TW201316123A - Coloring composition for color filter, color filter and display element - Google Patents

Abstract

The present invention provides a coloring composition for color filter having excellent chromaticity, good dispersibility and storage stability. The coloring composition for color filter is characterized by containing (A)colorant comprising quinophthalone pigment, (B)copolymer, (C)cross-linking agent. The (B)copolymer includes repeating unit represented by following formula (1) and repeating unit represented by following formula (2) and has amine value of 80-250mgKOH/g. [In formula(1), R1 represents a hydrogen atom or a methyl group, Z represents -NR2R3 or a substituted or unsubstituted nitrogen-containing heterocyclic group(R2 and R3 are independently of each other, represent hydrogen atoms or substituted or unsubstituted hydrocarbon groups.), X1 represents a divalent linking group. In formula(2), R4 represents a hydrogen atom or a methyl group, R5 represents a hydrocarbon group or an alicyclic aliphatic hydrocarbon group].

Description

Coloring composition, color filter and display element for color filters

The present invention relates to a coloring composition for a color filter, a color filter, and a display element, and more particularly to a coloring composition for a color filter used to form a coloring layer useful for a color filter. The color filter is used for a transmissive or reflective type color liquid crystal display element, a solid-state imaging element, an organic EL display element, electronic paper, or the like; a color filter including a coloring layer formed using the colored composition; A display element of the color filter.

When a color filter is produced using a coloring sensitizing radiation composition, a method is known in which a pigment dispersion type sensitizing radiation linear composition is applied onto a substrate and dried, and the dried coating film is applied in a desired pattern shape. Radiation rays (hereinafter referred to as "exposure") are irradiated and developed to obtain pixels of respective colors (for example, Patent Documents 1 and 2). Further, a method of forming a black matrix by using a photopolymerizable composition in which carbon black is dispersed is also known (for example, Patent Document 3). Further, a method of obtaining pixels of respective colors by an inkjet method using a pigment dispersion type colored resin composition is also known (for example, Patent Document 4).

However, in the field of color filters used for liquid crystal display elements or solid-state imaging elements, the pigments used tend to be more and more micronized with the demand for higher brightness and higher contrast. It is known that it is effective to use a dispersant in order to achieve stable and good dispersion of such microparticulated pigments. It has been proposed to use the dispersant to improve the dispersibility of the pigment, and to improve not only the contrast and the dispersion stability but also various developability and the like. Method (for example, Patent Documents 5 to 6).

[Previous Technical Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open No. 2-144502

[Patent Document 2] Japanese Patent Laid-Open No. 3-53201

[Patent Document 3] Japanese Patent Laid-Open No. Hei 6-35188

[Patent Document 4] Japanese Patent Laid-Open Publication No. 2000-310706

[Patent Document 5] Japanese Patent Laid-Open Publication No. 2003-26949

[Patent Document 6] Japanese Patent Laid-Open Publication No. 2009-25813

However, even in the methods described in Patent Documents 5 to 6, it has been difficult to achieve high contrast, high color purity, and high brightness of color liquid crystal display elements in recent years. In particular, when a quinophthalone pigment represented by CI Pigment Yellow 138 is used as a colorant, there is a problem in that the pigment dispersion solution prepared by the conventional dispersion method and a known dispersant has high viscosity, and The storage stability is deteriorated and it is difficult to be practical, and the contrast of the color filter prepared using the pigment dispersion solution is insufficient. For this reason, it has been strongly demanded to develop a coloring composition for a color filter which is excellent in dispersibility and storage stability, and which is required to achieve high contrast, high color purity, and high brightness in recent years.

Therefore, an object of the present invention is to provide a coloring composition for a color filter which is excellent in chromaticity characteristics and excellent in dispersibility and storage stability, using a quinophthalone pigment represented by C.I. Pigment Yellow 138 as a coloring agent. . Further, another object of the present invention is to provide a color filter including a coloring layer formed of the coloring composition, and a display element including the color filter.

In view of the above, the inventors of the present invention conducted intensive studies and found that the above problems can be solved by using a copolymer having a specific repeating unit, and completed the present invention.

That is, the present invention provides a coloring composition for a color filter comprising the following components (A), (B), and (C): (A) a coloring agent containing a quinophthalone pigment; (B) a repeating unit represented by the following formula (1) (hereinafter also referred to as "repeating unit (1)") and a repeating unit represented by the following formula (2) [hereinafter also referred to as "repeating unit (2)"), and an amine A copolymer having a valence of 80 to 250 mgKOH/g (hereinafter also referred to as "(B) copolymer"); and (C) a crosslinking agent.

[In the formula (1), R ¹ represents a hydrogen atom or a methyl group, and Z represents -NR ² R ³ (wherein R ² and R ³ independently of each other represent a hydrogen atom or a substituted or unsubstituted hydrocarbon group) or a substitution or a non- Substituted nitrogen-containing heterocyclic group, X ¹ represents a divalent linking group. ]

In the formula (2), R ⁴ represents a hydrogen atom or a methyl group, and R ⁵ represents an aliphatic hydrocarbon group or an alicyclic hydrocarbon group. ]

Further, the present invention provides a color filter including a coloring layer formed using the colored composition, and a display element including the color filter. Here, the "colored layer" refers to each color pixel, black matrix, black spacer, or the like used for the color filter.

Further, the present invention provides a pigment dispersion liquid for a color filter comprising the following components (a1), (B) and (F): (a1) quinophthalone pigment; (B) containing a repeat a unit (1) and a repeating unit (2), and a copolymer having an amine value of 80 to 250 mgKOH/g; and (F) a solvent.

The coloring composition for a color filter of the present invention is excellent in chromaticity characteristics, and is excellent in dispersibility and storage stability. When the colored composition of the present invention is used, a color filter having pixels of various colors having high contrast can be obtained.

Therefore, the coloring composition for a color filter of the present invention can be extremely suitably used for producing a color filter for color liquid crystal display elements, a color filter for color separation of solid-state imaging elements, and color filter for organic EL display elements. Various color filters including chips and electronic paper color filters.

[Formation of the Invention]

Hereinafter, the present invention will be described in detail.

Coloring composition for color filter

Hereinafter, the constituent components of the coloring composition for a color filter (hereinafter, simply referred to as "coloring composition") of the present invention will be described.

- (A) colorant -

The colored composition of the present invention contains (a1) a quinophthalone pigment as the (A) colorant.

The quinacridone pigment is preferably C.I. Pigment Yellow 138 from the viewpoint of availability of the raw material and absorption spectrum.

In the present invention, the (a1) quinacridone pigment may be used singly or in combination of two or more. Further, the colored composition of the present invention may further contain (a2) another coloring agent while containing the (a1) quinacridone pigment. The other coloring agent (a2) is not particularly limited. For example, by using the (a1) quinacridone pigment together with a green coloring agent, a coloring composition for forming a green pixel can be obtained. Further, by using the (a1) quinacridone pigment together with a red coloring agent, a colored composition for forming a red pixel or a yellow pixel can be obtained.

In the case of (a2) other coloring agents, any of pigments, dyes, and natural colors other than the quinophthalone pigment may be used, but in terms of obtaining pixels having high luminance and color purity, it is preferably Organic pigments, organic dyes. As the organic pigment, a compound classified as a pigment in a color index (C.I.; issued by The Society of Dyers and Colourists), that is, a compound having a color index (C.I.) name as described below can be cited.

CI Pigment Yellow 12, CI Pigment Yellow 13, CI Pigment Yellow 14, CI Pigment Yellow 17, CI Pigment Yellow 20, CI Pigment Yellow 24, CI Pigment Yellow 31, CI Pigment Yellow 55, CI Pigment Yellow 83, CI Pigment Yellow 93, CI Pigment Yellow 109, CI Pigment Yellow 110, CI Pigment Yellow 138, CI Pigment Yellow 139, CI Pigment Yellow 150, CI Pigment Yellow 153, CI Pigment Yellow 154, CI Pigment Yellow 155, CI Pigment Yellow 166, CI Pigment Yellow 168, CI Pigment Yellow 180, CI Pigment Yellow 211; CI Pigment Orange 5, CI Pigment Orange 13, CI Pigment Orange 14, CI Pigment Orange 24, CI Pigment Orange 34, CI Pigment Orange 36, CI Pigment Orange 38, CI Pigment Orange 40, CI Pigment Orange 43, CI Pigment Orange 46, CI Pigment Orange 49, CI Pigment Orange 61, CI Pigment Orange 64, CI Pigment Orange 68, CI Pigment Orange 70, CI Pigment Orange 71, CI Pigment Orange 72, CI Pigment Orange 73, CI Pigment Orange 74; CI Pigment Red 1, CI Pigment Red 2, CI Pigment Red 5, CI Pigment Red 17, CI Pigment Red 31, CI Pigment Red 32, CI Pigment Red 41, CI Pigment Red 122, CI Pigment Red 123, CI Pigment Red 144, CI Pigment Red 149, CI Pigment Red 166, CI Pigment Red 168, CI Pigment Red 1 70, CI Pigment Red 171, 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 185, CI Pigment Red 187, CI Pigment Red 202, CI Pigment Red 206, CI Pigment Red 207, CI Pigment Red 209, CI Pigment Red 214, CI Pigment Red 220, CI Pigment Red 221, CI Pigment Red 224, CI Pigment Red 242, CI Pigment Red 243, CI Pigment Red 254, CI Pigment Red 255, CI Pigment Red 262, CI Pigment Red 264, CI Pigment Red 272; CI pigment violet 1, CI pigment violet 19, CI pigment violet 23, CI pigment violet 29, CI pigment violet 32, CI pigment violet 36, CI pigment violet 38; CI pigment blue 1, CI pigment blue 15, CI pigment blue 15: 3, CI Pigment Blue 15:4, CI Pigment Blue 15:6, CI Pigment Blue 60, CI Pigment Blue 80; CI Pigment Green 7, CI Pigment Green 36, CI Pigment Green 58; CI Pigment Brown 23, CI Pigment Brown 25 C. Pigment Black 1 and CI Pigment Black 7; the xanthene-based lake pigments described in Japanese Laid-Open Patent Publication No. 2010-26334, and the Japanese Patent Publication No. 2011-22502 The triaryl methane-based lake pigment described in JP-A-2011-138094, and JP-A-2011-22502; JP-A-2010-237569, JP-A-2011-6602 Various lake pigments described in Japanese Laid-Open Patent Publication No. 2011-150195.

Further, as the organic dye, for example, a compound having the color index (C.I.) name as described below can be mentioned.

CI Acid Yellow 11, CI Acid Orange 7, CI Acid Red 37, CI Acid Red 180, CI Acid Blue 29, CI Direct Red 28, CI Direct Red 83, CI Direct Yellow 12, CI Direct Orange 26, CI Direct Green 28, CI Direct Green 59, CI Reactive Yellow 2, CI Reactive Red 17, CI Reactive Red 120, CI Reactive Black 5, CI Disperse Orange 5, CI Disperse Red 58, CI Disperse Blue 165, CI Basic Blue 41, CI Alkali Red 18, CI mordant red 7, CI mord yellow 5 , CI mordant black 7 and other azo dyes; CI Indigo 4, CI Acid Blue 40, CI Acid Green 25, CI Reactive Blue 19, CI Reactive Blue 49, CI Disperse Red 60, CI Disperse Blue 56, CI Disperse Blue 60 Isocyanine dyes; phthalocyanine dyes such as CI Indigo 5; succinimide dyes such as CI Basic Blue 3, CI Basic Blue 9; CI Solvent Yellow 33, CI Acid Yellow 3, CI Disperse Yellow 64, etc. A phthalic dye; a nitro dye such as CI acid yellow 1, CI acid orange 3, CI disperse yellow 42, and a methine dye such as CI disperse yellow 201.

