TWI605308B - Coloring composition, color filter and display device - Google Patents

Description

Coloring composition, color filter, and display element

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

When a color filter is produced using a coloring sensitizing radiation composition, it is known to apply a pigment dispersion type color sensitizing radiation linear composition on a substrate, and then irradiate the radiation to make the dried coating film desired. A pattern shape (hereinafter referred to as "exposure") is developed to obtain a pixel of each color (for example, refer to Patent Documents 1 and 2). Further, a method of forming a black matrix by using a photopolymerizable composition in which carbon black is dispersed is also known (for example, see Patent Document 3). In addition, a method of obtaining a pixel of each color by an inkjet method using a pigment-dispersed colored thermosetting composition is known (for example, see Patent Document 4).

Further, in order to achieve high luminance and high color purity of the display element or high definition of the solid-state imaging device, it is known to use a dye as a colorant. However, when a dye is used as a coloring agent, there is a problem that heat resistance, light resistance, and the like are poor. Therefore, for example, in Patent Document 5, use of a lake pigment which has been subjected to dyeing of a dye is proposed.

Prior technical literature Patent literature

Patent Document 1 JP-A-2-144502

Patent Document 2 Japanese Patent Publication No. 3-53201

Patent Document 3, JP-A-6-35188

Patent Document 4, JP-A-2000-310706

Patent Document 5, JP-A-2001-081348

However, the color filter is manufactured by heating, post-development heating (post-baking) or polyimine alignment film formation, which is usually performed by a heating step of more than 200 ° C, even if a lake pigment is used. In the heating step of high temperature, there is also a problem that the reduction in chromaticity characteristics cannot be avoided.

Therefore, an object of the present invention is to provide a coloring composition and a color filter which can be exhibited without losing the excellent chromaticity characteristics of a dye or a lake pigment even after a high-temperature heating step. Furthermore, an object of the present invention is to provide a display element including the color filter.

As a result of intensive review by the present inventors, it has been found that the above problems can be solved by using a dye or a lake pigment together with a specific polymer.

That is, the present invention provides a coloring composition characterized by comprising: (A) at least one coloring agent selected from the group consisting of a dye and a lake pigment, and (B) having an ethylenic unsaturated group selected from the group consisting of having a sulfo group. a monomer, a group of ethylenically unsaturated monomers having a phosphinomethoxy group, and a salt thereof A polymer of a repeating unit (hereinafter also referred to as "specific polymer") and (C) a crosslinking agent.

Moreover, the present invention provides a color filter comprising a colored layer comprising: at least one coloring agent selected from the group consisting of a dye and a lake pigment, a specific polymer; and a display element It has the color filter. Here, the "colored layer" means a color pixel, a black matrix, a black spacer, or the like which is used for a color filter.

According to the present invention, it is possible to provide a coloring composition which can be exerted without losing the excellent chromaticity characteristics of the dye or the lake pigment even after a high-temperature heating step.

Therefore, the coloring composition of the present invention can be suitably applied to a color filter for a color liquid crystal display element, a color filter for color separation of a solid-state image sensor, a color filter for an organic EL display element, and color for electronic paper. The production of various color filters led by filters.

[Formation of the Invention]

Hereinafter, the present invention will be described in detail.

Coloring composition

Hereinafter, the constituent components of the colored composition of the present invention will be described.

- (A) colorant -

The coloring composition of the present invention contains (A) at least one selected from the group consisting of a dye and a lake pigment as a colorant. Here, the lake pigment refers to a pigment which makes the soluble dye insoluble by the precipitating agent. As the precipitating agent, for example, barium chloride, calcium chloride, ammonium sulfate, aluminum chloride, aluminum acetate, lead acetate, tannic acid, catanol, Tamol, homologue may be mentioned. A polymeric acid, a complex heteropolymeric acid called a complex acid, or the like. Examples of the homopolymeric acid include, for example, homopolymeric tungstic acid, homologously polymerized vanadic acid, and homologously polymerized molybdic acid, and examples of the complex heteropolymeric acid include phosphotungstic acid, phosphomolybdic acid, and phosphorus. Tungsten ‧ molybdic acid, lanthanum tungsten molybdate, tungstic acid, lanthanum molybdate Among these, as the precipitating agent, a homopolymeric acid or a complex heteropolymeric acid is preferred.

The dye which is also contained in the raw material of the lake pigment is not particularly limited, and a suitable dye such as an acid dye, a basic dye, an oil-soluble dye or a direct dye can be used. In the present invention, the use of a laked alkaline lake pigment of a basic dye and/or a basic dye together with a specific polymer is preferred in that the desired effect can be more remarkably obtained. In the present invention, the dye and the lake pigment may be used singly or in combination of two or more kinds, and the dye may be used in combination with a lake pigment.

The above-mentioned basic dye is an ionic dye in which a cationic portion is a chromophore, and for example, Dye, Dye, thio Dyes, azo dyes, anthraquinone dyes, xanthene dyes, diarylmethane dyes, triarylmethane dyes, phthalocyanine dyes, ketimine dyes, thiazole dyes, acridine systems Dyes, quinoline dyes, cyanine dyes, methine dyes, and the like. Specifically, the following color index (CI) name can be cited.

