JP2021099394A - Colored composition, cured colored film, and color filter, display element, light receiving element and light emitting element - Google Patents

Abstract

To provide a colored composition allowing for formation of colored film which is suppressed in light leakage in display of black and has a superior contrast ratio.SOLUTION: A colored composition is provided in which a colorant includes a quinophthalone compound represented by a formula (1) below.SELECTED DRAWING: None

Description

The present invention relates to a coloring composition, a colored cured film, and a color filter, a display element, a light receiving element, and a light emitting element. More specifically, a transmissive or reflective color liquid crystal display element, a solid-state imaging element, and an organic EL display element. , A coloring composition used for forming a colored cured film used for electronic paper, a colored cured film which is a cured product of the coloring composition, and a color filter, a display element, a light receiving element, and a color filter provided with the colored cured film. Regarding the light emitting element.

A color filter of a liquid crystal display device or the like has a red pixel (R), a green pixel (G), and a blue pixel (B), and each of these pixels cures a coloring composition in which an organic pigment is dispersed. It has a structure in which a film is provided on a substrate. As the organic pigment, organic pigments of each color of red, green and blue are used. For example, when forming green pixels, C.I. I. Pigment Green 7, C.I. I. A green pigment such as Pigment Green 36 is used. However, since it is difficult to sufficiently obtain the desired characteristics such as color reproducibility and contrast ratio with only the green pigment, C.I. I. Pigment Green 7 and C.I. I. At least one green pigment selected from Pigment Green 36 and C.I. I. Pigment Yellow 139, C.I. I. Pigment Yellow 150 and C.I. I. It has been proposed to adjust the emission spectrum by combining with at least one yellow pigment selected from Pigment Yellow 185 (Patent Document 1).

Japanese Unexamined Patent Publication No. 2010-26268

The pixels of the color filter are normally displayed in black (dark state) when the applied voltage is low or when the voltage is not applied, but black is displayed in the color filter including the green pixels containing the metal halide phthalocyanine pigment as the colorant. Even if an attempt is made, the present inventors have found that a phenomenon in which a slight amount of light leaks from a green pixel and appears to be tinged with green (hereinafter referred to as "light leakage") is likely to occur specifically.
An object of the present invention is to provide a coloring composition capable of forming a colored cured film having an excellent contrast ratio while suppressing light leakage in black display. Further, an object of the present invention is to provide a colored cured film formed by using the colored composition, and a color filter, a display element, a light receiving element, and a light emitting element provided with the colored cured film.

As a result of detailed studies in view of such circumstances, the present inventors have added a metal halide phthalocyanine pigment as a colorant together with a binder resin and a polymerizable compound, and have determined a specific structure for the metal halide phthalocyanine pigment. It has been found that a coloring composition capable of forming a colored cured film having an excellent contrast ratio while suppressing light leakage in black display can be obtained by containing the quinophthalone compound having a specific amount ratio.

That is, the present invention is a coloring composition containing (A) a colorant containing a metal halide phthalocyanine pigment, (B) a binder resin, and (C) a polymerizable compound.
(A) The colorant further contains a quinophthalone compound represented by the following formula (1).
(A ¹⁾ and the halogenated metal phthalocyanine pigment, in (A ²⁾ mass ratio of the quinophthalone compound represented by the following formula ^{(1) [(A 1)} / (A 2)] is 99 / 1-85 / 15 It provides a certain coloring composition.

[In equation (1),
R ^{1 to} R ¹³ are independently hydrogen atom; halogen atom; alkyl group which may have a substituent; alkoxy group which may have a substituent; and an aryl group which may have a substituent; showing a or an optionally substituted sulfamoyl group; -SO ₃ H, -COOH or a monovalent to trivalent metal salt or alkyl ammonium salt thereof acidic group; an optionally substituted phthalimidomethyl group .. However, ^{at least one adjacent set of groups from R 1 to} R ⁴ and / or at least one adjacent set of groups from R ^{10 to} R ¹³ together have a substituent. Form an aromatic ring which may be used. ]

The present invention also provides a colored cured film which is a cured product of the colored composition, and a color filter, a display element, a light receiving element, and a light emitting element provided with the colored cured film. Here, examples of the colored cured film include each color pixel used in a display element and a solid-state image pickup device, a bank (partition wall) that defines a region for forming a light emitting layer, a black matrix, and the like. Above all, it is preferable that the green pixels of the color filter used for the display element and the solid-state image pickup element are used because the effects of the present invention can be easily enjoyed.

According to the present invention, it is possible to provide a coloring composition capable of forming a colored cured film having an excellent contrast ratio while suppressing light leakage in black display. Therefore, the coloring composition of the present invention can be extremely suitably used for manufacturing a color liquid crystal display element, an organic EL display element, a display element such as electronic paper, and a solid-state image sensor such as a CMOS image sensor.

Hereinafter, the present invention will be described in detail.
Coloring Composition- (A) Colorant-

The (A) colorant according to the present invention contains (A ¹ ) a metal halide phthalocyanine pigment.
(A ¹ ) Metal halide Examples of the metal constituting the phthalocyanine pigment include zinc, copper, aluminum, magnesium, titanium, vanadium, manganese, iron, cobalt, nickel, tin, germanium, indium and the like. ^{Examples of the (A 1} ) halogenated metal phthalocyanine pigment having such a metal include zinc halide phthalocyanine pigment, copper halide phthalocyanine pigment, magnesium halide phthalocyanine pigment, aluminum halide phthalocyanine pigment, titanium halide phthalocyanine pigment, and halogenated. Vanadium phthalocyanine pigments, manganese halogenated phthalocyanine pigments, iron halide phthalocyanine pigments, cobalt halide phthalocyanine pigments, nickel halide phthalocyanine pigments, tin halide phthalocyanine pigments, germanium phthalocyanine halogenated pigments, indium halogenated indium phthalocyanine pigments, etc. it can.
Examples of the halogen constituting the (A ¹ ) metal halide phthalocyanine pigment include fluorine, chlorine, bromine and iodine, and one or more of them can be used. Of these, chlorine and bromine are preferable.

Among them, as the (A ¹ ) metal halide phthalocyanine pigment, one selected from copper halide phthalocyanine pigment, zinc halide phthalocyanine pigment and aluminum halide aluminum phthalocyanine pigment from the viewpoint of suppressing light leakage and improving the contrast ratio. Alternatively, two or more are preferable, and zinc halide phthalocyanine pigments and aluminum halogenated aluminum phthalocyanine pigments are more preferable, from brominated zinc phthalocyanine pigments, brominated chlorinated zinc phthalocyanine pigments, brominated aluminum phthalocyanine pigments and brominated chlorinated aluminum phthalocyanine pigments. At least one selected is more preferable, and a brominated chlorinated zinc phthalocyanine pigment and a brominated chlorinated aluminum phthalocyanine pigment are even more preferable.
As the brominated chlorinated zinc phthalocyanine pigment and the brominated chlorinated aluminum phthalocyanine pigment, the brominated chlorinated zinc phthalocyanine pigment represented by the following formula (2) is preferable, and for example, in the color index (CI) name, C. I. Pigment Green 58, C.I. I. Pigment Green 59, C.I. I. It can be obtained as a pigment classified into Pigment Green 62.

[In equation (2),
M represents zinc or aluminum.
X independently represents a hydrogen atom, a chlorine atom or a bromine atom. However, of all X, at least one is a chlorine atom, 10 to 15 are bromine atoms, and the remainder is a hydrogen atom. ]

In the formula (2), it is preferable that the number of chlorine atoms is 1 to 6 among all Xs. In this case, the bromine atom can be appropriately selected within the range of 10 to 15 so that the total number of X is 16, and even if all X are composed of bromine atom and chlorine atom. Good.

In the present invention, the ^{metal halide phthalocyanine pigment (A 1} ) may contain one kind or two or more kinds.

The (A) colorant according to the present invention further contains (A ² ) a quinophthalone compound represented by the following formula (1) (hereinafter, ^{also referred to as “(A 2} ) quinophthalone compound”).