In the present invention, (a2) the other coloring agents may be used singly or in combination of two or more.

In the present invention, the pigment may be purified and used by a recrystallization method, a reprecipitation method, a solvent washing method, a sublimation method, a vacuum heating method, or a combination thereof. Further, the pigment may be used by modifying the surface of the particles with a resin as needed. For example, the resin for modifying the surface of the pigment particles, for example, the color-developing resin described in JP-A-2001-108817, or various commercially available pigment dispersion resins. For the resin coating method on the surface of the carbon black, a method described in, for example, JP-A-H09-71733, JP-A-H09-95625, JP-A-9-124969, and the like can be employed. Further, the organic pigment can be used by refining the primary particles by a so-called salt polishing method. For the method of the salt milling method, for example, a method disclosed in Japanese Laid-Open Patent Publication No. Hei 08-179111 can be employed.

When the coloring composition of the present invention is used for the formation of a green pixel, the (A) coloring agent preferably contains a coloring agent selected from the group consisting of CI Pigment Green 7, CI Pigment Green, and the (a1) quinacridone pigment. At least one of 36 and CI Pigment Green 58. In this case, the content ratio of the (a1) quinacridone pigment is preferably from 1 to 80% by mass, more preferably from 2 to 70% by mass, based on the total amount of the coloring agent, and is selected from CI Pigment Green 7, CI Pigment Green 36, and CI. The total content of at least one of the pigment greens 58 is preferably from 20 to 99% by mass, and more preferably from 30 to 98% by mass, based on the total of the colorants.

In view of forming a pixel having high luminance, excellent color purity, or a black matrix having excellent light-shielding properties, the content of the colorant (A) is usually 5 to 70% by mass, preferably 5, in the solid content of the colored composition. ~60% by mass. Here, the solid component is a component other than the solvent described later.

-(B) Copolymer -

The (B) copolymer in the present invention is a copolymer having a repeating unit (1) and a repeating unit (2) and having an amine value of 80 to 250 mgKOH/g, and functions as a dispersing agent for the (A) coloring agent.

The repeating unit (1) is a repeating unit represented by the above formula (1).

In the above formula (1), in the case of R ¹ , a methyl group is preferred among the hydrogen atom and the methyl group.

In the above formula (1), Z represents -NR ² R ³ or a substituted or unsubstituted nitrogen-containing heterocyclic group, and R ² and R ³ independently of each other represent a hydrogen atom, or a substituted or unsubstituted hydrocarbon group, in the present invention The term "hydrocarbon group" means a concept including an aliphatic hydrocarbon group, an alicyclic hydrocarbon group, and an aromatic hydrocarbon group, and may be any of a linear form, a branched form, and a cyclic form, and may be a saturated hydrocarbon group or a Unsaturated hydrocarbon group. Further, the unsaturated bond of the unsaturated hydrocarbon group may be at any position within the molecular chain and at the end of the molecular chain.

The aliphatic hydrocarbon group is preferably an aliphatic hydrocarbon group having 1 to 20 carbon atoms, more preferably 1 to 12 carbon atoms, and more specifically, 1 to 20 carbon atoms, and more preferably 1 carbon atom. The alkyl group of ~12, an alkenyl group having 2 to 20 carbon atoms, more preferably 2 to 12 carbon atoms, an alkynyl group having 2 to 20 carbon atoms, more preferably 2 to 12 carbon atoms. Specifically, examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a secondary butyl group, a tertiary butyl group, a pentyl group, and an isopentyl group. , hexyl, heptyl, octyl, decyl, dodecyl and the like. Further, examples of the alkenyl group include a vinyl group, a 1-propenyl group, a 1-butenyl group, a 1,3-butadienyl group, a 1-pentenyl group, a 2-pentenyl group, and a 1-hexyl group. Alkenyl, 2-ethyl-2-butenyl, 2-octenyl, (4-vinyl)-5-hexenyl, 2-decenyl, etc., and examples of the alkynyl group include Ethynyl, 1-propynyl, 1-butynyl, 1-pentynyl, 3-pentynyl, 1-hexynyl, 2-ethyl-2-butynyl, 2-octynyl, (4-ethynyl)-5-hexynyl, 2-decynyl and the like.

Further, the alicyclic hydrocarbon group is preferably an alicyclic hydrocarbon group having 3 to 20 carbon atoms, more preferably 3 to 12 carbon atoms, and specific examples thereof include 3 to 20 carbon atoms and further More preferably, it is a cycloalkyl group of 3 to 12, and more specifically, a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, a cyclodecyl group, a cyclododecyl group Wait. Here, the "alicyclic hydrocarbon group" in the present invention means a general term for removing an aromatic compound in a carbocyclic compound having a structure in which a carbon atom is bonded to a ring, and further includes the above aliphatic hydrocarbon group as a substituent or - The base of the COO-connection.

Further, in the above aromatic hydrocarbon group, it is preferably 6 carbon atoms More preferably, it is 6 to 14, more preferably 6 to 10, of an aromatic hydrocarbon group, and more specifically, it has 6 to 20 carbon atoms, more preferably 6 to 14 carbon atoms, and still more preferably Good for 6 to 10 aryl groups. Here, the "aryl group" in the present invention means a monocyclic to 3-ring aromatic hydrocarbon group, and specific examples thereof include a phenyl group, a naphthyl group, an anthracenyl group, a phenanthryl group, an anthracenyl group and the like.

In addition, examples of the substituent of the hydrocarbon group include a halogen atom, a hydroxyl group, and an alkoxy group having 1 to 6 carbon atoms. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, and examples of the alkoxy group having 1 to 6 carbon atoms include a methoxy group, an ethoxy group, and a propoxy group. Base, isopropoxy, butoxy, pentyloxy, phenoxy and the like.

In the present invention, the "nitrogen-containing heterocyclic group" means a heterocyclic group having at least one nitrogen atom as a constituent element of the ring, preferably a monoheterocyclic group or a condensed condensed product of two of them. Ring base. These heterocyclic groups may be either an unsaturated ring or a saturated ring, or may have a hetero atom other than a nitrogen atom (for example, an oxygen atom or a sulfur atom) in the ring.

Examples of the unsaturated heterocyclic ring include a pyridine ring, an imidazole ring, and a thiazole ring. An azole ring, a triazole ring, an imidazoline ring, a tetrahydropyrimidine ring, and the like. Further, as for the saturated heterocyclic ring, for example, Phenanthene ring, piperidine ring, piperazine Ring and so on. Further, examples of the substituent in the nitrogen-containing heterocyclic group include an alkyl group having 1 to 6 carbon atoms, a halogen atom, a carboxyl group, an alkoxycarbonyl group, an alkoxy group, a hydroxyl group, an amine group, and a decylamine. Base, thiol group, thioether group, and the like. Examples of the alkyl group having 1 to 6 carbon atoms include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a tertiary butyl group, a pentyl group, a hexyl group and the like. A fluorine atom, a chlorine atom, a bromine atom, and an iodine atom are mentioned. The alkoxycarbonyl group is, for example, preferably an alkoxycarbonyl group having 2 to 7 carbon atoms, and specific examples thereof include a methoxycarbonyl group, an ethoxycarbonyl group, a methyloxy group, and an ethyloxy group. Benzoyloxy and the like. The alkoxy group is preferably an alkoxy group having 1 to 6 carbon atoms, and specific examples thereof include a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, a butoxy group, and a pentyl group. Oxyl, phenoxy, and the like. Examples of the amine group include an amine group, a methylamino group, a diethylamino group, and a diphenylamino group. Examples of the guanamine group include a formamidine group and an acetamide. Base, propylamine, and the like. The thioether group is preferably a thioether group having 1 to 6 carbon atoms, and specific examples thereof include a methyl sulfide group, an ethyl sulfide group, and a butyl sulfide group.

The monoheterocyclic group is preferably a 5- to 7-membered ring, and specifically, a group having a basic skeleton represented by the following formula (1-1), and these monoheterocyclic groups may have a substituent.

In the formula (1-1), "*" indicates a bonding site (bonding hand).

In addition, the condensed heterocyclic group may specifically be a group having a basic skeleton represented by the following formulas (1-2) to (1-4), and these condensed heterocyclic groups may have a substituent.

In the formulas (1-2) to (1-4), "*" indicates a bonding site.

In the above formula (1), the divalent linking group (X ¹ ) may, for example, be an alkyldiyl group having 1 to 10 carbon atoms and 1 to 6 carbon atoms; and 6 to 20 carbon atoms; There are 6 to 14 exoaryl groups; -CONH-R ¹⁰ - groups; -COO-R ¹¹ - groups and the like. Here, R ¹⁰ and R ¹¹ are each independently a single bond, a C 1 to 10 carbon atom, an alkyl 2 group having 1 to 6 carbon atoms, or an alkylene oxide alkyl group having 2 to 10 carbon atoms. Examples of the alkanediyl group include a methylene group, an ethylidene group, an ethane-1,1-diyl group, a propane-1,1-diyl group, a propane-1,2-diyl group, and a propane-1. ,3-diyl, propane-2,2-diyl, butane-1,2-diyl, butane-1,3-diyl, butane-1,4-diyl, pentane-1, 4-diyl, pentane-1,5-diyl, hexane-1,5-diyl, hexane-1,6-diyl and the like. Further, examples of the aryl group include a stretching phenyl group, a stretching naphthyl group, a stretching biphenyl group, an anthranylene group, and the like. Examples of the alkyleneoxyalkylene group having 2 to 10 carbon atoms include an exoethyloxyethyl group, an exoethoxy propyl group, a propoxy propyl group, and an ethoxylated butyl group.

Among them, in the case of X ¹ , a -COO-R ¹¹ - group is preferred, and in the case of R ¹¹ , an alkanediyl group having 2 to 6 carbon atoms is preferred.

The repeating unit (2) is a repeating unit represented by the above formula (2).

In the above formula (2), in the case of R ⁴ , a methyl group is preferred among the hydrogen atom and the methyl group.

The aliphatic hydrocarbon group in R ⁵ may, for example, be an alkyl group, an alkenyl group or an alkynyl group. The aliphatic hydrocarbon group may be in any one of a linear form and a branched form. When the aliphatic hydrocarbon group is an alkenyl group or an alkynyl group, the position of the unsaturated bond may be at any position within the molecular chain and at the end of the molecular chain.

Further, examples of the alicyclic hydrocarbon group in R ⁵ include a cycloalkyl group, a cycloalkenyl group, a condensed polycyclic hydrocarbon group, a bridged cyclic hydrocarbon group, a spirocyclic hydrocarbon group, and a cyclic terpene group. The alicyclic hydrocarbon group may further have a substituent, and examples of the substituent include a halogen atom, a hydroxyl group, and an alkoxy group having 1 to 6 carbon atoms. Specific examples of the substituents include the same substituents as described above.

In particular, R ^{5 is} preferably an alkyl group having 1 to 15 carbon atoms, more preferably 1 to 12 carbon atoms, and an alicyclic hydrocarbon group having 3 to 20 carbon atoms, more preferably 4 to 15 carbon atoms. In particular, it is preferably methyl, ethyl, propyl, butyl, isobutyl, tert-butyl, 2-ethylhexyl, isodecyl, dodecyl, cyclohexyl, tert-butyl ring Hexyl, decahydro-2-naphthyl, tricyclo[5.2.1.0 ^2,6 ]decane-8-yl, adamantyl, dicyclopentenyl, pentacyclopentadecyl, tricyclopentenyl, Heteroquinone.