CI alkaline red 2, CI alkaline red 5, CI alkaline red 8, etc. Dye; CI Basic Blue 3, CI Basic Blue 12, CI Basic Blue 49, CI Basic Blue 75, CI Basic Blue 87, CI Basic Blue 101, CI Basic Blue 104, CI Basic Blue 122 , CI alkaline blue 124, CI alkaline blue 151, CI alkaline blue 153, etc. Dyes; CI basic blue 9, CI alkaline blue 17, CI alkaline blue 24, CI alkaline green 5, etc. Dye dye; CI alkaline red 18, CI alkaline red 22, CI alkaline red 29, CI alkaline red 30, CI alkaline red 39, CI alkaline red 41, CI alkaline red 46, CI alkaline red 55 , CI alkaline red 60, CI alkaline red 72, CI alkaline red 73, CI alkaline red 76, CI alkaline red 78, CI alkaline red 79, CI alkaline red 80, CI alkaline red 81, CI Basic red 84, CI alkaline red 95, CI alkaline red 100, CI alkaline red 101, CI alkaline red 102, CI alkaline red 104, CI alkaline red 109, CI alkaline red 113, CI alkaline Red 114, CI Basic Blue 38, CI Basic Blue 40, CI Basic Blue 41, CI Basic Blue 42, CI Basic Blue 53, CI Basic Blue 54, CI Basic Blue 66: 1, CI Alkaline Blue 102, CI Basic Blue 103, CI Basic Blue 118, CI Basic Blue 119, CI Basic Blue 136, CI Basic Blue 137, CI Basic Blue 142, CI Basic Blue 146, CI Basic Blue 159 , CI alkaline yellow 15, CI alkaline yellow 24, CI alkaline yellow 25, CI alkaline yellow 32, CI alkaline yellow 36, CI alkaline yellow 41, CI alkaline yellow 73, CI alkaline yellow 80, CI An azo dye such as alkaline orange 24; CI basic blue 22, CI basic blue 94, CI basic blue 115, CI basic blue 120, CI basic blue 123, CI basic blue 150, etc. Dye; CI alkaline red 1, CI alkaline 1:1, CI alkaline red 3, CI alkaline red 4, CI alkaline red 108, CI alkaline purple 10, CI alkaline purple 11, CI alkaline purple 11:1, etc. Sexual blue 50, CI basic blue 77 and other diaryl methane dyes; CI basic red 9, CI alkaline red 77, CI alkaline blue 1, CI alkaline blue 2, CI basic blue 5, CI alkali Sex Blue 7, CI Alkaline Blue 8, CI Alkaline Blue 11, CI Alkaline Blue 18, CI Basic Blue 23, CI Basic Blue 26, CI Basic Blue 36, CI Basic Blue 55, CI Basic Blue 56, CI alkaline blue 89: 1, CI alkaline blue 112, CI alkaline blue 121, CI alkaline blue 130, CI alkaline blue 158, CI alkaline green 1, CI alkaline green 4, CI alkaline purple 1, CI alkaline violet 2, CI alkaline violet 3, CI alkaline violet 4, CI alkaline violet 14 and other triarylmethane dyes; CI alkaline blue 33, CI alkaline blue 82, CI alkaline blue 100 , CI Basic Blue 126, CI Basic Blue 138, CI Basic Blue 140, CI Basic Blue 157, CI Basic Blue 160, CI Basic Blue 161, CI Basic Blue 163, CI Basic Blue 164, etc. Indigo cyanine dye; ketimine dye of CI basic yellow 2; thiazole dye of CI basic yellow 1; CI basic yellow 4, CI basic yellow 8, CI alkaline yellow 9, etc. Pyridine dye; CI basic yellow 31, C I quinoline dyes such as basic yellow 98; CI basic red 12, CI basic red 14, CI basic yellow 13, CI alkaline purple 7, CI alkaline orange 21, CI alkaline orange 24, etc. Cyan dye; CI alkaline red 13, CI alkaline red 27, CI alkaline red 37, CI alkaline red 49, CI alkaline red 53, CI alkaline red 88, CI alkaline red 90, CI alkaline red 93, CI alkaline red 98, CI alkaline red 99, CI alkaline red 105, CI alkaline blue 110, CI alkaline blue 111, CI alkaline blue 134, CI alkaline blue 145, CI alkaline yellow 11, A sub-methyl dye such as CI basic yellow 13, CI basic yellow 21, CI basic yellow 23, CI basic yellow 28, CI basic yellow 51, CI basic violet 16, and the like.

In addition, Japanese Patent Publication No. 2007-503477, International Publication No. 09/107734, International Publication No. 10/123071, Special Publication No. 2010-32999, and JP-A-2011-7847, etc. The basic dyes are described.

Further, examples of the basic lake pigment include those having the following color index (C.I.).

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, etc. 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 24, Pigment Blue 24:1, C.1. Pigment Blue 56, CI Pigment blue 61, CI pigment blue 62, CI pigment violet 3, CI pigment violet 3:1, CI pigment violet 3:3, CI pigment violet 27, CI pigment violet 39, CI pigment green 1, CI pigment green 4, etc. Methane-based lake pigment.

Examples of the dye other than the basic dye include the following color index (C.I.).

CI Acid Yellow 11, CI Acid Orange 7, CI Acid Red 37, CI Acid Red 180, CI Acid Blue 29, CI Solvent Red 89, CI Direct Red 28, CI Direct Red 83, CI Direct Yellow 12, CI Direct Orange 26, CI Direct Green 28, CI Direct Green 59, CI Reactive Yellow 2, CI Reactive Red 17, CI Reactive Red 120, CI Disperse Orange 5, CI Disperse Red 58, CI Disperse Blue 165, CI Basic Blue 41, CI Azo dyes such as mordant red 7 and CI mordant yellow 5; CI Indigo 4, CI Acid Blue 40, CI Acid Green 25, CI Reactive Blue 19, CI Reactive Blue 49, CI Disperse Red 60, CI Disperse Blue 56, CI disperse blue 60 and other lanthanide dyes; CI paddy blue 5 and other phthalocyanine dyes; CI solvent yellow 33, CI acid yellow 3, CI disperse yellow 64 and other quinoline dyes; CI acid yellow 1. A nitro-based dye such as CI Acid Orange 3, CI Disperse Yellow 42, or a methine dye such as CI Solvent Yellow 179.

In addition, Japanese Patent Application Laid-Open No. 2010-168531, No. 3, No. 4, No. 2010-170073, No. 2010-170074, and No. 2010-275531 An azo dye described in JP-A-2010-275533 or the like.

Further, examples of the lake pigment other than the basic lake pigment include the following color index (C.I.).

C.I. Pigment Red 48:1, C.I. Pigment Red 48:2, C.I. Pigment Red 48:3, C.I. Pigment Red 48:4, C.I. Pigment Red 48:5, C.I. 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 Yellow 61, CI Pigment Yellow 61:1, CI Pigment Yellow 62, CI Pigment Red 64:1, CI Pigment Red 68, CI Pigment Red 247, CI Pigment Red 200, CI Pigment Yellow 100, CI Pigment Yellow 104, CI Pigment Yellow 133, CI Pigment Yellow 168, CI Pigment Yellow 169, CI Pigment Yellow 183, CI Pigment Yellow 191, CI Pigment Yellow 191:1 Such as azo-based lake pigment; CI pigment blue 17:1 and other phthalocyanine lake pigments.

In the present invention, as the coloring agent, other coloring agents may be used together with the dye and the lake pigment. The other coloring agent is not particularly limited, and the color or material can be appropriately selected in accordance with the use of the color filter. Specifically, any of the pigments other than the lake pigment and the natural pigment may be used, but in the coloring layer constituting the color filter, from the viewpoints of high color purity, brightness, contrast, light blocking property, etc., Good use of pigments.

The pigment is preferably an organic pigment, and specific examples thereof include CI Pigment Red 166, CI Pigment Red 177, CI Pigment Red 224, CI Pigment Red 242, and CI Pigment Red 254 having an excellent index (CI) name. CI Pigment Green 7, CI Pigment Green 36, CI Pigment Green 58, CI Pigment Blue 15: 6, CI Pigment Blue 80, CI Pigment Yellow 83, CI Pigment Yellow 138, CI Pigment Yellow 139, CI Pigment Yellow 150, CI Pigment Yellow 180, CI Pigment Yellow 211, CI Pigment Orange 38, CI Pigment Violet 23, and the like.

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

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

In the present invention, when a pigment is used as the colorant, it may be used together with a dispersing agent or a dispersing aid as desired. As the dispersing agent, for example, a suitable dispersing agent such as a cationic type, an anionic type or a nonionic type can be used, but a polymer dispersing agent is preferable. Specific examples thereof include a urethane dispersant, a polyethyleneimine dispersant, a polyoxyethylene alkyl ether dispersant, a polyoxyethylene alkyl phenyl ether dispersant, and polyethylene glycol II. An ester-based dispersant, a sorbitan fatty acid ester-based dispersant, a polyester-based dispersant, an acrylic dispersant, and the like.

