TW201339252A - Coloring composition, color filter, display device and pigment dispersion liquid - Google Patents

Abstract

A coloring composition suitable to form a colored layer which has both heat resistance and solvent resistance is provided. The coloring composition contains a coloring agent (A) containing a lake pigment, a dispersant (B) and a crosslinking agent (C). The coloring composition is characterized in that the dispersant (B) contains a copolymer (B-1) having a repeating unit containing a saturated heterocyclic group having oxygen, or contains both a dispersant (B-2) with a urethane bonding and a (metha)acrylic dispersant (B-3) in which the component (B-1) is excluded.

Description

Coloring composition, color filter, display element, and pigment dispersion

The present invention relates to a coloring composition, a color filter and a display element, and more particularly to a transmissive or reflective type color liquid crystal display element, a solid-state imaging element, and an organic electroluminescence (EL) display element. A coloring composition suitable for use in a color filter such as an electronic paper, a color filter including a coloring layer formed using the coloring composition, and a display element including the color filter.

A method of obtaining pixels of respective colors by the following method (for example, refer to Patent Document 1 to Patent Document 2): when a color filter is produced using a coloring radiation-sensitive composition, a pigment dispersion type coloring radiation is applied onto a substrate. The composition is dried, and then the dried coating film is irradiated with radiation (hereinafter referred to as "exposure") in a desired pattern shape, and developed. Further, a method of forming a black matrix by using a photopolymerizable composition in which carbon black is dispersed is also known (for example, see Patent Document 3). Further, it is also known to use a pigment dispersion type colored resin composition, which is obtained by an inkjet method. A method of each color pixel (for example, refer to Patent Document 4).

In the manufacture of color filters, in general, a high temperature step exceeding 200 ° C is required, so that high heat resistance is required for the color filter. Moreover, in recent years, color filters having excellent chromaticity characteristics have been demanded. In order to achieve these requirements at the same time, studies on the application of lake pigments to coloring agents for coloring compositions for color filters have begun. For example, in Patent Document 5, a color filter including a coloring layer formed using a coloring composition containing a lake pigment and a specific dispersing agent is reported. Moreover, in Patent Document 6, a color filter which is formed using a coloring composition containing a lake pigment and a resin having an ethylenically unsaturated double bond in a side chain is reported.

[Previous Technical Literature] [Patent Literature]

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

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

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

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

[Patent Document 5] Japanese Patent Laid-Open Publication No. 2011-6602

[Patent Document 6] Japanese Patent Laid-Open Publication No. 2012-8421

However, according to the study by the inventors of the present invention, the color of the coloring layer including the coloring composition disclosed in Patent Document 5 and Patent Document 6 is known. The balance between heat resistance and solvent resistance of the filter is poor.

Accordingly, an object of the present invention is to provide a coloring composition suitable for forming a coloring layer capable of simultaneously achieving heat resistance and solvent resistance. Further, an object of the present invention is to provide a color filter including a coloring layer formed using the coloring composition, and a display element including the color filter.

In view of this fact, the inventors of the present invention conducted intensive studies and found that the above problem can be solved by using a coloring agent containing a lake pigment together with a specific dispersing agent.

That is, the present invention provides a coloring composition comprising (A) a coloring agent comprising a lake pigment, (B) a dispersing agent, and (C) a crosslinking agent, characterized in that (B) a dispersing agent is contained (B-1) a copolymer comprising a repeating unit having an oxygen-containing saturated heterocyclic group; or (B-2) a dispersing agent having a urethane bond and (B-3) (meth)acrylic acid Both of the dispersants, except for the (B-3) (meth)acrylic dispersant, except for the component (B-1).

Further, the present invention 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" refers to each color pixel, black matrix, black spacer, or the like used in the color filter.

Further, the present invention provides a pigment dispersion liquid comprising (a1) a lake pigment, (B-1) a copolymer comprising a repeating unit having an oxygen-containing saturated heterocyclic group, and (F) a solvent.

When the coloring composition of the present invention is used, a coloring layer which simultaneously achieves high heat resistance and high solvent resistance can be formed. Therefore, the coloring composition of the present invention can be used as a color filter for display elements, a color filter for color separation of solid-state imaging elements, a color filter for organic EL display elements, and a color filter for electronic paper. It is extremely suitable for use in the production of various color filters.

Hereinafter, the present invention will be described in detail.

Coloring composition

Hereinafter, the constituent components of the coloring composition of the present invention will be described in detail.

- (A) colorant -

The coloring composition of the present invention contains (a1) a lake pigment as a colorant. The lake pigment refers to a pigment which makes a soluble dye into an insoluble pigment by a precipitating agent, and examples of the precipitating agent include barium chloride, calcium chloride, ammonium sulfate, aluminum chloride, aluminum acetate, lead acetate, tannic acid, and card. Katanol, tamol, isopolyacid, heteropolyacid, and the like. Examples of the polypoly acid include the same polytungstic acid, the same polyvanadic acid, the same polymolybdic acid, and the like, and examples of the heteropoly acid include phosphotungstic acid, phosphomolybdic acid, and phosphotungstic acid. Molybdic acid, lanthanum tungsten molybdate, lanthanum tungstic acid, lanthanum molybdate, etc. Among these compounds, the precipitating agent is preferably the same as the polyacid, the heteropoly acid, and more preferably contains the molybdenum atom. Heteropoly acid, further more preferably tungsten tungsten. Molybdic acid.

Such a lake pigment may, for example, be a lake pigment with a color index (C.I.) name as described below.

CI Pigment Yellow 61, CI Pigment Yellow 61:1, CI Pigment Yellow 62, CI Pigment Yellow 100, CI Pigment Yellow 104, CI Pigment Yellow 133, CI Pigment Yellow 169, CI Pigment Yellow 183, CI Pigment Yellow 191, CI Pigment Yellow 191:1, CI Pigment Yellow 206, CI Pigment Yellow 209, CI Pigment Yellow 209:1, CI Pigment Yellow 212; CI Pigment Red 48:1, CI Pigment Red 48:2, CI Pigment Red 48:3, CI Pigment Red 48:4, CI Pigment Red 48:5, CI Pigment Red 49, CI Pigment Red 49:1, CI Pigment Red 49:2, CI Pigment Red 49:3, CI Pigment Red 52:1, CI Pigment Red 52:2 , CI Pigment Red 53:1, CI Pigment Red 54, CI Pigment Red 57:1, CI Pigment Red 58, CI Pigment Red 58:1, CI Pigment Red 58:2, CI Pigment Red 58:3, CI Pigment Red 58 : 4, CI Pigment Red 60: 1, CI Pigment Red 63, CI Pigment Red 63: 1, CI Pigment Red 63: 2, CI Pigment Red 63: 3, CI Pigment Red 64: 1, CI Pigment Red 68, CI Pigment Red 81, CI Pigment Red 81:1, CI Pigment Red 200, CI Pigment Red 237, CI Pigment Red 239, CI Pigment Red 247; CI Pigment Violet 2, CI Pigment Violet 3, CI Pigment Violet 3:1, C. I. Pigment violet 3:3, CI pigment violet 27, CI pigment violet 39; CI pigment blue 1, CI pigment blue 2, CI pigment blue 3, CI pigment blue 9, CI pigment blue 10, CI pigment blue 14, CI pigment Blue 17:1, CI Pigment Blue 24, CI Pigment Blue 24:1, CI Pigment Blue 56, CI Pigment Blue 61, CI Pigment Blue 62; CI Pigment Green 1, CI Pigment Green 4.

Among these lake pigments, at least one selected from the group consisting of a triarylmethane-based lake pigment and a xanthene-based lake pigment is preferable, and CI pigment blue 1, CI pigment is particularly preferable from the viewpoint of chromaticity characteristics. Blue 2, CI Pigment Blue 3, CI Pigment Blue 9, CI Pigment Blue 10, CI Pigment Blue 14, CI Pigment Blue 61, CI Pigment Blue 62, CI Pigment Violet 1, CI Pigment Violet 2, CI Pigment Violet 3, CI Pigment Triaryl methane type lake pigment such as purple 27, CI pigment purple 39, CI pigment red 81, CI pigment red 81:1, CI pigment red 81:2, CI pigment red 81:3, CI pigment red 81:4, CI Pigment red 81:5, CI Pigment Red 169, CI Pigment Violet 1, CI Pigment Violet 1:1, CI Pigment Violet 1: 2, CI Pigment Violet 2 and other oxonium type lake pigments. Further, a triarylmethane-based lake prepared by using a polyacid or a heteropolyacid as a precipitating agent disclosed in Japanese Laid-Open Patent Publication No. 2011-150043, and the like. pigment.

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

The coloring composition of the present invention may contain other colorants as a colorant together with the lake pigment. The other coloring agent is not particularly limited, and a color or a material can be appropriately selected depending on the use.

Other pigments, dyes, and natural pigments other than the lake pigment may be used as the other colorants. However, in the sense of obtaining pixels having high luminance and color purity, organic pigments other than the lake pigments and organic dyes are preferable.

The organic pigment other than the lake pigment can be exemplified by the color index (C.I.; issued by The Society of Dyers and Colourists). A compound classified as a pigment, that is, an organic pigment having a color index (C.I.) name as described below.

Red pigments such as CI Pigment Red 166, CI Pigment Red 177, CI Pigment Red 224, CI Pigment Red 242, CI Pigment Red 254, CI Pigment Red 264; green pigments such as CI Pigment Green 7, CI Pigment Green 36, CI Pigment Green 58 ; CI Pigment Blue 15:6, CI Pigment Blue 80 and other blue pigments; CI Pigment Yellow 83, CI Pigment Yellow 129, CI Pigment Yellow 138, CI Pigment Yellow 139, CI Pigment Yellow 150, CI Pigment Yellow 179, CI Pigment Yellow 180, yellow pigment such as CI Pigment Yellow 185, CI Pigment Yellow 211, CI Pigment Yellow 215; orange pigment such as CI Pigment Orange 38; purple pigment such as CI Pigment Violet 23; black pigment such as CI Pigment Black 1, CI Pigment Black 7.

In the case where a triarylmethane-based lake pigment is used as a colorant, the coloring composition of the present invention is preferably used in the formation of a blue pixel or a red pixel. In the case where the coloring composition of the present invention is used in the formation of a blue pixel, from the viewpoint of chromaticity characteristics, it is preferred to at least 1 of a lake pigment and a group selected from the group consisting of a purple pigment and a blue pigment. In combination with the coloring agent (A), it is particularly preferably used in combination with at least one selected from the group consisting of CI Pigment Blue 15:6 and CI Pigment Violet 23. Further, in the case where the coloring composition of the present invention is used in the formation of a red pixel, it is preferable that at least 1 of the lake pigment and a group selected from the group consisting of a red pigment and a purple pigment are used from the viewpoint of chromaticity characteristics. Used together as a coloring agent (A), particularly preferably selected from the group consisting of CI Pigment Red 177 and CI Pigment Red 254 At least one of the groups formed is used in combination.

In the present invention, in the case where a pigment is used as the other coloring agent, the pigment may be purified by a recrystallization method, a reprecipitation method, a solvent cleaning method, a sublimation method, a vacuum heating method, or a combination of these methods. Further, the pigment may be used by modifying the surface of the particles with a resin as needed. The resin which is modified by the surface of the particle of the pigment is, for example, a vehicle resin described in JP-A-2001-108817, or a commercially available resin for dispersion of various pigments. For the resin coating method of the surface of the carbon black, for example, the method described in JP-A-H09-71733, JP-A-H09-95625, JP-A-H09-124969, and the like can be used. Further, the organic pigment can also be used to refine the primary particles by so-called salt polishing. For the method of salt polishing, for example, the method disclosed in Japanese Laid-Open Patent Publication No. Hei 8-179111 can be employed.

In the present invention, in the case where a pigment is used as the other coloring agent, a known dispersing aid may be further contained. Examples of the known dispersing aid include pigment derivatives such as copper phthalocyanine, diketopyrrolopyrrole, and sulfonic acid derivatives of quinacridone.

Further, the dye may be appropriately selected from various oil-soluble dyes, direct dyes, acid dyes, metal complex dyes and the like, and examples thereof include dyes having a color index (C.I.) name as described below.

CI Solvent Yellow 4, CI Solvent Yellow 14, CI Solvent Yellow 15, CI Solvent Yellow 24, CI Solvent Yellow 82, CI Solvent Yellow 88, CI Solvent Yellow 94, CI Solvent Yellow 98, CI Solvent Yellow 162, CI Solvent Yellow 179; CI solvent red 45, CI solvent red 49; C.I. Solvent Orange 2, C.I. Solvent Orange 7, C.I. Solvent Orange 11, C.I. Solvent Orange 15, C.I. Solvent Orange 26, C.I. Solvent Orange 56; C.I. Solvent Blue 35, C.I. Solvent Blue 37, C.I. Solvent Blue 59, C.I. Solvent Blue 67.