(B) The copolymer may have a repeating unit other than the above, and examples of such a repeating unit include a repeating unit represented by the following formula (3) (hereinafter also referred to as "repeating unit (3)"); a repeating unit having an acidic group [hereinafter also referred to as "repeating unit (4)]; a repeating unit derived from a monomer such as a styrene monomer such as styrene or α-methylstyrene; (A) arylalkyl (meth) acrylate such as benzyl acrylate; (meth) propylene oxiranyl ethyl (4-benzylidene benzyl) dimethyl ammonium bromide, (meth) propylene oxime (Meth) acrylate having a quaternary ammonium salt structure such as benzyl dimethyl ammonium chloride or (meth) propylene oxiranyl oxyethyl dimethyl ammonium chloride; (meth) acrylonitrile, etc. (Methyl) propylene fluorene halogen monomer; (meth) acrylamide, N-methylol acrylamide (methyl) acrylamide monomer; vinyl acetate; acrylonitrile; allyl shrinkage Glycerol ether; glycidyl butenoate; N-methyl propylene sulfhydryl Monomer such as phenyl. Among them, from the viewpoint of dispersibility, it is preferred to have at least one of the repeating unit (3) and the repeating unit (4), and more preferably, the repeating unit (3). Here, in the present invention, "(meth) acrylate" means "acrylate or methacrylate".

[In the formula (3), R ⁶ represents a hydrogen atom or a methyl group, R ⁷ independently of each other represents an alkanediyl group having 2 to 4 carbon atoms, R ⁸ represents an alkyl group having 1 to 6 carbon atoms, and n represents 1 An integer of ~150. ]

In the formula (3), in the case of R ⁶ , a methyl group is preferred among the hydrogen atom and the methyl group.

Further, examples of the alkanediyl group of R ⁷ include an exoethyl group, an ethane-1,1-diyl group, a propane-1,1-diyl group, a propane-1,2-diyl group, and a propane- 1,3-diyl, propane-2,2-diyl, butane-1,2-diyl, butane-1,3-diyl, butane-1,4-diyl, and the like.

The alkyl group of R ⁸ may be the same as the above.

n represents an integer of 1 to 150, preferably an integer of 1 to 20, more preferably an integer of 1 to 10, and particularly preferably an integer of 1 to 5.

The repeating unit (4) has an acidic group, and the acidic group is not particularly limited, and examples thereof include a phenolic hydroxyl group, a carboxyl group, a sulfo group, -SO ₂ NH ₂ , and -C(CF ₃ ) ₂ -OH. In the present invention, the acidic group is preferably a phenolic hydroxyl group or a carboxyl group, and particularly preferably a carboxyl group, from the viewpoint of dispersibility and alkali developability of the obtained coloring composition.

The repeating unit (4) is, for example, a repeating unit represented by the following formula (4).

In the formula (4), R ⁹ represents a hydrogen atom or a methyl group, A represents an acidic group, and X ² represents a single bond or a divalent linking group. ]

In the above formula (4), in the case of R ⁹ , a methyl group is preferred among a hydrogen atom and a methyl group.

Examples of the divalent linking group (X ² ) include an alkyldiyl group having 1 to 10 carbon atoms and 1 to 6 carbon atoms, an extended aryl group, a -CONH-R ¹² - group, and a -COO-R. ¹³ -based, -OCOR ¹⁴ -yl, -R ¹⁵ -OCO-R ¹⁶ -, -COO-(C _m H _2m COO) _l -C _m H _2m -yl, -COO-R ¹⁷ -OCO-R ¹⁸ - Wait. Here, R ¹² to R ¹⁶ each independently represent a single bond, a C 1 to 10 carbon number, a 1 to 6 alkylenediyl group, or a C 2 to 10 alkyloxyalkylene group, and m represents 1 An integer of ~10, l represents an integer of 1 to 4, R ¹⁷ represents a carbon number of 1 to 10, and an alkyl 2 group of 1 to 6, and R ¹⁸ represents a single bond, a carbon number of 1 to 10, and 1 to 6 alkanediyl, cyclohexane-1,2-diyl or phenyl (for example, 1,2-phenylene, 1,4-phenylene). Specific examples of the alkanediyl group, the extended aryl group, and the alkoxyalkylene group include the same groups as described above.

Wherein, in the case of X ² , a single bond, a phenyl group, a -COO-R ¹³ - group, a -COO-(C _m H _2m COO) _l -C _m H _2m - group or -COO-R ^{17 is} preferred. -OCO-R ¹⁸ -.

In the (B) copolymer, the copolymerization ratio of each repeating unit is not particularly limited as long as the amine value of the copolymer is in the range of 80 to 250 mgKOH/g, and from the viewpoint of dispersibility, the following is preferred ( Any of i) to (iii), more preferably any of (ii) and (iii).

(i) When the (B) copolymer is composed only of the repeating structure (1) and the repeating structure (2), the copolymerization ratio of the repeating structure (1) is preferably from 20 to 80% by mass, more preferably 30%, in all the repeating units. ~70% by mass, further preferably 40 to 60% by mass, and the copolymerization ratio of the repeating structure (2) is the remainder.

(ii) When the (B) copolymer has a repeating unit (3) other than the repeating structure (1) and the repeating structure (2), the copolymerization ratio of the repeating structure (1) is preferably 20 to 70 mass in all the repeating units. %, more preferably 30 to 65% by mass, still more preferably 40 to 60% by mass, and the copolymerization ratio of the repeating structure (2) is preferably 5 to 50% by mass, more preferably 10 to 45% by mass in all the repeating units. Further, it is more preferably 15 to 40% by mass, and the copolymerization ratio of the repeating structure (3) is preferably 5 to 40% by mass, and more preferably 10 to 30% by mass, based on all the repeating units.

(iii) (B) Copolymer having a repeating unit (3) and a repeating unit (4) other than the repeating structure (1) and the repeating structure (2), copolymerization of the repeating structure (1) The ratio is preferably 20 to 70% by mass, more preferably 30 to 65% by mass, still more preferably 40 to 60% by mass in all the repeating units, and the copolymerization ratio of the repeating structure (2) is preferably in all the repeating units. 5 to 50% by mass, more preferably 10 to 45% by mass, still more preferably 15 to 40% by mass, and the copolymerization ratio of the repeating structure (3) is preferably 5 to 40% by mass in all the repeating units, further preferably It is 10 to 30% by mass, and the copolymerization ratio of the repeating structure (4) is preferably from 1 to 10% by mass, and more preferably from 1 to 5% by mass, based on all the repeating units.

(B) The amine value of the copolymer is from 80 mgKOH/g to 250 mgKOH/g, and from the viewpoint of further improving the contrast, it is preferably from 100 to 250 mgKOH/g, more preferably from 150 to 250 mgKOH/g, still more preferably from 150 to 200 mgKOH. /g, particularly preferably 155 to 190 mgKOH/g. In the present invention, the "amine value" refers to the number of mg of KOH required for neutralizing the acid equivalent of 1 g of the nonvolatile component obtained by removing the solvent of the copolymer solution, and specifically, the following description is carried out. The value obtained by the method described in the example.

On the other hand, when the (B) copolymer has a repeating unit (4), the acid value of the (B) copolymer is preferably 30 mgKOH/g or less, more preferably 25 mgKOH/g or less, from the viewpoint of storage stability, and further More preferably, it is 20 mgKOH/g or less. The lower limit is not particularly limited, but is preferably 0.5 mgKOH/g or more, more preferably 1 mgKOH/g or more. In the present invention, the term "acid value" means the number of mg of KOH required to neutralize 1 g of the nonvolatile component obtained by removing the solvent of the copolymer solution, and specifically, it is described in the examples described later. The value obtained by the method.

(B) the copolymer has no repeating unit (1) and repeating unit (2) Particularly, from the viewpoint of further improving the dispersibility, a block copolymer comprising an A block having a repeating unit (1) and having no repeating unit (2), and repeating is preferred. Unit (3) and repeating unit (4), which has no repeating unit (1) but has repeating unit (2) and repeating unit (3) and has repeating unit (4) as needed. The block copolymer is preferably an A-B block copolymer or a B-A-B block copolymer.

In the A block, two or more kinds of repeating units (1) may be contained in one A block. In this case, in the A block, each of the random copolymer and the block copolymer may be contained. Repeat unit.

Further, the A block may contain a repeating unit other than the repeating unit (1), and examples of such a repeating unit include a repeating of the (meth) acrylate having the above quaternary ammonium salt structure. unit.

On the other hand, in the B block, the repeating unit (2), the repeating unit (3), and the repeating unit (4) may be contained in any of random copolymerization and block copolymerization. (B) When the copolymer is a BAB block copolymer, it may be a B1-A-B2 block copolymer having a B1 block and a B2 block having a repeating unit (2) and a repeating unit (3) And without repeating unit (4) having repeating unit (2) and repeating unit (4) and having no repeating unit (3). Further, two or more of the repeating unit (2), the repeating unit (3), and the repeating unit (4) may be contained in one B block, and in this case, random copolymerization and block may be used in the B block. Any of the forms of copolymerization contains each repeating unit.

(B) The copolymer can be produced by a known method. However, when the (B) copolymer is a block copolymer, for example, it can be produced by living-polymerizing a monomer introduced into each of the above repeating units. In terms of living polymerization, For example, the following method can be employed: Japanese Laid-Open Patent Publication No. Hei 9-62002; Japanese Laid-Open Patent Publication No. 2002-31713; P. Lutz, P. Masson et al, Polym. Bull. 12, 79 (1984); BC Anderson, GD Andrews Et al, Macromolecules, 14, 1601 (1981); K. Hatada, K. Ute, et al, Polym. J. 17, 977 (1985); K. Hatada, K. Ute, et al, Polym. J. 18, 1037 (1986); Right Hand Hao Yi, Putian Gengyi, Polymer Processing, 36.366 (1987); Dong Cun Min Yan, Ze Benguang, Molecular Proceedings, 46, 189 (1989); M. Kuroki, T. Aida, J. Am. Soc, 109, 4737 (1987); Xiangtian Zhuo San, Inoue Xiangping, Organic Synthetic Chemistry, 43, 300 (1985); DY Sogoh, WR Hertler et al, Macromolecules, 20, 1473 (1987); J. Polym. Sci. Part A Polym .Chem., 47, 3773-3794 (2009); J. Polym. Sci. Part A Polym. Chem., 47, 3544-3557 (2009), etc., a well-known method.

Examples of the monomer which provides the repeating unit (1) include dimethylaminoethyl (meth)acrylate, diethylaminoethyl (meth)acrylate, and dimethylamino (meth)acrylate. Propyl ester, diethylaminopropyl (meth)acrylate, and the like. These monomers may be used singly or in combination of two or more kinds.

Examples of the monomer that provides the repeating unit (2) include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, and isopropyl (meth)acrylate. Butyl (meth)acrylate, isobutyl (meth)acrylate, tertiary butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, isodecyl (meth)acrylate, (A) Base) lauryl acrylate, cyclohexyl (meth) acrylate, tricyclo [5.2.1.0 ^2,6 ]decane-8-yl ester, isodecyl (meth) acrylate, Adamantyl (meth)acrylate, dicyclopentenyl (meth)acrylate, decahydro-2-naphthyl (meth)acrylate, pentacyclopentadecyl (meth)acrylate, (methyl) ) Tricyclopentene acrylate or the like. These monomers may be used singly or in combination of two or more.

Examples of the monomer which provides the repeating unit (3) include 2-methoxyethyl (meth)acrylate, methoxydiethylene glycol (meth)acrylate, and methoxytriethylene. Alcohol (meth) acrylate, methoxy propylene glycol (meth) acrylate, methoxy dipropylene glycol (meth) acrylate, and the like. These monomers may be used singly or in combination of two or more.