[In equation (1),
R ^{1 to} R ¹³ are independently hydrogen atom; halogen atom; alkyl group which may have a substituent; alkoxy group which may have a substituent; and an aryl group which may have a substituent; showing a or an optionally substituted sulfamoyl group; -SO ₃ H, -COOH or a monovalent to trivalent metal salt or alkyl ammonium salt thereof acidic group; an optionally substituted phthalimidomethyl group .. However, ^{at least one adjacent set of groups from R 1 to} R ⁴ and / or at least one adjacent set of groups from R ^{10 to} R ¹³ together have a substituent. Form an aromatic ring which may be used. ]

Examples of the halogen atom in R ^{1 to} R ¹³ include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. Of these, chlorine atoms and bromine atoms are preferable.
The alkyl group in R ^{1 to} R ¹³ may be in either a linear form or a branched chain form, and the number of carbon atoms is preferably 1 to 30, more preferably 1 to 20, further preferably 1 to 12, and 1 to 6 Is particularly preferable. Specific examples of the alkyl group include, for example, a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, a hexyl group, a heptyl group, an octyl group and a nonyl group. Decyl group, undecyl group, 1-methyldecyl group, dodecyl group, 1-methylundecyl group, 1-ethyldecyl group, tridecyl group, tetradecyl group, tert-dodecyl group, pentadecyl group, 1-heptyloctyl group, hexadecyl group, octadecyl The groups can be mentioned. Examples of the substituent of the alkyl group include a halogen atom, an alkoxy group which may have a substituent, a nitro group, an aryl group which may have a substituent and the like. The position and number of the substituents are arbitrary, and when there are two or more substituents, the substituents may be the same or different. Specific examples of the alkyl group having a substituent include, for example, a trichloromethyl group, a trifluoromethyl group, a 2,2,2-trifluoroethyl group, a 2,2-dibromoethyl group, and 2,2,3,3-. Tetrafluoropropyl group, 2-ethoxyethyl group, 2-butoxyethyl group, 2-nitropropyl group, penzyl group, 4-methylpentyl group, 4-tert-ptylbenzyl group, 4-methoxypentyl group, 4-nitrobenzyl group Groups, 2,4-dichlorobenzyl group and the like can be mentioned.

The alkoxy group in R ^{1 to} R ¹³ may be in either a linear form or a branched chain form, and the number of carbon atoms is preferably 1 to 20, more preferably 1 to 12, and even more preferably 1 to 6. Specific examples of the alkoxy group include, for example, a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, a butoxy group, an isoptyloxy group, a tert-ptyloxy group, a neopentyloxy group, a hexyloxy group, an octyloxy group and an octadecyl. Examples thereof include an oxy group, a 2,3-dimethyl-3-pentoxy group, a 2-ethylhexyloxy group and the like. Examples of the substituent of the alkoxy group include a halogen atom, an alkoxy group which may have a substituent, a nitro group, an aryl group which may have a substituent and the like. The position and number of the substituents are arbitrary, and when there are two or more substituents, the substituents may be the same or different. Specific examples of the alkoxy group having a substituent include, for example, a trichloromethoxy group, a trifluoromethoxy group, a 2,2,2-trifluoroethoxy group, a 2,2,3,3-tetrafluoropropyloxy group, 2, Examples thereof include 2-ditrifluoromethylpropoxy group, 2-ethoxyethoxy group, 2-butoxyethoxy group, 2-nitropropoxy group, benzyloxy group and the like.

The aryl group in R ^{1 to} R ¹³ has preferably 6 to 20, more preferably 6 to 14, and even more preferably 6 to 10 carbon atoms. Specific examples of the aryl group include a phenyl group, a naphthyl group, an anthryl group, a phenanthryl group, a biphenyl group, an azulenyl group, a 9-fluorenyl group and the like. Examples of the substituent of the aryl group include a halogen atom, a nitro group, an alkoxy group which may have a substituent, an amino group which may have a substituent, a hydroxyl group, and an alkyl group which may have a substituent. And so on. The position and number of the substituents are arbitrary, and when there are two or more substituents, the substituents may be the same or different. Specific examples of the aryl group having a substituent include, for example, a p-bromophenyl group, a p-nitrophenyl group, a p-methoxyphenyl group, a 2,4-dichlorophenyl group, a pentafluorophenyl group, a 2-aminophenyl group, and the like. 2-Methyl-4-chlorophenyl group, 4-hydroxy-1-naphthyl group, 6-methyl-2-naphthyl group, 4,5,8-trichloro-2-naphthyl group, anthraquinonyl group, 2-aminoanthraquinonyl group And so on.

Acid groups in R ¹ to R ¹³ is a -SO ₃ H or -COOH, they acidic group may be a monovalent to trivalent metal salt or alkyl ammonium salts. Examples of the metal salt include sodium salt, potassium salt, magnesium salt, calcium salt, iron salt, aluminum salt and the like. Examples of the alkylammonium salt include ammonium salts of long-chain monoalkylamines such as octylamine, laurylamine and stearylamine, and quaternary alkylammoniums such as palmityltrimethylammonium, dilauryldimethylammonium and distearyldimethylammonium salts. Ammonium can be mentioned.

The substituents on the phthalimidomethyl group (C ₆ H ₄ (CO) ₂ N-CH ₂ −) and sulfamoyl group (H ₂ NSO ₂ −) in R ^{1 to} R ¹³ may have a halogen atom or a substituent. Examples thereof include a good alkyl group, an alkoxy group which may have a substituent, an aryl group which may have a substituent and the like. Specific examples of these groups include those similar to those described above.

Further, ^{at least one adjacent set of groups from R 1 to} R ⁴ and / or at least one adjacent set of groups from R ^{10 to} R ¹³ together have a substituent. Form an aromatic ring which may be used. Examples of the aromatic ring include a hydrocarbon aromatic ring and a heteroaromatic ring. Examples of the hydrocarbon aromatic ring include a benzene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring and the like, and examples of the heteroaromatic ring include a pyridine ring, a pyrazine ring, a pyrrole ring, a quinoline ring, a quinoxalin ring and a furan. Examples thereof include a ring, a benzofuran ring, a thiophene ring, a benzothiophene ring, an oxazole ring, a thiazole ring, an imidazole ring, a pyrazole ring, an indole ring, and a carbazole ring. Of these, a hydrocarbon aromatic ring is preferable, and a benzene ring is even more preferable. Examples of the substituent of the aromatic ring include a halogen atom, a nitro group, an alkoxy group which may have a substituent, an amino group which may have a substituent, a hydroxyl group, and an alkyl group which may have a substituent. And so on. Of these, a halogen atom is preferable.

As the ^{quinophthalone compound (A 2} ), quinophthalone compounds represented by the following formulas (1A) to (1C) are preferable.

[In formulas (1A) to (1C),
R ¹ to R ¹³ are the same as R ¹ to R ¹³ in Formula (1),
R ^{21 to} R ²⁴ and R ^{31 to} R ³⁴ each independently have a hydrogen atom; a halogen atom; an alkyl group which may have a substituent; an alkoxy group which may have a substituent; and a substituent. be an aryl group; a or a substituent; -SO ₃ H, -COOH or a monovalent to trivalent metal salt or alkyl ammonium salt thereof acidic group; an optionally substituted phthalimidomethyl group It also shows a good sulfamoyl group. ]

Halogen atoms in R ^{21 to} R ²⁴ and R ^{31 to} R ³⁴ , alkyl groups which may have substituents, alkoxy groups which may have substituents, aryl groups which may have substituents, acidic Specific configurations of the monovalent to trivalent metal salt or alkylammonium salt of the group, the phthalimidomethyl group which may have a substituent, and the sulfamoyl group which may have a substituent are described in ^{R 1 to} R ^13. As you did.

Among them, R ^{1 to} R ⁴ , R ^{10 to} R ¹³ , R ^{21 to} R ²⁴ , and R ^{31 to} R ³⁴ are preferably independent hydrogen atoms or halogen atoms, and R ^{5 to} R ⁹ are independent of each other. In addition, a hydrogen atom, an alkoxy group which may have a substituent or an aryl group which may have a substituent are preferable.

Specific examples of the (A ² ) quinophthalone compound include, but are not limited to, the quinophthalone compounds (a) to (r) shown below.

In the present invention, the (A ² ) quinophthalone compound may contain one kind or two or more kinds.