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

The content ratio of the (A) coloring agent is usually 5% by mass to 70% in the solid content of the coloring composition from the viewpoint of forming a pixel having high luminance and excellent color purity or a black matrix having excellent light shielding properties. %, preferably 5% by mass to 60% by mass. The solid matter referred to herein is a component other than the solvent described later.

Further, the content ratio of the lake pigment can be appropriately adjusted according to the desired chromaticity, and if the coloring composition of the present invention is used, even if the content ratio of the lake pigment is 30% by mass or more in all the colorants, even When it is 60% by mass or more, a coloring layer excellent in heat resistance and solvent resistance can be formed.

- (B) Dispersant -

The present invention is characterized in that (B) the dispersant contains: (B-1) a copolymer comprising a repeating unit having an oxygen-containing saturated heterocyclic group (hereinafter also referred to as "(B-1) copolymer"); or Containing (B-2) a dispersant having a urethane bond and (B-3) a (meth)acrylic dispersant, but in the (B-3) (meth)acrylic dispersant The component (B-1) is excluded.

First, the (B-1) copolymer will be described. The (B-1) copolymer in the present invention is a repeating unit comprising an oxygen-containing saturated heterocyclic group (hereinafter also referred to as "heavy The copolymer of the complex unit (3)") functions as a dispersant for the (A) colorant.

The "oxygen-containing saturated heterocyclic group" in the present invention is a saturated heterocyclic group having an oxygen atom as a hetero atom constituting a hetero ring, and among them, a cyclic ether group having 3 to 7 atoms in the ring is preferable. Specific examples thereof include an oxiranyl group such as a glycidyl group, a 2-methylglycidyl group, or a glycidyloxy group; 3-methyl propylene oxide-3-yl group and 3-ethyl propylene oxide-3- Ethylene oxide group such as 3-methyl propylene oxide-3-ylmethoxy or 3-ethyl propylene oxide-3-ylmethoxy; 3,4-epoxycyclohexyl; tetrahydrofuran-2 a tetrahydrofuranyl group such as a benzyl group or a tetrahydrofuran-3-yl group; a tetrahydropyranyl group such as a tetrahydropyran-2-yl group or a tetrahydropyran-3-yl group; and the like. Among these groups, an oxiranyl group, an oxypropylene group, a 3,4-epoxycyclohexyl group, or a tetrahydrofuranyl group is preferable in terms of obtaining a desired effect more remarkably.

The repeating unit (3) is, for example, a repeating unit represented by the following formula (3).

In the formula (3), R ⁸ represents a hydrogen atom or a methyl group, Q represents an oxygen-saturated heterocyclic group, and X ² represents a single bond or a divalent linking group.

In the above formula (3), R ⁸ is preferably a hydrogen atom and a methyl group in the methyl group.

Examples of the divalent linking group (X ² ) include -CONH-R ⁹ -(* ² ) group, -COO-R ¹⁰ -(* ² ) group, -COO-R ¹¹ -OOCNH-R ¹² -(* ² ) a group, a -C ₆ H ₄ CH ₂ -(* ² ) group, a -C ₆ H ₄ CH ₂ OR ¹³ -(* ² ) group or the like. Here, R ⁹ and R ¹⁰ each independently represent a single bond, an alkanediyl group having a hydroxyl group of 1 to 10 or an alkanediyloxyalkyldiyl group having 2 to 10 carbon atoms, and R ¹¹ and R ¹² independently represents an alkanediyl group having 1 to 10 carbon atoms, R ¹³ represents an alkanediyl group having 1 to 10 carbon atoms which may have a hydroxyl group, and (* ² ) represents a linking bond to Q.

The alkanediyl group in R ⁹ to R ¹² is preferably an alkanediyl group having 1 to 6 carbon atoms, and the alkanediyl group in R ¹³ is preferably an alkanediyl group having 2 to 6 carbon atoms. Specific examples thereof include a methylene group, an ethylidene group, an ethane-1,1-diyl group, a propane-1,1-diyl group, a propane-1,2-diyl group, a propane-1,3-diyl group, Propane-2,2-diyl, butane-1,2-diyl, butane-1,3-diyl, butane-1,4-diyl, pentane-1,4-diyl, pentane Alkyl-1,5-diyl, hexane-1,5-diyl, hexane-1,6-diyl and the like. In the present specification, the "alkanediyloxyalkyldiyl group" means a group in which two alkanediyl groups are bonded via an oxygen atom. The alkanediyloxyalkyldiyl group is preferably an alkanediyloxyalkyldiyl group having 2 to 6 carbon atoms, and examples thereof include an exoethyloxyethyl group, a stretching ethyloxypropyl group, and a stretching propyloxy group. Base, exoethyloxybutylene and the like.

Among them, X ² is preferably a -COO-R ¹⁰ -(* ² ) group or a -COO-R ¹¹ -OOCNH-R ¹² -(* ² ) group.

(B-1) the copolymer may have a repeating unit other than the above, as such Examples of the repeating unit include 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)"); a repeating unit represented by the following formula (4) (hereinafter also referred to as "repeating unit (4)"); a repeating unit having an acidic group (hereinafter also referred to as "repeating unit (5)) ") a repeating unit derived from a monomer: a styrene monomer such as styrene or α-methylstyrene; an aralkyl (meth)acrylate such as benzyl (meth)acrylate; ) propylene methoxyethyl (4-benzylidene benzyl) dimethyl ammonium bromide, (meth) propylene oxiranyl ethyl benzyl dimethyl ammonium chloride, (meth) propylene oxime (meth) acrylate having a quaternary ammonium salt structure such as ethyl ethyl benzyl diethyl ammonium chloride; (meth) propylene fluorene halogen monomer such as (meth) acrylonitrile chloride; (meth) propylene (Meth) acrylamide monomer such as decylamine or N-methylol acrylamide; vinyl acetate; acrylonitrile; allyl glycidyl ether; allyl (meth) acrylate; )Acrylic-2-(2-vinyloxyethoxy)B ; Crotonic acid glycidyl ether; N-methyl-morpholine monomer Bing Xixi group.

In particular, it is preferable to have a repeating unit (1) from the viewpoint of heat resistance; and it is preferable to have a repeating unit (2) from the viewpoint of self-dispersibility; and it is preferable to further have a repeating unit from the viewpoint of further improving the dispersibility ( 4). Here, the term "(meth)acrylate" in the present invention means "acrylate or methacrylate".

[Chemical 2]

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

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

[Chemical 4]

In the formula (4), R ¹⁴ represents a hydrogen atom or a methyl group, R ¹⁵ independently represents an alkanediyl group having 2 to 4 carbon atoms, R ¹⁶ represents an alkyl group having 1 to 6 carbon atoms, and n represents 1 to 2; An integer of 150.

In the formula (5), R ¹⁷ represents a hydrogen atom or a methyl group, A represents an acidic group, and X ³ represents a single bond or a divalent linking group.

In the above formula (1), R ¹ is preferably a hydrogen atom and a methyl group in 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 of each other represent a hydrogen atom or a substituted or unsubstituted hydrocarbon group. Here, the "hydrocarbon group" in the present invention is a concept including an aliphatic hydrocarbon group, an alicyclic hydrocarbon group, and an aromatic hydrocarbon group, and may be in any form of a linear chain, a branched chain, or a cyclic chain. The aliphatic hydrocarbon group and the alicyclic hydrocarbon group may be a saturated hydrocarbon group or an unsaturated hydrocarbon group, and may have an unsaturated bond at any position.

The aliphatic hydrocarbon group is preferably an aliphatic hydrocarbon group having 1 to 20 carbon atoms, and more preferably an aliphatic hydrocarbon group having 1 to 12 carbon atoms. More specifically, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, and an alkynyl group having 2 to 20 carbon atoms are exemplified. The alkyl group is preferably an alkyl group having 1 to 12 carbon atoms, and specific examples thereof include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a second butyl group, a tert-butyl group, and a pentyl group. , isoamyl, hexyl, heptyl, octyl, decyl, dodecyl and the like. Further, the alkenyl group is preferably an alkenyl group having 2 to 12 carbon atoms, and specific examples thereof include a vinyl group, a 1-propenyl group, a 1-butenyl group, a 1,3-butadienyl group, and a 1-pentenyl group. -pentenyl, 1-hexenyl, 2-ethyl-2-butenyl, 2-octenyl, (4-vinyl)-5-hexenyl, 2-decenyl and the like. The alkynyl group is preferably an alkynyl group having 2 to 12 carbon atoms, and specific examples thereof include an ethynyl group, a 1-propynyl group, a 1-butynyl group, a 1-pentynyl group, a 3-pentynyl group, and a 1-hexynyl group. 2-Ethyl-2-butynyl, 2-octynyl, (4-ethynyl)-5-hexynyl, 2-decynyl, and the like.

Further, the alicyclic hydrocarbon group is preferably an alicyclic hydrocarbon group having 3 to 20 carbon atoms, more preferably an alicyclic hydrocarbon group having 3 to 12 carbon atoms. Specifically, a cycloalkyl group having 3 to 20 carbon atoms is exemplified. The cycloalkyl group is preferably a cycloalkyl group having 3 to 12 carbon atoms, and specific examples thereof include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, a cyclodecyl group, and a ring twelve. Alkyl and the like. Here, the term "alicyclic hydrocarbon group" as used in the present invention means having In the carbocyclic compound having a structure in which a carbon atom is bonded to a ring, a group other than the aromatic compound is also a group including a substituent having the above-mentioned aliphatic hydrocarbon group as a substituent or a linking group with a nitrogen atom or the like.

Further, the aromatic hydrocarbon group is preferably an aromatic hydrocarbon group having 6 to 20 carbon atoms, and more preferably an aromatic hydrocarbon group having 6 to 14 carbon atoms. More specifically, an aryl group having 6 to 20 carbon atoms is preferable, and an aryl group is preferably an aryl group having 6 to 14 carbon atoms. Here, the "aryl group" in the present invention means a monocyclic to 3-ring aromatic hydrocarbon group, and specific examples thereof include a phenyl group, a naphthyl group, an anthracenyl group, a phenanthryl group, an anthracenyl group and the like.

Examples of the substituent in 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. Specific examples of the alkoxy group having 1 to 6 carbon atoms include a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, a butoxy group, a pentyloxy group, and a phenoxy group.

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, preferably a heteromonocyclic group or a condensation of two of these heterocyclic groups. Heterocyclic group. These heterocyclic groups may be an unsaturated ring or a saturated ring, and may have a hetero atom other than a nitrogen atom in the ring. Examples of the hetero atom other than the nitrogen atom include an oxygen atom and a sulfur atom.

Examples of the unsaturated heterocyclic ring include a pyridine ring, an imidazole ring, a thiazole ring, an oxazole ring, a triazole ring, an imidazoline ring, and a piperazine ring. Further, examples of the saturated heterocyclic ring include a morpholine ring, a piperidine ring, and a tetrahydropyrimidine ring.

Further, examples of the substituent in the nitrogen-containing heterocyclic group include an alkyl group having 1 to 6 carbon atoms, a halogen atom, a carboxyl group, an ester group, an alkoxy group, a hydroxyl group, an amine group, and a decylamino group. Mercapto group, thioether group and the like. Examples of the alkyl group having 1 to 6 carbon atoms include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a tert-butyl group, a pentyl group, and a hexyl group. Examples of the halogen atom include the same halogen atoms as described above. The ester group is preferably, for example, an ester group having 1 to 7 carbon atoms, and specific examples thereof include a methoxycarbonyl group, an ethoxycarbonyl group, a methyloxy group, an etecyloxy group, a benzamethyleneoxy group and the like. The alkoxy group is preferably an alkoxy group having 1 to 6 carbon atoms, and specific examples thereof include the same alkoxy groups as described above. Examples of the amine group include an amine group, a methylamino group, a diethylamino group, and a diphenylamino group. Examples of the guanamine group include a formamidine group, an ethenyl group, and a propylamine group. 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 heteromonocyclic group is preferably a 5-membered ring to a 7-membered ring, and specific examples thereof include a group having a basic skeleton represented by the following formula (1-1), and these heteromonocyclic groups may further have a substituent.

In the formula (1-1), "*" indicates a link key.

Further, the condensed heterocyclic group is specifically a group having a basic skeleton represented by the following formula (1-2) to formula (1-4), and these condensed heterocyclic groups may be further Has 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 thereof include the same specific examples as described above.

In the formula (1-2) to the formula (1-4), "*" indicates a link.

In the above formula (1), examples of the divalent linking group (X ¹ ) include an alkanediyl group having 1 to 10 carbon atoms, an extended aryl group having 6 to 20 carbon atoms, and -CONH-R ⁶ - (* ^1). ), -COO-R ⁷ -(* ¹ ) group, and the like. Here, R ⁶ and R ⁷ each independently represent a single bond, an alkanediyl group having 1 to 10 carbon atoms, or an alkanediyloxyalkyldiyl group having 2 to 10 carbon atoms, and (* ¹ ) represents Z and Linked link.