Further, examples of the monomer which provides the repeating unit (4) include (meth)acrylic acid, maleic acid, maleic anhydride, itaconic acid, itaconic anhydride, and carboxymethyl (meth)acrylate. 2-carboxyethyl (meth)acrylate, mono[2-(methyl)propenyloxyethyl] succinate, ω-carboxypolycaprolactone mono(meth)acrylate, p-vinylbenzoic acid, P-hydroxystyrene, p-hydroxy-α-methylstyrene, 2-propenyloxyethylsulfonic acid, 2-methylpropenyloxyethylsulfonic acid, sodium 2-propoxysulfonate, 2- Lithium ethoxide oxime sulfonate, ammonium 2-propenyl ethoxide sulfonate, imidazolium salt of 2-propenyl oxy oxy sulfonate, pyridinium salt of 2-propenyl oxy oxy sulfonate, 2-methyl Sodium propylene oxiranium sulfonate, lithium 2-methyl propylene sulfonium oxysulfonate, ammonium 2-methyl propylene sulfonium oxy sulfonate, imidazolium salt of 2-methyl propylene oxy oxy sulfonate, 2-methylpropenyl oxyethyl sulfonate pyridinium salt, styrene sulfonic acid, and the like. These monomers may be used singly or in combination of two or more.

The molecular weight of the (B) copolymer is Mw in terms of polymethyl methacrylate measured by GPC, preferably from 1,000 to 30,000, particularly preferably from 5,000 to 15,000.

In addition, (B) the Mw of the block copolymer and the use of GPC (eluent solvent: The ratio of Mn (Mw/Mn) in terms of polymethyl methacrylate measured by DMF) is preferably 1.0 to 1.9, more preferably 1.0 to 1.8, still more preferably 1.0 to 1.7, still more preferably 1.0 to 1.0. 1.5, especially good is 1.0~1.3. When the (B) copolymer is in this state, a colored composition excellent in dispersibility and alkali developability can be obtained.

(B) The copolymer may be used singly or in combination of two or more. The content of the (B) copolymer is usually from 1 to 100 parts by mass, preferably from 5 to 70 parts by mass, still more preferably from 10 to 50 parts by mass, per 100 parts by mass of the (A) colorant. If the content of the (B) copolymer is too large, the developability may be impaired.

In the present invention, in order to improve the dispersibility, a known dispersant may be further contained. Examples of the known dispersant include a polyurethane dispersant, a polyethyleneimine dispersant, a polyoxyethylene alkyl ether dispersant, and a polyoxyethylene alkylphenyl ether dispersion. Agent, polyethylene glycol diester dispersant, sorbitan fatty acid ester dispersant, polyester dispersant, acrylic dispersant, pigment derivative, and the like.

Such a dispersing agent can be obtained by a commercial pipe. For example, in the case of an acrylic dispersing agent, Disperbyk-2000, Disperbyk-2001, BYK-LPN6919, BYK-LPN21116, BYK-LPN21324 (above, BYK CHEMIE) can be cited. Examples of the polyurethane dispersant include Disperbyk-161, Disperbyk-162, Disperbyk-165, Disperbyk-167, Disperbyk-170, Disperbyk-182 (above, BYK CHEMIE), and Solsperse 76500 ( In the case of the polyethyleneimine dispersant, SolSperse 24000 (manufactured by LUBRIZOL Co., Ltd.) can be used as the polyester dispersion. Examples of the agent include Adisper PB821, Adisper PB822, Adisper PB880, and Adisper PB881 (manufactured by Ajinomoto Fine Chemical Co., Ltd.). Further, specific examples of the pigment derivative include a copper phthalocyanine, a diketopyrrolopyrrole, a sulfonic acid derivative of quinacridone, and the like.

-(C) Crosslinker -

In the present invention, the (C) crosslinking agent means a compound having two or more polymerizable groups. Examples of the group which can be polymerized include an ethylenically unsaturated group, an epoxy group, an oxetanyl group, and an N-alkoxymethylamino group. In the present invention, the (C) crosslinking agent is preferably a compound having two or more (meth)acryl fluorenyl groups or a compound having two or more N-alkoxymethylamino groups.

Specific examples of the compound having two or more (meth) acryloyl fluorenyl groups include polyfunctional (meth) acrylates and caprolactone obtained by reacting an aliphatic polyhydroxy compound with (meth)acrylic acid. Polyfunctional methacrylate obtained by reacting a modified polyfunctional (meth) acrylate, an alkylene oxide-modified polyfunctional (meth) acrylate, a hydroxyl group-containing (meth) acrylate, and a polyfunctional isocyanate A polyfunctional (meth) acrylate having a carboxyl group obtained by reacting a (meth) acrylate, a (meth) acrylate having a hydroxyl group, and an acid anhydride.

Here, examples of the aliphatic polyhydroxy compound include a binary aliphatic polyhydroxy compound such as ethylene glycol, propylene glycol, polyethylene glycol, or polypropylene glycol, such as glycerin or trimethylolpropane. A trivalent or higher aliphatic polyhydroxy compound such as neopentyl alcohol or dipentaerythritol. Examples of the (meth) acrylate having a hydroxyl group include 2-hydroxyethyl (meth)acrylate and trimethylolpropane di(methyl). Acrylate, pentaerythritol tri(meth)acrylate, dipentaerythritol penta(meth)acrylate, glyceryl dimethacrylate, and the like. The polyfunctional isocyanate may, for example, be toluene diisocyanate, hexamethylene diisocyanate, diphenylmethylene diisocyanate or isophorone diisocyanate. The acid anhydride may, for example, be an acid anhydride of a dibasic acid such as succinic anhydride, maleic anhydride, glutaric anhydride, itaconic anhydride, phthalic anhydride or hexahydrophthalic anhydride, such as a pyromelli-4. A tetrabasic acid dianhydride such as acid dianhydride, biphenyltetracarboxylic dianhydride, or benzophenone tetracarboxylic dianhydride.

In addition, the above-described caprolactone-modified polyfunctional (meth) acrylate may, for example, be a compound described in paragraphs [0015] to [0018] of JP-A-11-44955. The above-mentioned alkylene oxide-modified polyfunctional (meth) acrylate is modified by at least one selected from the group consisting of ethylene oxide selected from bisphenol A and propylene oxide of bisphenol A. Tri(meth)acrylic acid obtained by modifying at least one of bis(meth) acrylate obtained by using at least one selected from the group consisting of ethylene oxide of isomeric cyanuric acid and isomeric cyanuric acid a tris(meth)acrylate obtained by modifying at least one of ethylene oxide selected from ethylene oxide of trimethylolpropane and propylene oxide of trimethylolpropane, and using a selected one from the group a tri(meth)acrylate obtained by modifying at least one of ethylene oxide of an alcohol and propylene oxide of neopentyltetraol, using ethylene oxide selected from neopentyltetraol and neopentaerythritol At least one of propylene oxide of an alcohol is modified with at least one of tetrakis (meth) acrylate, and at least one selected from the group consisting of ethylene oxide selected from dipentaerythritol and propylene oxide of dipentaerythritol a modified one of five (meth) acrylates obtained by modifying at least one selected from the group consisting of ethylene oxide selected from dipentaerythritol and propylene oxide of dipentaerythritol six( Yl) acrylate.

In addition, examples of the compound having two or more N-alkoxymethylamino groups include a compound having a melamine structure, a benzoguanamine structure, and a urea structure. In addition, the melamine structure and the benzoguanamine structure mean that there are one or more three Ring or phenyl substituted three The chemical structure of the ring as a basic skeleton is also a concept including melamine, benzoguanamine or a condensate thereof. Specific examples of the compound having two or more N-alkoxymethylamino groups include N,N,N',N',N",N"-hexa(alkoxymethyl)melamine, N,N,N',N'-tetrakis(alkoxymethyl)benzoguanamine, N,N,N',N'-tetrakis(alkoxymethyl)glycolil and the like.

Among these crosslinking agents, a polyfunctional (meth) acrylate obtained by reacting a trivalent or higher aliphatic polyhydroxy compound with (meth)acrylic acid, or a caprolactone-modified polyfunctional (methyl) is preferred. Acrylate, polyfunctional urethane (meth) acrylate, polyfunctional (meth) acrylate having carboxyl group, N, N, N', N', N", N"-hexa (alkoxy) Methyl) melamine, N, N, N', N'-tetrakis(alkoxymethyl)benzoguanamine. The trivalent or higher aliphatic polyhydroxy compound is used in view of the fact that the strength of the colored layer is high, the surface smoothness of the colored layer is excellent, and the surface of the unexposed portion and the light shielding layer are less likely to cause floating stains and film residues. Among the polyfunctional (meth) acrylates obtained by the reaction of methyl methacrylate, trimethylolpropane triacrylate, neopentyl glycol triacrylate, di pentaerythritol pentaacrylate, and hexaacrylic acid are particularly preferred. Pentaerythritol ester; among polyfunctional (meth) acrylates having a carboxyl group, a compound obtained by reacting pentaerythritol triacrylate with succinic anhydride, dipentaerythritol pentaacrylate and amber are particularly preferred. The compound obtained by the reaction of an acid anhydride.

In the present invention, the (C) crosslinking agent may be used singly or in combination of two or more kinds. Used together.

The content of the (C) crosslinking agent in the present invention is preferably from 10 to 1,000 parts by mass, particularly preferably from 20 to 500 parts by mass, per 100 parts by mass of the (A) coloring agent. In this case, if the content of the crosslinking agent is too small, sufficient hardenability may not be obtained. On the other hand, when the content of the crosslinking agent is too large, the alkali developability of the colored composition of the present invention is lowered, and the alkali developability is lowered, and the surface of the unexposed portion or the light shielding layer is likely to be easily stained. The tendency of film residue and the like.

-(D) Adhesive Resin -

The coloring composition of the present invention may contain (D) a binder resin (excluding the above (B)). Thereby, the alkali developability of the colored composition and the adhesiveness to the substrate can be improved. The binder resin is not particularly limited, but is preferably a resin having an acidic functional group such as a carboxyl group or a phenolic hydroxyl group. In particular, a polymer having a carboxyl group (hereinafter referred to as a "carboxy group-containing polymer") is exemplified, and examples thereof include an ethylenically unsaturated monomer having one or more carboxyl groups (hereinafter referred to as "unsaturated monomer (d1)". ") Copolymer with other copolymerizable ethylenically unsaturated monomer (hereinafter referred to as "unsaturated monomer (d2)").

Examples of the unsaturated monomer (d1) include (meth)acrylic acid, maleic acid, maleic anhydride, succinic acid mono[2-(methyl)acryloxyethyl ester, and ω. - Carboxypolycaprolactone mono(meth)acrylate, p-vinylbenzoic acid, and the like.

These unsaturated monomers (d1) may be used alone or in combination of two or more.