The coloring composition of the present invention are (A ¹⁾ and the halogenated metal phthalocyanine pigment, (A ²⁾ mass ratio of the quinophthalone compound ^{[(A 1) / (A} 2)] is 99 / 1-85 / 15 However, from the viewpoint of suppressing light leakage and improving the contrast ratio, 98.9 / 1.1 to 86.3 / 13.7 is preferable, and 98.9 / 1.1 to 86.5 / 13.5 is more preferable. It is preferable, 98.7 / 1.3 to 86.7 / 13.3 is more preferable.
The content of the (A ¹ ) metal halide phthalocyanine pigment is preferably 61 to 79% by mass, more preferably 63 to 77% by mass, and even more preferably 65 to 75% by mass with respect to the total colorant.
Further, the content ratio of the (A ² ) quinophthalone compound is preferably 0.5 to 11% by mass, more preferably 0.8 to 10.5% by mass, and further preferably 1 to 10% by mass with respect to the total colorant. preferable.

The coloring composition of the invention may contain (A) a colorant as (A ¹⁾ halogenated metal phthalocyanine pigment and (A ²⁾ quinophthalone other coloring agents other than the compounds. The other colorants are not particularly limited, and colors and materials can be appropriately selected according to the intended use, ^{except for (A 1} ) metal halide phthalocyanine pigments and (A ² ) quinophthalone compounds. For example, any of pigments, dyes and natural pigments can be used. Above all, from the viewpoint of improving brightness and contrast, the pigment is preferably an organic pigment, and the dye is preferably an organic dye. In addition, other colorants may contain one kind or two or more kinds.

As the organic pigment, for example, a compound classified as a pigment in the color index (CI; The Society of Dyers and Colorists), that is, the following color index (CI) number is assigned. You can list what you are doing.

C. I. Pigment Yellow 150, C.I. I. Azo pigments such as Pigment Yellow 180; C.I. I. Pigment Yellow 138 and other quinophthalone pigments ( ^{excluding (A 2} ) quinophthalone compounds);
C. I. Pigment Yellow 139, C.I. I. Isoindoline pigments such as Pigment Yellow 185;
C. I. Anthraquinone pigments such as Pigment Red 177;
C. I. Perylene pigments such as Pigment Red 123;
C. I. Pigment Orange 43 and other perinone pigments;
C. I. Quinacridone pigments such as Pigment Red 122;
C. I. Dioxazine pigments such as Pigment Violet 23;
C. I. Isoindolinone pigments such as Pigment Yellow 109;
C. I. Pigment Orange 66, C.I. I. Indigo pigments such as Pigment Red 88.

Moreover, as an inorganic pigment, carbon black, titanium black and the like can be mentioned. In addition, JP-A-2001-081348, JP-A-2010-0263334, JP-A-2010-237384, JP-A-2010-237569, JP-A-2011-006602, JP-A-2011-145346, etc. The rake pigment described in the above can be mentioned.

Among them, as the pigment, at least one selected from azo pigments and quinophthalone pigments (excluding (A ² ) quinophthalone compounds) is preferable in that light leakage is effectively suppressed and the contrast ratio is further enhanced. , More preferably C.I. I. Pigment Yellow 138, C.I. I. Pigment Yellow 150 and C.I. I. Pigment Yellow 180 is at least one selected from 180.

In the present invention, (A ¹ ) metal halide phthalocyanine pigment, (A ² ) quinophthalone compound and other pigments to be mixed optionally are recrystallized, reprecipitated, solvent washed, sublimated, vacuum heated or It can also be purified and used by combining these. Further, these pigments may be used by modifying the surface of the particles with a resin, if desired. Examples of the resin for modifying the particle surface of the pigment include the vehicle resin described in JP-A-2001-108817 and various commercially available resins for dispersing pigments. Further, the organic pigment may be used by refining the primary particles by so-called salt milling. As the salt milling method, for example, the method disclosed in Japanese Patent Application Laid-Open No. 8-179111 can be adopted.

The dye is not particularly limited, and for example, a known dye may be used in addition to a compound classified as a die in the color index (CI; The Society of Dyers and Colorists). Can be done. Examples of such dyes include xanthene dyes, triarylmethane dyes, cyanine dyes, anthraquinone dyes, azo dyes, dipyrromethene dyes, quinophthalone dyes, coumarin dyes, pyrazolone dyes, quinoline dyes, nitro dyes, quinoneimine dyes, and phthalocyanine dyes. Examples thereof include squarylium dyes, acrydin dyes, and indigo dyes. Further, as the dye, any of an acid dye, a basic dye and a nonionic dye can be used.

Further, in the present invention, a known dispersant and dispersion aid can be further contained together with ^{(A 1} ) metal halide phthalocyanine pigment, (A ^{2) quinophthalone compound and other colorants to be mixed optionally.}
Known dispersants include, for example, urethane dispersants, polyethyleneimine dispersants, polyoxyethylene alkyl ether dispersants, polyoxyethylene alkyl phenyl ether dispersants, polyethylene glycol diester dispersants, and sorbitan fatty acid ester dispersants. Dispersants, polyester dispersants, acrylic dispersants and the like can be mentioned.

Such dispersants are commercially available, for example, as acrylic dispersants, Disperbyk-2000, Disperbyk-2001, BYK-LPN6919, BYK-LPN21116, BYK-LPN22102 (above, BYK). As urethane dispersants such as (manufactured by), Disperbyk-161, Disperbyk-162, Disperbyk-165, Disperbyk-167, Disperbyk-170, Disperbyk-182 (all manufactured by Big Chemie (BYK)), Solspers 76500 (Lubrisol). As a polyethyleneimine-based dispersant such as (manufactured by Lubrizol Co., Ltd.), etc., as a polyester-based dispersant such as Solspers 24000 (manufactured by Lubrizol Co., Ltd.) BYK-LPN21324 (manufactured by Big Chemie (BYK)) can be mentioned in addition to (manufactured by BYK Co., Ltd.) and the like.

Examples of the pigment derivative include sulfonic acid derivatives of copper phthalocyanine, diketopyrrolopyrrole, and quinophthalone.

The content ratio of the colorant (A) is usually 5 to 70% by mass, preferably 10 to 10% by mass in the solid content of the coloring composition, from the viewpoint of suppressing light leakage and forming pixels having excellent brightness and contrast ratio. It is 60% by mass. Here, the solid content is a component other than the solvent described later. When another colorant is contained, the content ratio of the other colorant can be appropriately selected within a range that does not impair the object of the present invention, but is preferably 50% by mass or less based on the total colorant, and is 40%. More preferably, it is by mass or less. The lower limit is not particularly limited, but may be 0.01% by mass or more.

-(B) Binder resin-
The coloring composition of the present invention contains a binder resin as a component (B).
The binder resin (B) is not particularly limited, but is preferably a resin having an acidic functional group such as a carboxy group or a phenolic hydroxyl group. Among them, a polymer having a carboxy group (hereinafter, also referred to as “carboxy group-containing polymer”) is preferable, and for example, an ethylenically unsaturated monomer having one or more carboxy groups (hereinafter, “unsaturated single amount”) is preferable. A copolymer of "body (b1)") and another copolymerizable ethylenically unsaturated monomer (hereinafter, also referred to as "unsaturated monomer (b2)") can be mentioned. .. The binder resin (B) may contain one type or two or more types.

Examples of the unsaturated monomer (b1) include (meth) acrylic acid, maleic acid, maleic anhydride, succinic acid mono [2- (meth) acryloyloxyethyl], and ω-carboxypolycaprolactone mono (meth). Examples thereof include acrylate and p-vinylbenzoic acid. As the unsaturated monomer (b1), one type or two or more types can be used.