Such a dispersing agent can be obtained commercially, for example, as an acrylic dispersing agent, and examples thereof include Disperbyk-2000, Disperbyk-2001, BYK-LPN6919, BYK-LPN21116, BYK-LPN21324 (above, trade name, BYK chemistry (BYK) Co., Ltd., as a urethane dispersant, may include Disperbyk-161, Disperbyk-162, Disperbyk-165, Disperbyk-167, Disperbyk-170, Disperbyk-182 (above, trade name, BYK Chemistry ( As a polyethyleneimine-based dispersant, Solsperse 24000 (trade name, manufactured by LUBRIZOL Co., Ltd.), as a polyester system, is available as a polyester-based dispersant. Examples of the dispersing agent include Ajisper PB821, Ajisper PB822, Ajisper PB880, and Ajisper PB881 (the above are trade names, manufactured by Ajinomoto Precision Technology Co., Ltd.).

In addition, examples of the dispersing aid include a pigment derivative, and specific examples thereof include a copper phthalocyanine, a diketopyrrolopyrrole, and a sulfonic acid derivative of quinacone. Further, the content of the dispersing agent and the dispersing aid can be appropriately determined within the range not impairing the object of the present invention.

- (B) specific polymer -

The colored composition of the present invention is characterized by containing a specific polymer, i.e., having a group selected from the group consisting of ethylenically unsaturated monomers having a sulfo group, ethylenically unsaturated monomers having a phosphinomethoxy group, and salts thereof. A polymer of at least one repeating unit (hereinafter also referred to as "repeating unit (b1)"). In the coloring composition, a polymer having a carboxyl group is usually used, but the present inventors considered that a polymer having a sulfo group, a phosphinomethoxy group or a salt form having a higher acidity than a carboxyl group has a carboxyl group. The polymer, particularly in interaction with a basic dye, protects the dye molecules to improve heat resistance, and achieves the present invention.

In the repeating unit (b1), the repeating unit derived from the ethylenically unsaturated monomer having a sulfo group is not particularly limited as long as it has a sulfo group, and examples thereof include the following formulas (1) to (4). ) The repeating unit shown.

[In the formula (1), R ¹ represents a hydrogen atom or a methyl group, R ² represents a single bond or a divalent aliphatic hydrocarbon group or an alicyclic hydrocarbon group which may have a substituent, and X represents a single bond, -COO-(* ¹ ) Or -CONH-(* ¹ ), (* ¹ ) represents a bond to the R ² bond].

[In the formula (2), R ¹ represents a hydrogen atom or a methyl group, and Y represents a single bond, -CH ₂ O-(* ² ), -COO-(* ² ), -CONH-(* ² ), -COO- R ³ -O-(* ² ) or -CONH-R ³ -O-(* ² ) (R ³ represents a divalent aliphatic hydrocarbon group or an alicyclic hydrocarbon group which may have a substituent), and ring A represents a phenyl group or The naphthyl group, (* ² ) represents a bond to the ring A bond].

[In the formula (3), R ⁴ represents an alkanediyl group which may have a substituent, R ⁵ represents a monovalent hydrocarbon group which may contain an oxygen atom, and n represents an integer of from 1 to 30].

[In the formula (4), R ¹ represents a hydrogen atom or a methyl group, R ⁶ represents an alkanediyl group which may have a substituent, R ⁷ represents a monovalent hydrocarbon group, and m represents an integer of 1 to 50].

First, the definition of the symbols in the above formulas (1) to (4) will be described.

R ¹ represents a hydrogen atom and a methyl group.

R ² represents a single bond or a divalent aliphatic hydrocarbon group or an alicyclic hydrocarbon group which may have a substituent. The divalent aliphatic hydrocarbon group is preferably an alkanediyl group, and may be linear or branched. The carbon number of the divalent aliphatic hydrocarbon group is preferably from 1 to 12, particularly preferably from 1 to 6. Specifically, a methylene group, an ethane-1,1-diyl group, an ethane-1,2-diyl group, a propane-1,1-diyl group, a propane-1,2-diyl group, a propane- 1,3-diyl, propane-2,2-diyl, butane-1,2-diyl, butane-1,3-diyl, butane-1,4-diyl, pentane-1 , 4-diyl, pentane-1,5-diyl, hexane-1,5-diyl, hexane-1,6-diyl, 2-methylpropane-1,2-diyl and the like. Further, as the divalent alicyclic hydrocarbon group, a cycloalkyl group is preferred. The carbon number of the divalent alicyclic hydrocarbon group is preferably from 3 to 8, particularly preferably from 3 to 6. Specifically, a cyclopentylene group, a cyclohexylene group, and the like can be given. In addition, the divalent aliphatic hydrocarbon group and the alicyclic hydrocarbon group may have a substituent, and examples of the substituent include a halogen atom, a hydroxyl group, and an alkoxy group. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. The alkoxy group is preferably an alkoxy group having 1 to 6 carbon atoms, and specific examples thereof include a methoxy group, an ethoxy group, a propoxy group, and an isopropoxy group. Among them, as the substituent, a halogen atom or a hydroxyl group is preferred. Further, the position and number of the substituent are arbitrary, and when two or more substituents are contained, the substituents may be the same or different.

Among these, R ^{2 is} preferably a single bond or a divalent aliphatic hydrocarbon group which may have a substituent, and particularly preferably a single bond or an alkyl 2 group which may have a substituent.

R ³ represents a divalent aliphatic hydrocarbon group or an alicyclic hydrocarbon group which may have a substituent, and may be the same as the "divalent aliphatic hydrocarbon group or alicyclic hydrocarbon group which may have a substituent" in the above R ² . Among them, R ^{3 is} preferably a divalent aliphatic hydrocarbon group which may have a substituent, and particularly preferably an alkanediyl group which may have a substituent. The substituent is preferably a halogen atom or a hydroxyl group.

R ⁴ and R ^{6 each} represent an alkanediyl group which may have a substituent, and may be the same as the alkanediyl group in the above R ² . Among them, R ⁴ and R ^{6 are} preferably an alkanediyl group having 1 to 6 carbon atoms, particularly preferably an ethane-1,2-diyl group or a propane-1,2-diyl group. Examples of the substituent include a halogen atom and a hydroxyl group.

R ⁵ represents a monovalent hydrocarbon group which may contain an oxygen atom, and examples of the monovalent hydrocarbon group include (i) an aliphatic hydrocarbon group, (ii) an alicyclic hydrocarbon group, and (iii) an aliphatic group having an alicyclic hydrocarbon group as a substituent. Hydrocarbyl group (hereinafter referred to as "alicyclic hydrocarbon-substituted aliphatic hydrocarbon group"), (iv) aromatic hydrocarbon group, (v) aromatic hydrocarbon group having an aliphatic hydrocarbon group as a substituent (hereinafter referred to as "aliphatic hydrocarbon-substituted aromatic hydrocarbon group" And (vi) an aliphatic hydrocarbon group having an aromatic hydrocarbon group as a substituent (hereinafter referred to as "aromatic hydrocarbon-substituted aliphatic hydrocarbon group").