Further, the unsaturated monomer (d2) may, for example, be an N-position substituted maleimide such as N-phenylmaleimide or N-cyclohexylmaleimide; An aromatic vinyl compound such as styrene, α-methylstyrene, p-hydroxystyrene, p-hydroxy-α-methylstyrene, p-vinylbenzyl glycidyl ether or decene; such as (methyl) Methyl acrylate, n-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, allyl (meth)acrylate, (meth)acrylic acid Benzyl ester, polyethylene glycol (degree of polymerization 2~10) methyl ether (meth) acrylate, polypropylene glycol (degree of polymerization 2~10) methyl ether (meth) acrylate, polyethylene glycol (degree of polymerization) 2~10) mono (meth) acrylate, polypropylene glycol (degree of polymerization 2~10) mono (meth) acrylate, cyclohexyl (meth) acrylate, isodecyl (meth) acrylate, (methyl Tricyclohexyl acrylate [5.2.1.0 ^2,6 ]decane-8-yl ester, dicyclopentenyl (meth)acrylate, glycerol mono(meth)acrylate, 4-hydroxyphenyl (meth)acrylate Ethylene oxide modified (meth) propylene of p-cumylphenol Ester, glycidyl (meth)acrylate, 3,4-epoxycyclohexylmethyl (meth)acrylate, 3-[(meth)acryloxymethyl]oxetane, 3-[ (Meth) acrylate such as (meth)acryloxymethyl]-3-ethyloxetane; such as cyclohexyl vinyl ether, isodecyl vinyl ether, tricyclic [5.2.1.0 a vinyl ether such as ^2,6 ]decane-8-yl vinyl ether, pentacyclopentadecyl vinyl ether or 3-(vinyloxymethyl)-3-ethyloxetane; a macromonomer having a mono(meth)acryloyl group at the end of a polymer molecular chain such as styrene, poly(methyl) methacrylate, poly(methyl) methacrylate, or polyoxyalkylene .

These unsaturated monomers (d2) may be used alone or in combination of two or more.

In the copolymer of the unsaturated monomer (d1) and the unsaturated monomer (d2), the copolymerization ratio of the unsaturated monomer (d1) in the copolymer is preferably from 5 to 50% by mass, further preferably from 10 ~40% by mass. By copolymerizing the unsaturated monomer (d1) in such a range, a coloring composition excellent in alkali developability and storage stability can be obtained.

Specific examples of the copolymer of the unsaturated monomer (d1) and the unsaturated monomer (d2) include, for example, JP-A-7-140654, JP-A-8-259876, and JP-A Japanese Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. The disclosed copolymers.

In the present invention, for example, Japanese Laid-Open Patent Publication No. Hei 5-19467, Japanese Patent Application Laid-Open No. Hei No. Hei. No. Hei. No. Hei. A carboxyl group-containing polymer having a polymerizable unsaturated bond such as a (meth) acrylonitrile group in a side chain may be used as a binder resin, as disclosed in JP-A-2008-181095, and the like.

The weight average molecular weight of the binder resin in the present invention measured by GPC (eluent solvent: tetrahydrofuran) in terms of polystyrene is usually 1,000 to 100,000, preferably 3,000 to 50,000. If the Mw is too small, the residual film ratio of the obtained film may be lowered, or the pattern shape, heat resistance, and the like may be impaired, and electrical characteristics may be deteriorated. On the other hand, if the film thickness is too large, the resolution may be lowered or the pattern shape may be impaired. When the coating is performed by the slit nozzle method, it becomes easy to generate dry foreign matter.

Further, the ratio (Mw'/Mn') of the weight average molecular weight (Mw') to the number average molecular weight (Mn') of the binder resin in the present invention is preferably from 1.0 to 5.0, more preferably from 1.0 to 3.0. Incidentally, Mw' and Mn' refer to a weight average molecular weight and a number average molecular weight in terms of polystyrene measured by GPC (eluent solvent: tetrahydrofuran).

The binder resin in the present invention can be produced by a known method, and can be disclosed, for example, in JP-A-2003-222717, JP-A-2006-259680, and International Publication No. 07/029871. The method is to control the structure, Mw, Mw/Mn of the binder resin.

In the present invention, the binder resin may be used singly or in combination of two or more.

In the present invention, the content of the binder resin is usually 10 to 1,000 parts by mass, preferably 20 to 500 parts by mass, per 100 parts by mass of the (A) colorant. If the content of the binder resin is too small, for example, the alkali developability may be lowered or the storage stability of the obtained colored composition may be lowered. On the other hand, if the amount of the colorant is excessively decreased, it may be difficult to form a film as a film. Achieve target color density.

-(E) Photopolymerization Initiator -

The colored composition of the present invention may contain (E) a photopolymerization initiator. Thereby, the coloring composition can be imparted with radiation. The (E) photopolymerization initiator used in the present invention is a compound which generates an active species capable of initiating polymerization of the above (C) crosslinking agent by exposure to radiation such as visible light, ultraviolet light, far ultraviolet light, electron beam or X-ray.

As such a photopolymerization initiator, for example, oxygen sulfur can be mentioned. Compound, acetophenone compound, biimidazole compound, three Compound, O-mercapto oxime compound, sulfonium salt compound, benzoin compound, benzophenone compound, α-diketone compound, polycyclic guanidine compound, diazo compound, quinone a sulfonate compound or the like.

In the present invention, the photopolymerization initiators may be used singly or in combination of two or more. In the case of a photopolymerization initiator, it is preferably selected from the group consisting of oxygen and sulfur Compound, acetophenone compound, biimidazole compound, three At least one of a compound and an O-indenyl lanthanide compound.

Among the preferred photopolymerization initiators in the present invention, oxygen and sulfur Specific examples of the compound are oxysulfur 2-chlorooxosulfur 2-methyloxosulfur 2-isopropyloxysulfur 4-isopropyloxysulfur 2,4-dichlorooxosulfur 2,4-dimethyloxosulfur 2,4-diethyloxysulfide 2,4-diisopropyloxysulfide Wait.

Further, as a specific example of the above acetophenone-based compound, 2-methyl-1-[4-(methylthio)phenyl]-2- Lolinylpropan-1-one, 2-benzyl-2-dimethylamino-1-(4- Polinylphenyl)butan-1-one, 2-(4-methylbenzyl)-2-(dimethylamino)-1-(4- Polinylphenyl)butan-1-one and the like.

Further, specific examples of the biimidazole-based 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.

Further, when a biimidazole-based compound is used as the photopolymerization initiator, it is preferred to use a hydrogen donor in combination from the viewpoint of improving sensitivity. The term "hydrogen donor" as used herein refers to a compound capable of supplying a hydrogen atom to a radical generated by a biimidazole compound by exposure. Examples of the hydrogen donor include 2-mercaptobenzothiazole and 2-mercaptobenzoene. An amine-based hydrogen donor such as a thiol-derived hydrogen donor, 4,4'-bis(dimethylamino)benzophenone or 4,4'-bis(diethylamino)benzophenone. In the present invention, the hydrogen donors may be used singly or in combination of two or more. However, in view of further improving the sensitivity, it is preferred to supply one or more kinds of thiol-based hydrogen donors and one or more amines. Hydrogen is used in combination.

In addition, the above three Specific examples of the compound are 2,4,6-tris(trichloromethyl)-all. 2-methyl-4,6-bis(trichloromethyl)-all three ,2-[2-(5-methylfuran-2-yl)vinyl]-4,6-bis(trichloromethyl)-all three ,2-[2-(furan-2-yl)vinyl]-4,6-bis(trichloromethyl)-all three ,2-[2-(4-diethylamino-2-methylphenyl)vinyl]-4,6-bis(trichloromethyl)-all three , 2-[2-(3,4-dimethoxyphenyl)vinyl]-4,6-bis(trichloromethyl)-all three , 2-(4-methoxyphenyl)-4,6-bis(trichloromethyl)-all three , 2-(4-ethoxystyryl)-4,6-bis(trichloromethyl)-all three , 2-(4-n-butoxyphenyl)-4,6-bis(trichloromethyl)-all three Three with a halogenated methyl group a compound.

Further, as a specific example of the O-indenyl lanthanide compound, 1,2-octanedione-1-[4-(phenylthio)phenyl]-2-(O-benzamide) can be mentioned. ), Ethyl Ketone-1-[9-Ethyl-6-(2-methylbenzylidene)-9H-indazol-3-yl]-1-(O-acetamidine), Ethyl Ketone-1 -[9-ethyl-6-(2-methyl-4-tetrahydrofurylmethoxybenzylidene)-9H-indazol-3-yl]-1-(O-acetamidine), ethyl ketone -1-{9-ethyl-6-[2-methyl-4-(2,2-dimethyl-1,3-dioxolanyl)methoxybenzylidene]-9H-indole Zyrid-3-yl}-1-(O-acetamidine) and the like. O-mercaptosystem For the commercial product of the compound, NCI-831, NCI-930 (the above is manufactured by ADEKA Co., Ltd.), or the like can be used.

In the present invention, when a photopolymerization initiator other than the biimidazole compound such as an acetophenone-based compound is used, a sensitizer may be used in combination. Examples of such a sensitizer include 4,4'-bis(dimethylamino)benzophenone, 4,4'-bis(diethylamino)benzophenone, and 4-di Ethyl acetophenone, 4-dimethylaminopropiophenone, ethyl 4-dimethylaminobenzoate, 2-ethylhexyl 4-dimethylaminobenzoate, 2,5-bis (4- Diethylaminobenzylidene)cyclohexanone, 7-diethylamino-3-(4-diethylaminobenzimidyl)coumarin, 4-(diethylamino)chalcone, and the like.

In the present invention, the content of the photopolymerization initiator is preferably 0.01 to 120 parts by mass, particularly preferably 1 to 100 parts by mass, per 100 parts by mass of the (C) crosslinking agent. In this case, if the content of the photopolymerization initiator is too small, the hardening by exposure is likely to be insufficient, and if it is too large, there is a tendency that the formed coloring layer becomes easily detached from the substrate during development. .

-(F) solvent -

The coloring composition of the present invention is usually produced by using (a1) a coloring agent containing a quinophthalone pigment and (B) a copolymer in a solvent (F) using, for example, a bead mill, a roll mill, or the like. Mixing and dispersing together with a part of the other dispersing agent and (D) binder resin as needed to prepare a pigment dispersion liquid, and then adding (C) a crosslinking agent to the pigment dispersion liquid, if necessary ( D) a binder resin, (E) a photopolymerization initiator, and a further added solvent (F) are mixed. As the solvent (F), as long as the components (A) to (C) constituting the colored composition are dispersed, other components are dispersed. Alternatively, a solvent which is dissolved and does not react with these components and has a moderate volatility can be appropriately selected and used. However, when preparing the above-mentioned pigment dispersion liquid, it is preferred that (f1) a solvent having a hydroxyl group (hereinafter also referred to as "solvent (f1)") and (f2) having no hydroxyl group from the viewpoint of dispersibility and stability. A solvent (hereinafter also referred to as "solvent (f2)") is used in combination.

In such a solvent, examples of the solvent (f1) include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono-n-propyl ether, ethylene glycol mono-n-butyl ether, and diethyl ether. 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 single Ethyl 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, dipropylene glycol monoethyl ether, dipropylene glycol mono-n-propyl (poly)alkylene glycol monoalkyl ethers such as ether, dipropylene glycol mono-n-butyl ether, tripropylene glycol monomethyl ether, tripropylene glycol monoethyl ether; alkyl lactate such as methyl lactate or ethyl lactate ; (cyclo) alkyl alcohols such as methanol, ethanol, propanol, butanol, isopropanol, isobutanol, tertiary butanol, octanol, 2-ethylhexanol, cyclohexanol; diacetone alcohol, etc. Keto alcohols and the like.

Among these solvents (f1), preferred are (poly)alkylene glycol monoalkyl ethers, particularly preferably propylene glycol monomethyl ether or propylene glycol monoethyl ether. The solvent (f1) may be used singly or in combination of two or more.

