TWI626508B - Coloring composition for color filter, color filter and display element - Google Patents

Abstract

The present invention relates to a coloring composition for a color filter, a color filter, and a display element. The present invention provides a coloring composition for a color filter having excellent chromaticity characteristics, good dispersibility, and good storage stability. The coloring composition for a color filter includes the following components (A), (B), and (C): (A) a coloring agent containing a quinophthalone pigment; and (B) containing the following formula ( A copolymer having a repeating unit (1) represented by 1) and a repeating unit (2) represented by the following formula (2) and having an amine value of 80 to 250 mgKOH / g; and (C) a crosslinking agent.

[In 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 represent a hydrogen atom or a substituted or unsubstituted hydrocarbon group) or a substituted or unsubstituted A substituted nitrogen-containing heterocyclic group, X ¹ represents a divalent linking group. In 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].

Description

Coloring composition for color filter, color filter and display element

The present invention relates to a coloring composition for a color filter, a color filter, and a display element. More specifically, the present invention relates to a coloring composition for a color filter that is used to form a coloring layer useful for a color filter. The color filter is used for a transmissive or reflective color liquid crystal display element, solid-state imaging element, organic EL display element, electronic paper, etc .; a color filter provided with a coloring layer formed using the coloring composition; and A display element of the color filter.

When manufacturing a color filter using a colored radiation-sensitive composition, a method is known in which a pigment-dispersed colored radiation-sensitive composition is coated on a substrate and dried, and then the dried coating film is formed in a desired pattern shape. Radiation (hereinafter referred to as "exposure") is irradiated and developed to obtain pixels of each color (for example, Patent Documents 1 to 2). A method of forming a black matrix using a photopolymerizable composition in which carbon black is dispersed is also known (for example, Patent Document 3). In addition, a method of obtaining pixels of each color by an inkjet method using a pigment-dispersed 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, with the demand for higher brightness and higher contrast, the pigments used tend to become more and more finer. It is known that the use of a dispersant is effective for achieving stable and good dispersion of such a micronized pigment. Various methods have been proposed using the dispersant to improve the dispersibility of pigments, not only to improve contrast and dispersion stability, but also to improve developability. Method (for example, Patent Documents 5 to 6).

[Prior technical literature] [Patent Literature]

[Patent Document 1] Japanese Unexamined Patent Publication No. 2-144502

[Patent Document 2] Japanese Unexamined Patent Publication No. 3-52201

[Patent Document 3] Japanese Unexamined Patent Publication No. 6-35188

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

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

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

However, even if the methods described in these Patent Documents 5 to 6 are used, it has been difficult to achieve the requirements of 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 are problems in that a pigment dispersion solution prepared by using a conventionally proposed dispersion method and a well-known dispersant has not only high viscosity, but also The storage stability deteriorates and it is difficult to withstand practical use. In addition, the color filter prepared using the pigment dispersion solution has insufficient contrast. Therefore, there is a strong demand for the development of a coloring composition for a color filter that can achieve the requirements of high contrast, high color purity, and high brightness in recent years, and that has excellent dispersibility and storage stability.

Therefore, an object of the present invention is to provide a coloring composition for a color filter that uses a quinophthalone pigment represented by C.I. Pigment Yellow 138 as a colorant and has excellent chromaticity characteristics, good dispersibility, and storage stability. . 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-mentioned actual situation, the present inventors conducted intensive studies and found that the above-mentioned 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-based pigment; (B) ) Contains 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 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 represent a hydrogen atom or a substituted or unsubstituted hydrocarbon group) or a substituted or unsubstituted A substituted nitrogen-containing heterocyclic group, X ¹ represents a divalent linking group. ]

[In 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 present invention also provides a color filter including a coloring layer formed using the coloring composition, and a display element including the color filter. Here, the "colored layer" means each color pixel, a black matrix, a black spacer, and the like used in a color filter.

The present invention also provides a pigment dispersion liquid for a color filter, which contains the following components (a1), (B), and (F): (a1) a quinophthalone-based pigment; and (B) a repeating agent A copolymer of the unit (1) and the repeating unit (2) and having an amine value of 80 to 250 mgKOH / g; and (F) a solvent.

The coloring composition for color filters of the present invention is excellent in chromaticity characteristics, and also excellent in dispersibility and storage stability. By using the coloring composition of the present invention, a color filter having pixels of each color with high contrast can be obtained.

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

[Form of Implementing Invention]

Hereinafter, the present invention will be described in detail.

Coloring composition for color filter

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

-(A) Colorant-

The coloring composition of this invention contains (a1) a quinophthalone type pigment as (A) coloring agent.

The quinophthalone pigment is preferably C.I. Pigment Yellow 138 from the viewpoints of availability of raw materials and absorption spectrum.

In the present invention, (a1) a quinophthalone-based pigment may be used alone or as a mixture of two or more thereof. In addition, the coloring composition of the present invention may contain (a1) a quinophthalone-based pigment, and may further contain (a2) another coloring agent. (A2) The other coloring agent is not particularly limited. For example, by using (a1) a quinophthalone pigment with a green coloring agent, a coloring composition for forming a green pixel can be prepared. In addition, by using (a1) a quinophthalone-based pigment together with a red coloring agent, a coloring composition for forming a red pixel or a yellow pixel can be prepared.

(A2) As for other colorants, any of pigments, dyes, and natural pigments other than quinophthalone-based pigments may be used, but in terms of obtaining pixels with high brightness and color purity, it is preferable Organic pigments, organic dyes. Examples of the organic pigment include compounds classified as pigments in the color index (C.I .; issued by The Society of Dyers and Colourists), that is, compounds having the name of the color index (C.I.) as described below.

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 ; CI Pigment Black 1, CI Pigment Black 7; Xanthene lake pigments described in JP 2010-26334; JP 2010-191304 and JP 2011-22502 Damin-based lake pigments; Triarylmethane-based lake pigments described in JP-A-2011-138094 and JP-A-2011-22502; JP-A-2010-237569 and JP-A-2011-6602 Various lake pigments described in Japanese Patent Application Publication No. 2011-150195.

Examples of the organic dye include compounds having a name of a color index (C.I.) as described below.

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 Active Yellow 2, CI Active Red 17, CI Active Red 120, CI Active Black 5, CI Disperse Orange 5, CI Disperse Red 58, CI Disperse Blue 165, CI Basic Blue 41, CI Basic Red 18.CI Mordant Red 7, CI Mordant Yellow 5 , CI mordant black 7 and other azo dyes; CI 瓮 blue 4, CI acid blue 40, CI acid green 25, CI active blue 19, CI active blue 49, CI disperse red 60, CI disperse blue 56, CI disperse blue 60 Anthraquinone-based dyes; Phthalocyanine-based dyes such as CI Sapphire Blue 5; Quinimine-based dyes such as CI Basic Blue 3 and CI Basic Blue 9; CI Solvent Yellow 33, CI Acid Yellow 3, CI Disperse Yellow 64 Phenol dyes; CI acid yellow 1, CI acid orange 3, CI disperse yellow 42 and other nitro dyes; CI disperse yellow 201 and other methine dyes.

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

In the present invention, the pigment may be used after being purified by a recrystallization method, a reprecipitation method, a solvent washing method, a sublimation method, a vacuum heating method, or a combination thereof. In addition, the pigment can be used by modifying the surface of its particles with a resin if necessary. Examples of the resin in which the particle surface of the pigment is modified include a color developing resin described in Japanese Patent Application Laid-Open No. 2001-108817 or various commercially available resins for dispersing pigments. As a method for covering the carbon black surface, for example, the methods described in Japanese Patent Application Laid-Open No. 9-71733, Japanese Patent Application Laid-Open No. 9-95625, Japanese Patent Application Laid-Open No. 9-124969, and the like can be used. The organic pigment can be used by miniaturizing the primary particles by a so-called salt milling method. As a method of the salt grinding method, for example, a method disclosed in Japanese Patent Application Laid-Open No. 08-179111 can be adopted.

When the coloring composition of the present invention is used to form a green pixel, it is preferable that (A) the colorant contains (a1) a quinophthalone-based pigment and is selected from the group consisting of CI Pigment Green 7 and CI Pigment Green. 36 and at least one of CI Pigment Green 58. At this time, the content ratio of the (a1) quinophthalone pigment is preferably 1 to 80% by mass, more preferably 2 to 70% by mass of the total colorant, and is selected from CI Pigment Green 7, CI Pigment Green 36, and CI. The total content of at least one of pigment green 58 is preferably 20 to 99% by mass, and even more preferably 30 to 98% by mass in the total colorant.