The (i) aliphatic hydrocarbon group is preferably an alkyl group and may be linear or branched. The carbon number of the aliphatic hydrocarbon group is preferably from 1 to 20, particularly preferably from 1 to 12. Specific examples thereof include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a decyl group, a decyl group, an eleven group, a dodecyl group and the like. As the (ii) alicyclic hydrocarbon group, a cycloalkyl group is preferred. The alicyclic hydrocarbon group preferably has a carbon number of from 3 to 20, particularly preferably from 3 to 12. Specific examples thereof include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a tert-butylcyclohexyl group and the like. Further, as the (iii) alicyclic hydrocarbon-substituted aliphatic hydrocarbon group, an alicyclic saturated hydrocarbon-substituted alkyl group is preferred, and the alkyl group may be linear or branched. The carbon number of the alicyclic hydrocarbon-substituted aliphatic hydrocarbon group is preferably from 4 to 20, particularly preferably from 6 to 14. Specifically, a cyclohexylmethyl group, a cyclohexylethyl group, etc. are mentioned. The (iv) aromatic hydrocarbon group preferably has a carbon number of 6 to 14, and particularly preferably 6 to 10. Specifically, a phenyl group, a naphthyl group, etc. are mentioned. The (v) aliphatic hydrocarbon-substituted aromatic hydrocarbon group is preferably an alkyl-substituted phenyl group, and the alkyl moiety may be linear or branched. fat The carbon number of the aliphatic hydrocarbon-substituted aromatic hydrocarbon group is preferably from 7 to 30, particularly preferably from 7 to 20. Specific examples thereof include a tolyl group, a xylyl group, an ethylphenyl group, an isopropylphenyl group, and a nonylphenyl group. Further, as the (vi) aromatic hydrocarbon-substituted aliphatic hydrocarbon group, an aralkyl group is preferred. The aromatic ring of the aralkyl group may have an alkyl group (hereinafter also referred to as "alkyl-substituted aralkyl group"). The alkyl group may be linear or branched, and its carbon number is preferably from 1 to 20, particularly preferably from 1 to 12. The total carbon number of the aromatic hydrocarbon-substituted aliphatic hydrocarbon group is preferably from 7 to 30, particularly preferably from 7 to 20. Specific examples of the aralkyl group include a benzyl group and a phenethyl group. Specific examples of the alkyl-substituted aralkyl group include ethylphenethyl, butylphenethyl and nonylphenylethyl. Wait.

Further, among the monovalent hydrocarbon groups, -CH ₂ - constituting the hydrocarbon group may be substituted by -O-, and examples thereof include an alkoxyalkyl group, a phenoxyalkyl group, and an alkyl-substituted phenoxyalkylene group. Alkyl, aralkyloxyalkyl, alkyl-substituted aralkyloxyalkyl, and the like.

Among these, as R ⁵ , an (i) aliphatic hydrocarbon group and (vi) an aromatic hydrocarbon-substituted aliphatic hydrocarbon group are preferred, and an alkyl group, an alkoxyalkyl group or an alkyl-substituted aralkyl group is particularly preferred. Phenoxyalkyl, alkyl substituted phenoxyalkyl, aralkyloxyalkyl, alkyl substituted aralkyloxyalkyl.

R ⁷ represents a monovalent hydrocarbon group, and the monovalent hydrocarbon group is the same as the "monovalent hydrocarbon group" in the above R ⁵ . Among them, R ^{7 is} preferably an (i) aliphatic hydrocarbon group, and particularly preferably an alkyl group, from the viewpoint of chromaticity characteristics.

X represents a single bond, -COO-(* ¹ ) and -CONH-(* ¹ ), and can be suitably selected in combination with R ² . Here, (* ¹ ) represents a bond bonded to R ² .

Y represents a single bond, -CH ₂ O-(* ² ), -COO-(* ² ), -CONH-(* ² ), -COO-R ³ -O-(* ² ) or -CONH-R ³ - O-(* ² ), from the viewpoint of chromaticity characteristics, preferably a single bond, -CH ₂ O-(* ² ), -COO-R ³ -O-(* ² ), -CONH-R ³ -O-(* ² ). Here, (* ² ) represents a bond bonded to ring A, and ring A is a phenyl or naphthyl group.

n represents an integer from 1 to 30, preferably an integer from 5 to 20.

m represents an integer of 1 to 50, preferably an integer of 10 to 50.

Specific examples of the repeating unit represented by the above formula (1) include repeating units represented by the following formulas (1-1) to (1-7).

[In the above formulae (1-1) to (1-6), R ¹ is synonymous with R ¹ in the above formula (1)].

In addition, specific examples of the repeating unit represented by the above formula (2) include repeating units represented by the following formulas (2-1) to (2-6).

[In the above formulae (2-1) to (2-6), R ¹ is synonymous with R ¹ in the above formula (2)].

Specific examples of the repeating unit represented by the above formula (3) include repeating units represented by the following formulas (3-1) to (3-2).

The monomer to which the repeating unit of the above formula (3-1) to (3-2) is supplied is commercially available, and examples thereof include Adeka Reasoap SE-10N and Adeka Reasoap SR-10 (the above are trade names, Asahi Amadeon KH-10 (trade name, manufactured by Daiichi Kogyo Co., Ltd.), etc.

Specific examples of the repeating unit represented by the above formula (4) include a repeating unit represented by the following formula (4-1). A monomer supplied to such a repeating unit, for example, Aqualon HS-40 (trade name, manufactured by Dai-Il Pharmaceutical Co., Ltd.), is commercially available.

[In the above formula (4-1), R ¹ is synonymous with R ¹ in the above formula (4)].

The repeating unit derived from the ethylenically unsaturated monomer having a phosphinomethoxy group is not particularly limited as long as it has a phosphinomethoxy group, and examples thereof include a repeating unit represented by the following formula (5).

[In the formula (5), R ¹ represents a hydrogen atom or a methyl group, R ⁸ represents an alkanediyl group which may have a substituent, and r represents an integer of 1 to 20].

In the above formula (5), a hydrogen atom or a methyl group is represented.

R ⁸ is the same as the above-mentioned alkanediyl group in R ² . Among them, R ^{8 is} preferably a C 1 to 6 alkanediyl group which may have a substituent, and particularly preferably an ethane-1,2-diyl group or a propane-1,2-diyl group which may have a substituent. . The substituent is preferably a halogen atom or a hydroxyl group.

r represents an integer of 1 to 20, but is preferably an integer of 1 to 10, more preferably an integer of 1 to 6.

In addition, specific examples of the repeating unit represented by the above formula (5) include repeating units represented by the following formulas (5-1) to (5-5).

[The above formulas (5-1) to (5-5), R ¹ is the above-described system of the formula (5) R ¹ is synonymous].

Examples of the cation in the salt of the ethylenically unsaturated monomer having a sulfo group or a phosphiniumoxy group include an alkali metal cation, an ammonium cation, a mono-, di-, tri- or tetraalkylammonium cation, a pyridinium cation, and an alkyl group. Instead of a pyridinium cation, a 1-alkylpyridinium cation or the like. The number of carbon atoms of the alkyl moiety constituting the cation is preferably from 1 to 20, particularly preferably from 1 to 12. Among them, an ammonium cation or a pyridinium cation is preferred from the viewpoint of enhancing the desired effect.

Among the specific polymers, it is preferred to have other repeating units (b2) together with the repeating unit (b1). The other repeating unit (b2) is not particularly limited, and examples thereof include repeating units derived from the following ethylenically unsaturated monomers.

