and mixed to prepare a color resist composition (1). The color resist composition (1) is used to produce the coating film layer. According to the following method, the ability to inhibit the generation of foreign matter (the foreign matter derived from the pigment) in the coating film layer (inhibition) and the alkalinity of the coating film layer The developability of the solution was evaluated.

<Method for evaluating the inhibition of foreign matter in the coating layer>

The color resist composition (1) was spin-coated on a 7cm×7cm glass plate under the conditions of a rotation speed of 1000 rpm and a rotation time of 10 seconds, and then dried at 80°C for 3 minutes to obtain a dry coating film layer article. For the dried coating layer, use a high-pressure mercury lamp to irradiate active energy rays at 50 mJ/cm ² to obtain an article with a hardened coating layer. After that, the article was heated at 270°C for 1 hour, and then the coating layer was observed with a digital microscope VHX-900 manufactured by Keynes, and evaluated based on the following criteria. The evaluation results are shown in Table 2.

○: No more than one foreign matter can be confirmed in the coating layer of 1cm×1cm square.

△: There are 2-9 foreign objects that can be confirmed in the coating layer of 1cm×1cm square.

×: The number of foreign objects that can be confirmed in the coating layer of 1cm×1cm square is more than 10 on average.

<The evaluation method of the developability of the coating layer>

The color resist composition (1) was spin-coated on a 7cm×7cm glass plate under the conditions of a rotation speed of 1000 rpm and a rotation time of 10 seconds, and then dried at 80°C for 3 minutes to obtain a dry coating film layer article. For the dried coating layer, use a 20-fold diluted aqueous solution of Semi Clean DL-A4 (alkaline developer manufactured by Yokohama Oil & Fat Co., Ltd.) for spray development (200 rpm, 45 seconds), and then visually observe The following criteria evaluate the residual film rate of the dried coating film.

○: The residual film rate is less than 10%.

△: The residual film rate is 10-50%.

×: The residual film rate is greater than 50%.

Example 6 (same as above)

Relative to 6.2g of yellow pigment dispersion (2), 1.2g of alkali-soluble resin (copolymer of benzyl methacrylate and acrylic acid), 0.6g of ARONIX M-402, and BASF Japan Co., Ltd. as a photopolymerization initiator are added 0.05 g of Irgacure #369 manufactured by the company, 0.0017 g of the random copolymer (1) in terms of solid content, and 2.2 g of PGMEA were mixed to prepare a color resist composition (2). The coating film layer was produced in the same manner as in Example 5, and the ability to suppress the generation of foreign matter (pigment-derived foreign matter) in the coating film layer (inhibition property) and the developability of the coating film with an alkaline solution were evaluated. The evaluation results are shown in Table 2.

Example 7 (same as above)

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

Example 8 (same as above)

The 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). The coating film layer was produced in the same manner as in Example 5, and the ability to suppress the generation of foreign matter (pigment-derived foreign matter) in the coating film layer (inhibition property) and the developability of the coating film with an alkaline solution were evaluated. The evaluation results are shown in Table 2.

Example 9 (same as above)

Use yellow pigment dispersion (5) instead of yellow pigment dispersion (2), in addition to that, The color resist composition (5) was prepared in the same manner as in Example 6. The coating film layer was produced in the same manner as in Example 5, and the ability to suppress the generation of foreign matter (pigment-derived foreign matter) in the coating film layer (inhibition property) and the developability of the coating film with an alkaline solution were evaluated. The evaluation results are shown in Table 2.

Example 10 (same as above)

Except that the yellow pigment dispersion liquid (6) was used instead of the yellow pigment dispersion liquid (2), a color resist composition (6) was prepared in the same manner as in Example 6. The coating film layer was produced in the same manner as in Example 5, and the ability to suppress the generation of foreign matter (pigment-derived foreign matter) in the coating film layer (inhibition property) and the developability of the coating film with an alkaline solution were evaluated. The evaluation results are shown in Table 2.

Example 11 (same as above)

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

Example 12 (same as above)

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

Example 13 (same as above)

The random copolymer (4) is used instead of the random copolymer (1). Otherwise, the same as in Example 5 The color resist composition (9) was prepared in the same manner. The coating film layer was produced in the same manner as in Example 5, and the ability to suppress the generation of foreign matter (pigment-derived foreign matter) in the coating film layer (inhibition property) and the developability of the coating film with an alkaline solution were evaluated. The evaluation results are shown in Table 2.