The aryl group in X ¹ is preferably an extended aryl group having 6 to 14 carbon atoms, and the alkanediyl group in X ¹ , R ⁶ and R ⁷ is preferably an alkanediyl group having 1 to 6 carbon atoms, and R ⁶ and R ⁷ The alkanediyloxyalkyldiyl group in the above is preferably an alkanediyloxyalkyldiyl group having 2 to 6 carbon atoms. Specific examples of these groups include the same specific examples as described above. Further, examples of the extended aryl group include a stretching phenyl group, a stretching naphthyl group, a stretching phenyl group, and a stretching group.

Among them, X ¹ is preferably a -COO-R ⁷ -(* ¹ ) group, and R ⁷ is preferably an alkanediyl group having 2 to 6 carbon atoms.

In the formula (2), R ⁴ is preferably a hydrogen atom or a methyl group in a methyl group.

The aliphatic hydrocarbon group in R ⁵ may be the same as the above.

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

Among them, R ⁵ is preferably an alkyl group having 1 to 15 carbon atoms or an alicyclic hydrocarbon group having 3 to 20 carbon atoms, more preferably an alkyl group having 1 to 12 carbon atoms or an alicyclic hydrocarbon group having 4 to 15 carbon atoms. . Specific examples thereof include methyl, ethyl, propyl, butyl, isobutyl, tert-butyl, 2-ethylhexyl, isodecyl, dodecyl, cyclohexyl, and tert-butylcyclohexyl. , decahydro-2-naphthyl, tricyclo[5.2.1.0 ^2,6 ]decane-8-yl, adamantyl, dicyclopentenyl, pentacyclopentadecanyl, tricyclopentene Base, isobornyl base.

In the formula (4), R ¹⁴ is preferably a hydrogen atom or a methyl group in a methyl group.

Further, examples of the alkanediyl group in R ¹⁵ include an exoethyl group, an ethane-1,1-diyl group, a propane-1,1-diyl group, a propane-1,2-diyl group, and a propane-1,3- group. Diyl, propane-2,2-diyl, butane-1,2-diyl, butane-1,3-diyl, butane-1,4-diyl, and the like.

The alkyl group in R ¹⁶ may be the same alkyl group 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 (5) 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, the acid group is preferably a phenolic hydroxyl group or a carboxyl group, and particularly preferably a carboxyl group, from the viewpoint of self-dispersibility and alkali developability of the obtained coloring composition.

In the above formula (5), R ¹⁷ is preferably a hydrogen atom and a methyl group in a methyl group.

Examples of the divalent linking group (X ³ ) include an alkanediyl group having 1 to 10 carbon atoms, an extended aryl group, a —CONH-R ¹⁸ —(* ³ ) group, a —COO—R ¹⁹ —(* ³ ) group, and -OCOR ²⁰ -(* ³ ) group, -R ²¹ -OCO-R ²² -(* ³ ) group, -COO-(C _m H _2m COO) _l -C _m H _2m -(* ³ ) group, -COO -R ²³ -OCO-R ²⁴ -(* ³ ) group and the like. Here, R ¹⁸ to R ²² each independently represent a single bond, an alkanediyl group having 1 to 10 carbon atoms, or an alkanediyloxyalkyldiyl group having 2 to 10 carbon atoms, and m represents an integer of 1 to 10 , l represents an integer from 1 to 4, R ²³ represents an alkanediyl group having a carbon number of 1 to 10, R ²⁴ represents a single bond, an alkanediyl group having a carbon number of 1 to 10, and a cyclohexane-1,2-diyl group. Or a phenyl group, (* ³ ) indicates a linkage to A.

The alkanediyl group in X ³ , R ¹⁸ to R ²² , R ²³ and R ²⁴ is preferably an alkanediyl group having 1 to 6 carbon atoms, and the exoaryl group in X ³ is preferably an exoaryl group having 6 to 14 carbon atoms. The alkanediyloxyalkyldiyl group in R ¹⁸ to R ²² is preferably an alkanediyloxyalkyldiyl group having 2 to 6 carbon atoms. Specific examples of the alkanediyl group, the extended aryl group and the alkyleneoxyalkylene group include the same specific examples as described above. Further, specific examples of the stretching phenyl group include 1,2-phenylene and 1,4-phenylene.

Wherein X ³ is preferably a single bond, a phenyl group, a -COO-R ¹⁹ -(* ³ ) group, a -COO-(C _m H _2m COO) _l -C _m H _2m -(* ³ ) group or -COO- R ²³ -OCO-R ²⁴ -(* ³ ) group.

In the (B-1) copolymer, the content ratio of each repeating unit is not particularly limited, and the content of the repeating unit (3) is preferably 1% by mass in all the repeating units from the viewpoint of solvent resistance and heat resistance. ~50% by mass, more preferably 3% by mass to 40% by mass, still more preferably 5% by mass to 30% by mass.

In the case where the (B-1) copolymer further includes the repeating unit (1) and the repeating unit (2) in addition to the repeating unit (3), the content of the repeating unit (1) is preferably at all from the viewpoint of heat resistance. The repeating unit is 5% by mass to 60% by mass, more preferably 5% by mass to 50% by mass, still more preferably 10% by mass to 40% by mass, and particularly preferably 10% by mass to 30% by mass. Further, from the viewpoint of self-dispersibility, the content ratio of the repeating unit (2) is preferably from 5% by mass to 80% by mass, more preferably from 10% by mass to 75% by mass, more preferably in all repeating units. It is selected from 15% by mass to 70% by mass.

Further, in the case where the (B-1) copolymer further contains the repeating unit (4) in addition to the repeating unit (1), the repeating unit (2), and the repeating unit (3), the repeating unit is considered from the viewpoint of dispersibility ( The content ratio of 4) is preferably from 5% by mass to 50% by mass, more preferably from 10% by mass to 40% by mass, even more preferably from 10% by mass to 30% by mass, based on all the repeating units.

Further, in the case where the (B-1) copolymer further contains a repeating unit (5) in addition to the repeating unit (1), the repeating unit (2), the repeating unit (3), and the repeating unit (4), self-dispersing In view of the above, the content of the repeating unit (5) is preferably 15% by mass or less, more preferably 10% by mass or less, and still more preferably 6% by mass or less in all the repeating units. Further, the lower limit of the content ratio of the repeating unit (5) is not particularly limited, and may be 0% by mass, and preferably 0.5% by mass, based on all the repeating units.

(B-1) The amine value of the copolymer is not particularly limited, and from the viewpoint of heat resistance, the upper limit is preferably 250 mgKOH/g, more preferably 200 mgKOH/g, still more preferably 150 mgKOH/g, particularly It is preferably 100 mgKOH/g, particularly preferably 60 mgKOH/g; the lower limit is preferably 1 mgKOH/g, more preferably 10 mgKOH/g, still more preferably 15 mgKOH/g. Here, the "amine valence" in the present invention means the number of mg of KOH equivalent to the amount of acid necessary for neutralizing the non-volatile component 1 g of the solvent of the copolymer solution, specifically, the following The values measured by the methods described in the examples.

On the other hand, in the case where the (B-1) copolymer contains the repeating unit (5) The acid value of the (B-1) copolymer is preferably 30 mgKOH/g or less, more preferably 25 mgKOH/g or less, and still more preferably 20 mgKOH/g or less from the viewpoint of storage stability of the coloring composition. . Further, the lower limit of the acid value is not particularly limited, and may be 0 mgKOH/g, and preferably 1 mgKOH/g. Here, the "acid value" in the present invention is the number of mg of KOH necessary for neutralizing the non-volatile component 1 g of the solvent of the copolymer solution.

(B-1) The copolymer is not particularly limited as long as it contains the repeating unit (3), and is preferably an AB block copolymer containing an A block and a B block and a BAB from the viewpoint that the desired effect is more remarkable. a block copolymer comprising no repeating unit (3), repeating unit (2), repeating unit (4) and repeating unit (5) but comprising repeating unit (1), said The repeating unit (3) is not included, and at least one selected from the group consisting of the repeating unit (2), the repeating unit (4), and the repeating unit (5) is optionally included.

In the A block, two or more types of repeating units (1) may be contained in one A block. In this case, each repeating unit may be contained in any form of random copolymerization and block copolymerization in the A block. In the paragraph.

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

On the other hand, in the B block, each of the repeating units may be contained in any form of random copolymerization or block copolymerization, or may be contained in two or more types. In the case where the (B-1) copolymer is a B-A-B block copolymer, a repeating single constituting two B blocks The combination of the elements is not particularly limited, and may be, for example, a B1-A-B2 block copolymer comprising a B1 block and a B2 block, the B1 block comprising a repeating unit (3), a repeating unit (2), and a repeating unit. (4) and without repeating unit (5), the B2 block comprises repeating unit (3) and repeating unit (5) and does not contain repeating unit (2) and repeating unit (4).

(B-1) The weight average molecular weight (Mw) in terms of polystyrene measured by gel permeation chromatography (hereinafter abbreviated as GPC) (the elution solvent is dimethylformamide) is preferably 1,000~ 100,000, more preferably 3,000 to 50,000, still more preferably 5,000 to 30,000. By adopting such a form, heat resistance and solvent resistance can be achieved at a high level.

Further, the ratio (Mw/Mn) of the weight average molecular weight (Mw) to the number average molecular weight (Mn) of the (B-1) copolymer in the present invention is preferably from 1.0 to 5.0, more preferably from 1.0 to 3.0. In addition, the term "Mn" as used herein means a polystyrene-equivalent number average molecular weight measured by GPC (the elution solvent is dimethylformamide).

(B-1) The copolymer can be produced by a known method. When the (B-1) copolymer is a block copolymer, for example, it can be produced by living-polymerizing a monomer introduced into each of the above repeating units. For the living polymerization, for example, Japanese Patent Laid-Open Publication No. Hei 9-62002; Japanese Patent Laid-Open Publication No. 2002-31713; P. Lutz, P. Masson et al., Polymer Bulletin (Polym. Bull.) 12 , 79 (1984); BC Anderson, GD Andrews et al., Macromolecules, 14, 1601 (1981); K. Hatada, K. Ute et al., Polymers (Polym. J.) 17, 977 (1985) K. Hatada, K. Ute et al., Polymer Journal 18, 1037 (1986); Right Hand Hao Yi, Putian Gengyi, High Score Sub-Processing, 36, 366 (1987); Dong Cun Min Yan, Ze Benguang male, Polymer Proceedings, 46, 189 (1989); M. Kuroki, T. Aida, J. Am. Chem. Soc, 109, 4737 (1987); Xiangtian Zhuo San, Inoue Xiangping, Organic Synthetic Chemistry, 43, 300 (1985); DY Sogoh, WR Hertler et al., Macromolecules, 20, 1473 (1987); Journal of Polymer Science, Series A: Polymer Chemistry (J. Polym. Sci. Part A Polym. Chem.), 47, 3773-3794 (2009); Journal of Polymer Science, Series A: Polymer Chemistry (J. Polym. Sci. Part A Polym. .), a well-known method described in 47, 3544-3557 (2009) or the like.

Examples of the monomer which provides the repeating unit (3) include glycidyl (meth)acrylate, 2-methylglycidyl (meth)acrylate, and 4-glycidoxybutyl (meth)acrylate. -3,4-epoxycyclohexylmethyl (meth)acrylate, p-vinylbenzyl glycidyl ether, 3-(vinyloxymethyl)-3-ethyl propylene oxide, 3-[(A Base) propylene methoxymethyl] propylene oxide, 3-[(meth) propylene methoxymethyl]-3-ethyl propylene oxide, tetrahydrofurfuryl (meth) acrylate, (methyl) , 3-tetrahydrofurfuryl acrylate, 2-(tetrahydrofurfuryloxy)ethyl (meth)acrylate, and the like. These monomers may be used singly or in combination of two or more.

Examples of the monomer which provides the repeating unit (1) include dimethylaminoethyl (meth)acrylate, dimethylaminopropyl (meth)acrylate, and dimethylaminobutyl (meth)acrylate. , diethylaminoethyl (meth)acrylate, diethylaminopropyl (meth)acrylate, diethylaminobutyl (meth)acrylate, dimethylamino (meth)acrylate Ethoxyethyl ester, dimethylaminoethoxypropyl (meth)acrylate, diethylaminobutoxybutyl (meth)acrylate, and the like. These monomers can be used alone or in combination of two or more Mixed use.

Examples of the monomer which provides the repeating unit (2) include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, isopropyl (meth)acrylate, and (meth)acrylic acid. Butyl ester, isobutyl (meth)acrylate, tert-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, isodecyl (meth)acrylate, (meth)acrylic acid Dodecyl ester, cyclohexyl (meth)acrylate, tricyclo[5.1.02 ^2,6 ]decane-8-yl ester, isobornyl (meth)acrylate, (A) Adamantyl acrylate, dicyclopentenyl (meth)acrylate, decahydro-2-naphthyl (meth)acrylate, pentacyclopentadecyl (meth)acrylate, (methyl) Tricyclopentenyl acrylate or the like. These monomers may be used singly or in combination of two or more.