Further, as the unsaturated monomer (b2), for example,
N-substituted maleimides such as N-phenylmaleimide and N-cyclohexylmaleimide;
Aromatic vinyl compounds such as styrene, α-methylstyrene, p-hydroxystyrene, p-hydroxy-α-methylstyrene, p-vinylbenzylglycidyl ether, and acenaphthylene;

Methyl (meth) acrylate, n-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, allyl (meth) acrylate, benzyl (meth) acrylate, polyethylene glycol (degree of polymerization 2- 10) Methyl ether (meth) acrylate, polypropylene glycol (polymerization degree 2 to 10) Methyl ether (meth) acrylate, polyethylene glycol (polymerization degree 2 to 10) mono (meth) acrylate, polypropylene glycol (polymerization degree 2 to 10) mono (Meta) acrylate, cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, tricyclo [5.2.1.0 ^2,6 ] decane-8-yl (meth) acrylate, dicyclopentenyl (meth) acrylate, glycerol mono (Meta) acrylate, 4-hydroxyphenyl (meth) acrylate, ethylene oxide-modified (meth) acrylate of paracumylphenol, glycidyl (meth) acrylate, 3,4-epoxycyclohexylmethyl (meth) acrylate, 3-[(meth) (Meta) acrylic acid esters such as acryloyloxymethyl] oxetane and 3-[(meth) acryloyloxymethyl] -3-ethyloxetane;

Vinyl ethers such as cyclohexyl vinyl ether, isobornyl vinyl ether, tricyclo [5.2.1.0 ^2,6 ] decane-8-ylvinyl ether, pentacyclopentadecanyl vinyl ether, 3- (vinyloxymethyl) -3-ethyloxetane ;
Examples thereof include macromonomers having a mono (meth) acryloyl group at the end of polymer molecular chains such as polystyrene, polymethyl (meth) acrylate, poly-n-butyl (meth) acrylate, and polysiloxane. As the unsaturated monomer (b2), one type or two or more types can be used.

In the copolymer of the unsaturated monomer (b1) and the unsaturated monomer (b2), the copolymerization ratio of the unsaturated monomer (b1) in the copolymer is preferably 5 to 50% by mass. , More preferably 10 to 40% by mass. By copolymerizing the unsaturated monomer (b1) in such a range, a coloring composition having excellent alkali developability and storage stability can be obtained.

Specific examples of the copolymer of the unsaturated monomer (b1) and the unsaturated monomer (b2) include JP-A-7-140654, JP-A-8-259876, and JP-A-10-31308. No., JP-A-10-300922, JP-A-11-174224, JP-A-11-258415, JP-A-2000-56118, JP-A-2004-101728 and the like. Coalescence can be mentioned.

Further, in the present invention, for example, JP-A-5-19467, JP-A-6-230212, JP-A-7-207211, JP-A-9-325494, JP-A-11-140144, and Japanese Patent Application Laid-Open No. As disclosed in Japanese Patent Application Laid-Open No. 2008-181095, a carboxy group-containing polymer having a polymerizable unsaturated bond such as a (meth) acryloyl group in the side chain can also be used as the binder resin.

The binder resin (B) in the present invention usually has a polystyrene-equivalent weight average molecular weight (Mw) of 1,000 to 100, measured by gel permeation chromatography (hereinafter abbreviated as GPC) (eluting solvent: tetrahydrofuran). 000, preferably 3,000 to 50,000. The ratio (Mw / Mn) of (B) the binder resin Mw to the number average molecular weight (Mn) is preferably 1.0 to 5.0, and more preferably 1.0 to 3.0. Mn is a polystyrene-equivalent number average molecular weight measured by GPC (eluting solvent: tetrahydrofuran). With such an aspect, it is possible to obtain a coloring composition excellent not only in suppressing light leakage and improving the contrast ratio but also in alkali developability and storage stability.

The binder resin (B) can be produced by a known method, and is disclosed in, for example, JP-A-2003-222717, JP-A-2006-259680, Pamphlet International Publication No. 2007/029871 and the like. The structure, Mw, and Mw / Mn can be controlled by the method.

The content of the binder resin (B) is usually 10 to 1,000 parts by mass, preferably 20 to 500 parts by mass, more preferably 50 to 200 parts by mass, still more preferably, with respect to 100 parts by mass of the (A) colorant. Is 80 to 150 parts by mass. By adopting such an embodiment, not only the light leakage is suppressed and the contrast ratio is improved, but also the alkali developability, the storage stability of the coloring composition, the pattern shape, and the chromaticity characteristics are further enhanced, and the precipitates and It is possible to suppress the generation of foreign matter in the coating film.

-(C) Polymerizable compound-
As used herein, the term "polymerizable compound" refers to a compound having two or more polymerizable groups. Examples of the polymerizable group include an ethylenically unsaturated group, an oxylanyl group, an oxetanyl group, an N-alkoxymethylamino group and the like. Examples of the ethylenically unsaturated group include a vinyl group, an allyl group, a (meth) acryloyl group and the like. Among them, as the polymerizable compound, a compound having two or more (meth) acryloyl groups or a compound having two or more N-alkoxymethylamino groups is used from the viewpoint of suppressing dye transferability and improving heat resistance. Preferably, a compound having two or more (meth) acryloyl groups is more preferred. (C) The polymerizable compound can be contained alone or in combination of two or more.

Specific examples of the compound having two or more (meth) acryloyl groups include polyfunctional (meth) acrylate, which is a reaction product of an aliphatic polyhydroxy compound and (meth) acrylic acid, and caprolactone-modified polyfunctional (meth). ) Acrylate, alkylene oxide-modified polyfunctional (meth) acrylate, polyfunctional urethane (meth) acrylate which is a reaction product of (meth) acrylate having a hydroxyl group and polyfunctional isocyanate, (meth) acrylate having a hydroxyl group and acid anhydride. Examples thereof include polyfunctional (meth) acrylates having a carboxy group, which is a reaction product with a substance.

Examples of the aliphatic polyhydroxy compound include divalent aliphatic polyhydroxy compounds such as ethylene glycol, propylene glycol, polyethylene glycol, and polypropylene glycol; and trivalent or higher valent or higher such as glycerin, trimethylolpropane, pentaerythritol, and dipentaerythritol. Aliphatic polyhydroxy compounds can be mentioned. Examples of the (meth) acrylate having a hydroxyl group include 2-hydroxyethyl (meth) acrylate, trimethylolpropane di (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, and glycerol dimethacrylate. And so on. Examples of the polyfunctional isocyanate include tolylene diisocyanate, hexamethylene diisocyanate, diphenylmethylene diisocyanate, isophorone diisocyanate and the like. Examples of the acid anhydride include dibasic acid anhydrides such as succinic anhydride, maleic anhydride, glutaric anhydride, itaconic anhydride, phthalic anhydride, and hexahydrophthalic anhydride, pyromellitic anhydride, and biphenyltetracarboxylic acid. Examples thereof include tetrabasic acid dianhydrides such as dianhydrides and benzophenonetetracarboxylic dianhydrides.

Examples of the caprolactone-modified polyfunctional (meth) acrylate include the compounds described in paragraphs [0015] to [0018] of JP-A-11-44955. The alkylene oxide-modified polyfunctional (meth) acrylate is modified with at least one selected from bisphenol A di (meth) acrylate modified with at least one selected from ethylene oxide and propylene oxide, ethylene oxide and propylene oxide. Trimethylol propanol tri (meth) acrylate modified with at least one selected from tri (meth) acrylate, ethylene oxide and propylene oxide, and penta modified with at least one selected from ethylene oxide and propylene oxide. Pentaerythritol modified with at least one selected from erythritol tri (meth) acrylate, ethylene oxide and propylene oxide Dipentaerythritol penta modified with at least one selected from tetra (meth) acrylate, ethylene oxide and propylene oxide ( Examples thereof include dipentaerythritol hexa (meth) acrylate modified with at least one selected from meta) acrylate, ethylene oxide and propylene oxide.

Examples of the compound having two or more oxylanyl groups include an epoxy resin, a (co) polymer of an ethylenically unsaturated monomer having an oxylanyl group, and a polyfunctional epoxy resin such as EHPE3150 (manufactured by Daicel Co., Ltd.). Can be used.
Examples of the compound having two or more oxetane groups include a (co) polymer of an ethylenically unsaturated monomer having an oxylanyl group, Aron oxetane OXT-121, and OXT-221 (above, Toagosei Co., Ltd.). (Made) can be mentioned.
In addition, aliphatic conjugated diene compounds such as 1,3-butadiene, 2-methyl-1,3-butadiene, 2-chloro-1,3-butadiene, 2,3-dimethyl-1,3-butadiene; divinylbenzene, Non-conjugated divinyl compounds such as diisopropenylbenzene and trivinylbenzene can also be used.