Further, as the solvent (f2), for example, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monomethyl ether acetate, and diethyl ether may be mentioned. Glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, dipropylene glycol monomethyl ether acetate Ester, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, etc. (poly)alkylene glycol monoalkyl ether acetate; diethylene glycol dimethyl ether, two Ethylene glycol methyl ethyl ether, diethylene glycol diethyl ether, tetrahydrofuran and other ethers; methyl ethyl ketone, cyclohexanone, 2-heptanone, 3-heptanone and other ketones; propylene glycol diethyl Diacetate such as acid ester, 1,3-butanediol diacetate or 1,6-hexanediol diacetate; methyl 3-methoxypropionate, 3-methoxypropionic acid Alkoxycarboxylates such as ester, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl ethoxyacetate, 3-methyl-3-methoxybutyl propionate Class; ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, n-amyl formate, isoamyl acetate, n-butyl propionate, ethyl butyrate, butyric acid Propyl ester, isopropyl butyrate, n-butyl butyrate, methyl pyruvate, ethyl pyruvate, n-propyl pyruvate, methyl acetate, ethyl acetate, ethyl 2-oxobutyrate Other esters such as esters; aromatic hydrocarbons such as toluene and xylene; N,N-dimethylformamide, N,N-dimethyl B Amine, N- methylpyrrolidone Amides or Lactams amines.

Among these solvents (f2), preferred are (poly)alkylene glycol monoalkyl ether acetates, ethers, ketones, diacetates, alkoxycarboxylates, and particularly preferably ethylene. Alcohol monomethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, 3-methoxybutyl acetate, dipropylene glycol monomethyl ether acetate, diethylene glycol Dimethyl ether, diethylene glycol methyl ethyl ether, cyclohexanone, 1,3-butylene glycol diacetate, 1,6-hexanediol diacetate, ethyl 3-methoxypropionate , 3-ethoxypropionate methyl ester, 3-ethoxy group Ethyl propionate. The solvent (f2) may be used singly or in combination of two or more.

In the present invention, the mass ratio (f1/f2) of the solvent (f1) and the solvent (f2) in the colorant dispersion is preferably 0.5/99.5 to 40/60, more preferably 1/99 to 30/70. , especially good is 5/95~25/75.

The content of the solvent is not particularly limited, and the total concentration of each component after removing the solvent of the pigment dispersion or the coloring composition is preferably from 5 to 50% by mass, particularly in the case of a pigment dispersion or a coloring composition. It is an amount of 10 to 40% by mass. By setting it to such a state, the coloring agent dispersion liquid which is excellent in dispersibility and stability, and the coloring composition which is excellent in applicability and stability can be obtained.

-additive-

The colored composition of the present invention may further contain various additives as needed.

Examples of the additive include a filler such as glass or alumina; a polymer compound such as polyvinyl alcohol or poly(fluoroalkyl acrylate); a surfactant such as a fluorine surfactant or a lanthanoid surfactant; ; vinyl trimethoxy decane, vinyl triethoxy decane, vinyl tris(2-methoxyethoxy) decane, N-(2-aminoethyl)-3-aminopropylmethyl Dimethoxydecane, N-(2-aminoethyl)-3-aminopropyltrimethoxydecane, 3-aminopropyltriethoxydecane, 3-glycidoxypropyltrimethoxy Baseline, 3-glycidoxypropylmethyldimethoxydecane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxydecane, 3-chloropropylmethyldimethoxydecane , adhesion promoters such as 3-chloropropyltrimethoxydecane, 3-methylpropenyloxypropyltrimethoxydecane, 3-mercaptopropyltrimethoxydecane; 2,2-thiobis(4-methyl) Antibiotics such as -6-6-tert-butylphenol), 2,6-di-tributylphenol Oxidizing agent; ultraviolet absorber such as 2-(3-tert-butyl-5-methyl-2-hydroxyphenyl)-5-chlorobenzotriazole or alkoxybenzophenone; Agglutinating agent; malonic acid, adipic acid, itaconic acid, citraconic acid, fumaric acid, mesaconic acid, 2-aminoethanol, 3-amino-1-propanol, 5-amino-1- Residue improver such as pentanol, 3-amino-1,2-propanediol, 2-amino-1,3-propanediol, 4-amino-1,2-butanediol; succinic acid mono[2-(A Base) propylene oxiranyl ethyl ester, phthalic acid mono [2-(methyl) propylene oxy oxy] ester, ω-carboxy polycaprolactone mono (meth) acrylate, etc. .

Color filter and manufacturing method thereof

The color filter of the present invention comprises a coloring layer formed using the colored composition of the present invention.

As for the method of manufacturing a color filter, the following method is mentioned first. First, a light shielding layer (black matrix) is formed on the surface of the substrate so as to divide the portion where the pixel is formed, as needed. Next, on the substrate, for example, a liquid composition of the radiation sensitive composition of the present invention in which a red colorant containing a quinophthalone pigment is dispersed is applied, and then prebaked to evaporate the solvent to form a coating film. Next, the coating film was exposed through a photomask, and then developed with an alkali developing solution to dissolve and remove the unexposed portion of the coating film. Then, by performing post-baking, a pixel array in which red pixel patterns are arranged in a predetermined sequence is formed.

Next, using each of the green or blue colored radiation-linear compositions, coating, prebaking, exposure, development, and post-baking of each coloring radiation composition are sequentially performed in the same manner as described above, and sequentially formed on the same substrate. Green pixel array and blue pixel array. Thereby, color filtering of a pixel array in which three primary colors of red, green, and blue are disposed on the substrate is obtained sheet. However, in the present invention, the order in which the pixels of the respective colors are formed is not limited to the above order.

Further, the black matrix may be formed by forming a metal film such as chromium formed by sputtering or vapor deposition into a desired pattern by photolithography, or using a color-sensing radiation-linear composition in which a black pigment is dispersed, and the above The case of pixel formation is similarly formed.

Examples of the substrate used in forming the color filter include glass, ruthenium, polycarbonate, polyester, aromatic polyamide, polyamidimide, and polyimine.

Further, for these substrates, an appropriate pretreatment such as reagent treatment such as a decane coupling agent, plasma treatment, ion plating, sputtering, gas phase reaction method, or vacuum vapor deposition may be carried out as needed.

When the coloring sensitizing radiation composition is applied onto a substrate, an appropriate coating method such as a spray coating method, a roll coating method, a spin coating method (spin coating method), a slit die coating method, or a bar coating method may be employed. In order to adopt a spin coating method or a slit die coating method.

Prebaking is usually carried out by combining reduced pressure drying and heat drying. Drying under reduced pressure usually proceeds to 50 to 200 Pa. In addition, the conditions of heat drying are usually about 1 to 10 minutes at 70 to 110 °C.

The coating thickness is usually 0.6 to 8 μm, preferably 1.2 to 5 μm, in terms of the film thickness after drying.

Examples of the light source for radiation used in forming the pixel and/or 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 mercury. Light source such as lamp, argon ion laser, YAG laser, XeCl excimer laser, nitrogen laser, etc. Laser light source, etc. In the case of an exposure light source, an ultraviolet LED can also be used. However, radiation having a wavelength in the range of 190 to 450 nm is preferred.

The exposure amount of the radiation is generally preferably from 10 to 10000 J/m ² .

Further, as the above alkaline developing solution, for example, sodium carbonate, sodium hydrogencarbonate, sodium hydroxide, potassium hydroxide, tetramethylammonium hydroxide, choline or 1,8-diazabicyclo[5.4 is preferred. .0] an aqueous solution of 7-undecene, 1,5-diazabicyclo[4.3.0]-5-nonene or the like.

In the above alkaline developing solution, a water-soluble organic solvent such as methanol or ethanol, a surfactant, or the like may be added in an appropriate amount. Further, after alkaline development, water washing is usually carried out.

As the development treatment method, a shower development method, a spray development method, a dip development method, an immersion (immersion) development method, or the like can be applied. The development conditions are preferably 5 to 300 seconds at normal temperature.

The post-baking conditions are usually about 10 to 60 minutes at 180 to 280 °C.

The film thickness of the pixel thus formed is usually 0.5 to 5 μm, preferably 1 to 3 μm.

In the second method of producing a color filter, a method of obtaining pixels of respective colors by an inkjet method disclosed in Japanese Laid-Open Patent Publication No. Hei. No. Hei. In this method, first, a partition wall having a light blocking function is formed on the surface of the substrate. Next, a liquid composition of the colored composition of the present invention in which, for example, a red pigment is dispersed is ejected into the partition walls formed by an inkjet device, and then prebaked to evaporate the solvent. Next, after exposing the coating film as needed, post-baking is performed to harden it to form a red pixel. pattern.

Next, using the green or blue colored composition, the green pixel pattern and the blue pixel pattern were sequentially formed on the same substrate in the same manner as described above. Thereby, a color filter in which pixel patterns of three primary colors of red, green, and blue are arranged on the substrate is obtained. However, in the present invention, the order in which the pixels of the respective colors are formed is not limited to the above order.

Further, the partition wall not only functions as a light-shielding function but also functions to prevent color mixing of the coloring compositions discharged into the divided regions, and thus the film thickness is thicker than that of the black matrix used in the first method. Therefore, the partition walls are usually formed using a black sensitizing radioactive composition.

The substrate used for forming the color filter, the light source of the radiation, and the method and conditions of the prebaking and postbaking are the same as those of the first method described above. Thus, the film thickness of the pixel formed by the inkjet method is the same as that of the black matrix.

On the pixel pattern thus obtained, a protective film is formed as needed, and then a transparent conductive film is formed by sputtering. After the transparent conductive film is formed, a spacer may be further formed to form a color filter. The separator is usually formed using a radiation-sensitive composition, and may be formed into a light-shielding separator (black separator). At this time, the colored composition of the present invention can also be suitably used to form the black spacer by using a color-sensing radiation composition in which a black colorant is dispersed.

The color filter of the present invention thus obtained has extremely high luminance and color purity, and thus is extremely useful for a color liquid crystal display element, a color image tube element, a color sensor, an organic EL display element, an electronic paper, and the like.

Display component

The display element of the present invention includes the color filter 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 having the color filter of the present invention can adopt a suitable structure. For example, a color filter may be formed on a substrate different from a driving substrate on which a thin film transistor (TFT) is disposed, and the driving substrate and the substrate on which the color filter is formed may be disposed to face each other via the liquid crystal layer; Further, a structure in which a substrate on which a color filter is formed on a surface of a driving substrate on which a thin film transistor (TFT) is disposed and a substrate on which an ITO (tin-doped indium oxide) electrode is formed may be used. The liquid crystal layer is aligned. The structure of the latter can significantly increase the aperture ratio, and has the advantage of obtaining a bright and high-definition liquid crystal display element.

A color liquid crystal display device including the color filter of the present invention may include a backlight unit using a white LED as a light source in addition to a cold cathode fluorescent lamp (CCFL). The white LED includes, for example, a white LED in which a combination of a red LED, a green LED, and a blue LED is mixed to obtain white light, and the blue LED, the red LED, and the green phosphor are combined to obtain white light. The white LED combines the blue LED, the red illuminating phosphor and the green illuminating phosphor to obtain a white LED with white light. The white LED is obtained by mixing the blue LED and the YAG phosphor. The blue LED, the orange illuminating phosphor and the green illuminating phosphor are combined to obtain a white LED with white light, and the ultraviolet LED, the red illuminating phosphor, the green luminescent phosphor and the blue luminescent phosphor are combined. A white LED or the like which obtains white light by combining colors.

A color liquid crystal display element having the color filter of the present invention can be applied with TN (Twisted Nematic) type, STN (Super Twisted Nematic) type, and IPS (In-Planes Switching). A suitable liquid crystal mode such as a VA (Vertical Alignment) type or an OCB (Optically Compensated Birefringence) type.

Further, the organic EL display element having the color filter of the present invention may have a suitable structure, and for example, a structure disclosed in Japanese Laid-Open Patent Publication No. Hei 11-307242 may be employed.

Further, the electronic paper having the color filter of the present invention may have a suitable structure, and for example, a structure disclosed in Japanese Laid-Open Patent Publication No. 2007-41169 may be employed.