Examples of the monomer which provides the repeating unit (4) include 2-methoxyethyl (meth)acrylate, methoxydiethylene glycol (meth) acrylate, and methoxytriethylene glycol (methyl). ) acrylate, methoxypropylene glycol (meth) acrylate, methoxy dipropylene glycol (meth) acrylate, and the like. The monomer providing the repeating unit (4) may also be PME-100, PME-200 (manufactured by Nippon Oil Co., Ltd.) or the like. These monomers may be used singly or in combination of two or more.

Further, examples of the monomer which provides the repeating unit (5) having an acidic group include (meth)acrylic acid, maleic acid, maleic anhydride, itaconic acid, itaconic anhydride, and carboxymethyl (meth)acrylate. 2-Carboxyethyl (meth)acrylate, mono[2-(methyl)propenyloxyethyl] succinate, ω-carboxypolycaprolactone mono(meth)acrylate, vinyl Benzoic acid, p-hydroxystyrene, p-hydroxy-α-methylstyrene, 2-propenyloxyethylsulfonic acid, 2-methylpropenyloxyethylsulfonic acid, 2-propenyloxyethyl Sulfonic acid Sodium, lithium 2-propenyl methoxyethyl sulfonate, ammonium 2-propenyl oxy oxy sulfonate, imidazolium 2-propenyloxyethyl sulfonate, pyridine 2-propenyl methoxyethyl sulfonate Bismuth, sodium 2-methylpropenyloxyethyl sulfonate, lithium 2-methylpropenyloxyethyl sulfonate, ammonium 2-methylpropenyloxyethyl sulfonate, 2-methylpropene oxime Imidazolium oxyethylsulfonate, pyridinium 2-methylpropenyloxyethylsulfonate, sodium styrenesulfonate, sodium styrenesulfonate, lithium styrenesulfonate, ammonium styrenesulfonate, styrenesulfonate Acid imidazolium, pyridinium styrenesulfonate, and the like. These monomers may be used singly or in combination of two or more.

In the present invention, the content of the (B-1) copolymer is preferably 5 parts by mass to 300 parts by mass, and particularly preferably 10 parts by mass to 200 parts by mass, per 100 parts by mass of the (A) coloring agent. By adopting such a form, it becomes easy to achieve both heat resistance and solvent resistance.

The (B-2) dispersant having a urethane bond (hereinafter also referred to as "urethane-based dispersant") in the present invention means having at least one urethane bond in the structure. The general term for the compound.

In the present invention, the urethane bond of the urethane dispersant is preferably a urethane formed by reacting an aromatic polyisocyanate and/or an alicyclic polyisocyanate with a (poly)alcohol. key. Specifically, a dispersing agent described in JP-A-H09-19844, JP-A-2007-269873, and the like can be mentioned. When two or more urethane bonds are present in the urethane dispersant, the urethane bonds may be the same or different.

A urethane dispersant is commercially available, for example, in addition to EFKA-4046 (non-volatile content is 39% by mass to 41% by mass, amine price) It is 17 mgKOH/g~21 mgKOH/g), EFKA-4047 (non-volatile content is 34% by mass to 36% by mass, and the amine price is 14 mgKOH/g~20 mgKOH/g) [above by EFKA) Made by the company], Disperbyk-161 (30% by mass of nonvolatile matter, 11 mgKOH/g of amine), Disperbyk-162 (38% by mass of nonvolatile matter, 13 mgKOH/g of amine), Disperbyk-163 ( Nonvolatile content: 45 mass%, amine price: 10 mgKOH/g), Disperbyk-164 (nonvolatile content: 60% by mass, amine price: 18 mgKOH/g), Disperbyk-166 (nonvolatile content: 30% by mass, The amine price was 20 mgKOH/g), Disperbyk-167 (nonvolatile content: 52% by mass, amine price: 13 mgKOH/g), Disperbyk-168 (nonvolatile content: 30% by mass, amine price: 11 mgKOH/g) , Disperbyk-182 (43% by mass of nonvolatile matter, 13 mgKOH/g of amine), Disperbyk-2164 (60% by mass of nonvolatile matter, 14 mgKOH/g of amine) [above BYK (BYK) )Manufactured by the company], Solsperse 76500 (a non-volatile component of 50% by mass and an amine price of 15 mgKOH/g), which is manufactured by Lubrizol Co., Ltd., may also be used in Disparlon (manufactured by Nanben Chemical Co., Ltd.). The "amine price" herein means the number of mg of KOH equivalent to the amount of acid necessary to neutralize 1 g of the dispersant solid.

In the above urethane dispersant, the amine value is preferably 80 mgKOH/g or less, more preferably 50 mgKOH/g or less, still more preferably 30 mgKOH/g or less. Further, the lower limit of the amine value may be 0 mgKOH/g, but is preferably 5 mgKOH/g, more preferably 10 mgKOH/g.

The polystyrene-equivalent weight average molecular weight (Mw) measured by GPC in the urethane dispersing agent of the present invention is usually 5,000 to 50,000, preferably 7,000 to 20,000.

In the present invention, the urethane dispersing agents may be used singly or in combination of two or more.

The content of the urethane dispersant is usually 0.5 parts by mass to 100 parts by mass, preferably 1 part by mass to 70 parts by mass, more preferably 10 parts by mass, per 100 parts by mass of the lake pigment in the colorant. 50 parts by mass, particularly preferably 35 parts by mass to 50 parts by mass. In this case, when the content of the urethane dispersant is less than 0.5 part by mass, the stability and heat resistance of the pigment dispersion liquid tend to be lowered. On the other hand, if it exceeds 100 parts by mass, the content may be impaired. It is a possibility of performance such as developability of a coloring resist.

The term "(B-3) (meth)acrylic dispersant" as used in the present invention means a package A compound containing a (co)polymer of a (meth)acrylic monomer (excluding the component (B-1)). Further, the "(meth)acrylic monomer" means a polymerizable compound having a (meth)acryloyl group in the molecule, and "(meth)acryloyl group" means a propylene group or a methacrylium group. base.

In the present invention, the (meth)acrylic dispersant is preferably a block comprising a polymerized (meth)acrylic monomer having a pigment adsorbing group and a (meth)acrylic acid having no pigment adsorbing group. A block copolymer of a block polymerized. Examples of the pigment adsorbing group include a carboxymethyl group, a sulfo group, a phosphonooxy group, an (N-substituted) amine group, an (N-substituted) ammonium group, a group containing an aromatic ring, and the like, and a sulfo group or a phosphonium oxy group is preferred. The (N-substituted) amine group or the (N-substituted) ammonium group is more preferably an (N-substituted) amine group or an (N-substituted) ammonium group. Specific examples include the block copolymers described in JP-A-2002-31713, JP-A-2009-25813, and JP-A-2010-134419.

Such a dispersing agent is commercially available, and examples thereof include Disperbyk-2000 (40% by mass of a nonvolatile matter, 4 mgKOH/g of an amine value), and Disperbyk-2001 (46% by mass of a nonvolatile matter and 29 mgKOH of an amine value). /g), BYK-LPN6919 (60% by mass of nonvolatile matter, 72 mgKOH/g of amine), BYK-LPN21116 (40% by mass of nonvolatile matter, 29 mgKOH/g of amine) BYK-LPN21324 (amine price is 0 mgKOH/g) [above manufactured by BYK Chemical Co., Ltd.] and the like.

Among the above (meth)acrylic dispersants, a (meth)acrylic dispersant having an amine value of 130 mgKOH/g or less is preferable, and 100 mgKOH/g or less is more preferable, and still more preferably 80 mgKOH/g or less. Further, the lower limit of the amine value may be 0 mgKOH/g, preferably 1 mgKOH/g, more preferably 3 mgKOH/g.

In the present invention, the (meth)acrylic dispersant may be used singly or in combination of two or more.

The content of the (meth)acrylic dispersant is usually 0.5 parts by mass to 100 parts by mass, preferably 1 part by mass to 70 parts by mass, more preferably 1 part by mass, per 100 parts by mass of the lake pigment in the colorant. ~50 parts by mass. In this case, when the content of the (meth)acrylic dispersant is less than 0.5 part by mass, the stability and solvent resistance of the pigment dispersion liquid tend to be lowered. On the other hand, if it exceeds 100 parts by mass, it is present. The possibility of performance such as developability as a coloring resist is impaired.

The mass ratio [(B-2)/(B-3)] of the (B-2) dispersant having a urethane bond to the (B-3) (meth)acrylic dispersant is preferably 5 From /95 to 95/5, more preferably from 10/90 to 90/10, still more preferably from 70/30 to 90/10. When the ratio of the dispersing agent having a urethane bond to the (meth)acrylic dispersing agent is less than 5/95, the heat resistance tends to be lowered. When the ratio of the dispersing agent having a urethane bond to the (meth)acrylic dispersing agent exceeds 95/5, the solvent resistance tends to be lowered.

In the present invention, in addition to the above (B-1) to (B-3), it may be more Known dispersant. Examples of the known dispersant include a polyethyleneimine dispersant, a polyoxyethylene alkyl ether dispersant, a polyoxyethylene alkylphenyl ether dispersant, a polyethylene glycol diester dispersant, and sorbitol. An anhydride fatty acid ester dispersant, a polyester dispersant, and the like.

Such dispersants are commercially available, for example, Solsperse 24000 (manufactured by Lubrizol Corporation) and the like as polyethyleneimine dispersants, Ajisper PB821, Ajisper PB822, Ajisper PB880, Ajisper PB881 (above As a polyester-based dispersant, it is produced by Ajinomoto Fine-Techno. Co., Inc., and the like.

-(C) Crosslinker -

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

Specific examples of the compound having two or more (meth) acrylonitrile groups include a polyfunctional (meth) acrylate obtained by reacting an aliphatic polyhydroxy compound with (meth)acrylic acid, and a change in caprolactone. a polyfunctional (meth) acrylate, an alkylene oxide-modified polyfunctional (meth) acrylate, a polyfunctional amine group obtained by reacting a (meth) acrylate having a hydroxyl group with a polyfunctional isocyanate An acid ester (meth) acrylate or a polyfunctional (meth) acrylate having a carboxyl group obtained by reacting a (meth) acrylate having a hydroxyl group with an acid anhydride.

Here, examples of the aliphatic polyhydroxy compound include a 2-membered aliphatic polyhydroxy compound such as ethylene glycol, propylene glycol, polyethylene glycol, and polypropylene glycol; for example, glycerin, trimethylolpropane, pentaerythritol, and A trivalent or higher aliphatic polyhydroxy compound such as pentaerythritol. Examples of the (meth) acrylate having a hydroxyl group include 2-hydroxyethyl (meth)acrylate, trimethylolpropane di(meth)acrylate, pentaerythritol tri(meth)acrylate, and dipentaerythritol. (Meth) acrylate, glycerin dimethacrylate, and the like. Examples of the polyfunctional isocyanate include toluene diisocyanate, hexamethylene diisocyanate, diphenylmethylene diisocyanate, and isophorone diisocyanate. Examples of the acid anhydride include acid anhydrides of dibasic acids such as succinic anhydride, maleic anhydride, glutaric anhydride, itaconic anhydride, phthalic anhydride, and hexahydrophthalic anhydride, such as pyromellitic dianhydride and hydrazine. A tetrabasic dianhydride such as benzenetetracarboxylic dianhydride or benzophenone tetracarboxylic dianhydride.

Further, the above-described caprolactone-modified polyfunctional (meth) acrylate may, for example, be a compound described in paragraphs [0015] to [0018] of JP-A-11-44955. The above-mentioned alkylene oxide-modified polyfunctional (meth) acrylate may, for example, be selected from at least one modified bisphenol A di(meth) acrylate selected from the group consisting of ethylene oxide and propylene oxide. At least one modified tris(meth)acrylate of ethylene oxide and propylene oxide, at least one modified trimer selected from ethylene oxide and propylene oxide a propane tri(meth)acrylate, at least one modified pentaerythritol tri(meth)acrylate selected from the group consisting of ethylene oxide and propylene oxide, at least selected from the group consisting of ethylene oxide and propylene oxide 1 modified pentaerythritol tetra(meth) acrylate, at least one modified dipentaerythritol penta (meth) propylene selected from the group consisting of ethylene oxide and propylene oxide The acid ester is dipentaerythritol hexa(meth)acrylate modified by at least one selected from the group consisting of ethylene oxide and propylene oxide.