From the viewpoint of forming a pixel with high brightness and excellent color purity, or a black matrix with excellent light-shielding properties, the content of the colorant (A) in the solid content of the coloring composition is usually 5 to 70% by mass, preferably 5 ~ 60% by mass. The solid content here is a component other than the solvent mentioned 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 dispersant for the (A) colorant.

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

In the above formula (1), R ¹ is preferably a methyl group among a hydrogen atom and a 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 represent a hydrogen atom or a substituted or unsubstituted hydrocarbon group. In the present invention, Herein, the "hydrocarbon group" refers to a concept including an aliphatic hydrocarbon group, an alicyclic hydrocarbon group, and an aromatic hydrocarbon group, and may have any of linear, branched, and cyclic forms, and may be a saturated hydrocarbon group or Unsaturated hydrocarbyl. In addition, the unsaturated bond of the unsaturated hydrocarbon group may be within the molecular chain or at any 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, and more specifically, 1 to 20 carbon atoms, and more preferably 1 Alkyl group of ~ 12, alkenyl group having 2 to 20 carbon atoms, more preferably 2 to 12, alkynyl group having 2 to 20 carbon atoms, and more preferably 2 to 12 carbon atoms. Specific examples of the alkyl group include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, secondary butyl, tertiary butyl, pentyl, and isopentyl. , Hexyl, heptyl, octyl, decyl, dodecyl and the like. Examples of alkenyl include vinyl, 1-propenyl, 1-butenyl, 1,3-butadienyl, 1-pentenyl, 2-pentenyl, and 1-hexyl. Examples of alkenyl, 2-ethyl-2-butenyl, 2-octenyl, (4-vinyl) -5-hexenyl, and 2-decenyl include alkynyl 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.

The alicyclic hydrocarbon group is preferably an alicyclic hydrocarbon group having 3 to 20 carbon atoms, and more preferably 3 to 12 carbon atoms. Specifically, the alicyclic hydrocarbon group includes 3 to 20 carbon atoms, and more preferably The cycloalkyl group is preferably 3 to 12, and more specifically, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclodecyl, cyclododecyl Wait. Herein, the "alicyclic hydrocarbon group" in the present invention refers to a general term for those who remove aromatic compounds from a carbocyclic compound having a structure in which carbon atoms are bonded to form a ring, and also includes the above-mentioned aliphatic hydrocarbon group as a substituent or -COO- the foundation of the connection.

The aromatic hydrocarbon group is preferably 6 carbon atoms. ~ 20, more preferably 6 to 14, and even more preferably 6 to 10 aromatic hydrocarbon groups, and more specifically, 6 to 20 carbon atoms, more preferably 6 to 14, and more It is preferably an aryl group of 6 to 10. Here, the "aryl group" in the present invention means a monocyclic to tricyclic aromatic hydrocarbon group, and specific examples thereof include a phenyl group, a naphthyl group, an anthryl group, a phenanthryl group, and a fluorenyl group.

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. Examples of the alkoxy group having 1 to 6 carbon atoms include a methoxy group, an ethoxy group, and a propoxy group. Group, isopropyloxy, butoxy, pentoxy, 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 a ring, and is preferably a single heterocyclic group or a condensed heterocyclic group obtained by condensing two of them. Ring base. These heterocyclic groups may be an unsaturated ring or a saturated ring, and may have a hetero atom (for example, an oxygen atom, a sulfur atom) other than a nitrogen atom in the ring.

Examples of the unsaturated heterocyclic ring include a pyridine ring, an imidazole ring, a thiazole ring, Azole ring, triazole ring, imidazoline ring, tetrahydropyrimidine ring and the like. Examples of the saturated heterocyclic ring include: Porphyrin ring, piperidine ring, piperidine Ring etc. 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 amidamine. Group, thiol group, thioether group, and the like. Examples of the alkyl group having 1 to 6 carbon atoms include methyl, ethyl, propyl, isopropyl, butyl, tertiary butyl, pentyl, and hexyl. For a halogen atom, Examples thereof include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. As the alkoxycarbonyl group, for example, an alkoxycarbonyl group having 2 to 7 carbon atoms is preferred. Specific examples include a methoxycarbonyl group, an ethoxycarbonyl group, a methylamino group, an ethoxy group, Benzyloxy and the like. The alkoxy group is preferably an alkoxy group having 1 to 6 carbon atoms. Specific examples include a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, a butoxy group, and a pentyl group. Oxy, phenoxy, etc. Examples of the amino group include amino group, methylamino group, diethylamino group, and diphenylamino group. Examples of the amino group include methylamino group and ethylamino group. Group, propylamino group 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 monocyclic group is preferably a 5- to 7-membered ring. Specifically, a group having a basic skeleton represented by the following formula (1-1) may be mentioned, and these monocyclic groups may have a substituent.

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

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

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

In the above formula (1), examples of the divalent linking group (X ¹ ) include alkanediyl groups having 1 to 10 carbon atoms and 1 to 6 carbon atoms; 6 to 20 carbon atoms; There are 6 to 14 arylene groups; -CONH-R ¹⁰ -groups; -COO-R ¹¹ -groups and the like. Here, R ¹⁰ and R ¹¹ are each independently a single bond, an alkanediyl group having 1 to 10 carbon atoms, or an alkoxyalkylene group having 2 to 10 carbon atoms. Examples of the alkanediyl group include methylene, ethylene, ethane-1,1-diyl, propane-1,1-diyl, propane-1,2-diyl, and 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. Examples of the arylene group include a phenylene group, a naphthyl group, a biphenylene group, and an anthryl group. Examples of the alkoxyalkylene group having 2 to 10 carbon atoms include ethoxylate, ethoxylate, propyloxylate, and ethoxylate.

Among them, a —COO-R ¹¹ — group is preferred for X ¹ , and an alkyldiyl group having 2 to 6 carbon atoms is preferred for R ¹¹ .

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

In the above formula (2), R ⁴ is preferably a methyl group among a hydrogen atom and a methyl group.

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

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 alkenyl group. The alicyclic hydrocarbon group may further have a substituent. Examples of the substituent include a halogen atom, a hydroxyl group, and an alkoxy group having 1 to 6 carbon atoms. Specific examples of these substituents include the same substituents as described above.

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

(B) The copolymer may have repeating units other than the above, and examples of such repeating units include, for example, 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 "repeat unit (4)]; a repeating unit derived from a monomer which is a styrene-based monomer such as styrene, α-methylstyrene; Aryl) (meth) acrylates such as benzyl acrylate; (meth) acrylic acid ethoxyethyl (4-benzylidene benzyl) dimethyl ammonium bromide, (meth) acrylic acid ethoxylate (Meth) acrylic acid esters having a quaternary ammonium salt structure such as benzyl dimethyl ammonium chloride, (meth) acrylic acid oxyethyl benzyl diethyl ammonium chloride; (meth) acrylic acid chloride, etc. (Meth) acrylic acid halogenated monomers; (meth) acrylic acid amines, (meth) acrylic acid amines, and other (meth) acrylic acid amines; vinyl acetate; acrylonitrile; Glyceryl ether; Butyric acid glycidyl ether; N-methacryl Monomers such as phthaloline. Among these, from the viewpoint of dispersibility, it is preferable to have at least one of a repeating unit (3) and a repeating unit (4), and it is more preferable to have a repeating unit (3). Here, in the present invention, "(meth) acrylate" means "acrylate or methacrylate".

[In 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 formula (3), R ⁶ is preferably a methyl group among a hydrogen atom and a methyl group.

Examples of the alkanediyl group of R ⁷ include ethylene, ethane-1,1-diyl, propane-1,1-diyl, propane-1,2-diyl, and propane- 1,3-diyl, propane-2,2-diyl, butane-1,2-diyl, butane-1,3-diyl, butane-1,4-diyl, and the like.

Examples of the R ⁸ alkyl group include the same ones as described 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 , -C (CF ₃ ) ₂ -OH, and the like. In the present invention, from the viewpoint of dispersibility and alkali developability of the obtained coloring composition, the acidic group is preferably a phenolic hydroxyl group or a carboxyl group, and particularly preferably a carboxyl group.

Examples of the repeating unit (4) include a repeating unit represented by the following formula (4).

[In 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 formula (4), R ⁹ is preferably a methyl group among a hydrogen atom and a methyl group.