Examples thereof include (meth)acrylic acid, maleic acid, maleic anhydride, mono[2-(methyl)acryloxyethylethyl succinate, and ω-carboxypolycaprolactone mono(meth)acrylic acid. An ethylenically unsaturated monomer having a carboxyl group of an ester or a p-vinylbenzoic acid; for example, an N-position substituted maleimide of N-phenylmaleimide or N-cyclohexylmaleimide; Styrene, α-methylstyrene, p-hydroxystyrene, p-hydroxy-α-methylstyrene, p-vinylbenzylepoxypropyl ether, terpene aromatic vinyl compound; such as (methyl) Methyl acrylate, n-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, allyl (meth)acrylate, (meth)acrylic acid Benzyl ester, polyethylene glycol (degree of polymerization 2~10) methyl ether (meth) acrylate, polypropylene glycol (degree of polymerization 2~10) methyl ether (meth) acrylate, polyethylene glycol (degree of polymerization) 2~10) mono (meth) acrylate, polypropylene glycol (degree of polymerization 2~10) mono (meth) acrylate, cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, tricyclic [ 5.2.1.0 ^2,6] dec-8-yl (meth) acrylate, (meth Dicyclopentyl acrylate, glycerol mono(meth) acrylate, 4-hydroxyphenyl (meth) acrylate, ethylene oxide modified (meth) acrylate of p-cumyl phenol, (a) Glycidyl acrylate, 3,4-epoxycyclohexylmethyl (meth)acrylate, 3-[(meth)acryloxymethyl]propene oxide, 3-[(methyl) (meth) acrylate of propylene methoxymethyl]-3-ethyl propylene oxide; such as cyclohexyl vinyl ether, isobornyl vinyl ether, tricyclo [5.2.1.0 ^2,6 ] decane- 8-vinyl vinyl ether, pentacyclopentadecyl vinyl ether, vinyl ether of 3-(vinyloxymethyl)-3-ethyl propylene oxide; such as polystyrene, poly(methyl) acrylate A macromonomer having a mono(meth)acrylonitrile group at the end of the polymer molecular chain, such as an ester, n-butyl poly(meth)acrylate, or polyoxyalkylene.

Among the specific polymers, the other repeating units (b2) may be used alone or in combination of two or more.

In the specific polymer, the copolymerization ratio of the repeating unit (b1) is in all the repeating units, preferably from 1 to 30% by mass, more preferably from 1 to 20% by mass, particularly preferably from 1 to 15% by mass. When the copolymerization ratio of the repeating unit (b1) is too small, the desired effect is not obtained, and if it is too large, the patterning property at the time of alkali development is lowered.

The weight average molecular weight (Mw) in terms of polystyrene measured by GPC (dissolving solvent: tetrahydrofuran) of the specific polymer is preferably from 1,000 to 100,000, more preferably from 3,000 to 50,000. When the Mw is too small, the coating property is lowered. On the other hand, if it is too large, the patterning property at the time of alkali development is lowered.

Further, the ratio (Mw/Mn) of the weight average molecular weight of the specific polymer to the number average molecular weight (Mn) in terms of polystyrene measured by GPC (solvent solvent: tetrahydrofuran) is preferably 1.0 to 5.0, more preferably It is 1.0~3.0.

The specific polymer may be produced by, for example, radically polymerizing a monomer or the like supplied to the repeating unit (b1), but may be controlled by a living radical polymerization method, a living anionic polymerization method, a living cationic polymerization method, or the like. The residual amount of Mw/Mn or unreacted monomer. Further, a star-shaped polymer may be formed by radical polymerization in the presence of a trifunctional or higher polyvalent mercaptan.

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

In the coloring composition of the present invention, a polymer having no repeating unit (b1) can be contained together with a specific polymer, whereby adhesion to a substrate, alkali developability, and storage stability can be improved. As such a polymer, a polymer having a carboxyl group is preferred.

Specific examples of the polymer having a carboxyl group include JP-A-5-19467, JP-A-6-230212, JP-A-7-140654, JP-A-7-207211, and JP-A 8-259876 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. The polymer disclosed in JP-A-2000-56118, JP-A-2002-296778, JP-A-2004-101728, JP-A-2008-181095, and the like.

In the present invention, the polymer having no repeating unit (b1) may be used alone or in combination of two or more.

In the present invention, the content of the specific polymer is usually 10 to 1,000 parts by mass, preferably 20 to 500 parts by mass, per 100 parts by mass of the (A) colorant. If the content of the specific polymer is too small, the desired effect may not be obtained. On the other hand, if the content is too large, the patterning property during alkali development may be lowered.

When the polymer having no repeating unit (b1) is used, the content thereof is preferably from 10 to 1,000 parts by mass, particularly preferably from 20 to 500 parts by mass, per 100 parts by mass of the (A) coloring agent. By containing a polymer having no repeating unit (b1) in such a content ratio, a coloring composition excellent in adhesion to a substrate, alkali developability, and storage stability can be obtained.

-(C) Crosslinker -

The colored composition of the present invention contains (C) a crosslinking agent. The (C) crosslinking agent in the present invention means a compound having two or more polymerizable groups. Examples of the polymerizable group include an ethylenically unsaturated group, an epoxy group, an oxypropylene group, and an N-alkoxymethylamino group. In the present invention, as the (C) crosslinking agent, a compound having two or more (meth)acryl fluorenyl groups and/or a compound having two or more N-alkoxymethylamino groups is preferably used.

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. a lactone-modified polyfunctional (meth) acrylate, an alkylene oxide-modified polyfunctional (meth) acrylate, a (meth) acrylate having a hydroxyl group and a polyfunctional isocyanate A polyfunctional urethane (meth) acrylate obtained by reacting an acid ester, a polyfunctional (meth) acrylate having a carboxyl group obtained by reacting a (meth) acrylate having a hydroxyl group with an acid anhydride, or the like.

Here, examples of the aliphatic polyhydroxy compound include divalent aliphatic polyhydroxy compounds such as ethylene glycol, propylene glycol, polyethylene glycol, and polypropylene glycol, such as glycerin, trimethylolpropane, pentaerythritol, and An aliphatic polyhydroxy compound having a trivalent or higher valence of pentaerythritol. Examples of the (meth) acrylate having a hydroxyl group include 2-hydroxyethyl (meth)acrylate, trimethylolpropane di(meth)acrylate, pentaerythritol tri(meth)acrylate, and Pentaerythritol penta (meth) acrylate, glycerin dimethacrylate, and the like. Examples of the polyfunctional isocyanate include tolylene diisocyanate, hexamethylene diisocyanate, diphenylmethylene diisocyanate, and isophorone diisocyanate. Examples of the acid anhydride include anhydrides of dibasic acids such as succinic anhydride, maleic anhydride, glutaric anhydride, itaconic anhydride, phthalic anhydride, and hexahydrophthalic anhydride, such as pyromellitic anhydride and biphenyl. Tetracarboxylic acid dianhydride of tetracarboxylic dianhydride and diphenyl ketone tetracarboxylic dianhydride.

In addition, the compound described in paragraphs [0015] to [0018] of JP-A-11-44955 is exemplified as the above-mentioned caprolactone-modified polyfunctional (meth) acrylate. Examples of the above-mentioned alkylene oxide-modified polyfunctional (meth)acrylate include ethylene oxide and/or propylene oxide-modified di(meth)acrylate of bisphenol A and isomeric cyanuric acid. Ethylene oxide and/or propylene oxide modified tri(meth)acrylate, trimethylolpropane ethylene oxide and/or propylene oxide modified tri(meth)acrylate, pentaerythritol ring Oxyethane and/or propylene oxide modified tris(meth)acrylic acid Ethylene oxide and/or propylene oxide-modified tetra(meth)acrylate of ester, pentaerythritol, ethylene oxide and/or propylene oxide-modified penta(meth)acrylate, dipentaerythritol of dipentaerythritol Ethylene oxide and/or propylene oxide modified hexa(meth)acrylate.