Further, examples of the compound having two or more N-alkoxymethylamino groups include a compound having a melamine structure, a benzoguanamine structure, and a urea structure. In addition, the melamine structure and the benzoguanamine structure refer to a chemical structure having one or more triazine rings or a phenyl-substituted triazine ring as a basic skeleton, and also includes melamine, benzoguanamine or a condensate thereof. the concept of. Specific examples of the compound having two or more N-alkoxymethylamino groups include N,N,N',N',N",N"-hexa(alkoxymethyl)melamine, N,N, N',N'-tetrakis(alkoxymethyl)benzoguanamine, N,N,N',N'-tetrakis(alkoxymethyl)glycolil and the like.

Among these crosslinking agents, a polyfunctional (meth) acrylate obtained by reacting a trivalent or higher aliphatic polyhydroxy compound with (meth)acrylic acid or a polyfunctional (meth)acrylic acid modified by caprolactone is preferable. Ester, polyfunctional urethane (meth) acrylate, polyfunctional (meth) acrylate with carboxyl group, N, N, N', N', N", N"-hexa (alkoxy Base) melamine, N,N,N',N'-tetrakis(alkoxymethyl)benzoguanamine. The strength of the colored layer is high, and the surface smoothness of the colored layer is excellent, and it is difficult to cause slag or film residue on the substrate of the unexposed portion and the light shielding layer, and the aliphatic polyhydroxy compound having three or more elements is Among the polyfunctional (meth) acrylates obtained by the reaction of methyl methacrylate, trimethylolpropane triacrylate, pentaerythritol triacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, and polyfunctional groups having a carboxyl group are particularly preferable. Among the (meth) acrylates, a compound obtained by reacting pentaerythritol triacrylate with succinic anhydride, and reacting dipentaerythritol pentaacrylate with succinic anhydride are particularly preferable. The resulting compound.

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

The content of the (C) crosslinking agent in the present invention is preferably 10 parts by mass to 1,000 parts by mass, particularly preferably 20 parts by mass to 500 parts by mass, per 100 parts by mass of the (A) coloring agent. In this case, if the content of the crosslinking agent is too small, the curability may be insufficient. On the other hand, when the content of the crosslinking agent is too large, when the alkali developability is imparted to the coloring composition of the present invention, the alkali developability is lowered, and slag is easily formed on the substrate of the unexposed portion or on the light shielding layer. And the tendency of film residue and the like.

-(D) Adhesive Resin -

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

Examples of the unsaturated monomer (d1) include (meth)acrylic acid, maleic acid, maleic anhydride, succinic acid mono [2-(methyl) propylene oxiranyl ethyl] ester, and ω-carboxyl polyhexene. Ester mono(meth)acrylate, p-vinylbenzoic acid, and the like.

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

Further, examples of the unsaturated monomer (d2) include an N-position substituted maleimide such as N-phenylmaleimide or N-cyclohexylmaleimide; for example, styrene, An aromatic vinyl compound such as α-methylstyrene, p-hydroxystyrene, p-hydroxy-α-methylstyrene, p-vinylbenzyl glycidyl ether or hydrazine; such as methyl (meth)acrylate, N-butyl methacrylate, 2-ethylhexyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, allyl (meth)acrylate, benzyl (meth)acrylate Ester, polyethylene glycol (degree of polymerization 2~10) methyl ether (meth) acrylate, polypropylene glycol (degree of polymerization 2~10) methyl ether (meth) acrylate, polyethylene glycol (degree of polymerization is 2~10) mono (meth) acrylate, polypropylene glycol (degree of polymerization: 2 to 10) mono (meth) acrylate, cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, ( Trimethyl [meth) acrylate [5.2.1.0 ^2,6 ]decane-8-yl ester, dicyclopentenyl (meth)acrylate, glycerol mono(meth)acrylate, (meth)acrylic acid Ethylene oxide modification of -4-hydroxyphenyl ester and p-cumylphenol ( Methyl) acrylate, glycidyl (meth) acrylate, 3,4-epoxycyclohexyl methyl (meth) acrylate, 3-[(meth) propylene methoxymethyl] propylene oxide, a (meth) acrylate such as 3-[(methyl)acryloxymethyl]-3-ethyl propylene oxide; such as cyclohexyl vinyl ether, isobornyl vinyl ether, tricyclic [5.2. a vinyl ether such as 1.0 ^2,6 ]decane-8-yl vinyl ether, pentacyclopentadecyl vinyl ether or 3-(vinyloxymethyl)-3-ethyl propylene oxide; a macromonomer having a mono(meth)acryloyl group at the end of a polymer molecular chain such as styrene, poly(methyl) methacrylate, poly(methyl) methacrylate, or polyoxyalkylene .

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

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

Specific examples of the copolymer of the unsaturated monomer (d1) and the unsaturated monomer (d2) include, for example, Japanese Patent Laid-Open No. Hei. Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. A copolymer disclosed in, for example, Japanese Patent Publication No. 2004-101728.

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

The polystyrene-equivalent weight average molecular weight (Mw) of the binder resin in the present invention measured by GPC (the elution solvent is tetrahydrofuran) is usually 1,000 to 100,000, preferably 3,000 to 50,000. When the Mw is too small, the residual film ratio of the obtained film is lowered, the pattern shape, heat resistance, and the like are impaired, and the electrical characteristics are deteriorated. On the other hand, if the Mw is too large, the resolution is lowered and the pattern shape is impaired. Moreover, when coating by a slit nozzle method, it becomes easy to generate a dry foreign material.

Further, the ratio (Mw/Mn) of the weight average molecular weight (Mw) to the number average molecular weight (Mn) of the binder resin in the present invention is preferably from 1.0 to 5.0, more preferably from 1.0 to 3.0. In addition, the term "Mn" as used herein means a polystyrene-equivalent number average molecular weight measured by GPC (the elution solvent is tetrahydrofuran).

The adhesive resin in the present invention can be produced by a known method, and can be disclosed, for example, in the specification of Japanese Patent Laid-Open Publication No. 2003-222717, Japanese Patent Laid-Open No. Hei. No. 2006-259680, and International Publication No. 07/029871. The method controls its structure or Mw, Mw/Mn.

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

In the present invention, the content of the binder resin is usually 10 parts by mass to 1,000 parts by mass, preferably 20 parts by mass to 500 parts by mass, per 100 parts by mass of the (A) colorant. When the content of the binder resin is too small, for example, the alkali developability is lowered, and the storage stability of the obtained coloring composition is lowered. On the other hand, if the amount is too large, the relative concentration of the colorant is lowered, so that it becomes difficult to achieve The film is set as a target color density.

-(E) Photopolymerization initiator -

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

Examples of such a photopolymerization initiator include a thioxanthone compound, an acetophenone compound, a biimidazole compound, a triazine compound, an O-mercaptoquinone compound, a phosphonium salt compound, a benzoin compound, and the like. A benzophenone compound, an α-diketone compound, a polynuclear quinone compound, a diazo compound, a quinone sulfonate compound, or the like.

In the present invention, the photopolymerization initiator may be used singly or in combination of two or more. The photopolymerization initiator is preferably at least one selected from the group consisting of a thioxanthone compound, an acetophenone compound, a biimidazole compound, a triazine compound, and an O-mercaptoquinone compound.

Among the preferred photopolymerization initiators in the present invention, specific examples of the thioxanthone compound include thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, and 2-isopropylthioxanthone. , 4-isopropylthioxanthone, 2,4-dichlorothioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2,4-diisopropyl Thioxanthone and the like.

Further, specific examples of the above acetophenone-based compound include 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one and 2-benzyl-2- Dimethylamino-1-(4-morpholinophenyl)butan-1-one, 2-(4-methylbenzyl)-2-(dimethylamino)-1-(4- Morpholinophenyl)butan-1-one and the like.

Further, specific examples of the biimidazole compound include 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole, 2. 2'-bis(2,4-dichlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis(2,4,6- Trichlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole and the like.

Further, in the case of using a biimidazole compound as a photopolymerization initiator, it is preferred to use a hydrogen donor in combination in terms of improving sensitivity. Here, the "hydrogen donor" means a compound capable of supplying a hydrogen atom to a radical generated by a biimidazole compound by exposure. Examples of the hydrogen donor include mercaptan hydrogen donors such as 2-mercaptobenzothiazole and 2-mercaptobenzoxazole; 4,4'-bis(dimethylamino)benzophenone, 4,4' An amine hydrogen donor such as bis(diethylamino)benzophenone. In the present invention, the hydrogen donor may be used singly or in combination of two or more. In terms of further improving the sensitivity, one or more thiol donor hydrogen donors and one or more amine hydrogen donors are preferably used. Used in combination.

Further, specific examples of the above triazine compound include 2,4,6-tris(trichloromethyl)-s-triazine and 2-methyl-4,6-bis(trichloromethyl)-s-triazine. ,2-[2-(5-methylfuran-2-yl)vinyl]-4,6-bis(trichloromethyl)-s-triazine, 2-[2-(furan-2-yl)ethylene 4-[6,6-bis(trichloromethyl)-s-triazine, 2-[2-(4-diethylamino-2-methylphenyl)vinyl]-4,6-bis ( Trichloromethyl)-s-triazine, 2-[2-(3,4-dimethoxyphenyl)vinyl]-4,6-bis(trichloromethyl)-s-triazine, 2-( 4-methoxyphenyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(4-ethoxystyryl)-4,6-bis(trichloromethyl)- A triazine compound having a halo methyl group such as s-triazine or 2-(4-n-butoxyphenyl)-4,6-bis(trichloromethyl)-s-triazine.

Further, specific examples of the O-mercaptoquinone compound include 1,2-octanedione, 1-[4-(phenylthio)phenyl]-, 2-(O-benzamide), and ethyl ketone. ,1-[9-ethyl-6-(2-methylbenzhydryl)-9H-indazol-3-yl]-, 1-(O-acetamidine), ethyl ketone, 1-[9 -ethyl-6-(2-methyl-4-tetrahydrofurylmethoxybenzylidene)-9H-indazol-3-yl]-, 1-(O-acetamidine), ethyl ketone, 1 -[9-ethyl-6-{2-methyl-4-(2,2-dimethyl-1,3-dioxolyl)methoxybenzylidene}-9H-oxime Zyrid-3-yl]-, 1-(O-acetamidine) and the like. As a commercial item of the O-mercaptopurine compound, NCI-831, NCI-930 (above, manufactured by ADEKA Co., Ltd.), or the like can be used.

In the present invention, in the case of using a photopolymerization initiator other than a biimidazole compound such as an acetophenone compound, a sensitizer may be used in combination. Examples of such a sensitizer include 4,4'-bis(dimethylamino)benzophenone, 4,4'-bis(diethylamino)benzophenone, and 4-diethylamine. Acetophenone, 4-dimethylaminopropiophenone, ethyl 4-dimethylaminobenzoate, 2-ethylhexyl 4-dimethylaminobenzoate, 2,5-bis ( 4-diethylaminobenzylidene)cyclohexanone, 7-diethylamino-3-(4-diethylaminobenzimidyl)coumarin, 4-(diethylamino) ) Chalcone and so on. Further, in the present invention, the sensitivity of the coloring composition can be improved by containing a polyfunctional thiol which functions as a chain transfer agent. Examples of such a chain transfer agent include trimethylolpropane tris(3-mercaptopropionate), pentaerythritol tetrakis(3-mercaptopropionate), 2,4,6-tridecyl-s-triazine, 2-( N,N-dibutylamino)-4,6-dimercapto-s-triazine and the like.

In the present invention, the content of the photopolymerization initiator is preferably 0.01 parts by mass to 120 parts by mass, particularly preferably 1 part by mass to 100 parts by mass, per 100 parts by mass of the (C) crosslinking agent. In this case, if the content of the photopolymerization initiator is too small, There is a possibility that the hardening due to the exposure may be insufficient. On the other hand, if the amount is too large, the formed coloring layer tends to be easily detached from the substrate during development.

-(F) solvent -

In the case where the colored composition of the present invention contains the component (A) to the component (D) and the other component arbitrarily added, the solvent is usually formulated (F) to prepare a liquid composition.

Further, when the coloring composition of the present invention contains the component (A) to the component (C) and the other component arbitrarily added, it is usually prepared by using, for example, a bead mill, a roll mill, or the like. (a1) a coloring agent containing a lake pigment, which is pulverized together with a part of (B) a dispersing agent and (D) a binder resin in a solvent (F), mixed and dispersed to prepare a pigment dispersion liquid, followed by To the pigment dispersion liquid, (C) a crosslinking agent, an optional (D) binder resin, (E) a photopolymerization initiator, and a further (F) solvent are added and mixed.

The solvent may be appropriately selected and used as long as it is a component which disperses or dissolves a component constituting the coloring composition and does not react with these components and has a moderate volatility.