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

Among them, X ^{2 is} preferably a single bond, phenylene, -COO-R ¹³ -based, -COO- (C _m H _2m COO) ₁ -C _m H _2m -based, or -COO-R ¹⁷ -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. From the viewpoint of dispersibility, the following ( Any one of i) to (iii) is more preferably any one 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 20 to 80% by mass, and more preferably 30 in all repeating units. ~ 70% by mass, more preferably 40 ~ 60% by mass, and the copolymerization ratio of the repeating structure (2) is the remainder.

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

(iii) (B) When the copolymer has repeating units (3) and (4) other than repeating structure (1) and repeating structure (2), copolymerization of repeating structure (1) The proportion in all the repeating units is preferably 20 to 70% by mass, more preferably 30 to 65% by mass, and even more preferably 40 to 60% by mass. 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, even more preferably 15 to 40% by mass, and the copolymerization ratio of the repeating structure (3) is preferably 5 to 40% by mass among all the repeating units, further preferably It is 10 to 30% by mass, and the copolymerization ratio of the repeating structure (4) is preferably 1 to 10% by mass, and more preferably 1 to 5% by mass in all the repeating units.

(B) The amine value of the copolymer is 80mgKOH / g ~ 250mgKOH / g. From the viewpoint of further improving the contrast, it is preferably 100 ~ 250mgKOH / g, more preferably 150 ~ 250mgKOH / g, even more preferably 150 ~ 200mgKOH / g, especially preferred is 155 ~ 190mgKOH / g. Herein, in the present invention, the "amine value" refers to the number of mg of KOH of acid equivalents required for neutralizing 1 g of the non-volatile component obtained by neutralizing the solvent from which the copolymer solution is removed, and specifically, it is carried out by the method described later. The value measured by the method described in the example.

On the other hand, when the (B) copolymer has a repeating unit (4), from the viewpoint of storage stability, the acid value of the (B) copolymer is preferably 30 mgKOH / g or less, more preferably 25 mgKOH / g or less, 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, and more preferably 1 mgKOH / g or more. Here, in the present invention, the "acid value" means the number of mg of KOH required to neutralize 1 g of the non-volatile component obtained by neutralizing the solvent of the copolymer solution, and specifically, it is described in the examples described later. The value measured by the method.

(B) The copolymer has no repeating unit (1) and repeating unit (2). It is particularly limited, and from the viewpoint of further improving the dispersibility, a block copolymer including an A block and a B block, the A block having a repeating unit (1) instead of the repeating unit (2), The unit (3) and the repeating unit (4), the B block has no repeating unit (1) but has repeating units (2) and repeating units (3) and has repeating units (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 types of repeating units (1) may be contained in one A block. In this case, the A block may contain each of random copolymerization and block copolymerization. Repeating unit.

The A block may contain repeating units other than the repeating unit (1). Examples of such repeating units include repeats derived from the (meth) acrylic acid ester having a quaternary ammonium salt structure described above. unit.

On the other hand, the B block may contain a repeating unit (2), a repeating unit (3), and a repeating unit (4) in any form 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, the B1 block having a repeating unit (2) and a repeating unit (3) ) And does not have repeating units (4), the B2 block has repeating units (2) and repeating units (4) and does not have repeating units (3). In addition, one B block may contain two or more types of repeating unit (2), repeating unit (3), and repeating unit (4). In this case, the B block may be randomly copolymerized and blocked. Either aspect of the copolymerization includes each repeating unit.

The (B) copolymer can be produced by a known method, but when the (B) copolymer is a block copolymer, it can be produced, for example, by living polymerization of a monomer introduced into each of the above repeating units. As far as living polymerization is concerned, For example, the following methods can be used: Japanese Patent Application Laid-Open No. 9-62002; Japanese Patent Application Laid-Open No. 2002-31713; P. Lutz, P. Masson et al, Polym. Bull. 12, 79 (1984); BCAnderson, GDAndrews 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 Koichi, Puta Kenichi, Polymer Processing, 36.366 (1987); Tomura Toshiyuki, Sawamoto Mitsuo, Polymer Essays, 46,189 (1989); M. Kuroki, T. Aida, J. Am. Chem. Soc, 109, 4737 (1987); Aida Takusan, Inoue Shoji, Organic Synthetic Chemistry, 43, 300 (1985); DYSogoh, WHertler 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) and other well-known methods.

Examples of the monomer providing 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 can be used individually or in mixture of 2 or more types.

Examples of the monomer that provides the repeating unit (2) include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, Butyl (meth) acrylate, isobutyl (meth) acrylate, tertiary butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, isodecyl (meth) acrylate, (formyl) (Lauryl) dodecyl acrylate, cyclohexyl (meth) acrylate, tricyclo [5.2.1.0 ^2,6 ] decane-8-yl (meth) acrylate, isoamyl (meth) acrylate, Adamantyl (meth) acrylate, dicyclopentenyl (meth) acrylate, decahydro-2-naphthyl (meth) acrylate, pentacyclopentadecyl (meth) acrylate, (methyl ) Tricyclopentenyl acrylate and the like. These monomers can be used individually or in mixture of 2 or more types.

Examples of the monomer that provides the repeating unit (3) include 2-methoxyethyl (meth) acrylate, methoxydiethylene glycol (meth) acrylate, and methoxytriethylene glycol. Alcohol (meth) acrylate, methoxypropylene glycol (meth) acrylate, methoxydipropylene glycol (meth) acrylate, and the like. These monomers can be used individually or in mixture of 2 or more types.

Examples of the monomer that provides the repeating unit (4) include (meth) acrylic acid, maleic acid, maleic anhydride, itaconic acid, itaconic anhydride, carboxymethyl (meth) acrylate, 2-carboxyethyl (meth) acrylate, mono [2- (meth) acryloxyethyl] succinate, ω-carboxy polycaprolactone mono (meth) acrylate, p-vinylbenzoic acid, P-hydroxystyrene, p-hydroxy-α-methylstyrene, 2-propenyloxyethylsulfonic acid, 2-methacrylic acid oxyethylsulfonic acid, 2-propenyloxyethyl sulfonic acid sodium, 2- Lithium propylene oxide ethyl sulfonate, 2-propylene amine oxide ethyl sulfonate, 2-propylene oxamine ethyl sulfonic acid imidazolium salt, 2-propene oxethane ethyl sulfonic acid pyridinium salt, 2-methyl Sodium propylene oxide ethoxylate, lithium 2-methacrylic acid ethoxylate, 2-methylpropylene ammonium oxyethyl sulfonate, 2-methylpropylene ethoxylate sulfonic acid imidazolium salt, 2-Methacrylic acid oxyethylsulfonate pyridinium salt, styrene sulfonic acid and the like. These monomers can be used individually or in mixture of 2 or more types.

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

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

The (B) copolymer may be used alone or as a mixture of two or more. The content of the (B) copolymer relative to 100 parts by mass of the (A) colorant is usually 1 to 100 parts by mass, preferably 5 to 70 parts by mass, and still more preferably 10 to 50 parts by mass. If the content of the (B) copolymer is too large, the developability may be impaired.

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

Such dispersants can be obtained through commercial channels. For example, as the acrylic dispersant, Disperbyk-2000, Disperbyk-2001, BYK-LPN6919, BYK-LPN21116, BYK-LPN21324 (the above are manufactured by BYK CHEMIE), Examples of the polyurethane-based dispersant include Disperbyk-161, Disperbyk-162, Disperbyk-165, Disperbyk-167, Disperbyk-170, Disperbyk-182 (the above are manufactured by BYK CHEMIE), Solsperse 76500 ( LUBRIZOL (manufactured by LUBRIZOL), as the polyethyleneimine-based dispersant, Solsperse 24000 (manufactured by LUBRIZOL), and polyester-based dispersion Examples of the agent include Adisper PB821, Adisper PB822, Adisper PB880, and Adisper PB881 (manufactured by Ajinomoto Fine Chemical Co., Ltd.). Specific examples of the pigment derivative include copper phthalocyanine, diketopyrrolopyrrole, and a sulfonic acid derivative of quinophthalone.

-(C) Crosslinking agent-

In the present invention, (C) a crosslinking agent refers to a compound having two or more polymerizable groups. Examples of the polymerizable group include an ethylenically unsaturated group, an epoxyethyl 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) acrylfluorenyl groups or a compound having two or more N-alkoxymethylamino groups.