Among these polymerizable compounds, polyfunctional (meth) acrylate, which is a reaction product of trivalent or higher aliphatic polyhydroxy compound and (meth) acrylic acid, caprolactone-modified polyfunctional (meth) acrylate, and polyfunctional urethane. (Meta) acrylates, polyfunctional (meth) acrylates having a carboxy group, and (co) polymers of ethylenically unsaturated monomers having an oxylanyl group are preferable. Among the polyfunctional (meth) acrylates, which are reactants of trivalent or higher aliphatic polyhydroxy compounds and (meth) acrylic acid, from the viewpoint of suppressing light leakage and improving the contrast ratio, trimethyl propantri Acrylate, pentaerythritol triacrylate, dipentaerythritol pentaacrylate, and dipentaerythritol hexaacrylate are preferable, and among polyfunctional (meth) acrylates having a carboxy group, a reaction product of pentaerythritol triacrylate and succinic anhydride, dipenta A reaction product of erythritol pentaacrylate and arsenic anhydride is preferable.

The content of the polymerizable compound (C) is preferably 10 to 1,000 parts by mass, more preferably 20 to 800 parts by mass, and even more preferably 100 to 500 parts by mass with respect to 100 parts by mass of the (A) colorant. .. With such an aspect, it is possible to suppress light leakage and improve the contrast ratio at a higher level.

Further, in the coloring composition of the present invention, the mass ratio [(B) / (C)] of (B) the binder resin and (C) the polymerizable compound is from the viewpoint of suppressing light leakage and improving the contrast ratio. , 95/5 to 61/39, more preferably 93/7 to 63/37, and even more preferably 90/10 to 66/35.

-(D) Photopolymerization Initiator-
The coloring composition of the present invention may contain a photopolymerization initiator. Thereby, the coloring composition can be imparted with radiation sensitivity. The photopolymerization initiator used in the present invention is a compound that generates an active species capable of initiating the polymerization of the (C) polymerizable compound by exposure to radiation such as visible light, ultraviolet rays, far ultraviolet rays, electron beams, and X-rays. .. (D) The photopolymerization initiator may contain one kind or two or more kinds.

Examples of such a photopolymerization initiator include thioxanthone-based compounds, acetophenone-based compounds, biimidazole-based compounds, triazine-based compounds, O-acyloxime-based compounds, onium salt-based compounds, benzoin-based compounds, benzophenone-based compounds, and α. -Diketone compounds, polynuclear quinone compounds, diazo compounds, imide sulfonate compounds, onium salt compounds and the like can be mentioned. Among them, as the (D) photopolymerization initiator, at least one selected from the group of thioxanthone-based compounds, acetophenone-based compounds, biimidazole-based compounds, triazine-based compounds, and O-acyloxime-based compounds is preferable.

Among the preferable photopolymerization initiators in the present invention, specific examples of the thioxanthone-based compound include thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,4-dichlorothioxanthone, and 2 , 4-Dimethylthioxanthone, 2,4-diethylthioxanthone, 2,4-diisopropylthioxanthone and the like.

Specific examples of the acetophenone compound include 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropane-1-one and 2-benzyl-2-dimethylamino-1- (4-). Examples thereof include morpholinophenyl) butane-1-one, 2- (4-methylbenzyl) -2- (dimethylamino) -1- (4-morpholinophenyl) butane-1-one, and the like.

Specific examples of the biimidazole compound include 2,2'-bis (2-chlorophenyl) -4,4', 5,5'-tetraphenyl-1,2'-biimidazole, 2,2'-. Bis (2,4-dichlorophenyl) -4,4', 5,5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis (2,4,6-trichlorophenyl) -4,4 ', 5,5'-Tetraphenyl-1,2'-biimidazole and the like can be mentioned.

When a biimidazole-based compound is used as the photopolymerization initiator, it is preferable to use a hydrogen donor in combination because the sensitivity can be improved. The term "hydrogen donor" as used herein means a compound capable of donating a hydrogen atom to a radical generated from a biimidazole compound by exposure. Examples of the hydrogen donor include mercaptan hydrogen donors such as 2-mercaptobenzothiazole and 2-mercaptobenzoxazole; 4,4'-bis (dimethylamino) benzophenone, 4,4'-bis (diethylamino) benzophenone and the like. Amine-based hydrogen donors can be mentioned. In the present invention, the hydrogen donor can be used alone or in combination of two or more, but one or more mercaptan hydrogen donors and one or more amine hydrogen donors are used in combination. It is preferable to do so because the sensitivity can be further improved.

Specific examples of the triazine-based compounds include 2,4,6-tris (trichloromethyl) -s-triazine, 2-methyl-4,6-bis (trichloromethyl) -s-triazine, and 2- [2- [2-. (5-Methylfuran-2-yl) ethenyl] -4,6-bis (trichloromethyl) -s-triazine, 2- [2- (fran-2-yl) ethenyl] -4,6-bis (trichloromethyl) ) -S-Triazine, 2- [2- (4-diethylamino-2-methylphenyl) ethenyl] -4,6-bis (trichloromethyl) -s-triazine, 2- [2- (3,4-dimethoxyphenyl) ) Ethenyl] -4,6-bis (trichloromethyl) -s-triazine, 2- (4-methoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4-ethoxystyryl)- List triazine compounds having a halomethyl group such as 4,6-bis (trichloromethyl) -s-triazine and 2- (4-n-butoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine. Can be done.

Specific examples of the O-acyloxime compound include 1,2-octanedione, 1- [4- (phenylthio) phenyl]-, 2- (O-benzoyloxime), etanone, 1- [9-ethyl. -6- (2-Methylbenzoyl) -9H-Carbazole-3-yl]-, 1- (O-acetyloxime), Etanone, 1- [9-Ethyl-6- (2-Methyl-4-tetrahydrofuranylmethoxy) Benzoyl) -9H-carbazole-3-yl]-, 1- (O-acetyloxime), etanone, 1- [9-ethyl-6- {2-methyl-4- (2,2-dimethyl-1,3) -Dioxolanyl) methoxybenzoyl} -9H-carbazole-3-yl]-, 1- (O-acetyloxime) and the like can be mentioned. As commercially available O-acyloxime compounds, NCI-831, NCI-930 (all manufactured by ADEKA Corporation) and the like can also be used.

In the present invention, when a photopolymerization initiator other than the biimidazole-based compound such as an acetophenone-based compound is used, a sensitizer can also be used in combination. Examples of such a sensitizer include 4,4'-bis (dimethylamino) benzophenone, 4,4'-bis (diethylamino) benzophenone, 4-diethylaminoacetophenone, 4-dimethylaminopropiophenone, and 4-dimethyl. Ethyl aminobenzoate, 2-ethylhexyl 4-dimethylaminobenzoate, 2,5-bis (4-diethylaminobenzal) cyclohexanone, 7-diethylamino-3- (4-diethylaminobenzoyl) coumarin, 4- (diethylamino) chalcone, etc. Can be mentioned.

The content of the (D) photopolymerization initiator is preferably 0.01 to 120 parts by mass, more preferably 1 to 100 parts by mass with respect to 100 parts by mass of the (C) polymerizable compound. As a result, it is possible to suppress light leakage and improve the contrast ratio at a higher level.

-(E) Solvent-
As the solvent, (A) a colorant, (B) a binder resin and (C) a polymerizable compound, and other components constituting the coloring composition are dispersed or dissolved, and the solvent does not react with these components. As long as it has an appropriate volatility, it can be appropriately selected and used. As the solvent (E), an organic solvent is usually used. (E) The solvent may be contained alone or in combination of two or more.