Examples of such a solvent include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono-n-propyl ether, ethylene glycol mono-n-butyl ether, diethylene glycol monomethyl ether, and diethylene glycol monoethyl ether. , diethylene glycol mono-n-propyl ether, diethylene glycol mono-n-butyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-n-propyl ether, propylene glycol Single Zhengding (poly)alkylene glycol monoalkyl ethers such as ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol mono-n-propyl ether, dipropylene glycol mono-n-butyl ether, tripropylene glycol monomethyl ether, tripropylene glycol monoethyl ether; Methyl lactate such as methyl lactate or ethyl lactate; methanol, ethanol, propanol, butanol, isopropanol, isobutanol, tert-butanol, octanol, 2-ethylhexanol, cyclohexanol Ketone alcohols such as (cyclo)alkyl alcohols; diacetone alcohols; ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol Alcohol monoethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, dipropylene glycol monomethyl ether acetate, acetic acid-3-methoxybutyl ester, acetic acid-3-methyl-3- (poly)alkylene glycol monoalkyl ether acetates such as methoxybutyl ester; diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol diethyl ether, tetrahydrofuran and other ethers; methyl Ketones such as ethyl ketone, cyclohexanone, 2-heptanone, 3-heptanone; propylene glycol diacetate, 1,3-butanediol diacetate, 1,6-hexanediol diacetate Diacetate; 3-methoxypropionic acid Methyl ester, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl ethoxyacetate, 3-methyl-3-propionic acid Alkoxycarboxylates such as methoxybutyl ester; ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, n-amyl formate, isoamyl acetate, propionic acid N-butyl ester, ethyl butyrate, n-propyl butyrate, isopropyl butyrate, n-butyl butyrate, methyl pyruvate, pyruvate Other esters such as ester, n-propyl pyruvate, methyl acetate, ethyl acetate, ethyl 2-oxobutanoate; aromatic hydrocarbons such as toluene and xylene; N,N-dimethyl A decylamine such as formamide, N,N-dimethylacetamide or N-methylpyrrolidone or an indoleamine.

Among these solvents, it is preferable to contain at least 1 selected from the group consisting of (poly)alkylene glycol monoalkyl ethers and (poly)alkylene glycol monoalkyl ether acetates from the viewpoints of solubility, pigment dispersibility, and coating properties. Preferably, it contains at least one selected from the group consisting of propylene glycol monomethyl ether, propylene glycol monoethyl ether, ethylene glycol monomethyl ether acetate, propylene glycol monomethyl ether acetate, and propylene glycol monoethyl ether acetate.

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

The content of the solvent is not particularly limited, and the total concentration of each component from which the solvent is removed in the coloring composition is preferably from 5% by mass to 50% by mass, and more preferably from 10% by mass to 40% by mass. By adopting such a form, a colorant dispersion liquid having good dispersibility and stability and a coloring composition excellent in coatability can be obtained.

-additive-

The coloring composition of the present invention may also contain various additives as needed.

Examples of the additive include a thermal polymerization initiator such as an azo compound or an organic peroxide; a filler such as glass or alumina; a polymer compound such as polyvinyl alcohol or poly(fluoroalkyl acrylate); and a fluorine-based surface active agent; Surfactants such as surfactants, terpenoid surfactants; vinyl trimethoxy decane, vinyl triethoxy decane, vinyl tris(2-methoxyethoxy) decane, N-(2-amino B 3-aminopropylmethyldimethoxy Decane, N-(2-aminoethyl)-3-aminopropyltrimethoxydecane, 3-aminopropyltriethoxydecane, 3-glycidoxypropyltrimethoxydecane, 3 - glycidoxypropylmethyldimethoxydecane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxydecane, 3-chloropropylmethyldimethoxydecane, 3-chloro Adhesion promoter such as propyltrimethoxydecane, 3-methylpropenyloxypropyltrimethoxydecane, 3-mercaptopropyltrimethoxydecane; 2,2-thiobis(4-methyl-6) -T-butylphenol), 2,6-di-t-butylphenol and other antioxidants; 2-(3-tert-butyl-5-methyl-2-hydroxyphenyl)-5-chlorobenzotriene Ultraviolet absorber such as azole or alkoxybenzophenone; aggregation inhibitor such as sodium polyacrylate; malonic acid, adipic acid, itaconic acid, citraconic acid, fumaric acid, mesaconic acid, 2-amine Ethanol, 3-amino-1-propanol, 5-amino-1-pentanol, 3-amino-1,2-propanediol, 2-amino-1,3-propanediol, 4-amino group- Residue improver such as 1,2-butanediol; succinic acid mono [2-(methyl) propylene methoxyethyl] ester, phthalic acid mono [2-(methyl) propylene oxiranyl ethyl] Ester, ω-carboxyl polymerization A developability improving agent such as a caprolactone mono(meth)acrylate; a siloxane oligomer having a reactive functional group disclosed in JP-A-2008-242078 or the like.

Color filter and manufacturing method thereof

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

The method of manufacturing a color filter may be exemplified by the following method. First, on the surface of the substrate, a light shielding layer (black matrix) is formed in such a manner as to divide the portion where the pixels are formed. Next, a liquid composition of the radiation sensitive coloring composition of the present invention in which a blue lake pigment is dispersed is applied onto the substrate, followed by prebaking. (prebake) The solvent is evaporated to form a coating film. Next, the coating film was exposed through a photomask, and then developed using an alkali developing solution to dissolve and remove the unexposed portion of the coating film. Thereafter, a pixel array in which a blue pixel pattern is arranged in a predetermined arrangement is formed by postbake.

Next, using the green or red radiation-sensitive coloring composition, the coating, prebaking, exposure, development, and post-baking of the respective radiation-sensitive coloring compositions are performed in the same manner as described above, and green pixel arrays are sequentially formed on the same substrate. And a red pixel array. Thus, a color filter in which three primary color pixel arrays of red, green, and blue are arranged on the substrate is obtained. However, in the present invention, the order in which the pixels of the respective colors are formed is not limited to the above order. Further, in the first method of manufacturing a color filter, any one or more of the blue, green, and red pixel arrays described above may be a coloring layer formed using the coloring composition of the present invention.

Further, the black matrix can be formed by forming a metal film such as chromium formed by sputtering or vapor deposition into a desired pattern by photolithography, or using a radiation-sensitive coloring combination in which a black colorant is dispersed. The object is formed in the same manner as in the case of forming the above-described pixels. The coloring composition of the present invention can also be suitably used in the formation of the black matrix.

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

Further, these substrates may be subjected to a chemical treatment such as a decane coupling agent, plasma treatment, ion plating, sputtering, gas phase reaction, or vacuum evaporation as needed. Suitable pretreatment such as plating.

When the radiation sensitive coloring composition is applied onto a substrate, a spray method, a roll coating method, a spin coating method (spin coating method), a slit die coating method, a bar coating method, or the like may be employed. As the coating method, a spin coating method or a slit die coating method is particularly preferably used.

Prebaking is usually carried out by combining reduced pressure drying with heat drying. Drying under reduced pressure usually proceeds until it reaches 50 Pa to 200 Pa. Further, the conditions of heat drying are usually from about 1 minute to about 10 minutes at 70 ° C to 110 ° C.

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

Examples of the light source used for forming the pixel and/or the black matrix include a xenon lamp, a halogen lamp, a tungsten lamp, a high pressure mercury lamp, an ultrahigh pressure mercury lamp, a metal halide lamp, a medium pressure mercury lamp, a low pressure mercury lamp, or the like, or an argon ion. Laser sources such as lasers, YAG lasers, XeCl excimer lasers, and nitrogen lasers. The exposure light source can also use a Light Emitting Diode (LED). Radiation having a wavelength in the range of 190 nm to 450 nm is preferred.

The exposure amount of the radiation is usually preferably from 10 J/m ² to 10,000 J/m ² .

Further, the above alkaline developing solution is, for example, preferably sodium carbonate, sodium hydrogencarbonate, sodium hydroxide, potassium hydroxide, tetramethylammonium hydroxide, choline or 1,8-diazabicyclo-[5.4.0]-7. An aqueous solution of undecene, 1,5-diazabicyclo-[4.3.0]-5-nonene or the like.

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

The development processing method can be applied to a shower development method, a spray development method, a dip development method, a liquid immersion development method, or the like. The developing conditions are preferably from 5 seconds to 300 seconds at normal temperature.

The post-baking conditions are usually from about 10 minutes to about 60 minutes at from 120 ° C to 280 ° C. From the viewpoint of heat resistance of the colorant, the post-baking temperature is preferably 240 ° C or less, particularly preferably 230 ° C or less, further It is preferably 200 ° C or lower.

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

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

Next, using a green or red thermosetting coloring composition, a green pixel pattern and a red pixel pattern were sequentially formed on the same substrate in the same manner as described above. Thus, a color filter in which three primary color pixel patterns of red, green, and blue are arranged on the substrate is obtained. However, in the present invention, the order in which the pixels of the respective colors are formed is not limited to the above order. Further, in the second method of manufacturing a color filter, any one or more of the above-described blue, green, and red pixel arrays are those using the present invention. The coloring layer formed by coloring the composition may be used.

Further, the partition wall not only functions as a light-shielding function, but also functions to prevent the coloring composition of each color discharged into the divided region from being mixed, and thus is compatible with the black matrix used in the first method described above. In comparison, the film thickness is thicker. Therefore, the partition walls are usually formed using a black radiation-sensitive composition.

The substrate or the light source used in forming the color filter, and the method or conditions for prebaking or post-baking are the same as those of the first method described above. As described above, the film thickness of the pixel formed by the inkjet method is equivalent to the height of the partition wall.

A transparent conductive film can be formed by sputtering after forming a protective film as needed on the pixel pattern obtained as described above. After the transparent conductive film is formed, a spacer may be further formed to form a color filter. The spacer is usually formed using a radiation sensitive composition, but may be a spacer having a light blocking property (black spacer). In this case, the coloring composition of the present invention can be suitably used in the formation of the black spacer by using a radiation-sensitive coloring composition in which a black colorant is dispersed.

The color filter of the present invention obtained as described above is extremely useful in color liquid crystal display elements, color image sensor elements, color sensors, organic EL display elements, electronic paper, and the like because of extremely high luminance and color purity.

Display component

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

The color liquid crystal display element having the color filter of the present invention may be of a transmissive type or a reflective type, and a suitable structure may be employed. For example, the following structure can be used: A color filter is formed on a substrate different from the driving substrate on which the thin film transistor (TFT) is disposed, and the driving substrate and the substrate on which the color filter is formed are opposed to each other via the liquid crystal layer; and the following structure may be employed: a substrate on which a color filter is formed on a surface of a driving substrate on which a thin film transistor (TFT) is disposed, and an electrode in which ITO (indium oxide doped with tin) or IZO (mixture of indium oxide and zinc oxide) is formed The substrates face each other across the liquid crystal layer. The latter structure has an advantage in that the aperture ratio can be additionally increased to obtain a bright and high-definition liquid crystal display element.

A color liquid crystal display element having the color filter of the present invention may include a backlight unit using a white LED as a light source in addition to a CCFL (Cold Cathode Fluorescent Lamp). Examples of the white LED include a white LED in which a red LED is combined with a green LED and a blue LED to obtain a white light by color mixing, and a white LED is obtained by combining a blue LED, a red LED, and a green phosphor to obtain a white light. A blue LED is obtained by combining a blue LED with a red illuminating phosphor and a green illuminating phosphor to obtain white light, and a blue LED is mixed with a Yttrium Aluminum Garnet (YAG) phosphor. Obtaining white light white LED, combining blue LED with orange light emitting phosphor and green light emitting phosphor to obtain white light white LED by mixing colors, and ultraviolet LED and red light emitting phosphor and green light emitting phosphor A blue light-emitting phosphor combines to obtain a white light white LED or the like by color mixing.

Twisted Nematic (TN) type and super twisted nematic (Super Twisted) can be applied to the color liquid crystal display element having the color filter of the present invention. Suitable liquid crystal modes such as Nematic, STN) type, In-Planes Switching (IPS) type, Vertical Alignment (VA) type, and Optically Compensated Birefringence (OCB) type.

Further, the organic EL display element having the color filter of the present invention can be suitably configured, and for example, the structure disclosed in Japanese Laid-Open Patent Publication No. Hei 11-307242 can be cited.

Further, the electronic paper having the color filter of the present invention may have a suitable structure, and for example, the structure described in JP-A-2007-41169 can be cited.

[Examples]

Hereinafter, embodiments of the present invention will be more specifically described by way of examples. However, the invention is not limited to the following examples. In addition, the abbreviation of the raw material used in the following examples is as follows.