Comparative example 3 (manufacturing of resist composition for comparative control)

Except that the copolymer (1') for comparison and control was used instead of the random copolymer (1), the color resist composition (1') for comparison and control was prepared in the same manner as in Example 5. The coating film layer was produced in the same manner as in Example 5, and the ability to suppress the generation of foreign matter (pigment-derived foreign matter) in the coating film layer (inhibition property) and the developability of the coating film with an alkaline solution were evaluated. The evaluation results are shown in Table 3.

Comparative example 4 (same as above)

Except that the copolymer (1') for comparison and control was used instead of the random copolymer (1), in the same manner as in Example 6, a color resist composition (2') for comparison and control was prepared. The coating film layer was produced in the same manner as in Example 5, and the ability to suppress the generation of foreign matter (pigment-derived foreign matter) in the coating film layer (inhibition property) and the developability of the coating film with an alkaline solution were evaluated. The evaluation results are shown in Table 3.

Comparative example 5 (same as above)

The yellow pigment dispersion (3) was used instead of the yellow pigment dispersion (2), and the comparative copolymer (1') was used instead of the random copolymer (1), except that the same as in Example 6 In this way, a color resist composition (3') for comparison and control was prepared. The coating film layer was produced in the same manner as in Example 5, and the ability to suppress the generation of foreign matter (pigment-derived foreign matter) in the coating film layer (inhibition property) and the developability of the coating film with an alkaline solution were evaluated. The evaluation results are shown in Table 3.

Comparative example 6 (same as above)

The yellow pigment dispersion (4) was used instead of the yellow pigment dispersion (2), and the comparative copolymer (1') was used instead of the random copolymer (1), except that the same as in Example 6 In this way, a color resist composition (4') for comparison and control was prepared. The coating film layer was produced in the same manner as in Example 5, and the ability to suppress the generation of foreign matter (pigment-derived foreign matter) in the coating film layer (inhibition property) and the developability of the coating film with an alkaline solution were evaluated. The evaluation results are shown in Table 3.

Comparative example 7 (same as above)

The yellow pigment dispersion (5) was used instead of the yellow pigment dispersion (2), and the comparative copolymer (1') was used instead of the random copolymer (1), except that the same as in Example 6 In this way, a color resist composition (5') for comparison and control was prepared. The coating film layer was produced in the same manner as in Example 5, and the ability to suppress the generation of foreign matter (pigment-derived foreign matter) in the coating film layer (inhibition property) and the developability of the coating film with an alkaline solution were evaluated. The evaluation results are shown in Table 3.

Comparative example 8 (same as above)

The yellow pigment dispersion (6) was used instead of the yellow pigment dispersion (2), and the comparative copolymer (1') was used instead of the random copolymer (1), except that the same as in Example 6 In this way, a color resist composition (6') for comparison and control was prepared. The coating film layer was produced in the same manner as in Example 5, and the ability to inhibit the generation of foreign matter (foreign matter derived from the pigment) in the coating film layer (inhibition) And evaluation of the developability of the coating film with alkaline solution. The evaluation results are shown in Table 3.

Comparative Example 9 (same as above)

Except for using the copolymer (2') for comparison and control instead of the random copolymer (1), a color resist composition (7') for comparison and control was prepared in the same manner as in Example 5. The coating film layer was produced in the same manner as in Example 5, and the ability to suppress the generation of foreign matter (pigment-derived foreign matter) in the coating film layer (inhibition property) and the developability of the coating film with an alkaline solution were evaluated. The evaluation results are shown in Table 4.

Comparative Example 10 (same as above)

Except that the copolymer (2') for comparison and control was used instead of the random copolymer (1), the color resist composition (8') for comparison and control was prepared in the same manner as in Example 6. The coating film layer was produced in the same manner as in Example 5, and the ability to suppress the generation of foreign matter (pigment-derived foreign matter) in the coating film layer (inhibition property) and the developability of the coating film with an alkaline solution were evaluated. The evaluation results are shown in Table 4.