Specific examples of the compound having two or more (meth) acrylfluorenyl groups include polyfunctional (meth) acrylates and caprolactones obtained by reacting an aliphatic polyhydroxy compound with (meth) acrylic acid. Modified polyfunctional (meth) acrylate, polyalkylene oxide modified polyfunctional (meth) acrylate, hydroxyl (meth) acrylate and polyfunctional isocyanate A (meth) acrylate, a polyfunctional (meth) acrylate having a carboxyl group, and the like obtained by reacting a (meth) acrylate having a hydroxyl group and an acid anhydride.

Here, examples of the aliphatic polyhydroxy compound include binary aliphatic polyhydroxy compounds such as ethylene glycol, propylene glycol, polyethylene glycol, and polypropylene glycol, such as glycerol and trimethylolpropane. Trivalent or more aliphatic polyhydroxy compounds such as neopentyl tetraol and dipentaerythritol. Examples of the (meth) acrylate having a hydroxyl group include 2-hydroxyethyl (meth) acrylate and trimethylolpropane di (methyl). Acrylates, neopentaerythritol tri (meth) acrylate, dinepentaerythritol penta (meth) acrylate, glyceryl dimethacrylate, and the like. Examples of the polyfunctional isocyanate include toluene diisocyanate, hexamethylene diisocyanate, diphenylmethylene diisocyanate, isophorone diisocyanate, and the like. Examples of the acid anhydride include dibasic acid anhydrides such as succinic anhydride, maleic anhydride, glutaric anhydride, itaconic anhydride, phthalic anhydride, and hexahydrophthalic anhydride, such as pyromellitic acid. Tetracarboxylic dianhydrides such as acid dianhydride, biphenyltetracarboxylic dianhydride, and benzophenone tetraacid dianhydride.

Examples of the caprolactone-modified polyfunctional (meth) acrylate include compounds described in paragraphs [0015] to [0018] of Japanese Patent Application Laid-Open No. 11-44955. Examples of the alkylene oxide-modified polyfunctional (meth) acrylate include modification with at least one selected from the group consisting of ethylene oxide of bisphenol A and propylene oxide of bisphenol A. The obtained di (meth) acrylate and tri (meth) acrylic acid obtained by modifying at least one selected from the group consisting of ethylene oxide of isotricyanic acid and propylene oxide of isotricyanic acid. Esters, tri (meth) acrylates obtained by modifying at least one selected from the group consisting of trimethylolpropane ethylene oxide and trimethylolpropane propylene oxide, using neopentyl Tri (meth) acrylate obtained by modifying at least one of ethylene oxide of ethylene alcohol and propylene oxide of neopentyl tetraol, using ethylene oxide selected from neopentyl tetraol and neopentyl tetraethylene Tetrakis (meth) acrylate obtained by modifying at least one of propylene oxide of alcohol, and at least one selected from ethylene oxide of dipentaerythritol and propylene oxide of dipentaerythritol One penta (meth) acrylate obtained by modification, and one obtained by modification with at least one selected from the group consisting of ethylene oxide of dipentaerythritol and propylene oxide of dipentaerythritol six( Yl) acrylate.

Examples of the compound having two or more N-alkoxymethylamine groups include compounds having a melamine structure, a benzoguanamine structure, and a urea structure. In addition, a melamine structure and a benzoguanamine structure mean that it has one or more Ring or phenyl substituted tri The chemical structure of a ring as a basic skeleton is a concept that also includes 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) glycolurea and the like.

Among these crosslinking agents, a polyfunctional (meth) acrylate or a caprolactone-modified polyfunctional (meth) obtained by reacting a ternary or higher aliphatic polyhydroxy compound with (meth) acrylic acid is preferred. Acrylate, polyfunctional urethane (meth) acrylate, polyfunctional (meth) acrylate with carboxyl group, N, N, N ', N', N ", N" -hexa (alkoxy) (Meth) melamine, N, N, N ', N'-tetrakis (alkoxymethyl) benzoguanamine. Considering that the strength of the colored layer is high, the surface smoothness of the colored layer is excellent, and floating stains and film residues are not easily generated on the substrate and the light-shielding layer of the unexposed portion, the aliphatic polyhydroxy compound having a ternary or higher and ( Among the polyfunctional (meth) acrylates obtained by the reaction of (meth) acrylic acid, trimethylolpropane triacrylate, neopentaerythritol triacrylate, dinepentaerythritol pentaacrylate, and dihexamethylene diacrylate are particularly preferred. Neopentaerythritol; among polyfunctional (meth) acrylates having a carboxyl group, particularly preferred are compounds obtained by reacting neopentaerythritol triacrylate with succinic anhydride, dinepentaerythritol pentaacrylate and amber Compound obtained by acid anhydride reaction.

In the present invention, the (C) crosslinking agent may be used alone or as a mixture of two or more kinds. Used together.

The content of the (C) crosslinking agent in the present invention is preferably 10 to 1,000 parts by mass, and particularly preferably 20 to 500 parts by mass with respect to 100 parts by mass of the (A) colorant. 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 cross-linking agent is too large, when the alkali-developing property is imparted to the colored composition of the present invention, the alkali-developing property is reduced, and fouling tends to occur on the substrate of the unexposed portion or on the light-shielding layer. The tendency of the film to remain.

-(D) Binder resin-

The coloring composition of the present invention may contain (D) a binder resin (excluding the above (B)). This makes it possible to improve the alkali developability of the coloring composition and the adhesiveness to the substrate. The binder resin is not particularly limited, but a resin having an acidic functional group such as a carboxyl group or a phenolic hydroxyl group is preferred. Among them, a polymer having a carboxyl group (hereinafter referred to as a "carboxyl-containing polymer") is preferred, and examples thereof include an ethylenically unsaturated monomer having one or more carboxyl groups (hereinafter referred to as "unsaturated monomer (d1)" ") And other copolymerizable ethylenically unsaturated monomers (hereinafter referred to as" unsaturated monomers (d2) ").

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

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

Examples of the unsaturated monomer (d2) include N-substituted maleimide such as N-phenylmaleimide and N-cyclohexylmaleimide; Aromatic vinyl compounds such as styrene, α-methylstyrene, p-hydroxystyrene, p-hydroxy-α-methylstyrene, p-vinylbenzyl glycidyl ether, and pinene; 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 to 10), methyl ether (meth) acrylate, polypropylene glycol (degree of polymerization 2 to 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, isoamyl (meth) acrylate, (meth) ) Tricyclo [5.2.1.0 ^2,6 ] decane-8-yl acrylate, dicyclopentenyl (meth) acrylate, glyceryl mono (meth) acrylate, 4-hydroxyphenyl (meth) acrylate , Ethylene oxide modified (meth) propylene for cumyl phenol Ester, glycidyl (meth) acrylate, 3,4-epoxycyclohexyl methyl (meth) acrylate, 3-[(meth) acryloxymethyl] oxetane, 3- [ (Meth) acryloxymethyl] -3-ethyloxetane (meth) acrylates; such as cyclohexyl vinyl ether, isofluorenyl vinyl ether, tricyclic [5.2.1.0 ^2,6 ] vinyl ethers such as decane-8-yl vinyl ether, pentacyclopentadecyl vinyl ether, 3- (vinyloxymethyl) -3-ethyloxetane; such as poly Macromonomers such as styrene, polymethyl (meth) acrylate, poly-n-butyl (meth) acrylate, and polysiloxane having a mono (meth) acrylfluorene group at the end of a polymer molecular chain, etc. .

These unsaturated monomers (d2) can be used alone or as a mixture 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 5 to 50% by mass, and more preferably 10 ~ 40% by mass. By copolymerizing the unsaturated monomer (d1) in such a range, a colored composition having excellent 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, Japanese Unexamined Patent Publication No. 7-140654, Japanese Unexamined Patent Publication No. 8-259876, and Japanese Unexamined Patent Publication Japanese Patent Publication No. 10-31308, Japanese Patent Application Publication No. 10-300922, Japanese Patent Application Publication No. 11-174224, Japanese Patent Application Publication No. 11-258415, Japanese Patent Application Publication No. 2000-56118, Japanese Patent Application Publication No. 2004-101728, etc. Disclosed copolymers.