THF: tetrahydrofuran

nBMA: n-butyl methacrylate

MMA: Methyl methacrylate

AMA: allyl methacrylate

OXMA: 3-(methacryloxymethyl)-3-ethyl propylene oxide

THFMA: tetrahydrofurfuryl methacrylate

DAMA: dimethylaminoethyl methacrylate

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

AIBN: 2,2'-azobisisobutyronitrile

PGMEA: propylene glycol monomethyl ether acetate

<Synthesis of (B-1) Copolymer>

Synthesis Example 1

A three-necked flask having an internal volume of 1000 mL prepared by placing a stirrer and sufficiently nitrogen-substituted, and adding 231 g of toluene, 12 g of 1,2-dimethoxyethane, and a concentration of 0.5 mol/L under a nitrogen atmosphere. A solution of diisobutyl (2,6-di-t-butyl-4-methylphenoxy)aluminum in toluene (86 mL). After adjusting the temperature of the contents of the reaction vessel to 0 ° C, 4.3 mL of a cyclohexane solution of 1.0 mol/L of a second butyl lithium was added thereto, followed by stirring for 20 minutes. In this solution, a mixed solution of nBMA 10.5 g, PME-200 8.1 g, and OXMA 4.5 g was added dropwise thereto while stirring at 0 ° C for 60 minutes, and the reaction was further continued for 1 hour. Next, DAMA 6.9 g was added dropwise over 30 minutes, and the reaction was further continued for 1 hour. After confirming the completion of the reaction by gas chromatography analysis (hereinafter abbreviated as GC), 0.5 mL of methanol was added to the reaction solution to stop the polymerization reaction.

The toluene of the obtained solution was removed using a rotary evaporator, and the copolymer was recovered. After the recovered copolymer was dissolved in acetone, the solution was poured into hexane to obtain a precipitate. This operation was repeated 5 times to carry out purification, and then dried under vacuum at 60 ° C for 2 hours. Finally, the copolymer was dissolved in PGMEA and adjusted to a 40% by mass concentration solution. A solution containing a diblock copolymer derived from DAMA derived from nBMA, PME-, is obtained as described above, and is obtained as described above. 200 and OXMA Repeat unit. The obtained copolymer was referred to as "copolymer (B1)".

Synthesis Example 2

A three-necked flask having an internal volume of 500 mL which was thoroughly purged with nitrogen while being placed in a stirrer was added, and 231.0 g of THF and a 1,1-diphenyl-3-methyl group having a concentration of 0.25 mol/L were added under a nitrogen atmosphere. 13.3 mL of pentyl lithium in THF. In this solution, a mixed solution of nBMA 13.5 g, PME-200 8.1 g, and OXMA 1.5 g was added dropwise thereto while stirring at -70 ° C for 60 minutes, and the reaction was further continued for 1 hour. Next, DAMA 6.9 g was added dropwise over 30 minutes, and the reaction was further continued for 1 hour. After confirming completion of the reaction by GC, 0.5 mL of methanol was added to the reaction solution to stop the polymerization.

The obtained solution was poured into 1.5 L of hexane, and the resulting copolymer was precipitated and recovered. After the recovered copolymer was further dissolved in methanol, the solution was poured into hexane. This operation was repeated 5 times for purification, and then dried under vacuum at 60 ° C for 2 hours. Finally, the copolymer was dissolved in PGMEA and adjusted to a 40% by mass concentration solution. A solution containing a diblock copolymer derived from DAMA derived from nBMA, PME-, is obtained as described above, and is obtained as described above. 200 and OXMA repeat units. The obtained copolymer was referred to as "copolymer (B2)".

Synthesis Example 3

In a 300 mL flask with a stir bar, add toluene 30 g, nBMA 12.0 g, PME-200 10.9 g, THFMA 3.4 g, AIBN 236 mg, and pyrazole-1-dithiocarbamic acid cyano (dimethyl) A The ester was dissolved in 608 mg and was subjected to 30 Minutes of nitrogen replacement. Thereafter, stirring was gradually carried out to raise the temperature of the reaction solution to 60 ° C, and the temperature was maintained for 24 hours to carry out living radical polymerization.

Next, a solution in which AIBN 410 mg and DAMA 7.9 g were dissolved in 20 g of toluene and then subjected to nitrogen substitution for 30 minutes was added to the above reaction solution, and living radical polymerization was carried out at 60 ° C for 24 hours. Thereafter, it was adjusted to a concentration of 40% by mass of PGMEA solution by concentration under reduced pressure. A solution containing a diblock copolymer derived from DAMA derived from nBMA, PME-, is obtained as described above, and is obtained as described above. Repeat units of 200 and THFMA. The obtained diblock copolymer was referred to as "copolymer (B3)".

Synthesis Example 4

Toluene 30 g, MMA 8.8 g, PME-200 7.9 g, OXMA 2.9 g, AIBN 217 mg and pyrazole-1-dithiocarbamic acid cyano (dimethyl) A were added to a 300 mL flask with a stir bar. The ester was dissolved in 559 mg and subjected to nitrogen substitution for 30 minutes. Thereafter, stirring was gradually carried out to raise the temperature of the reaction solution to 60 ° C, and the temperature was maintained for 24 hours to carry out living radical polymerization.

Next, a solution in which AIBN 504 mg and DAMA 9.7 g were dissolved in 20 g of toluene and then subjected to nitrogen substitution for 30 minutes was added to the above reaction solution, and living radical polymerization was carried out at 60 ° C for 24 hours. Thereafter, it was adjusted to a concentration of 40% by mass of PGMEA solution by concentration under reduced pressure. A solution containing a diblock copolymer derived from DAMA having a derived from DMA derived from MMA, PME- is obtained as described above. 200 and Repeat unit of OXMA. The obtained diblock copolymer was referred to as "copolymer (B4)".

Synthesis Example 5

In a 300 mL flask with a stir bar, add toluene 30 g, MMA 10.2 g, nBMA 6.9 g, PME-200 3.3 g, THFMA 1.3 g, AIBN 278 mg, and pyrazole-1-dithiocarboxylic acid cyano (two Methyl)methyl ester was dissolved in 716 mg, and nitrogen substitution was carried out for 30 minutes. Thereafter, stirring was gradually carried out to raise the temperature of the reaction solution to 60 ° C, and the temperature was maintained for 24 hours to carry out living radical polymerization.

Next, a solution in which AIBN 199 mg and DAMA 3.8 g were dissolved in 20 g of toluene and then subjected to nitrogen substitution for 30 minutes was added to the above reaction solution, and living radical polymerization was carried out at 60 ° C for 24 hours. Thereafter, it was adjusted to a concentration of 40% by mass of PGMEA solution by concentration under reduced pressure. A solution containing a diblock copolymer derived from DAMA derived from MMA, nBMA, and a solution containing a diblock copolymer derived from A block and B block is obtained as described above. Repeat units of PME-200 and THFMA. The obtained diblock copolymer was referred to as "copolymer (B5)".

Synthesis Example 6

Toluene 30 g, nBMA 8.0 g, PME-200 3.2 g, OXMA 6.4 g, AIBN 168 mg and pyrazole-1-dithiocarbamic acid cyano (dimethyl) A were added to a 300 mL flask with a stir bar. The ester was dissolved in 433 mg, and nitrogen substitution was carried out for 30 minutes. Thereafter, stirring was gradually carried out to raise the temperature of the reaction solution to 60 ° C, and the temperature was maintained for 24 hours to carry out living radical polymerization.

Secondly, AIBN 749 mg and DAMA 14.4 g will be dissolved in toluene 20 A solution in which g was subjected to nitrogen substitution for 30 minutes was added to the above reaction solution, and living radical polymerization was carried out at 60 ° C for 24 hours. Thereafter, it was adjusted to a concentration of 40% by mass of PGMEA solution by concentration under reduced pressure. A solution containing a diblock copolymer derived from DAMA derived from nBMA, PME-, is obtained as described above, and is obtained as described above. 200 and OXMA repeat units. The obtained diblock copolymer was referred to as "copolymer (B6)".

Comparative Synthesis Example 1

In the synthesis example 2, a mixed solution of nBMA 13.5 g, PME-200 8.1 g, and OXMA 1.5 g was changed to a mixed solution of nBMA 15.0 g and PME-200 8.1 g, and the same procedure as in Synthesis Example 2 was carried out. Synthesis of a diblock copolymer, obtaining a 40% by mass concentration of PGMEA solution containing a diblock copolymer comprising an A block and a B block, the A block having a repeating unit derived from DAMA, the B embedded The segments have repeating units derived from nBMA and PME-200. The obtained diblock copolymer was referred to as "copolymer (b1)".

Comparative Synthesis Example 2

In the synthesis example 2, the mixed solution of nBMA 13.5 g, PME-200 8.1 g, and OXMA 1.5 g was changed to a mixed solution of nBMA 10.5 g, PME-200 8.1 g, and AMA 4.5 g, except for the same manner as in Synthesis Example 2. The synthesis of the diblock copolymer was carried out to obtain a 40% by mass concentration of PGMEA solution containing a diblock copolymer comprising an A block and a B block, the A block having a repeating unit derived from DAMA, The B block has a repeating single from nBMA, PME-200 and AMA yuan. The obtained diblock copolymer was referred to as "copolymer (b2)".

Comparative Synthesis Example 3

Add 30 g of toluene, MMA 8.7 g, PME-200 7.8 g, AIBN 188 mg and pyrazole-1-dithiocarbamic acid cyano (dimethyl) methyl ester 485 mg in a 300 mL flask with a stir bar. The dissolution was carried out, and nitrogen substitution was performed for 30 minutes. Thereafter, stirring was gradually carried out to raise the temperature of the reaction solution to 60 ° C, and the temperature was maintained for 24 hours to carry out living radical polymerization.

Next, a solution in which AIBN 647 mg and DAMA 12.4 g were dissolved in 20 g of toluene and then subjected to nitrogen substitution for 30 minutes was added to the above reaction solution, and living radical polymerization was carried out at 60 ° C for 24 hours. Thereafter, it was adjusted to a concentration of 40% by mass of PGMEA solution by concentration under reduced pressure. A solution containing a diblock copolymer derived from DAMA having DRAM derived from MMA and PME- is obtained as described above. 200 repeating unit. The obtained diblock copolymer was referred to as "copolymer (b3)".

Comparative Synthesis Example 4

Add toluene 30 g, MMA 8.2 g, nBMA 11.5 g, PME-200 6.3 g, AIBN 303 mg and pyrazole-1-dithiocarbamic acid cyano (dimethyl) A in a 300 mL flask with stir bar The ester was dissolved in 782 mg, and nitrogen substitution was carried out for 30 minutes. Thereafter, stirring was gradually carried out to raise the temperature of the reaction solution to 60 ° C, and the temperature was maintained for 24 hours to carry out living radical polymerization.

Secondly, AIBN 71 mg and DAMA 1.4 g will be dissolved in toluene 20 g. A solution in which nitrogen substitution was carried out for 30 minutes was added to the above reaction solution, and living radical polymerization was carried out at 60 ° C for 24 hours. Thereafter, it was adjusted to a concentration of 40% by mass of PGMEA solution by concentration under reduced pressure. Obtaining a solution containing a diblock copolymer derived from DAMA derived from MMA, nBMA, and a solution containing a diblock copolymer containing an A block and a B block, as described above Repeat unit of PME-200. The obtained diblock copolymer was referred to as "copolymer (b4)".

<Measurement of Mw and Mw/Mn of <(B-1) Copolymer>

Table 1 shows the Mw and Mn of the (B-1) copolymer obtained in each of the above Synthesis Examples together with the copolymerization ratio (% by mass) of each monomer. Further, Mw and Mn can be measured by GPC of the following specifications.

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

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

Mobile phase: DMF.

<Measurement of amine valence of <(B-1) copolymer>

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

0.5 g of the copolymer solution was precisely weighed in units of 1 mg and dispensed into a glass container. The solution was dissolved in acetic anhydride/acetic acid = 9/1 (volume ratio) 20 mL, and allowed to stand at room temperature for 3 hours. Thereafter, after further adding 30 mL of acetic acid, a potential difference measuring device AT-510 (manufactured by Kyoto Electronics Industry Co., Ltd.) was used, and 0.1 was used. Mol/L perchloric acid. The acetic acid solution was titrated. The blank test was performed in the same manner. According to (B-1) copolymer and blank test 0.1 mol / L perchloric acid. The amount of the acetic acid solution dropped was used to calculate the amine value (unit: mgKOH/g).

<(D) Synthesis of Adhesive Resin>

Synthesis Example 7

100 parts by mass of PGMEA was placed in a flask equipped with a condenser and a stirrer, and nitrogen substitution was performed. Heating to 80 ° C, 100 parts by mass of PGMEA, 20 parts by mass of methacrylic acid, 10 parts by mass of styrene, 5 parts by mass of benzyl methacrylate, and 2-hydroxyethyl methacrylate were added dropwise at the same temperature for 1 hour. 15 parts by mass, 23 parts by mass of 2-ethylhexyl methacrylate, 12 parts by mass of N-phenylmaleimide, 15 parts by mass of mono(2-propenyloxyethyl) succinate and 2 A mixed solution of 6 parts by mass of 2'-azobis(2,4-dimethylvaleronitrile) was maintained at this temperature for 2 hours. Thereafter, the temperature of the reaction solution was raised to 100 ° C, and further polymerization was carried out for 1 hour to obtain a binder resin solution (solid content concentration: 33% by mass). The resulting adhesive resin The polystyrene-converted Mw measured by GPC (mobile phase: THF) was 12,200, Mn was 6,500, and Mw/Mn was 1.87. This binder resin was referred to as "adhesive resin (D1)".