[Examples]

Hereinafter, embodiments of the present invention will be described more specifically by way of examples. However, the invention is not limited to the following examples.

<Measurement of Mw and Mw/Mn>

Mw and Mn of the (B) copolymer obtained in each of the following Synthesis Examples were measured by gel permeation chromatography (hereinafter abbreviated as GPC) of the following specifications. The measurement results are shown in Table 1 together with the copolymerization ratio (% by mass) of each monomer in the (B) copolymer.

Device: GPC-104 (made by Showa Denko Co., Ltd.).

Pipe column: KD-G, KF-603, KF-602, and KF-601 (manufactured by Showa Denko Co., Ltd.) are used in combination.

Mobile phase: DMF.

<(B) Synthesis of Copolymer>

Hereinafter, the abbreviation of the raw material used in the "synthesis of (B) copolymer" is as follows.

THF: tetrahydrofuran

EEMA: 1-ethoxyethyl methacrylate

MA: methacrylic acid

nBMA: n-butyl methacrylate

MMA: Methyl methacrylate

AIBN: 2,2'-azobisisobutyronitrile

DAMA: dimethylaminoethyl methacrylate

CHMA: cyclohexyl methacrylate

BzMA: benzyl methacrylate

PME-200: methoxypolyethylene glycol monomethacrylate (manufactured by Nippon Oil Co., Ltd., trade name PME-200, in the above formula (3), n 4)

PME-100: methoxypolyethylene glycol monomethacrylate (manufactured by Nippon Oil Co., Ltd., trade name PME-100, in the above formula (3), n=2)

Synthesis Example 1

516.1 g of THF, 34.1 g of lithium chloride (4.1% by mass in THF solution), and 3.6 g of diphenylethylene were placed in a 1000 mL flask equipped with a stir bar, and the mixture was cooled to -60 °C. After adding 9.2 g of n-butyllithium (15.4 mass% hexane solution), after aging for 10 minutes, a mixed liquid of 18.5 g of PME-200, 34.0 g of nBMA, and 6.1 g of EEMA was added dropwise, and the reaction was continued for 15 minutes.

Then, 55.4 g of DAMA was added dropwise, and after the dropwise addition, the reaction was continued for 30 minutes, and then 3.2 g of methanol was added to terminate the reaction. After adjusting the obtained copolymer to a solution of propylene glycol monomethyl ether acetate (hereinafter abbreviated as PGMEA) at a concentration of 25% by mass, 114 g of water was added thereto, and the mixture was heated to 100 ° C to cause a reaction 8 hour. By this reaction, EEMA is hydrolyzed to form a repeating unit derived from MA. The water was distilled off and adjusted to a 40% by mass concentration of PGMEA solution. There is thus obtained a block copolymer formed of an A block having a repeating unit derived from DAMA and a B block having repeating units derived from PME-200, nBMA and MA. The obtained copolymer was referred to as "copolymer (B-1)".

Synthesis Example 2

30 g of toluene, 4.2 g of PME-200, 5.6 g of MMA, 121 mg of AIBN, and 312 mg of cyano (dimethyl)methyl ester of pyrazole-1-dithiocarboxylate were added to a 300 mL flask equipped with a stirrer, and dissolved. Minute nitrogen replacement. Then, the mixture was slowly stirred to raise the temperature of the reaction solution to 60 ° C, and the temperature was maintained for 24 hours to carry out living radical polymerization.

Next, 983 mg of AIBN and 18.2 g of DAMA were dissolved in 20 g of toluene, and then nitrogen substitution was performed for 30 minutes, and the obtained solution was added to the above reaction solution, and living radical polymerization was carried out at 60 ° C for 24 hours. Then, the mixture was concentrated under reduced pressure to adjust to a 40% by mass concentration of PGMEA solution. There is thus obtained a block copolymer formed of an A block having a repeating unit derived from DAMA and a B block having a repeating unit derived from PME-200 and MMA. The obtained block copolymer was referred to as "copolymer (B-2)".

Synthesis Example 3

57.6 g of 987.6 g of THF and lithium chloride (3.9% by mass in THF solution) were placed in a 2000 mL flask equipped with a stir bar, and the mixture was cooled to -60 °C. 21.4 g of n-butyllithium (15.4% by mass concentration of hexane solution) was added, and after stirring for 10 minutes, 4.9 g of diisopropylamine was added and stirred for 15 minutes, followed by addition of isobutylene. Methyl ester 4.7 g was stirred for another 15 minutes. A mixture of MMA 87.9 g and PME-200 45.3 g was added dropwise, and the reaction was continued for 15 minutes.

Then, 133.6 g of DAMA was added dropwise, and after the dropwise addition, the reaction was continued for 30 minutes, and then 7.7 g of methanol was added to terminate the reaction. The obtained copolymer was adjusted to a 40% by mass concentration of PGMEA solution. There is thus obtained a block copolymer formed of an A block having a repeating unit derived from DAMA and a B block having a repeating unit derived from PME-200 and MMA. The obtained copolymer was referred to as "copolymer (B-3)".

Synthesis Example 4

30 g of toluene, 7.6 g of nBMA, 9.2 g of PME-200, 174 mg of AIBN, and 449 mg of cyano (dimethyl)methyl ester of pyrazole-1-dithiocarboxylate were placed in a 300 mL flask equipped with a stir bar and dissolved, and 30 Minute nitrogen replacement. Then, the mixture was slowly stirred to raise the temperature of the reaction solution to 60 ° C, and the temperature was maintained for 24 hours to carry out living radical polymerization.

Next, 716 mg of AIBN and 11.2 g of DAMA were dissolved in 20 g of toluene, and then nitrogen substitution was performed for 30 minutes, and the obtained solution was added to the above reaction solution, and living radical polymerization was carried out at 60 ° C for 24 hours. Then, the mixture was concentrated under reduced pressure to adjust to a 40% by mass concentration of PGMEA solution. There is thus obtained a block copolymer formed of an A block having a repeating unit derived from DAMA and a B block having a repeating unit derived from PME-200 and nBMA. The obtained block copolymer was referred to as "copolymer (B-4)".

Synthesis Example 5

20 g of toluene, 187 mg of AIBN, and 12.3 g of DAMA were placed in a 300 mL flask equipped with a stir bar and dissolved, and nitrogen substitution was performed for 30 minutes. then The mixture was slowly stirred, the temperature of the reaction solution was raised to 60 ° C, and the temperature was maintained for 24 hours to carry out living radical polymerization.

Next, MMA 2.2 g, PME-200 7.0 g, CHMA 5.6 g, MA 0.8 g, AIBN 809 mg, and pyrazole-1-dithiocarbamic acid cyano (dimethyl) methyl ester 461 mg were dissolved in 30 g of toluene, followed by After nitrogen substitution for 30 minutes, the obtained solution was added to the above reaction solution, and living radical polymerization was carried out at 60 ° C for 24 hours. Then, the mixture was concentrated under reduced pressure to adjust to a 40% by mass concentration of PGMEA solution. There is thus obtained a block copolymer formed of an A block having a repeating unit derived from DAMA, and a B block having repeating units derived from PME-200, MMA, CHMA and MA. The obtained block copolymer was referred to as "copolymer (B-5)".

Synthesis Example 6

59.5 g of THF 503.0 g and lithium chloride (4.1% by mass concentration THF solution) were placed in a 1000 mL flask equipped with a stir bar, and the mixture was cooled to -60 °C. After adding 11.9 g of n-butyllithium (15.4% by mass in a hexane solution) and stirring for 10 minutes, 2.8 g of diisopropylamine was added and stirred for 15 minutes, followed by the addition of 2.8 g of methyl isobutyrate, followed by stirring for 15 minutes. A mixed solution of 74.6 g of MMA and 32.2 g of PME-100 was added dropwise, and the reaction was continued for 15 minutes.

Then, 52.1 g of DAMA was added dropwise, and after the dropwise addition, the reaction was continued for 30 minutes, and then 4.5 g of methanol was added to terminate the reaction. The obtained copolymer was adjusted to a 40% by mass concentration of PGMEA solution. There is thus obtained a block copolymer formed of an A block having a repeating unit derived from DAMA and a B block having a repeating unit derived from PME-200 and MMA. The obtained copolymer was referred to as "copolymer (B-6)".

Comparative Synthesis Example 1

30 g of toluene, 5.6 g of PME-200, 13.1 g of BzMA, 196 mg of AIBN, and 506 mg of cyano (dimethyl)methyl ester of pyrazole-1-dithiocarboxylate were placed in a 300 mL flask equipped with a stirrer and dissolved, and 30 Minute nitrogen replacement. Then, the mixture was slowly stirred to raise the temperature of the reaction solution to 60 ° C, and the temperature was maintained for 24 hours to carry out living radical polymerization.

Next, 607 mg of AIBN and 9.2 g of DAMA were dissolved in 20 g of toluene, and then nitrogen substitution was performed for 30 minutes, and the obtained solution was added to the above reaction solution, and living radical polymerization was carried out at 60 ° C for 24 hours. Then, the mixture was concentrated under reduced pressure to adjust to a 40% by mass concentration of PGMEA solution. There is thus obtained a block copolymer formed of an A block having a repeating unit derived from DAMA and a B block having repeating units derived from PME-200 and BzMA. The obtained block copolymer was referred to as "copolymer (b-1)".

Comparative Synthesis Example 2

48.6 g of 498.6 g of THF and lithium chloride (4.1% by mass in THF solution) were placed in a 1000 mL flask equipped with a stir bar, and the mixture was cooled to -60 °C. After adding 8.7 g of n-butyllithium (15.4 mass% hexane solution), and stirring for 10 minutes, 1.8 g of diisopropylamine was added and stirred for 15 minutes, and then 1.8 g of methyl isobutyrate was added, followed by stirring for 15 minutes. A mixture of MMA 60.7 g, PME-200 33.6 g, and EEMA 11.8 g was added dropwise, and the reaction was continued for 15 minutes.

Then, 28.7 g of DAMA was added dropwise, and after the dropwise addition, the reaction was continued for 30 minutes, and then 2.4 g of water was added to terminate the reaction. After adjusting the obtained copolymer to a PGMEA solution having a concentration of 25% by mass, 135 g of water was added thereto, and the mixture was heated to 100 ° C to carry out a reaction for 8 hours, and EEMA was hydrolyzed by the reaction to form a repeating unit derived from MA. Distilled water and adjusted to a concentration of 40% by mass PGMEA solution. There is thus obtained a block copolymer formed of an A block having a repeating unit derived from DAMA, and a B block having repeating units derived from PME-200, MMA and MA. The obtained block copolymer was referred to as "copolymer (b-2)".

Comparative Synthesis Example 3

20 g of toluene, 66 mg of AIBN, and 21.0 g of DAMA were placed in a 300 mL flask equipped with a stir bar and dissolved, and nitrogen substitution was performed for 30 minutes. Then, the mixture was slowly stirred to raise the temperature of the reaction solution to 60 ° C, and the temperature was maintained for 24 hours to carry out living radical polymerization.

Next, 2.8 g of nBMA, 4.2 g of PME-200, 1259 mg of AIBN, and 170 mg of cyano (dimethyl)methyl ester of pyrazole-1-dithiocarboxylate were dissolved in 30 g of toluene, and then nitrogen substitution was carried out for 30 minutes. The solution was added to the above reaction solution, and living radical polymerization was carried out at 60 ° C for 24 hours. Then, the mixture was concentrated under reduced pressure to adjust to a 40% by mass concentration of PGMEA solution. There is thus obtained a block copolymer formed of an A block having a repeating unit derived from DAMA and a B block having a repeating unit derived from PME-200 and nBMA. The obtained block copolymer was referred to as "copolymer (b-3)".