Further, in the present invention, for example, Japanese Patent Laid-Open No. 5-19467, Japanese Patent Laid-Open No. 6-230212, Japanese Patent Laid-Open No. 7-207211, Japanese Patent Laid-Open No. 09-325494, and Japanese Patent Laid-Open No. 11 A carboxyl group-containing polymer having a polymerizable unsaturated bond such as a (meth) acrylfluorenyl group in a side chain may be used as a binder resin, as disclosed in Japanese Unexamined Patent Application Publication No. -140144 and Japanese Patent Application Laid-Open Publication No. 2008-181095.

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

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 1.0 to 5.0, and more preferably 1.0 to 3.0. In addition, Mw 'and Mn' refer to weight average molecular weight and number average molecular weight in terms of polystyrene measured by GPC (eluent: tetrahydrofuran).

The binder resin in the present invention can be produced by a well-known method. For example, the binder resin can be produced in accordance with Japanese Patent Application Laid-Open No. 2003-222717, Japanese Patent Application Laid-Open No. 2006-259680, International Publication No. 07/029871, and the like. Methods to control the structure, Mw, Mw / Mn of the binder resin.

In this invention, a binder resin can be used individually or in mixture of 2 or more types.

In the present invention, the content of the binder resin is usually 10 to 1,000 parts by mass, and preferably 20 to 500 parts by mass with respect to 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 resulting colored composition may be reduced. On the other hand, if the content is too large, the colorant concentration may be relatively reduced and the film may be difficult to use. Achieve the target color density.

-(E) Photopolymerization initiator-

The coloring composition of the present invention may contain a (E) photopolymerization initiator. This makes it possible to impart a sense of radiation to the colored composition. The (E) photopolymerization initiator used in the present invention is a compound that generates active species capable of initiating polymerization of the (C) crosslinking agent by exposure to radiation such as visible light, ultraviolet rays, extreme ultraviolet rays, electron beams, and X-rays.

Examples of such a photopolymerization initiator include oxygen and sulfur. Compounds, acetophenone compounds, biimidazole compounds, three Compounds, O-fluorenyl oxime compounds, onium salt compounds, benzoin compounds, benzophenone compounds, α-diketone compounds, polycyclic quinone compounds, diazo compounds, fluorenimines Sulfonate-based compounds and the like.

In this invention, a photoinitiator can be used individually or in mixture of 2 or more types. The photopolymerization initiator is preferably selected from oxygen and sulfur Compounds, acetophenone compounds, biimidazole compounds, three At least one of a system compound and an O-fluorenyl oxime system compound.

Among the preferred photopolymerization initiators in the present invention, Specific examples of the system compounds include oxygen sulfur 2-chlorooxysulfur 2-methyloxysulfur 2-isopropyloxysulfur 4-isopropyloxysulfur 2,4-dichlorooxysulfur 2,4-dimethyloxysulfur 2,4-diethyloxysulfur 2,4-diisopropyloxysulfur Wait.

In addition, specific examples of the acetophenone-based compound include 2-methyl-1- [4- (methylthio) phenyl] -2- Linylpropane-1-one, 2-benzyl-2-dimethylamino-1- (4- Phenylphenyl) butane-1-one, 2- (4-methylbenzyl) -2- (dimethylamino) -1- (4- Phenylphenyl) butane-1-one and the like.

Moreover, as a specific example of the said biimidazole-type compound, 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.

When a biimidazole-based compound is used as a photopolymerization initiator, it is preferable to use a hydrogen donor in combination in view of improving sensitivity. The "hydrogen donor" referred to herein means a compound capable of supplying a hydrogen atom to a radical generated from a biimidazole-based compound by exposure. Examples of the hydrogen donor include 2-mercaptobenzothiazole and 2-mercaptobenzo Thiol-based hydrogen donors such as azole, amine-based hydrogen donors such as 4,4'-bis (dimethylamino) benzophenone, and 4,4'-bis (diethylamino) benzophenone. In the present invention, the hydrogen donor may be used alone or in combination of two or more, but from the viewpoint of further improving the sensitivity, it is preferable to use one or more thiol-based hydrogen donors and one or more amine-based donors Hydrogen is used in combination.

In addition, the above three Specific examples of the system compounds include 2,4,6-tris (trichloromethyl) -mesotris , 2-methyl-4,6-bis (trichloromethyl) -mesanthine , 2- [2- (5-methylfuran-2-yl) vinyl] -4,6-bis (trichloromethyl) -mesanthine , 2- [2- (furan-2-yl) vinyl] -4,6-bis (trichloromethyl) -mesanthine , 2- [2- (4-Diethylamino-2-methylphenyl) vinyl] -4,6-bis (trichloromethyl) -mesanthine , 2- [2- (3,4-dimethoxyphenyl) vinyl] -4,6-bis (trichloromethyl) -mesanthine , 2- (4-methoxyphenyl) -4,6-bis (trichloromethyl) -mesanthine , 2- (4-ethoxystyryl) -4,6-bis (trichloromethyl) -mesanthine , 2- (4-n-butoxyphenyl) -4,6-bis (trichloromethyl) -mesanthine Halomethyl Department of compounds.

Specific examples of the O-fluorenyl oxime-based compound include 1,2-octanedione-1- [4- (phenylthio) phenyl] -2- (O-benzidine oxime ), Ethyl ketone-1- [9-ethyl-6- (2-methylbenzylidene) -9H-carbazol-3-yl] -1- (O-acetamoxime), ethyl ketone-1 -[9-ethyl-6- (2-methyl-4-tetrahydrofurylmethoxybenzyl) -9H-carbazol-3-yl] -1- (O-acetimoxime), ethyl ketone -1- {9-ethyl-6- [2-methyl-4- (2,2-dimethyl-1,3-dioxolyl) methoxybenzyl] -9H-carb Azol-3-yl} -1- (O-acetamoxime) and the like. O-fluorenyl oxime For commercially available products, NCI-831, NCI-930 (the above are manufactured by ADEKA Corporation), and the like can be used.

In the present invention, when a photopolymerization initiator other than a biimidazole-based 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, 4-di Ethylaminoacetophenone, 4-dimethylaminophenylacetone, ethyl 4-dimethylaminobenzoate, 2-ethylhexyl 4-dimethylaminobenzoate, 2,5-bis (4- Diethylaminobenzylidene) cyclohexanone, 7-diethylamino-3- (4-diethylaminobenzyl) 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 with respect to 100 parts by mass of the (C) crosslinking agent, and particularly preferably 1 to 100 parts by mass. In this case, if the content of the photopolymerization initiator is too small, the hardening by exposure is likely to be insufficient. On the other hand, if the content is too large, the colored layer formed tends to easily fall off the substrate during development. .

-(F) Solvent-

The coloring composition of the present invention is generally prepared by, for example, using a bead mill, a roll mill, and the like, and (a) a coloring agent containing a quinophthalone pigment and (B) a copolymer in (F) a solvent. It is mixed with other dispersants and a part of the (D) binder resin as needed, and then pulverized, mixed and dispersed to prepare a pigment dispersion. Then, (C) a cross-linking agent is added to the pigment dispersion, D) A binder resin, (E) a photopolymerization initiator, (F) a solvent, etc. which are further added, are mixed. As the (F) solvent, as long as the components (A) to (C) and other components constituting the coloring composition are dispersed, Alternatively, a solvent that dissolves and does not react with these components and has a moderate volatility can be appropriately selected and used. However, when the pigment dispersion liquid is prepared, from the viewpoints of dispersibility and stability, a solvent (f1) having a hydroxyl group (hereinafter also referred to as "solvent (f1)") and (f2) having no hydroxyl group are preferred. A solvent (hereinafter also referred to as "solvent (f2)") is used in combination.

Among such solvents, 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 mono 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 ethers, dipropylene glycol mono-n-butyl ether, tripropylene glycol monomethyl ether, and tripropylene glycol monoethyl ether; alkyl lactates such as methyl lactate and 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 so on.

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

Examples of the solvent (f2) include ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monomethyl ether acetate, and diethyl ether. Glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, dipropylene glycol monomethyl ether acetate (Poly) alkylene glycol monoalkyl ether acetates such as esters, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate; diethylene glycol dimethyl ether, 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 Esters, 1,3-butanediol diacetate, 1,6-hexanediol diacetate and other diacetates; methyl 3-methoxypropionate, ethyl 3-methoxypropionate Esters, alkoxycarboxylic acid esters such as 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, n-butyrate Propyl, isopropyl butyrate, n-butyl butyrate, methyl pyruvate, ethyl pyruvate, n-propyl pyruvate, methyl ethyl acetate, ethyl ethyl acetate, ethyl 2-oxobutanoate Esters and other esters; aromatic hydrocarbons such as toluene and xylene; N, N-dimethylformamide, N, N-dimethylethyl Amine, N- methylpyrrolidone Amides or Lactams amines.