In addition, examples of the compound having two or more N-alkoxymethylamino groups include a compound having a melamine structure, a benzoguanamine structure, and a urea structure. Furthermore, the so-called melamine structure and benzoguanamine structure means that there are one or more three Ring or phenyl substituted three The chemical structure of the ring as a basic skeleton also includes the concept of melamine, benzoguanamine or their condensate. 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, and a polycaprolactone-modified polyfunctional ( Methyl) acrylate, polyfunctional urethane (meth) acrylate, polyfunctional (meth) acrylate having carboxyl group, N, N, N', N', N", N"-six ( Alkoxymethyl)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 on the substrate of the unexposed portion and the light-shielding layer, it is less likely to cause stains and film residues, and the trivalent or higher aliphatic polyhydroxy compound is Among the polyfunctional (meth) acrylates obtained by the reaction of (meth)acrylic acid, trimethylolpropane triacrylate, pentaerythritol triacrylate, dipentaerythritol pentaacrylate, and the like are particularly preferred. Dipentaerythritol hexaacrylate; in a polyfunctional (meth) acrylate having a carboxyl group, particularly preferably a compound obtained by reacting pentaerythritol triacrylate with succinic anhydride, and reacting dipentaerythritol pentaacrylate with succinic anhydride 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 to 1,000 parts by mass, particularly preferably 20 to 500 parts by mass, per 100 parts by mass of the (A) coloring agent. At this time, if the content of the crosslinking agent is too small, sufficient curability may not be obtained. On the other hand, when the content of the crosslinking agent is too large, when the alkali developability is imparted to the colored composition of the present invention, the alkali developability is lowered, and the substrate is not easily exposed on the unexposed portion or on the light shielding layer. The tendency of stains, film residues, etc.

-(D) Photopolymerization Initiator -

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

Examples of such a photopolymerization initiator include a thioxanthone compound, an acetophenone compound, a bisimidazole compound, and the like. Compound, O-mercapto oxime compound, sulfonium salt compound, benzoin compound, diphenyl ketone compound, α-diketone compound, polynuclear oxime compound, diazo compound, iminosulfonate An acid ester compound, a phosphonium salt 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 a thioxanthone compound, an acetophenone compound, a biimidazole compound, or the like. At least one selected from the group consisting of a compound and an O-mercapto lanthanide compound.

Among the preferred photopolymerization initiators of the present invention, specific examples of the thioxanthone-based compound include thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, and 2-isopropyl group. Thioxanthone, 4-isopropylthioxanthone, 2,4-dichlorothioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2,4-di Isopropyl thioxanthone and the like.

Further, specific examples of the acetophenone-based compound include 2-methyl-1-[4-(methylthio)phenyl]-2- Orolinyl propan-1-one, 2-benzyl-2-dimethylamino-1-(4- Phenylphenyl)butan-1-one, 2-(4-methylbenzyl)-2-(dimethylamino)-1-(4- Polinylphenyl)butan-1-one and the like.

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

Further, when a diimidazole-based compound is used as the photopolymerization initiator, it is preferred to use a hydrogen donor in combination at a point where the sensitivity can be improved. The "hydrogen donor" as used herein means a compound which can be used for a hydrogen atom by a radical generated from a bisimidazole compound by exposure. Examples of the hydrogen donor include 2-mercaptobenzothiazole and 2-mercaptobenzoene. A thiol-based hydrogen donor such as oxazole, an amine-based hydrogen such as 4,4'-bis(dimethylamino)diphenyl ketone or 4,4'-bis(diethylamino)diphenyl ketone Subject. In the present invention, the hydrogen-providing system may be used alone or in combination of two or more. However, in order to further improve the sensitivity, it is preferred to combine one or more kinds of thiol-based hydrogen donors and one or more kinds of amine-based hydrogen donors. use.

Again, as the above three Specific examples of the compound include 2,4,6-para(trichloromethyl)-s-three. 2-methyl-4,6-bis(trichloromethyl)-s-three ,2-[2-(5-methylfuran-2-yl)vinyl]-4,6-bis(trichloromethyl)-s-three ,2-[2-(furan-2-yl)vinyl]-4,6-bis(trichloromethyl)-s-three 2-[2-(4-Diethylamino-2-methylphenyl)vinyl]-4,6-bis(trichloromethyl)-s-three ,2-[2-(3,4-dimethoxyphenyl)vinyl]-4,6-bis(trichloromethyl)-s-three , 2-(4-methoxyphenyl)-4,6-bis(trichloromethyl)-s-three , 2-(4-ethoxystyryl)-4,6-bis(trichloromethyl)-s-three ,2-(4-n-butoxyphenyl)-4,6-bis(trichloromethyl)-s-three Three of the halomethyl groups a compound.

Further, specific examples of the O-indenyl lanthanide compound include 1,2-octanedione, 1-[4-(phenylthio)phenyl]-, 2-(O-benzylidenefluorene). ), Ethyl Ketone, 1-[9-Ethyl-6-(2-methylbenzhydryl)-9H-indazol-3-yl]-, 1-(O-ethylindenyl), Ethyl Ketone ,1-[9-ethyl-6-(2-methyl-4-tetrahydrofurylmethoxybenzylidene)-9H-indazol-3-yl]-,1-(O-ethylindenyl) Ethylketone, 1-[9-ethyl-6-{2-methyl-4-(2,2-dimethyl-1,3-dioxolanyl)methoxybenzylidene] -9H-carbazol-3-yl]-, 1-(O-ethylindenyl) and the like. As a commercial item of the O-mercapto fluorene-based compound, NCI-831, NCI-930 (above, ADEKA Co., Ltd.), or the like can be used.

In the present invention, when a photopolymerization initiator other than the bisimidazole compound such as an acetophenone-based compound is used, a sensitizer may be used in combination. Examples of such a sensitizer include 4,4′-bis(dimethylamino)diphenyl ketone, 4,4′-bis(diethylamino)diphenyl ketone, and 4-di Ethylaminoacetophenone, 4-Dimethylaminopropiophenone, 4-dimethylaminobenzoic acid ethyl, 4-dimethylaminobenzoic acid 2-ethylhexyl, 2,5-bis(4-diethylamino) Benzylene)cyclohexanone, 7-diethylamino-3-(4-diethylaminobenzimidyl)coumarin, 4-(diethylamino)chalcone, and the like.

In the present invention, the content of the (D) photopolymerization initiator is preferably 0.01 to 120 parts by mass, particularly preferably 1 to 100 parts by mass, per 100 parts by mass of the (C) crosslinking agent. In this case, if the content of the photopolymerization initiator is too small, the curing by the exposure may be insufficient, and if it is too large, the coloring layer formed tends to be easily peeled off from the substrate during development.

- (E) Solvent -

The colored composition of the present invention contains the above components (A) to (C) and any other components added thereto, and is usually prepared by mixing a solvent to prepare a liquid composition.