<Measurement of acid value>

The acid value of the (B) copolymer obtained in each of the above Synthesis Examples was measured according to the following points. The measurement results are shown in Table 1.

0.5 g of the copolymer solution was accurately weighed to 1 mg unit and dispensed into a glass container. After diluting to 50 mL with propylene glycol monomethyl ether acetate, phenolphthalein was added, and titration was carried out with a 0.1 N aqueous solution of potassium hydroxide, and the point colored in pink was used as an end point. The blank test was performed in the same manner. By (B) The acid value (unit: mgKOH/g) was calculated from the amount of the 0.1 N ethanolic potassium hydroxide aqueous solution added to the copolymer and the blank test.

<Measurement of amine price>

The amine valence of the (B) copolymer obtained in each of the above Synthesis Examples was measured according to the following points. The measurement results are shown in Table 1.

0.5 g of the copolymer solution was accurately weighed to 1 mg unit and dispensed into a glass container. Acetic anhydride/acetic acid = 9/1 (volume ratio) 20 mL was added and dissolved, and allowed to stand at room temperature for 3 hours. Then, 30 mL of acetic acid was further added, and then titration was performed using a potential difference measuring apparatus AT-510 (manufactured by Kyoto Electronics Co., Ltd.) using a 0.1 mol/L perchloric acid ‧ acetic acid solution. The blank test was performed in the same manner. The amine value (unit: mgKOH/g) was calculated from the amount of the (B) copolymer and the 0.1 mol/L perchloric acid ‧ acetic acid solution of the blank test.

<Preparation of Pigment Dispersion> Preparation Example 1

12 parts by mass of CI Pigment Green 58 and 3 parts by mass of CI Pigment Yellow 138, 10 parts by mass of the copolymer (B-1) solution (nonvolatile content = 40 parts by mass), and 67 as a solvent were used as a coloring agent. A part by mass of propylene glycol monomethyl ether acetate and 8 parts by mass of propylene glycol monomethyl ether were treated by a bead mill to prepare a pigment dispersion liquid (A-1).

Preparation Examples 2 to 6 and Comparative Preparation Examples 1 to 3

In the same manner as in Preparation Example 1, the pigment dispersion liquids (A-2) to (A-9) were prepared in the same manner as in Preparation Example 1, except that the type of the (B) copolymer was changed as shown in Table 2.

<Evaluation of Colorant Dispersion>

The viscosity of the obtained pigment dispersion liquid was measured using an E-type viscometer (manufactured by Tokyo Keiki Co., Ltd.). Further, the obtained colorant dispersion was filled in a light-shielding glass container, and after standing at 23 ° C for 14 days in a sealed state, the viscosity was measured again using an E-type viscometer (manufactured by Tokyo Keiki Co., Ltd.). Then, the increase rate of the viscosity after storage for 14 days with respect to the viscosity immediately after preparation was calculated, and the case where the increase rate was less than 5% was evaluated as "A", and the increase rate was 5% or more and less than 10% was evaluated as "B" and the increase rate of 10% or more were evaluated as "C". The evaluation results are shown in Table 2.

In Table 2, "G58" means C.I. Pigment Green 58, "Y138" means C.I. Pigment Yellow 138, "PGMEA" means propylene glycol monomethyl ether acetate, and "PGME" means propylene glycol monomethyl ether.

<Synthesis of binder resin> Synthesis Example 7

In a flask equipped with a condenser and a stirrer, 30.0 g of BzMA, 20.0 g of nBMA, 15.0 g of hydroxyethyl methacrylate, 20.0 g of styrene, 15.0 g of MA, and 200 g of PGMEA were added and dissolved, and AIBN 3.0 g and α were further added. - Methylstyrene dimer 5.0 g, followed by nitrogen substitution for 15 minutes. Thereafter, the reaction mixture was heated to 80 ° C while stirring, and polymerization was carried out for 5 hours to obtain a solution containing 33% by mass of the binder resin (D-1). The binder resin (D-1) is determined by GPC (mobile phase: tetrahydrofuran) according to polyphenylene The olefin-converted weight average molecular weight was 10,000, and the ratio of the weight average molecular weight to the number average molecular weight was 2.5.

Synthesis Example 8

In a flask equipped with a condenser and a stirrer, 25.0 g of 3-methylpropenyloxymethyl-3-ethyloxetane, MA 18.0 g, and mono-2-propenyloxyethyl succinate were added. 9.0 g of ester, 10.0 g of N-phenylmaleimide, 24.0 g of BzMA, 14.0 g of hydroxyethyl methacrylate, and 300 g of PGMEA were dissolved, and AIBN 6.0 g and α-methylstyrene dimer 6.0 were further added. g, followed by a nitrogen substitution for 15 minutes. Thereafter, the reaction solution was stirred while heating to 80 ° C, and polymerization was carried out for 5 hours to obtain a precursor copolymer solution.

13.4 g of 2-methacryloxyethyl isocyanate and 0.2 g of 4-methoxyphenol as a polymerization inhibitor were added to the obtained 200 g of the precursor copolymer solution, and the mixture was reacted at 90 ° C for 2 hours. The reaction solution was washed twice with 75 g of ion-exchanged water each time, followed by concentration under reduced pressure to obtain a solution containing 33% by mass of the binder resin (D-2). The weight average molecular weight of the binder resin (D-2) measured by GPC (eluent solvent: tetrahydrofuran) in terms of polystyrene was 11,000, and the ratio of the weight average molecular weight to the number average molecular weight was 1.9.

<Preparation and evaluation of coloring composition> Preparation of coloring composition Example 1

100 parts by mass of the pigment dispersion liquid (A-1), 13.4 parts by mass of a binder resin (D-1) solution as a binder resin, and MAX-3510 (hexaacrylic acid) manufactured by Nippon Kayaku Co., Ltd. as a crosslinking agent. Dipentaerythritol ester as a main component) 5.0 parts by mass of 2-benzyl-2-dimethylamino-1-(4- as a photopolymerization initiator 2.8 parts by mass of a fluoro-based phenyl)butane-1-one (trade name: Irgacure 369, manufactured by Ciba Specialty Chemicals Co., Ltd.), 0.3 parts by mass of Megafac F-554 (manufactured by DIC Corporation) as a fluorine-based surfactant, and The solvent was mixed with 126.5 parts by mass of ethyl 3-ethoxypropionate to prepare a liquid colored composition.

Evaluation of chromaticity characteristics

The obtained coloring composition was applied onto a glass substrate by a spin coater, and then prebaked in a hot plate at 90 ° C for 2 minutes to form three coating films having different film thicknesses. Then, after cooling the substrates to room temperature, a high-pressure mercury lamp was used for the coating film on the substrate, and each coating film was exposed to a wavelength of 365 nm, 405 nm, and 436 nm without exposure of a mask at an exposure amount of 1,000 J/m ² . Radiation. Thereafter, post-baking was performed at 230 ° C for 60 minutes to form a cured film on the substrate. For the obtained three cured films, a color analyzer (MCPD2000 manufactured by Otsuka Electronics Co., Ltd.) was used to measure the chromaticity coordinate value (x, y) and the stimulus value (Y) in the CIE color system using a C light source and a 2 degree field of view. ). From the measurement results, the chromaticity coordinate value x and the stimulus value (Y) at the chromaticity coordinate value y=0.569 were obtained. The evaluation results are shown in Table 3. In addition, the larger the value of the stimulus value (Y), the higher the brightness.

Contrast evaluation

For the three cured films obtained in the above "Evaluation of Chromaticity Characteristics", the contrast was measured using a contrast meter (Hirsen Electric Mechanism Contrast Tester CT-1). The contrast at the chromaticity coordinate value y=0.569 was obtained from the measurement results. The evaluation results are shown in Table 3. In addition, the larger the value, the higher the contrast.

Examples 2 to 6 and Comparative Examples 1 to 3

In the same manner as in Example 1, except that the types and blending amounts of the pigment dispersion liquid, the binder resin, the crosslinking agent, the photopolymerization initiator, and the solvent were changed as shown in Table 3 in the first embodiment. The preparation and evaluation of the colored composition were carried out. The evaluation results are shown in Table 3.

The components in Table 3 are as follows.

C-1: a mixture of dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate (trade name: MAX-3510, manufactured by Nippon Kayaku Co., Ltd.)

C-2: a monoester of dipentaerythritol pentaacrylate and succinic acid, a mixture of dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate (trade name TO-1382, manufactured by Toagosei Co., Ltd.)

E-1: Ethyl ketone-1-[9-ethyl-6-(2-methylbenzylidene)-9H-indazol-3-yl]-1-(O-acetamidine) (trade name) IRGACURE OXE02, manufactured by Ciba Specialty Chemicals)

E-2: 2-benzyl-2-dimethylamino-1-(4- Polinylphenyl)butan-1-one (trade name Irgacure 369, manufactured by Ciba Specialty Chemicals)

EEP: 3-ethoxypropionate ethyl ester

MBA: 3-methoxybutyl acetate

Claims (8)

A coloring composition for a color filter comprising the following components (A), (B), and (C): (A) a coloring agent containing a quinophthalone pigment; (B) containing the following formula ( 1) a repeating unit represented by the following repeating unit represented by the following formula (2), and a copolymer having an amine value of 80 to 250 mgKOH/g; and (C) a crosslinking agent; In the formula (1), R ¹ represents a hydrogen atom or a methyl group, and Z represents -NR ² R ³ or a substituted or unsubstituted nitrogen-containing heterocyclic group, wherein R ² and R ³ independently of each other represent a hydrogen atom, or a substitution. Or an unsubstituted hydrocarbon group, X ¹ represents a divalent linking group, In the formula (2), R ⁴ represents a hydrogen atom or a methyl group, and R ⁵ represents an aliphatic hydrocarbon group or an alicyclic hydrocarbon group. The coloring composition for a color filter according to the first aspect of the invention, wherein the (B) copolymer further has at least one of a repeating unit represented by the following formula (3) or a repeating unit having an acidic group, In the formula (3), R ⁶ represents a hydrogen atom or a methyl group, R ⁷ independently represents an alkanediyl group having 2 to 4 carbon atoms, R ⁸ represents an alkyl group having 1 to 6 carbon atoms, and n represents 1 to 2; An integer of 150. The coloring composition for a color filter according to the first aspect of the invention, wherein the quinophthalone pigment is C.I. Pigment Yellow 138. The coloring composition for a color filter according to the first aspect of the invention, further comprising (D) a binder resin, the (D) binder resin not including the component (B). The coloring composition for a color filter according to the first aspect of the invention, further comprising (E) a photopolymerization initiator. A color filter comprising a coloring layer formed using the coloring composition according to any one of claims 1 to 5. A display element comprising a color filter as in claim 6 of the patent application. A pigment dispersion liquid for a color filter, comprising the following components (a1), (B), and (F): (a1) quinophthalone pigment; (B) comprising the following formula (1); a repeating unit and a repeating unit represented by the following formula (2), and a copolymer having an amine value of 80 to 250 mgKOH/g; and (F) a solvent; In the formula (1), R ¹ represents a hydrogen atom or a methyl group, and Z represents -NR ² R ³ or a substituted or unsubstituted nitrogen-containing heterocyclic group, wherein R ² and R ³ independently of each other represent a hydrogen atom, or a substitution. Or an unsubstituted hydrocarbon group, X ¹ represents a divalent linking group, In the formula (2), R ⁴ represents a hydrogen atom or a methyl group, and R ⁵ represents an aliphatic hydrocarbon group or an alicyclic hydrocarbon group.