As an organic solvent, for example
Ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono-n-propyl ether, ethylene glycol mono-n-butyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol mono-n-propyl ether, diethylene glycol mono-n- Butyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-n-propyl ether, propylene glycol mono-n-butyl ether, dipropylene glycol monomethyl ether, di (Poly) alkylene glycol monoalkyl ethers such as propylene glycol monoethyl ether, dipropylene glycol mono-n-propyl ether, dipropylene glycol mono-n-butyl ether, tripropylene glycol monomethyl ether, tripropylene glycol monoethyl ether;

Lactate alkyl esters such as methyl lactate and ethyl lactate;
(Cyclo) alkyl alcohols such as methanol, ethanol, propanol, butanol, isopropanol, isobutanol, t-butanol, octanol, 2-ethylhexanol, cyclohexanol;
Keto alcohols such as diacetone alcohol;

Ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, dipropylene glycol monomethyl ether acetate, 3-methoxybutyl acetate, (Poly) alkylene glycol monoalkyl ether acetate such as 3-methyl-3-methoxybutyl acetate;
Other ethers such as diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol diethyl ether, tetrahydrofuran;
Ketones such as methyl ethyl ketone, cyclohexanone, 2-heptanone, 3-heptanone;

Diacetates such as propylene glycol diacetate, 1,3-butylene glycol diacetate, 1,6-hexanediol diacetate;
Alkoxycarboxylic acid esters such as methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl ethoxyacetate, 3-methyl-3-methoxybutyl propionate;
Ethyl acetate, n-propyl acetate, i-propyl acetate, n-butyl acetate, i-butyl acetate, n-amyl formate, i-amyl acetate, n-butyl propionate, ethyl butyrate, n-propyl butyrate, i butyrate Other esters such as -propyl, n-butyl butyrate, methyl pyruvate, ethyl pyruvate, n-propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, ethyl 2-oxobutanoate;
Aromatic hydrocarbons such as toluene and xylene;
Examples thereof include amides such as N, N-dimethylformamide, N, N-dimethylacetamide, N-methylpyrrolidone, and lactams.

Among them, the solvent (E) includes propylene glycol monomethyl ether, propylene glycol monoethyl ether, ethylene glycol monomethyl ether acetate, propylene glycol monomethyl ether acetate, and propylene glycol monoethyl from the viewpoints of solubility, storage stability, coatability, and the like. Ether acetate, 3-methoxybutyl acetate, diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, cyclohexanone, 2-heptanone, 3-heptanone, 1,3-butylene glycol diacetate, 1,6-hexanediol diacetate, ethyl lactate, 3- Ethyl methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, 3-methyl-3-methoxybutyl propionate, n-butyl acetate, i-butyl acetate, n-amyl formate, i-acetate Amil, n-butyl propionate, ethyl butyrate, i-propyl butyrate, n-butyl butylate, ethyl pyruvate and the like are preferable.

The content of the solvent (E) is not particularly limited, but the total concentration of each component of the coloring composition excluding the solvent is preferably 5 to 50% by mass, preferably 10 to 40% by mass. The amount is more preferred. By adopting such an embodiment, it is possible to obtain a colorant dispersion liquid having good dispersibility and stability, and a coloring composition having good coatability.

-Additives-
The coloring composition of the present invention may also contain various additives, if necessary.
Examples of the additive include fillers such as glass and alumina; polymer compounds such as polyvinyl alcohol and poly (fluoroalkyl acrylate); surfactants such as fluorine-based surfactants and silicon-based surfactants; vinyl. Trimethoxysilane, vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxy Silane, 3-aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-chloropropylmethyl Adhesion promoters such as dimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloyloxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane; 2,2-thiobis (4-methyl-6-t-butylphenol) , Antioxidants such as 2,6-di-t-butylphenol; UV absorbers such as 2- (3-t-butyl-5-methyl-2-hydroxyphenyl) -5-chlorobenzotriazole, alkoxybenzophenones; Anti-aggregation agents such as sodium polyacrylate; malonic acid, adipic acid, itaconic acid, citraconic acid, fumaric acid, mesaconic acid, 2-aminoethanol, 3-amino-1-propanol, 5-amino-1-pentanol, Residue improvers such as 3-amino-1,2-propanediol, 2-amino-1,3-propanediol, 4-amino-1,2-butanediol; mono oxalate [2- (meth) acryloyloxy Developable improvers such as ethyl], mono-phthalic acid [2- (meth) acryloyloxyethyl], ω-carboxypolycaprolactone mono (meth) acrylate; reactivity disclosed in JP-A-2008-24208, etc. Examples thereof include a siloxane oligomer having a functional group.

The coloring composition of the present invention can be prepared by an appropriate method. For example, (A) a colorant, (B) a binder resin and (C) a polymerizable compound are prepared by mixing and dispersing them together with a solvent and other components to be optionally added using a bead mill, a roll mill or the like. Can be done.

Colored hardened film and method for forming the colored hardened film The colored hardened film of the present invention is a cured product formed by using the colored composition of the present invention.
Hereinafter, a colored cured film used for a color filter constituting a display element and a solid-state image sensor and a method for forming the colored cured film will be described.
The following methods are first mentioned as a method for manufacturing a color filter. First, a light-shielding layer (black matrix) is formed on the surface of the substrate so as to partition the portion forming the pixel, if necessary. Next, for example, a green liquid composition of the radiation-sensitive coloring composition of the present invention is applied onto this substrate, and then prebaking is performed to evaporate the solvent to form a coating film. Next, the coating film is exposed through a photomask and then developed with an alkaline developer to dissolve and remove the unexposed portion of the coating film. Then, by post-baking, a pixel array in which green pixel patterns (colored cured films) are arranged in a predetermined arrangement is formed.

Then, using each of the red or blue radiation-sensitive coloring compositions, application, pre-baking, exposure, development and post-baking of each radiation-sensitive coloring composition are performed in the same manner as described above to obtain a red pixel array and blue. Pixel arrays are sequentially formed on the same substrate. As a result, a color filter in which pixel arrays of the three primary colors of red, blue, and green are arranged on the substrate is obtained. However, in the present invention, the order in which the pixels of each color are formed is not limited to the above.

The black matrix can be formed by forming a metal thin film such as chromium formed by sputtering or vapor deposition into a desired pattern using a photolithography method, but the black colorant is dispersed in the black matrix. The coloring composition can also be used to form the pixels in the same manner as in the case of forming the pixels.

Examples of the substrate include glass, silicon, polycarbonate, polyester, aromatic polyamide, polyamide-imide, and polyimide.
Further, if desired, these substrates may be subjected to appropriate pretreatment such as chemical treatment with a silane coupling agent or the like, plasma treatment, ion plating, sputtering, vapor phase reaction method, vacuum deposition and the like.

When applying the coloring composition to the substrate, an appropriate coating method such as a spray method, a roll coating method, a rotary coating method (spin coating method), a slit die coating method (slit coating method), or a bar coating method is adopted. However, it is particularly preferable to adopt the spin coating method and the slit die coating method.

Pre-baking is usually at 70 to 110 ° C. for about 1 to 10 minutes.
The coating thickness is usually 0.6 to 8 μm, preferably 1.2 to 5 μm as the film thickness after drying.

Examples of the light source of radiation used when forming at least one selected from the pixel and the black matrix include a xenon lamp, a halogen lamp, a tungsten lamp, a high pressure mercury lamp, an ultrahigh pressure mercury lamp, a metal halide lamp, a medium pressure mercury lamp, and a low pressure. Examples thereof include a lamp light source such as a mercury lamp, a laser light source such as an argon ion laser, a YAG laser, an XeCl excimer laser, and a nitrogen laser. An ultraviolet LED can also be used as the exposure light source. The wavelength is preferably radiation in the range of 190-450 nm.
The exposure amount of radiation is generally preferably ^{10 to 10,000 J / m 2.}

Examples of the alkaline developer include sodium carbonate, sodium hydrogen carbonate, sodium hydroxide, potassium hydroxide, tetramethylammonium hydroxide, choline, 1,8-diazabicyclo- [5.4.0] -7-undecene. , 1,5-diazabicyclo- [4.3.0] -5-nonene and the like are preferable.
For example, a water-soluble organic solvent such as methanol or ethanol, a surfactant, or the like can be added in an appropriate amount to the alkaline developer. After alkaline development, it is usually washed with water.
As the developing method, a shower developing method, a spray developing method, a dip (immersion) developing method, a paddle (liquid filling) developing method and the like can be applied. The developing conditions are preferably 5 to 300 seconds at room temperature.

Post-baking conditions are usually 180 to 280 ° C. for about 10 to 60 minutes.
The film thickness of the pixels formed in this way is usually 0.5 to 5 μm, preferably 1.0 to 3 μm.

Further, as a second method for manufacturing a color filter, a method for obtaining pixels of each color by an inkjet method disclosed in JP-A-7-318723, JP-A-2000-310706 and the like can be adopted. .. In this method, first, a partition wall that also has a light-shielding function is formed on the surface of the substrate. Next, for example, the liquid composition of the green thermosetting coloring composition is discharged into the formed partition wall by an inkjet device, and then prebaked to evaporate the solvent. Next, the coating film is exposed as necessary and then cured by post-baking to form a green pixel pattern.