The solvent is appropriately selected and used as long as it disperses or dissolves the components (A) to (C) constituting the colored composition or other components, and does not react with these components, and has 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, and diethylene glycol monomethyl. Ether, diethylene glycol monoethyl ether, diethylene glycol mono-n-propyl ether, diethylene glycol mono-n-butyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, Propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-n-propyl ether, propylene glycol mono-n-butyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol mono-n-propyl ether, dipropylene glycol a (poly)alkane monoalkyl ether such as mono-n-butyl ether, tripropylene glycol monomethyl ether or tripropylene glycol monoethyl ether; Lactic acid alkyl esters such as methyl lactate and ethyl lactate; methanol, ethanol, propanol, butanol, isopropanol, isobutanol, tert-butanol, octanol, 2-ethylhexanol, cyclohexanol Ethyl alcohols such as dicyclohexanol; ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monomethyl ether acetate Ester, diethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, dipropylene glycol monomethyl ether acetate, 3-methoxybutyl B (poly)alkylene glycol monoalkyl ether acetates such as acid esters, 3-methyl-3-methoxybutyl acetate, etc.; diethylene glycol dimethyl ether, diethylene glycol methyl Other ethers such as ether, diethylene glycol diethyl ether, tetrahydrofuran; ketones such as methyl ethyl ketone, cyclohexanone, 2-heptanone, 3-heptanone; propylene glycol diacetate, a diacetate such as 1,3-butanediol diacetate or 1,6-hexanediol diacetate; methyl 3-methoxypropionate or ethyl 3-methoxypropionate; Methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl ethoxyacetate, 3-methyl-3-methoxy Alkoxycarboxylates such as propyl propionate; 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, ethyl pyruvate, n-propyl pyruvate, methyl ethyl acetate, B Other esters such as ethyl acetate and ethyl 2-oxobutanoate; aromatic hydrocarbons such as toluene and xylene; N,N-dimethylformamide, N,N-dimethylacetamidine An amine or an indoleamine such as an amine or N-methylpyrrolidone.

Among these solvents, propylene glycol monomethyl ether, propylene glycol monoethyl ether, ethylene glycol monomethyl ether acetate, and propylene glycol are preferred from the viewpoints of solubility, pigment dispersibility, and coatability. Monomethyl ether acetate, propylene glycol monoethyl ether acetate, 3-methoxybutyl acetate, diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, cyclohexanone , 2-heptanone, 3-heptanone, 1,3-butanediol diacetate, 1,6-hexanediol diacetate, ethyl lactate, ethyl 3-methoxypropionate, 3 - methyl ethoxypropionate, ethyl 3-ethoxypropionate, 3-methyl-3-methoxybutyl propionate, n-butyl acetate, isobutyl acetate, n-amyl formate, Isoamyl acetate, n-butyl propionate, ethyl butyrate, isopropyl butyrate, n-butyl butyrate, ethyl pyruvate and the like.

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

(E) The content of the solvent is not particularly limited, and the total concentration of each component excluding the solvent of the colored composition is preferably 5 to 5 from the viewpoints of coatability and stability of the obtained coloring composition. The amount of 50% by mass is particularly preferably from 10 to 40% by mass.

-additive-

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

Examples of the additive include a filler such as glass or alumina; a polymer compound such as polyvinyl alcohol or poly(fluoroalkyl acrylate); a fluorine-based surfactant; a polyfluorene-based surfactant; Surfactant; vinyl trimethoxy decane, vinyl triethoxy decane, vinyl ginseng (2-methoxyethoxy) decane, N-(2-aminoethyl)-3-aminopropyl Methyldimethoxydecane, N-(2-aminoethyl)-3-aminopropyltrimethoxydecane, 3-aminopropyltriethoxydecane, 3-epoxypropoxy Propyl Trimethoxydecane, 3-glycidoxypropylmethyldimethoxydecane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxydecane, 3-chloropropylmethyldi a adhesion promoter such as methoxydecane, 3-chloropropyltrimethoxydecane, 3-methylpropenyloxypropyltrimethoxydecane, 3-mercaptopropyltrimethoxydecane; 2,2-sulfur An antioxidant such as bis(4-methyl-6-tert-butylphenol) or 2,6-di-t-butylphenol; 2-(3-tert-butyl-5-methyl-2-hydroxyl Ultraviolet absorbers such as phenyl)-5-chlorobenzotriazole and alkoxydiphenyl ketone; coacervation inhibitors such as sodium polyacrylate; malonic acid, adipic acid, itaconic acid, and citric acid , fumaric acid, mesaconic acid, 2-aminoethanol, 3-amino-1-propanol, 5-amino-1-pentanediol, 3-amino-1,2-propanediol, 2-amine Residue improver of 1,3-1,3-propanediol, 4-amino-1,2-butanediol, etc.; succinic acid mono [2-(methyl) propylene methoxyethyl] ester, phthalic acid mono [ A developability improving agent such as 2-(methyl) propylene oxime oxyethyl] ester or ω-carboxy polycaprolactone mono (meth) acrylate, and the like disclosed in JP-A-2008-242078 A functionally functional siloxane alkane oligomer or the like.

The coloring composition of the present invention can be prepared by a suitable method, and the method disclosed in, for example, JP-A-2008-58642, JP-A-2010-132874, and the like. Further, when a pigment is used together with the dye, the dye solution passing through the first filter and the other dye solution can be passed through the first filter by modulating the dye solution as disclosed in Japanese Laid-Open Patent Publication No. 2010-132874. The prepared pigment dispersion liquid or the like is mixed, and the obtained coloring composition is prepared by passing through a second filter. Further, after the dye, the components (B) to (C) and optionally the component (D) and the additive component are dissolved in the solvent (E), the obtained solution may be passed through the first filter. The solution that will pass through the first filter A method of mixing with a separately prepared pigment dispersion liquid and passing the obtained coloring composition through a second filter. Further, by passing the dye solution through the first filter, the dye solution passing through the first filter, the components (B) to (C), and optionally the components (D) to (E) may be used. The additive component is mixed and dissolved, and the obtained solution is passed through a second filter, and the solution passing through the second filter is further mixed with the separately prepared pigment dispersion liquid, and the resulting colored composition is prepared by passing through a third filter.

Color filter and manufacturing method thereof

The color filter of the present invention comprises a coloring layer containing the component (A) and the component (B), and can be produced by the following method using the coloring composition of the present invention.

As a method of manufacturing a color filter, the following method is mentioned first. First, on the surface of the substrate, a light shielding layer (black matrix) is formed as needed to form a portion of the pixel. Next, on the substrate, for example, a liquid composition containing the blue radiation-sensitive linear composition of the present invention selected from at least one blue colorant containing a dye and a lake pigment is applied, followed by prebaking. Bake and evaporate the solvent 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. Then, by post-baking, a blue pixel pattern is formed to arrange the arranged pixel arrays in a specified arrangement.

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

Further, the black matrix system can be formed by using a lithography method to form a metal thin film such as chromium formed by sputtering or vapor deposition into a desired pattern, but a color-sensitive radiation composition containing a black colorant can also be used. It is formed in the same manner as the case of forming the above-described pixels. The colored composition of the present invention can also be applied to the formation of such a black matrix.

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

Further, as a substrate for such a substrate, a suitable pretreatment such as a drug treatment such as a decane coupling agent, a plasma treatment, ion plating, sputtering, a gas phase reaction method, or vacuum vapor deposition may be applied in advance.