Comparative Example 11 (same as above)

Use the yellow pigment dispersion (3) instead of the yellow pigment dispersion (2), and use the comparative copolymer (2') instead of the random copolymer (1), except that the same as in Example 6 Method Prepare the color resist composition (9') for comparison and control. The coating film layer was produced in the same manner as in Example 5, and the ability to suppress the generation of foreign matter (pigment-derived foreign matter) in the coating film layer (inhibition property) and the developability of the coating film with an alkaline solution were evaluated. The evaluation results are shown in Table 4.

Comparative example 12 (same as above)

The yellow pigment dispersion (4) was used instead of the yellow pigment dispersion (2), and the comparative copolymer (2') was used instead of the random copolymer (1), except that the same as in Example 6 Method Prepare a color resist composition (10') for comparison and control. The coating film layer was produced in the same manner as in Example 5, and the ability to suppress the generation of foreign matter (pigment-derived foreign matter) in the coating film layer (inhibition property) and the developability of the coating film with an alkaline solution were evaluated. The evaluation results are shown in Table 4.

Comparative Example 13 (same as above)

The yellow pigment dispersion (5) was used instead of the yellow pigment dispersion (2), and the comparative copolymer (2') was used instead of the random copolymer (1), except that the same as in Example 6 In this way, a color resist composition (11') for comparison and control was prepared. The coating film layer was produced in the same manner as in Example 5, and the ability to suppress the generation of foreign matter (pigment-derived foreign matter) in the coating film layer (inhibition property) and the developability of the coating film with an alkaline solution were evaluated. The evaluation results are shown in Table 4.

Comparative Example 14 (same as above)

The yellow pigment dispersion (6) was used instead of the yellow pigment dispersion (2), and the comparative copolymer (2') was used instead of the random copolymer (1), except that the same as in Example 6 Method Prepare the color resist composition (12') for comparison and control. The coating film layer was produced in the same manner as in Example 5, and the ability to suppress the generation of foreign matter (pigment-derived foreign matter) in the coating film layer (inhibition property) and the developability of the coating film with an alkaline solution were evaluated. The evaluation results are shown in Table 4.

Claims (14)

A color resist composition comprising: a random copolymer (A), a pigment (B), an alkali-soluble resin (C) and a polymerizable compound (D), the random copolymer (A) is a polymerizable monomer A random copolymer formed by living radical polymerization of body (a1) and polymerizable monomer (a2), and the ratio of weight average molecular weight (Mw) to number average molecular weight (Mn) (Mw/Mn) is 1.0~1.8 , The polymerizable monomer (a1) has a fluorinated alkyl group having 1 to 6 carbon atoms directly bonded to a fluorine atom and a polymerizable unsaturated group, and the polymerizable monomer (a2) has a bridged ring hydrocarbon Skeleton and polymerizable unsaturated group. For example, the color resist composition of item 1 of the scope of patent application, wherein the bridged cyclic hydrocarbon skeleton of the polymerizable monomer (a2) is an adamantane ring, a dicyclopentane ring, a dicyclopentene ring, and a

Alkane (norbornane) ring or norbornene ring. Such as the color resist composition of item 1 in the scope of patent application, wherein the bridged cyclic hydrocarbon skeleton of the polymerizable monomer (a2) is an adamantane ring. For example, the color resist composition of item 1 of the scope of patent application, wherein the polymerizable monomer (a1) is a monomer represented by the following general formula (1),

[In the general formula (1), R ¹ represents a hydrogen atom, a fluorine atom, a methyl group, a cyano group, a phenyl group, a benzyl group or -C _n H _2n -Rf' (n represents an integer from 1 to 8, Rf' represents Any one of the following formulas (Rf-1)~(Rf-4)), X represents any one of the following formulas (X-1)~(X-10), Rf represents the following formula (Rf -1)~(Rf-4) any one]; -OC _n H _2n- (X-1) -OCH ₂ CH ₂ OCH _2- (X-2)