Among these solvents (f2), (poly) alkylene glycol monoalkyl ether acetates, ethers, ketones, diacetates, and alkoxycarboxylic acid esters are preferred, and ethylene diethylene glycol is particularly preferred. 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-butanediol diacetate, 1,6-hexanediol diacetate, ethyl 3-methoxypropionate , Methyl 3-ethoxypropionate, 3-ethoxy Ethyl propionate. The solvent (f2) can be used alone or as a mixture 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 liquid is preferably 0.5 / 99.5 to 40/60, and more preferably 1/99 to 30/70. Especially good is 5/95 ~ 25/75.

The content of the solvent is not particularly limited. Regardless of whether it is a pigment dispersion or a coloring composition, the total concentration of each component after removing the solvent of the pigment dispersion or the coloring composition is preferably an amount of 5 to 50% by mass, particularly preferably The amount is 10 to 40% by mass. By setting it to such a state, a coloring agent dispersion liquid with good dispersibility and stability, and a coloring composition with good coatability and stability can be obtained.

-additive-

The coloring composition of the present invention may further contain various additives as necessary.

Examples of the additives include fillers such as glass and alumina; polymer compounds such as polyvinyl alcohol and poly (fluoroalkyl acrylate); and surfactants such as fluorine-based surfactants and silicon-based surfactants. ; Vinyltrimethoxysilane, vinyltriethoxysilane, vinyltri (2-methoxyethoxy) silane, N- (2-aminoethyl) -3-aminopropylmethyl Dimethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxy Silane, 3-glycidoxypropylmethyldimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-chloropropylmethyldimethoxysilane , Accelerators such as 3-chloropropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, etc .; 2,2-thiobis (4-methyl -6-tertiary-butylphenol), 2,6-tertiary-butylphenol, etc. Oxidant; 2- (3-tert-butyl-5-methyl-2-hydroxyphenyl) -5-chlorobenzotriazole, alkoxybenzophenones and other UV absorbers; sodium polyacrylate Agglutinating agent; malonic acid, adipic acid, itaconic acid, citraconic acid, fumaric acid, mesaconic acid, 2-aminoethanol, 3-amino-1-propanol, 5-amino-1- Residue improvers such as pentanol, 3-amino-1,2-propanediol, 2-amino-1,3-propanediol, 4-amino-1,2-butanediol; succinic acid mono [2- (formaldehyde Group) developing property improvers such as acryloxyethyl] acrylate, mono [2- (meth) acryloxyethyl] phthalate, ω-carboxy polycaprolactone mono (meth) acrylate, etc. .

Color filter and manufacturing method thereof

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

As a method of manufacturing a color filter, the following methods are mentioned first. First, as needed, a light-shielding layer (black matrix) is formed on the substrate surface in such a manner that a portion where a pixel is formed is divided. Next, a liquid composition in which the radiation-sensitive composition of the present invention in which a red colorant containing a quinophthalone pigment is dispersed is applied to the substrate, and then a pre-bake is performed to evaporate the solvent to form a coating film. Next, after exposing the coating film through a photomask, it was developed using an alkaline developer to dissolve and remove the unexposed portions of the coating film. Then, post-baking is performed to form a pixel array in which red pixel patterns are arranged in a predetermined sequence.

Next, coating, pre-baking, exposing, developing, and post-baking of each of the colored radiation-sensitive compositions is performed sequentially on the same substrate using each of the colored radiation-sensitive compositions in green or blue, as described above. Green pixel array and blue pixel array. As a result, a color filter having a pixel array in which the three primary colors of red, green, and blue are arranged on the substrate is obtained. sheet. However, in the present invention, the order of forming the pixels of each color is not limited to the order described above.

In addition, the black matrix may be formed by forming a desired pattern of a metal thin film such as chromium formed by sputtering or vapor deposition using a photolithography method, or using a color-sensitive radiation composition in which a black pigment is dispersed, as described above. When a pixel is formed, it is formed in the same manner.

Examples of the substrate used when forming a color filter include glass, silicon, polycarbonate, polyester, aromatic polyamine, polyimide, polyimide, and the like.

In addition, these substrates may be subjected to a suitable pretreatment such as a reagent treatment using a silane coupling agent, plasma treatment, ion plating, sputtering, vapor phase reaction method, or vacuum evaporation, if necessary.

When the colored radiation-sensitive composition is applied to the substrate, a suitable coating method such as a spray coating method, a roll coating method, a spin coating method (spin coating method), a slot die coating method, or a bar coating method is particularly preferred. Spin coating method and slit die coating method are adopted.

Pre-baking is usually performed by combining reduced pressure drying and heat drying. Drying under reduced pressure is usually performed to 50 to 200 Pa. The conditions for heating and drying are usually about 1 to 10 minutes at 70 to 110 ° C.

The coating thickness is 0.6 to 8 μm, preferably 1.2 to 5 μm, based on the film thickness after drying.

Examples of the radiation light source used when forming the pixels and / or the black matrix include xenon lamps, halogen lamps, tungsten lamps, high-pressure mercury lamps, ultra-high-pressure mercury lamps, metal halide lamps, medium-pressure mercury lamps, and low-pressure mercury. Lamp light sources, such as argon ion laser, YAG laser, XeCl excimer laser, nitrogen laser, etc. Laser light sources, etc. As the exposure light source, an ultraviolet LED can also be used. However, radiation with a wavelength in the range of 190 to 450 nm is preferred.

The radiation exposure is generally preferably 10 to 10,000 J / m ² .

In addition, as the alkaline developer, for example, sodium carbonate, sodium bicarbonate, sodium hydroxide, potassium hydroxide, tetramethylammonium hydroxide, choline, 1,8-diazabicyclo [5.4 .0] -7-undecene, 1,5-diazabicyclo [4.3.0] -5-nonene and other aqueous solutions.

An appropriate amount of a water-soluble organic solvent such as methanol, ethanol, and a surfactant may be added to the alkaline developer. After alkaline development, washing with water is usually performed.

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 developing conditions are preferably 5 to 300 seconds at room temperature.

Post-baking conditions are usually about 10-60 minutes at 180-280 ° C.

The film thickness of the pixel formed in this manner is usually 0.5 to 5 μm, and preferably 1 to 3 μm.

In addition, as a second method for manufacturing a color filter, a method of obtaining pixels of each color by an inkjet method disclosed in Japanese Patent Application Laid-Open No. 7-318723, Japanese Patent Application Laid-Open No. 2000-310706, and the like can be used. In this method, first, a partition wall having a light shielding function is formed on the substrate surface. Next, a liquid composition such as the colored composition of the present invention in which a red pigment is dispersed is ejected into the formed partition wall by an inkjet device, and then the pre-baking is performed to evaporate the solvent. Then, after exposing the coating film as necessary, post-baking is performed to harden it to form a red pixel. pattern.

Next, a green pixel pattern and a blue pixel pattern are sequentially formed on the same substrate using the respective colored compositions of green and blue, as described above. Thus, 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 of forming the pixels of each color is not limited to the order described above.

In addition, the partition wall not only exhibits a light-shielding function, but also functions to prevent the coloring compositions of the respective colors ejected into the divided area from mixing colors. Therefore, the film thickness is thicker than the black matrix used in the first method. Therefore, the partition wall is usually formed using a black radiation-sensitive composition.

The substrate used for forming the color filter, the light source of radiation, and the methods and conditions of pre-baking and post-baking are the same as the first method described above. In this way, the film thickness of the pixels formed by the inkjet method is about the same as that of the black matrix.

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

The color filter of the present invention thus obtained has extremely high brightness and color purity, and is therefore extremely useful for color liquid crystal display elements, color image tube elements, color sensors, organic EL display elements, electronic paper, and the like.

Display element

The display element of the present invention includes the color filter of the present invention. Examples of the display device include a color liquid crystal display device, an organic EL display device, and electronic paper.

A color liquid crystal display element including the color filter of the present invention may have a suitable structure. For example, the following structure may be adopted: a color filter is 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 are disposed to face each other across a liquid crystal layer; In addition, a structure in 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 in which an ITO (tin-doped indium oxide) electrode is formed may be used. The liquid crystal layers are oppositely arranged. The latter structure can significantly increase the aperture ratio, and has the advantage that a bright and high-definition liquid crystal display element can be obtained.