Next, using each of the red or blue thermosetting coloring compositions, a red pixel pattern and a blue pixel pattern are sequentially formed on the same substrate in the same manner as described above. As a result, a color filter in which pixel patterns of the three primary colors of red, blue, and green are arranged on the substrate can be obtained. However, in the present invention, the order in which the pixels of each color are formed is not limited to the above.

It should be noted that the partition wall not only has a light-shielding function but also a function of preventing the thermosetting coloring composition of each color discharged into the compartment from being mixed, so that the partition wall is compared with the black matrix used in the first method described above. , The film thickness is thick. Therefore, the septa are usually formed using a black radiation sensitive composition.
The substrate used for forming the color filter, the light source of radiation, and the pre-baking and post-baking methods and conditions are the same as those of the first method described above. The film thickness of the pixels formed by the inkjet method in this way is about the same as the height of the partition wall.

A protective film is formed on the pixel pattern thus obtained, if necessary, and then a transparent conductive film is formed by sputtering. After forming the transparent conductive film, a spacer may be further formed to form a color filter. The spacer is usually formed by using a radiation-sensitive composition, but a spacer having a light-shielding property (black spacer) can also be used. In this case, a radiation-sensitive coloring composition in which a black colorant is dispersed is used, and the curable composition of the present invention can also be suitably used for forming such a black spacer.

The coloring composition of the present invention can be suitably used in the formation of any colored cured film such as each color pixel, black matrix, and black spacer used in the color filter.
Since the color filter having the colored cured film of the present invention formed in this manner suppresses light leakage and has a high contrast ratio, it has a color liquid crystal display element, a color image pickup tube element, a color sensor, and an organic EL display. It is extremely useful for elements, electronic paper, etc.

Color filter The color filter of the present invention comprises the colored cured film of the present invention. Specifically, the colored cured film of the present invention may be provided as a member of each color pixel, black matrix, black spacer, etc. used in the color filter.

Display element The display element of the present invention comprises the colored cured film of the present invention. Examples of the display element include a color liquid crystal display element, an organic EL display element, and electronic paper.
The color liquid crystal display element provided with the colored cured film of the present invention may be a transmissive type or a reflective type, and may have an appropriate structure. For example, a color filter is formed on a substrate different from the driving substrate on which the thin film transistor (TFT) is arranged, and the driving substrate and the substrate on which the color filter is formed face each other via a liquid crystal layer. Can be taken. Further, a substrate in which a color filter is formed on the surface of a drive substrate on which a thin film transistor (TFT) is arranged and an ITO (tin-doped indium oxide) electrode or an IZO (mixture of acid value indium and zinc oxide) electrode It is also possible to adopt a structure in which the substrate on which the above is formed faces each other via a liquid crystal layer. The latter structure has an advantage that the aperture ratio can be remarkably improved and a bright and high-definition liquid crystal display element can be obtained. When the latter structure is adopted, the black matrix and the black spacer may be formed on either the substrate side on which the color filter is formed or the substrate side on which the ITO electrode or the IZO electrode is formed.

The color liquid crystal display element provided with the colored cured film of the present invention may include a cold cathode fluorescent tube (CCFL) and a backlight unit using a white LED as a light source. Examples of the white LED include a white LED that obtains white light by mixing colors by combining a red LED, a green LED, and a blue LED, a white LED that obtains white light by combining a blue LED, a red LED, and a green phosphor, and a blue LED. A white LED that obtains white light by mixing colors with a red light emitting phosphor and a green light emitting phosphor, a white LED that obtains white light by mixing a blue LED and a YAG-based phosphor, a blue LED, an orange light emitting phosphor, and a green light emitting fluorescence. Examples thereof include a white LED that obtains white light by mixing colors by combining bodies, and a white LED that obtains white light by mixing colors by combining an ultraviolet LED, a red light emitting phosphor, a green light emitting phosphor, and a blue light emitting phosphor.

The color liquid crystal display element provided with the colored cured film of the present invention includes TN (Twisted Nematic) type, STN (Super Twisted Nematic) type, IPS (In-Planes Switching) type, VA (Vertical Birefringence) type, and OCB (Optical). An appropriate liquid crystal mode such as a Compensated Birefringence) type can be applied.

Further, the organic EL display device provided with the colored cured film of the present invention can adopt an appropriate structure, and examples thereof include the structure disclosed in Japanese Patent Application Laid-Open No. 11-307242.
Further, the electronic paper provided with the colored cured film of the present invention can have an appropriate structure, and examples thereof include the structure disclosed in Japanese Patent Application Laid-Open No. 2007-41169.

Light-receiving element The light-receiving element of the present invention comprises the colored cured film of the present invention.
The light receiving element of the present invention may have an appropriate structure. For example, by using the colored cured film of the present invention as a color filter constituting the solid-state image sensor and combining it with a photodiode, an image sensor such as a solid-state image sensor can be obtained. Can be configured. Further, by using the cured film of the present invention as an infrared light transmission filter and combining it with a photodiode, it is possible to form a pixel for infrared light detection.

Light-emitting element The light-emitting element of the present invention comprises the colored cured film of the present invention.
The light emitting element of the present invention may have an appropriate structure. For example, it is protected in an organic EL light emitting element having a structure in which a transparent conductive layer of an anode made of a transparent electrode, a light emitting layer, and a cathode layer made of a metal electrode are laminated. The colored cured film of the present invention is used as a film, an insulating film, and an emission wavelength selection member. The light emitting layer can be formed by using the coloring composition of the present invention according to the method for forming a colored cured film of the present invention described above.

Hereinafter, embodiments of the present invention will be described in more detail with reference to examples. However, the present invention is not limited to the following examples.

<(B) Synthesis of binder resin>
Synthesis example B1
A flask equipped with a cooling tube and a stirrer was charged with 100 parts by mass of propylene glycol monomethyl ether acetate and substituted with nitrogen. The contents of the flask are heated to 80 ° C., and at the same temperature, 100 parts by mass of propylene glycol monomethyl ether acetate, 20 parts by mass of methacrylic acid, 10 parts by mass of styrene, 5 parts by mass of benzyl methacrylate, 15 parts by mass of 2-hydroxyethyl methacrylate, 2 by mass. Consists of 23 parts by mass of -ethylhexyl methacrylate, 12 parts by mass of N-phenylmaleimide, 15 parts by mass of mono (2-acryloyloxyethyl) oxalate and 6 parts by mass of 2,2'-azobis (2,4-dimethylvaleronitrile). The mixed solution was added dropwise over 1 hour, and the mixture was maintained at this temperature and polymerized for 2 hours. Then, the temperature of the reaction solution was raised to 100 ° C., and the temperature was maintained for another 1 hour to polymerize to obtain a binder resin solution (solid content concentration = 33.3% by mass). The obtained binder resin solution had Mw of 12,200 and Mn of 6,500. This binder resin solution is referred to as "resin solution (B-1)".

<Preparation of colorant dispersion>
Preparation Example 1
Colorant dispersion (A-1)
As a colorant, C.I. I. Pigment Green 58 by 7.2 parts by mass, quinophthalone compound (a) shown below by 0.1 parts by mass, C.I. I. Pigment Yellow 138 by 5.7 parts by mass, BYK-LPN22102 (manufactured by Big Chemie (BYK)) as a dispersant by 10.8 parts by mass (solid content concentration = 40% by mass), and resin solution (B-1) by 13. Using 0 parts by mass and 63.2 parts by mass of propylene glycol monomethyl ether acetate as a solvent, the mixture was mixed and dispersed by a bead mill to prepare a green colorant dispersion solution (A-1). The quinophthalone compound (a) was synthesized by the method described in Examples of JP2012-226110A.

Preparation Examples 2-57
Colorant dispersions (A-2) to (A-57)
Colorant dispersions (A-2) to (A-57) were prepared in the same manner as the colorant dispersion (A-1) except that the types and amounts of the colorants were changed to those shown in Table 1. Made. The quinophthalone compounds (b) to (g) shown in Table 1 are the following compounds, and were synthesized by the method described in Examples of JP2012-226110A.