[The n in the formulas (X-1), (X-3), (X-4), (X-5), (X-6) and (X-7) represents an integer from 1 to 8, the formula In (X-8), (X-9) and (X-10), m represents an integer from 1 to 8, and n represents an integer from 0 to 8. In the formula (X-6) and (X-7), Rf" represents any one of the following formulas (Rf-1)~(Rf-4)]; -C _n F _2n+1 (Rf-1) -C _n F _2n H (Rf-2) -C _n F _2n-1 (Rf-3) -C _n F _2n-3 (Rf-4) [In the formulas (Rf-1) and (Rf-2), n represents an integer from 1 to 6, the formula (Rf- 3) where n represents an integer from 2 to 6, and n in the formula (Rf-4) represents an integer from 4 to 6]. For example, the color resist composition of item 1 in the scope of patent application, wherein the ratio (Mw/Mn) of the weight average molecular weight (Mw) of the random copolymer (A) to the number average molecular weight (Mn) is 1.0 to 1.5. For example, the color resist composition of item 1 of the scope of patent application, wherein the pigment (B) is selected from CI Pigment Red 177, CI Pigment Red 207, CI Pigment Red 254, CI Pigment Green 7, CI Pigment Green 36, CI Pigment Green 58, CI Pigment Green 59, CI 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 Yellow 154, CI Pigment Yellow 180, CI Pigment Yellow 185, CI Pigment Blue 15:1, CI Pigment Blue 15:2, CI Pigment Blue 15:6 and CI Pigment Violet 23 are pigments of more than one kind. A color filter is formed with a coating film layer of the color resist composition of any one of items 1 to 6 in the scope of patent application on a substrate. A method for manufacturing a color resist composition, which is a method for manufacturing a color resist composition containing a random copolymer (A), a pigment (B), an alkali-soluble resin (C) and a polymerizable compound (D), and Features are: The random copolymer (A) is made by making polymerizable monomer (a1) and polymerizable monomer (a2) in the coexistence of polymerizable monomer (a1) and polymerizable monomer (a2) to carry out living radicals Manufactured by polymerization, the polymerizable monomer (a1) has a fluorinated alkyl group having 1 to 6 carbon atoms directly bonded to a fluorine atom and a polymerizable unsaturated group, and the polymerizable monomer (a2) has a bridge The backbone of the cyclic hydrocarbon and the polymerizable unsaturated group. For example, the manufacturing method of the color resist composition of item 8 of the scope of patent application, wherein the skeleton of the bridged cyclic hydrocarbon of the polymerizable monomer (a2) is an adamantane ring, a dicyclopentane ring, and a dicyclopentene Ring, drop

Alkyl ring or norbornene ring. For example, the manufacturing method of the color resist composition of item 8 of the scope of patent application, wherein the backbone of the bridged cyclic hydrocarbon of the polymerizable monomer (a2) is an adamantane ring. For example, the manufacturing method of the color resist composition of item 8 of the scope of patent application, wherein the polymerizable monomer (a1) is a monomer represented by the following general formula (1),

[In the general formula (1), R ¹ represents a hydrogen atom, a fluorine atom, a methyl group, a cyano group, a phenyl group, a benzyl group or -C _n H _2n -Rf' (n represents an integer from 1 to 8, Rf' represents Any one of the following formulas (Rf-1)~(Rf-4)), X represents any one of the following formulas (X-1)~(X-10), Rf represents the following formula (Rf -1)~(Rf-4) any one]; -OC _n H _2n- (X-1) -OCH ₂ CH ₂ OCH _2- (X-2)

[In the formulas (X-1), (X-3), (X-5), (X-6) and (X-7), n represents an integer from 1 to 8, the formula (X-8), The m in (X-9) and (X-10) represents an integer from 1 to 8, and n represents an integer from 0 to 8. The Rf" in the formulas (X-6) and (X-7) represents the following formula (Rf-1)~(Rf-4) any base]; -C _n F _2n+1 (Rf-1) -C _n F _2n H (Rf-2) -C _n F _2n-1 (Rf -3) -C _n F _2n-3 (Rf-4) [The _{n in} the formula (Rf-1) and (Rf-2) represents an integer from 1 to 6, and the n in the formula (Rf-3) represents An integer from 2 to 6, where n in the formula (Rf-4) represents an integer from 4 to 6]. For example, the manufacturing method of the color resist composition of item 8 of the scope of patent application, wherein the living radical polymerization is atom transfer radical polymerization. For example, the manufacturing method of the color resist composition of item 8 of the scope of patent application, which is to make the polymerizable monomer (a1) and polymerizable monomer (a2) in the polymerization initiator, transition metal compound, and the Atom transfer radical polymerization is carried out in the presence of a compound of a transition metal coordinated and a ligand and a solvent. For example, the manufacturing method of the color resist composition of item 8 of the scope of the patent application uses 50 to 900 parts by mass of the polymerizable monomer (a2) relative to 100 parts by mass of the polymerizable monomer (a1).

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