Synthesis Example 8

The flask with a condenser and a stirrer was charged with 30.0 g of benzyl methacrylate, 20.0 g of nBMA, 15.0 g of hydroxyethyl methacrylate, 20.0 g of styrene, 15.0 g of methacrylic acid and 200 g of PGMEA. Further, 5.0 g of AIBN 3.0 g and α-methylstyrene dimer were charged, followed by nitrogen substitution for 15 minutes. Then, the reaction liquid was heated to 80 ° C while stirring, and polymerization was carried out for 5 hours to obtain a binder resin solution (solid content concentration: 33% by mass). The viscosity of the adhesive resin measured by GPC (mobile phase: THF) was 10,000 in terms of polystyrene, Mn was 4,000, and Mw/Mn was 2.5. This adhesive resin was referred to as "adhesive resin (D2)".

<Preparation of Pigment Dispersion Containing (B-1) Copolymer>

Modulation example 1

12 parts by mass of a triarylmethane-based lake pigment (wherein x=1 to 2) represented by the following formula (6) as a coloring agent, and 10 parts by mass of a copolymer (B1) solution (nonvolatile content: 40) The mass %), 73 parts by mass of PGMEA as a solvent and 5 parts by mass of propylene glycol monomethyl ether were treated with a bead mill to prepare a pigment dispersion liquid (A-1).

[化10]

Modulation Example 2 to Modification Example 6 and Comparative Modulation Example 1 to Comparative Modulation Example 4

In the preparation example 1, the pigment dispersion liquid (A-2) to the pigment dispersion liquid (A-) was prepared in the same manner as in Preparation Example 1 except that the type of the (B-1) copolymer was changed as shown in Table 2. 10).

Modulation example 7

Using CI Pigment Red 254/CI Pigment Red 177/CI Pigment Red 81:2 as a colorant (oxonium-based lake pigment pigmented with hydrazine molybdate) = 10/70/20 (mass ratio) 12 parts by mass of the mixture, 10 parts by mass of the copolymer (B1) solution (40% by mass of the nonvolatile component), 73 parts by mass of PGMEA as a solvent, and 5 parts by mass of propylene glycol monomethyl ether, which were treated by a bead mill to prepare pigment dispersion. Liquid (A-11).

Modification Example 8, Modulation Example 9 and Comparative Modulation Example 5, Comparative Modulation Example 6

In the same manner as in Preparation Example 7, except that the type of the (B-1) copolymer was changed as shown in Table 2, the pigment dispersion liquid (A-12) to the pigment dispersion liquid (A-) was prepared. 15).

<Preparation and Evaluation of Colored Composition Containing (B-1) Copolymer>

Example 1

100 parts by mass of the pigment dispersion liquid (A-1), 52.9 parts by mass of a binder resin (D2) solution as a binder resin, and MAX-3510 (dipentaerythritol hexaacrylate) manufactured by Nippon Kayaku Co., Ltd. as a crosslinking agent a mixture of dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate as a main component) 32.9 parts by mass of 2-benzyl-2-dimethylamino-1-(4-morpholinobenzene) as a photopolymerization initiator 5.8 parts by mass of butane-1-one (trade name Irgaeure 369, manufactured by Ciba Specialty Chemicals Co., Ltd.) and 205.2 parts by mass of PGMEA as a solvent were mixed to prepare a liquid solution. Coloring composition (S-1).

The obtained coloring composition (S-1) was applied onto a soda glass substrate having a SiO ₂ film on the surface where sodium ions were prevented from eluting using a spin coater, and then prebaked on a hot plate at 90 ° C for 2 minutes. A coating film having a film thickness of 2.5 μm was formed.

Next, after the substrate was cooled to room temperature, radiation of each wavelength including 365 nm, 405 nm, and 436 nm was exposed to each coating film at a exposure amount of 400 J/m ² using a high-pressure mercury lamp through a photomask. . Thereafter, a developing solution containing a 0.04% by mass aqueous potassium hydroxide solution at 23 ° C was sprayed onto the substrate at a developing pressure of 1 kgf/cm ² (nozzle diameter of 1 mm) to carry out shower development for 90 seconds. Thereafter, the substrate was washed with ultrapure water, air-dried, and further post-baked in a clean oven at 200 ° C for 30 minutes to form a dot pattern of 200 μm × 200 μm on the substrate.

Evaluation of heat resistance

For the obtained dot pattern, the color coordinate value (x, y) and the stimulus value (Y) in the CIE color system were measured using a color analyzer (MCPD2000 manufactured by Otsuka Electronics Co., Ltd.) under a C light source and a 2 degree field of view. . Next, the chromaticity coordinate value (x, y) and the stimulating value (Y) after additional baking for 90 minutes at 200 ° C were measured, and the color change before and after the additional baking, that is, ΔE ^* _{ab was} evaluated. The evaluation results are shown in Table 3. Further, the smaller the value of ΔE ^* _ab , the higher the heat resistance.

Solvent resistance evaluation

The substrate on which the blue dot pattern was formed was immersed in N-methylpyrrolidone at 25 ° C for 30 minutes, and the dot pattern before and after the immersion was observed with a scanning electron microscope. When a pattern having a good edge shape and a film thickness ratio before and after immersion (film thickness after immersion × 100 / film thickness before immersion) were 95% or more, the film was evaluated as "○", and the film thickness before and after immersion was measured. When the ratio was less than 95% or the defect was confirmed in a part of the pattern, it was evaluated as "Δ", and the case where the pattern was completely peeled off from the substrate after the immersion was evaluated as "x". The evaluation results are shown in Table 3.

Example 2 to Example 9 and Comparative Example 1 to Comparative Example 6

In the same manner as in Example 1, except that the type of the pigment dispersion liquid was changed as shown in Table 3, the preparation and evaluation of the coloring composition were carried out. The evaluation results are shown in Table 3.

<Including (B-2) dispersing agent having a urethane bond and (B-3) (A) Preparation and evaluation of colored compositions of acrylic dispersants >

Example 10

15 parts by mass of a triarylmethane-based lake pigment (wherein x=1 to 2) represented by the above formula (6) as a coloring agent, as a urethane-based dispersant BYK2164 (non-volatile content: 60% by mass, amine price: 14 mgKOH/g, manufactured by BYK Chemical Co., Ltd.), 8.9 parts by mass, BYK-LPN21116 as a (meth)acrylic dispersant (40% by mass of nonvolatile matter, 1.8 mg parts by mass of an amine, a mass ratio of propylene glycol monomethyl ether acetate / propylene glycol monoethyl ether = 90/10 (mass ratio) as a solvent, the solid content was 20% by mass. The mixture was mixed, and mixed and dispersed in a bead mill for 12 hours to prepare a pigment dispersion liquid (M-1).

Next, 13.5 parts by mass of the pigment dispersion liquid (M-1), 9.9 parts by mass of a binder resin (D1) solution as a binder resin, and M-402 (dipentaerythritol hexaacrylate) manufactured by Toagosei Co., Ltd. as a crosslinking agent a mixture with dipentaerythritol pentaacrylate) 15.4 parts by mass of 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butan-1-one as a photopolymerization initiator (manufactured by Ciba Specialty Chemicals Co., Ltd., trade name: IRGACURE 369) 1.8 parts by mass, 0.2 parts by mass of Megafac F-554 (manufactured by DIC Corporation) as a fluorine-based surfactant, and propylene glycol monomethyl ether acetate as a solvent The ester was mixed to prepare a coloring composition (CR1) having a solid concentration of 20% by mass.

In the first embodiment, the coloring composition (CR1) was used in the same manner as in Example 1 except that the coloring composition (S-1) was used instead of the coloring composition (S-1), and the film thickness was 2.5. Μm coating film.

Next, in the same manner as in Example 1, a dot pattern of 200 μm × 200 μm was formed on the substrate.

The obtained dot pattern was evaluated for heat resistance and solvent resistance in the same manner as in Example 1. The evaluation results are shown in Table 5. In the evaluation of the heat resistance, the case where ΔE _ab * is less than 3.0 is evaluated as "◎", the case of 3.0 or more and less than 5.0 is evaluated as "○", and the case of 5.0 or more and less than 10 is evaluated as "△". ", the case of 10 or more is evaluated as "X".

Example 11 to Example 20, Comparative Example 7 to Comparative Example 10

In the same manner as in Example 10 except that the type and the amount of the coloring agent, the urethane dispersing agent, and the (meth)acrylic dispersing agent were changed as shown in Table 4, the same procedure as in Example 10 was carried out. Pigment dispersion (M-2) ~ pigment dispersion (M-15).

In the same manner as in Example 10 except that the pigment dispersion liquid (M-2) to the pigment dispersion liquid (M-15) was used instead of the pigment dispersion liquid (M-1), the coloring combination was prepared. (CR2) ~ coloring composition (CR15). Further, the obtained coloring composition was evaluated in the same manner as in Example 10. The evaluation results are shown in Table 5.

In Table 4, each component is as follows.

The "PB61" means CI Pigment Blue 61, the so-called "PB15:6" means CI Pigment Blue 15:6, the so-called "PR254" means CI Pigment Red 254, and the so-called "PR81:2" means CI Pigment Red 81: 2 (oxonium type lake pigment which was laked with hydrazine molybdate).

"BYK2164" means Disperbyk-2164 (60% by mass of nonvolatile matter, 14 mgKOH/g of amine, manufactured by BYK Chemical Co., Ltd.), and "BYK164" means Disperbyk-164 (nonvolatile content is 60% by mass) The amine price was 18 mgKOH/g, manufactured by BYK Chemical Co., Ltd., and the "S76500" means Solsperse 76500 (nonvolatile content: 50% by mass, amine price: 15 mgKOH/g, manufactured by Lubrizol Corporation).

"LPN21116" means BYK-LPN21116 (40% by mass of nonvolatile matter, 29 mgKOH/g of amine, manufactured by BYK Chemical Co., Ltd.), and "BYK2000" means Disperbyk-2000 (40% by mass of nonvolatile matter) The amine price was 4 mgKOH/g, manufactured by BYK Chemical Co., Ltd., and "LPN6919" means BYK-LPN6919 (nonvolatile content: 60% by mass, amine price: 72 mgKOH/g, manufactured by BYK Chemical Co., Ltd.).

Claims (12)

A coloring composition comprising (A) a coloring agent comprising a lake pigment, (B) a dispersing agent, and (C) a crosslinking agent, wherein the coloring composition is characterized in that (B) the dispersing agent contains: (B-1) a copolymer comprising a repeating unit having an oxygen-containing saturated heterocyclic group; or a (B-2) dispersing agent having a urethane bond and (B-3) a (meth)acrylic dispersing agent, but In the (B-3) (meth)acrylic dispersant, the (B-1) copolymer is excluded. The colored composition according to claim 1, wherein the (B-1) copolymer further comprises a repeating unit represented by the following formula (1) and a repeating unit represented by the following formula (2); , In the formula (1), R ¹ represents a hydrogen atom or a methyl group, and Z represents -NR ² R ³ or a substituted or unsubstituted nitrogen-containing heterocyclic group, wherein R ² and R ³ independently of each other represent a hydrogen atom. Or a substituted or unsubstituted hydrocarbon group, X ¹ represents a divalent linking group; [Chemical 2] In the formula (2), R ⁴ represents a hydrogen atom or a methyl group, and R ⁵ represents an aliphatic hydrocarbon group or an alicyclic hydrocarbon group. The coloring composition according to claim 2, wherein the upper limit of the amine value of the (B-1) copolymer is 150 mgKOH/g. The coloring composition according to claim 1, wherein: (B-2) mass ratio of the dispersing agent having a urethane bond to the (B-3) (meth)acrylic dispersing agent [(B-2)/(B-3)] is 5/95~95/5. The colored composition according to claim 1, wherein the (B-3) (meth)acrylic dispersant has an amine value of from 1 mgKOH/g to 130 mgKOH/g. The coloring composition of claim 1, wherein the lake pigment is prepared by using a heteropoly acid. The coloring composition according to claim 1, wherein the lake pigment is at least one selected from the group consisting of a triarylmethane-based lake pigment and a xanthene-based lake pigment. The colored composition according to claim 1, wherein the (A) colorant further contains a pigment, but the pigment is excluded from the lake pigment. The coloring composition of claim 1, wherein: Further, (D) a binder resin is contained, but in the (D) binder resin, the (B) dispersant is excluded. A color filter comprising a colored layer formed by using the coloring composition according to any one of claims 1 to 9. A display element comprising the color filter according to claim 10 of the patent application. A pigment dispersion liquid comprising (a1) a lake pigment, (B-1) a copolymer comprising a repeating unit having an oxygen-containing saturated heterocyclic group, and (F) a solvent.