<Preparation of coloring composition>
Example 1
Preparation of coloring composition (A) 42.0 parts by mass of colorant dispersion (A-1) as a colorant, (B) 10.4 parts by mass of a resin solution (B-1) solution as a binder resin, (C) polymerization 4.2 parts by mass of dipentaerythritol hexaacrylate (manufactured by Nippon Kayaku Co., Ltd., trade name KAYARAD DPHA) as a sex compound, (D) 2-benzyl-2-dimethylamino-1- (4-morpho) as a photopolymerization initiator Renophenyl) Butan-1-one (manufactured by Ciba Specialty Chemicals, trade name Irgacure 369) 0.7 parts by mass and ethanone-1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazole) -3-Il] -1- (O-Acetyloxym)] (BASF, trade name IRGACURE OXE02) 1.0 part by mass, Megafuck F-554 (manufactured by DIC Co., Ltd.) as a fluorine-based surfactant 0 A coloring composition (S-1) was prepared by mixing 0.05 parts by mass and 41.7 parts by mass of propylene glycol monomethyl ether acetate (PGMEA) as the solvent (E).

Examples 2 to 46, Comparative Examples 1 to 11
Coloring compositions (S-2) to (S-57)
Coloring composition (S-1) except that the type of colorant dispersion and the blending amounts of (B) binder resin, (C) polymerizable compound and (E) solvent were changed to those shown in Table 2. The coloring compositions (S-2) to (S-57) were prepared in the same manner as in the above.

<Preparation of light leakage evaluation cell>
After applying the coloring compositions (S-1) to (S-57) on the ITO film-forming substrate using a spinner, they are prebaked on a hot plate at 100 ° C. for 100 seconds to apply a film thickness of 2.4 μm. A film was formed. Using an exposure machine (TOPCON, TME-400R) ^{, the obtained coating film is exposed so that the integrated irradiation dose is 40 J / m 2,} and this substrate is heated at 230 ° C. for 20 minutes in a clean oven. As a result, a colored cured film was formed on the ITO film-forming substrate. Next, an alignment film for the IPS mode was applied onto the colored cured film using a spinner, and then prebaked on a hot plate at 100 ° C. for 100 seconds to form a coating film having a film thickness of 1000 Å. This substrate was heated at 230 ° C. for 20 minutes in a clean oven to prepare a substrate A. Further, in order to prepare the substrate on the opposite side, the substrate B was produced in the same manner as the above-mentioned alignment film film forming conditions by using the same ITO film forming substrate. Rubbing was carried out on the substrate A and the substrate B on which the alignment film was formed by using a rubbing apparatus (ING, EL03) under the condition of rubbing depth of 0.4 mm / 400 rpm.
The substrate A and the substrate B, which had been completed up to the rubbing of the alignment film, were subjected to the next cell manufacturing step. First, a Seal agent having a height of 5.5 μm was applied to the substrate A, and then prebaked on a hot plate at 100 ° C. for 60 seconds to volatilize the solvent. A 3.5 μm bead spacer was sprayed on the substrate B in the Glove box in order to maintain the cell Gap. The Seal agent was thermoset by stacking the substrate A on the substrate B, crimping it, and heating it in a clean oven at 230 ° C. for 60 minutes. Next, a vacuum liquid crystal injection device (SEIMITSU, CS320) was used to inject the liquid crystal for IPS into the cell. Then, the liquid crystal injection part was sealed with a UV curable type sealant. Furthermore, using a metal halide lamp exposure machine (USHIO, PLA-501F) ^{, exposure is performed so that the cumulative irradiation amount is 1 J / m 2,} and the light leakage evaluation cell is performed for 10 minutes on a hot plate at 80 ° C. Was produced.

<Light leakage evaluation method>
Polarizing plates were placed on the cloth above and below the cell produced by the above method, and were set to be displayed in black when no voltage was applied. A voltage of 4294A manufactured by Agilent was used, a voltage of 3 V was applied, and light leakage due to an electric field generated in the direction perpendicular to the rubbing direction was observed according to the following criteria. The evaluation results are shown in Table 3.

〔Evaluation criteria〕
◯: No light leakage △: Light leakage is weak (light leakage length is less than 0.3 mm)
X: Strong light leakage (light leakage length is 0.3 mm or more)

<Contrast ratio evaluation>
Evaluation of chromaticity characteristics Each of the obtained coloring compositions (S-1) to (S-57) was applied onto a glass substrate using a spin coater, and then prebaked on a hot plate at 100 ° C. for 2 minutes. Therefore, three coating films having different film thicknesses were formed. Next, after cooling these substrates to room temperature, a high-pressure mercury lamp was used for the coating film on the substrate, and radiation containing each wavelength of 365 nm, 405 nm, and 436 nm was applied to each coating film without using a photomask. Exposure was performed at an exposure rate of 000 J / m ^2. Then, post-baking was performed at 220 ° C. for 20 minutes to form a cured film on the substrate. The chromaticity coordinate values (x, y) in the CIE color system were measured with respect to the obtained three cured films using a color analyzer (MCPD2000 manufactured by Otsuka Electronics Co., Ltd.) with a C light source and a two-degree field of view. .. From the measurement results, the chromaticity coordinate value x and the stimulus value (Y) when the chromaticity coordinate value y = 0.59 were obtained.

The contrast of the three cured films obtained in the above "evaluation of chromaticity characteristics" was measured using a contrast meter (contrast measuring instrument CT-1 manufactured by Tsubosaka Electric Co., Ltd.). From the measurement result, the contrast ratio when the chromaticity coordinate value y = 0.59 was obtained. When the contrast ratio value was 9000 or more, it was evaluated as “◯”, when it was 8000 or more and less than 9000, it was evaluated as “Δ”, and when it was less than 8000, it was evaluated as “x”. The evaluation results are shown in Table 3.

Claims (11)

A coloring composition containing (A) a colorant containing a metal halide phthalocyanine pigment, (B) a binder resin, and (C) a polymerizable compound.
(A) The colorant further contains a quinophthalone compound represented by the following formula (1).
(A ¹⁾ and the halogenated metal phthalocyanine pigment, in (A ²⁾ mass ratio of the quinophthalone compound represented by the following formula ^{(1) [(A 1)} / (A 2)] is 99 / 1-85 / 15 is there,
Coloring composition.

[In equation (1),
R ^{1 to} R ¹³ are independently hydrogen atom; halogen atom; alkyl group which may have a substituent; alkoxy group which may have a substituent; and an aryl group which may have a substituent; showing a or an optionally substituted sulfamoyl group; -SO ₃ H, -COOH or a monovalent to trivalent metal salt or alkyl ammonium salt thereof acidic group; an optionally substituted phthalimidomethyl group .. However, ^{at least one adjacent set of groups from R 1 to} R ⁴ and / or at least one adjacent set of groups from R ^{10 to} R ¹³ together have a substituent. Form an aromatic ring which may be used. ] (A ¹ ) The coloring composition according to claim 1, wherein the content ratio of the metal halide phthalocyanine pigment is 61 to 79% by mass with respect to the total colorant. (A ² ) The coloring composition according to claim 1 or 2, wherein the content ratio of the quinophthalone compound is 0.5 to 11% by mass with respect to the total colorant. (A ¹ ) Any one of claims 1 to 3, wherein the metal halide phthalocyanine pigment is one or more selected from a halogenated copper phthalocyanine pigment, a halogenated zinc phthalocyanine pigment, and a halogenated aluminum phthalocyanine pigment. The coloring composition according to. The method according to any one of claims 1 to 4, wherein the mass ratio [(B) / (C)] of the binder resin (B) to the polymerizable compound (C) is 95/5 to 61/39. Coloring composition. The (A) colorant further comprises at least one selected from an azo pigment and a quinophthalone pigment other than the ^{(A 2} ) quinophthalone compound as a colorant other than the ^{(A 1} ) metal halide phthalocyanine pigment and the (A ^{2) quinophthalone compound.} The coloring composition according to any one of claims 1 to 5, which comprises. A colored cured film which is a cured product of the colored composition according to any one of claims 1 to 6. A color filter comprising the colored cured film according to claim 7. A display element comprising the colored cured film according to claim 7. A light receiving element comprising the colored cured film according to claim 7. A light emitting device comprising the colored cured film according to claim 7.