The color liquid crystal display element 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 tube (CCFL: Cold Cathode Fluorescent Lamp). The white LED includes, for example, a white LED obtained by combining red LEDs, green LEDs, and blue LEDs to obtain white light by mixing colors, and a white LED obtained by combining blue LEDs, red LEDs, and green phosphors by mixing colors. White LED by combining blue LED, red light emitting phosphor and green light emitting phosphor to obtain white light by mixing colors, and white light white LED by mixing color of blue LED and YAG series phosphor , Combining a blue LED, an orange light-emitting phosphor, and a green light-emitting phosphor by combining colors to obtain a white light white LED, and an ultraviolet LED, a red light-emitting phosphor, a green light-emitting phosphor, and a blue light-emitting phosphor A combination of white LEDs and the like that are obtained by mixing colors to obtain white light.

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

The organic EL display element including the color filter of the present invention may have a suitable structure, for example, a structure disclosed in Japanese Patent Application Laid-Open No. 11-307242.

The electronic paper provided with the color filter of the present invention may have a suitable structure, for example, a structure disclosed in Japanese Patent Application Laid-Open No. 2007-41169.

[Example 1]

Hereinafter, examples will be given to explain the embodiments of the present invention more specifically. However, the present invention is not limited to the following examples. In addition, Examples 4 and 6 are reference examples.

<Measurement of Mw and Mw / Mn>

The Mw and Mn of the (B) copolymer obtained in each of the following Synthesis Examples were measured by gel permeation chromatography (hereinafter, simply referred to 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 (manufactured by Showa Denko Corporation).

Column: KD-G, KF-603, KF-602, KF-601 (manufactured by Showa Denko Corporation) are used in combination.

Mobile phase: DMF.

<Synthesis of (B) copolymer>

Hereinafter, the abbreviations of the raw materials used in "synthesis of (B) copolymer" are 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: methoxy polyethylene glycol monomethacrylate (manufactured by Nippon Oil Co., Ltd., trade name PME-200, in the above formula (3), n 4)

PME-100: methoxy polyethylene 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 concentration in THF solution), and 3.6 g of diphenylethylene were added to a 1000 mL flask equipped with a stir bar, and cooled to -60 ° C. 9.2 g of n-butyllithium (15.4 mass% concentration of hexane solution) was added, and after aging for 10 minutes, a mixed solution of PME-200 18.5 g, nBMA 34.0 g, and EEMA 6.1 g was added dropwise, and the reaction was continued for 15 minutes.

Next, 55.4 g of DAMA was added dropwise. After the dropwise addition was continued for 30 minutes, 3.2 g of methanol was added to stop the reaction. After the obtained copolymer was adjusted to a 25% by mass propylene glycol monomethyl ether acetate (hereinafter referred to as PGMEA) solution, 114 g of water was added, and the temperature was raised to 100 ° C. to react 8 hour. By this reaction, EEMA is hydrolyzed to generate repeat units derived from MA. The water was distilled off and adjusted to a PGMEA solution having a concentration of 40% by mass. This gave a block copolymer formed of A blocks having repeating units from DAMA and B blocks having repeating units from PME-200, nBMA, and MA. Let the obtained copolymer be "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 pyrazole-1-dithiocarboxylate were added to a 300 mL flask equipped with a stir bar and dissolved. Minute nitrogen replacement. Then, the temperature of the reaction solution was raised to 60 ° C. with slow stirring, and the temperature was maintained for 24 hours to perform 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. The obtained solution was added to the reaction solution, and living radical polymerization was performed at 60 ° C. for 24 hours. Then, it concentrated under reduced pressure and adjusted to a 40 mass% concentration PGMEA solution. This gave a block copolymer formed of A blocks having repeating units from DAMA and B blocks having repeating units from PME-200 and MMA. Let the obtained block copolymer be "copolymer (B-2)".

Synthesis Example 3

987.6 g of THF and 51.4 g of lithium chloride (a THF solution with a concentration of 3.9% by mass) were added to a 2000 mL flask equipped with a stir bar and cooled to -60 ° C. 21.4 g of n-butyllithium (15.4% by mass concentration in hexane solution) was added, and after stirring for 10 minutes, 4.9 g of diisopropylamine was added and stirred for 15 minutes, and then isobutyl was added. 4.7 g of methyl acid ester was stirred for 15 minutes. A mixed solution of 87.9 g of MMA and 45.3 g of PME-200 was added dropwise, and the reaction was continued for 15 minutes.

Next, 133.6 g of DAMA was added dropwise. After the dropwise addition was continued for 30 minutes, 7.7 g of methanol was added to stop the reaction. The obtained copolymer was adjusted to a PGMEA solution having a concentration of 40% by mass. This gave a block copolymer formed of A blocks having repeating units from DAMA and B blocks having repeating units 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 pyrazole-1-dithiocarboxylic acid cyano (dimethyl) methyl ester were added to a 300 mL flask equipped with a stir bar and dissolved, and the mixture was subjected to 30 Minute nitrogen replacement. Then, the temperature of the reaction solution was raised to 60 ° C. with slow stirring, and the temperature was maintained for 24 hours to perform 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. The obtained solution was added to the reaction solution, and living radical polymerization was performed at 60 ° C. for 24 hours. Then, it concentrated under reduced pressure and adjusted to a 40 mass% concentration PGMEA solution. This gave a block copolymer formed from A blocks having repeating units from DAMA and B blocks having repeating units from PME-200 and nBMA. Let the obtained block copolymer be a "copolymer (B-4)".

Synthesis Example 5

20 g of toluene, 187 mg of AIBN, and 12.3 g of DAMA were added to a 300 mL flask equipped with a stir bar and dissolved, followed by nitrogen substitution for 30 minutes. then Stir slowly to raise the temperature of the reaction solution to 60 ° C., and maintain the temperature for 24 hours to perform living radical polymerization.

Next, 2.2 g of MMA, 7.0 g of PME-200, 5.6 g of CHMA, 0.8 g of MA, 809 mg of AIBN, and 461 mg of pyrazole-1-dithiocarboxylic acid cyano (dimethyl) methyl ester were dissolved in 30 g of toluene, followed by After 30 minutes of nitrogen substitution, the obtained solution was added to the above reaction solution, and living radical polymerization was performed at 60 ° C for 24 hours. Then, it concentrated under reduced pressure and adjusted to a 40 mass% concentration PGMEA solution. This gave a block copolymer formed from A blocks having repeating units from DAMA and B blocks having repeating units from PME-200, MMA, CHMA, and MA. Let the obtained block copolymer be "copolymer (B-5)".

Synthesis Example 6

503.0 g of THF and 59.5 g of lithium chloride (a THF solution with a concentration of 4.1% by mass) were added to a 1000 mL flask equipped with a stir bar and cooled to -60 ° C. 11.9 g of n-butyllithium (15.4 mass% concentration of hexane solution) was added, and after stirring for 10 minutes, 2.8 g of diisopropylamine was added and stirred for 15 minutes, and then 2.8 g of methyl isobutyrate was added, 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.

Next, 52.1 g of DAMA was added dropwise. After the dropwise addition was continued for 30 minutes, 4.5 g of methanol was added to stop the reaction. The obtained copolymer was adjusted to a PGMEA solution having a concentration of 40% by mass. This gave a block copolymer formed of A blocks having repeating units from DAMA and B blocks having repeating units 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 pyrazole-1-dithiocarboxylic acid cyano (dimethyl) methyl ester were added to a 300 mL flask equipped with a stir bar and dissolved. Minute nitrogen replacement. Then, the temperature of the reaction solution was raised to 60 ° C. with slow stirring, and the temperature was maintained for 24 hours to perform living radical polymerization.

Next, 607 mg of AIBN and 9.2 g of DAMA were dissolved in 20 g of toluene, and nitrogen substitution was performed for 30 minutes. The obtained solution was added to the reaction solution, and living radical polymerization was performed at 60 ° C. for 24 hours. Then, it concentrated under reduced pressure and adjusted to a 40 mass% concentration PGMEA solution. This gave a block copolymer formed of A blocks having repeating units from DAMA and B blocks having repeating units from PME-200 and BzMA. Let the obtained block copolymer be "copolymer (b-1)".

Comparative Synthesis Example 2

498.6 g of THF and 42.5 g of lithium chloride (a 4.1% by mass concentration of THF solution) were added to a 1000 mL flask equipped with a stir bar, and cooled to -60 ° C. 8.7 g of n-butyllithium (15.4 mass% concentration of hexane solution) was added, and after 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 mixed solution of 60.7 g of MMA, 33.6 g of PME-200, and 11.8 g of EEMA was added dropwise, and the reaction was continued for 15 minutes.

Next, 28.7 g of DAMA was added dropwise, the reaction was continued for 30 minutes after the dropwise addition, and 2.4 g of water was added to stop the reaction. After the obtained copolymer was adjusted to a 25% by mass PGMEA solution, 135 g of water was added, and the mixture was heated to 100 ° C. and reacted for 8 hours. This reaction was used to hydrolyze EEMA to generate repeat units derived from MA. Distill off the water and adjust to 40% by mass PGMEA solution. This gave a block copolymer formed of A blocks having repeating units from DAMA and B blocks having repeating units from PME-200, MMA, and MA. Let the obtained block copolymer be "copolymer (b-2)".

Comparative Synthesis Example 3

20 g of toluene, 66 mg of AIBN, and 21.0 g of DAMA were added to a 300 mL flask equipped with a stir bar and dissolved, and nitrogen substitution was performed for 30 minutes. Then, the temperature of the reaction solution was raised to 60 ° C. with slow stirring, and the temperature was maintained for 24 hours to perform 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 pyrazole-1-dithiocarboxylate were dissolved in 30 g of toluene, and nitrogen substitution was performed for 30 minutes to obtain the obtained product. The solution was added to the above reaction solution, and living radical polymerization was performed at 60 ° C for 24 hours. Then, it concentrated under reduced pressure and adjusted to a 40 mass% concentration PGMEA solution. This gave a block copolymer formed from A blocks having repeating units from DAMA and B blocks having repeating units from PME-200 and nBMA. Let the obtained block copolymer be "copolymer (b-3)".

<Measurement of acid value>

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

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

<Determination of Amine Value>

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

0.5g of the copolymer solution was precisely weighed to a unit of 1mg and dispensed into a glass container. 20 mL of acetic anhydride / acetic acid = 9/1 (volume ratio) was added and dissolved, and left at room temperature for 3 hours. Then, after further adding 30 mL of acetic acid, titration was performed with a 0.1 mol / L perchloric acid · acetic acid solution using a potential difference measuring device AT-510 (manufactured by Kyoto Electronics Industry Co., Ltd.). A blank test was performed similarly. The amine value (unit: mgKOH / g) was calculated from the dropwise addition amount of the perchloric acid ‧ acetic acid solution of the (B) copolymer and the blank test in 0.1 mol / L.

<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 a copolymer (B-1) solution (nonvolatile content = 40 parts by mass), and 67 as a solvent were used. Parts by mass of propylene glycol monomethyl ether acetate and 8 parts by mass of propylene glycol monomethyl ether were processed with a bead mill to prepare a pigment dispersion liquid (A-1).

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

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 to that shown in Table 2 in Preparation Example 1.

<Evaluation of colorant dispersion liquid>

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

In Table 2, "G58" refers to C.I. Pigment Green 58, "Y138" refers to C.I. Pigment Yellow 138, "PGMEA" refers to propylene glycol monomethyl ether acetate, and "PGME" refers to 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 -5.0 g of methylstyrene dimer, followed by nitrogen substitution for 15 minutes. Thereafter, the reaction solution was heated to 80 ° C. while being stirred, and polymerization was performed for 5 hours, thereby obtaining a 33% by mass solution containing a binder resin (D-1). The binder resin (D-1) was measured by GPC (mobile phase: tetrahydrofuran) in terms of polystyrene The weight average molecular weight in terms of olefin 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-methacryloxymethyl-3-ethyloxetane, 18.0 g of MA, and 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 dissolved, further added AIBN 6.0 g and α-methylstyrene dimer 6.0 g, followed by nitrogen substitution for 15 minutes. Thereafter, the reaction solution was heated to 80 ° C. while being stirred, and polymerization was performed for 5 hours to obtain a precursor copolymer solution.

13.2 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. This reaction solution was washed twice with 75 g of ion-exchanged water and then concentrated under reduced pressure, thereby obtaining a 33% by mass solution containing a binder resin (D-2). The polystyrene-equivalent weight average molecular weight of this binder resin (D-2) measured by GPC (eluent: tetrahydrofuran) 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 colored composition Example 1

100 parts by mass of a 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- Phenylphenyl) butane-1-one (trade name Irgacure 369, manufactured by Ciba Specialty Chemicals) 2.8 parts by mass, 0.3 parts by mass of Megafac F-554 (manufactured by DIC Corporation) as a fluorine-based surfactant, and 126.5 parts by mass of ethyl 3-ethoxypropionate in a solvent was mixed to prepare a liquid coloring composition.

Evaluation of chromaticity characteristics

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

Evaluation of contrast

With respect to the three cured films obtained in the above "Evaluation of chromaticity characteristics", the contrast was measured using a contrast meter (Usaka Denki Contrast Tester CT-1). From the measurement results, the contrast when the chromaticity coordinate value y = 0.569 was obtained. 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 Example 1, the types and blending amounts of the pigment dispersion liquid, the binder resin, the cross-linking agent, the photopolymerization initiator, and the solvent were changed as shown in Table 3. Except that they were the same as in Example 1 The preparation and evaluation of the coloring composition were carried out. The evaluation results are shown in Table 3.

Each component in Table 3 is as follows.

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

C-2: Dinepentaerythritol pentaacrylate and monoester of succinic acid, Mixture of dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate (trade name TO-1382, manufactured by Toa Synthesis Co., Ltd.)

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

E-2: 2-benzyl-2-dimethylamino-1- (4- Phenylphenyl) butane-1-one (trade name Irgacure369, manufactured by Ciba Specialty Chemicals)

EEP: ethyl 3-ethoxypropionate

MBA: 3-methoxybutyl acetate

Claims (7)

A coloring composition for a color filter, comprising the following components (A), (B), and (C): (A) a coloring agent containing a quinophthalone-based pigment; (B) containing the following formula ( A copolymer having a repeating unit represented by 1), a repeating unit represented by the following formula (2) and a repeating unit represented by the following formula (3), and having an amine value of 157 to 232 mgKOH / g; and (C) a crosslinking agent; In formula (1), R ¹ represents a hydrogen atom or a methyl group, Z represents -NR ² R ³ , wherein R ² and R ³ independently represent an unsubstituted alkyl group having 1 to 12 carbon atoms, and X ¹ represents Divalent linker, In formula (2), R ⁴ represents a hydrogen atom or a methyl group, R ⁵ represents an aliphatic hydrocarbon group or an alicyclic hydrocarbon group, In formula (3), R ⁶ represents a hydrogen atom or a methyl group, R ⁷ independently represents an alkyldiyl group having 2 to 4 carbon atoms, R ⁸ represents an alkyl group having 1 to 6 carbon atoms, and n represents 1 to An integer of 5. For example, the coloring composition for a color filter according to item 1 of the application, wherein the quinophthalone pigment is C.I. Pigment Yellow 138. For example, the coloring composition for a color filter according to item 1 of the application, further comprising (D) a binder resin, and the (D) binder resin does not include the component (B). For example, the coloring composition for a color filter according to item 1 of the patent application scope further contains (E) a photopolymerization initiator. A color filter includes a coloring layer formed using the coloring composition according to any one of claims 1 to 4. A display element is provided with a color filter as in item 5 of the patent application. A pigment dispersion liquid for a color filter, comprising the following components (a1), (B), and (F): (a1) a quinophthalone-based pigment; (B) containing the following formula (1) A repeating unit, a repeating unit represented by the following formula (2) and a repeating unit represented by the following formula (3), and a copolymer having an amine value of 157 to 232 mgKOH / g; and (F) a solvent; In formula (1), R ¹ represents a hydrogen atom or a methyl group, Z represents -NR ² R ³ , wherein R ² and R ³ independently represent an unsubstituted alkyl group having 1 to 12 carbon atoms, and X ¹ represents Divalent linker, In formula (2), R ⁴ represents a hydrogen atom or a methyl group, R ⁵ represents an aliphatic hydrocarbon group or an alicyclic hydrocarbon group, In formula (3), R ⁶ represents a hydrogen atom or a methyl group, R ⁷ independently represents an alkyldiyl group having 2 to 4 carbon atoms, R ⁸ represents an alkyl group having 1 to 6 carbon atoms, and n represents 1 to An integer of 5.