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

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

The coating thickness is usually 0.6 to 8 μm, preferably 1.2 to 5 μm, as 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, and a high pressure mercury lamp. A light source such as an ultrahigh pressure mercury lamp, a metal halide lamp, a medium pressure mercury lamp, a low pressure mercury lamp or the like, or a laser source such as an argon ion laser, a YAG laser, a XeCl excimer laser, or a nitrogen laser, preferably has a wavelength of Radiation in the range of 190 to 450 nm.

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

Further, as the alkali developing solution, for example, sodium carbonate, sodium hydroxide, potassium hydroxide, tetramethylammonium hydroxide, choline or 1,8-diazabicyclo-[5.4.0]-7-ten is preferable. An aqueous solution of monoene, 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 alkali developing solution in an appropriate amount. Further, after alkali development, it is usually washed with water.

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

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

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

Moreover, as a second method of producing a color filter, a method of obtaining pixels of respective colors by an inkjet method disclosed in Japanese Laid-Open Patent Publication No. Hei. No. Hei. In this method, first, a partition wall which also has a shading function is formed on the surface of the substrate. Next, in the partition formed, for example, the inkjet device discharges the contained The liquid composition of the colored thermosetting composition of the present invention selected from at least one of the blue colorants included in the group of the dye and the lake pigment is 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, a green pixel pattern and a red pixel pattern are sequentially formed on the same substrate in the same manner as described above, using green or red colored thermosetting compositions. Thereby, a color filter in which the pixel patterns of the three primary colors of red, green, and blue are arranged on the substrate is obtained. However, in the present invention, the order in which the pixels of the respective colors are formed is not limited to the above.

Further, since the partition wall not only functions as a shading function but also functions to prevent color mixing of the colored thermosetting composition of each color in the partition, the film thickness is thinner than that of the black matrix used in the first method. Thick. Therefore, the partition walls are usually formed using a black sensitizing radioactive composition.

The substrate or the source of radiation used in forming the color filter, and the method or condition of prebaking or postbaking are the same as the first method described above. As described above, the film thickness of the pixel formed by the ink jet method is the same as the height of the partition wall.

On the pixel pattern thus obtained, a protective film is formed as needed, and then a transparent conductive film is formed by sputtering. After the transparent conductive film is formed, a spacer may be further formed as a color filter. The spacer is usually formed using a radiation-sensitive composition, but may be a spacer having a light-shielding property (black spacer). At this time, a color-sensitive radiation composition containing a black colorant is used, but the coloring composition of the present invention can also be applied to the formation of the black spacer.

The color filter of the present invention thus obtained is extremely useful for 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 is provided with the color filter of the present invention. Examples of the display element include a color liquid crystal display element, an organic EL display element, and electronic paper.

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

A color liquid crystal display element having the color filter of the present invention may be provided with a backlight unit using a white LED as a light source in addition to a Cold Cathode Fluorescent Lamp (CCFL). Examples of the white LED include a white LED in which a combination of a red LED, a green LED, and a blue LED is mixed to obtain white light, and a combination of a blue LED, a red LED, and a green phosphor is mixed to obtain white light. White LED, a combination of a blue LED, a red-emitting phosphor and a green-emitting phosphor, a white LED that is white-lighted by color mixing, and a white light white by a color mixture of a blue LED and a YAG-based phosphor. LED, a combination of a blue LED and an orange-emitting phosphor and a green-emitting phosphor, a white LED that is white-lighted by color mixing, combined with an ultraviolet LED and a red-emitting phosphor and a green-emitting phosphor and a blue-emitting fluorescent A white LED or the like that obtains white light by color mixing.

In the color liquid crystal display device including the color filter of the present invention, a TN (twisted nematic) type, an STN (super twisted nematic) type, an IPS (in-plane switching) type, and a VA (vertical alignment) type can be applied. A suitable liquid crystal mode such as OCB (optical compensation birefringence) type.

In addition, the organic EL display element having the color filter of the present invention can have a suitable structure. For example, the structure disclosed in Japanese Laid-Open Patent Publication No. Hei 11-307242 can be cited.

In addition, the electronic paper including the color filter of the present invention can have an appropriate structure, and for example, the structure disclosed in JP-A-2007-41169 can be cited.

[Examples]

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

<Synthesis of specific polymers> Synthesis Example 1

In a flask equipped with a cooling tube and a stirrer, 7 parts by mass of 2,2'-azobis(2,4-dimethylvaleronitrile) and 200 parts by mass of propylene glycol monomethyl ether were added. Next, 90 parts by mass of methyl methacrylate and 10 parts by mass of 2-methylpropenyloxyethyl acid phosphate were added, and after nitrogen substitution, stirring was started slowly. By raising the temperature of the solution to 70 ° C and maintaining this temperature for 4 hours, a polymer containing a specific polymer (B1) is dissolved. Liquid (solid content concentration = 32% by mass). This specific polymer (B1) had Mw = 4,800 and Mw/Mn = 2.1.

Synthesis Example 2

In a flask equipped with a cooling tube and a stirrer, 7 parts by mass of 2,2'-azobis(2,4-dimethylvaleronitrile) and 200 parts by mass of propylene glycol monomethyl ether were added. Next, 95 parts by mass of methyl methacrylate and 5 parts by mass of 2-propenylamine-2-methylpropanesulfonic acid were added, and after nitrogen substitution, stirring was started slowly. By raising the temperature of the solution to 70 ° C and maintaining this temperature for 4 hours, a polymer solution (solid content concentration = 33% by mass) containing the specific polymer (B2) was obtained. This specific polymer (B2) had Mw = 3,200 and Mw/Mn = 2.0.

<Preparation of Pigment Dispersion> Modulation example 1

Using 15 parts by mass of CI Pigment Blue 15:6 as a colorant, and 12.5 parts by mass (solid content concentration = 40% by mass), BYK-LPN21116 (manufactured by BYK Chemical Co., Ltd.) as a dispersing agent, 72.5 parts by mass of propylene glycol The methyl ether acetate was treated as a solvent by a bead mill to obtain a pigment dispersion liquid (A-1).

Modulation example 2

A pigment dispersion liquid (A-2) was prepared in the same manner as in Preparation Example 1, except that C.I. Pigment Green 58 was used instead of C.I. Pigment Blue 15:6 as a colorant.

Modulation example 3

The pigment dispersion liquid (A-3) was prepared in the same manner as in Preparation Example 1, except that C.I. Pigment Blue 1 (triarylmethane-based basic lake pigment) was used instead of C.I. Pigment Blue 15:6 as a colorant.

Modulation example 4

A mixture of 15 parts by mass of CI Pigment Blue 15:6/triarylmethane-based lake pigment (wherein x=1~2)=60/40 (mass ratio) represented by the following formula is used as a coloring agent, 10 parts by mass (nonvolatile content = 40% by mass) of BYK-LPN21116 (manufactured by BYK Chemical Co., Ltd.) as a dispersing agent and 75 parts by mass of propylene glycol monomethyl ether acetate as a solvent, and the same as in Preparation Example 1. Ground, the pigment dispersion (A-4) was prepared.

<Modulation of Dye Solution> Modulation example 5

5 parts by mass of C.I. Basic Blue 7 (triarylmethane-based basic dye) and 95 parts by mass of propylene glycol monomethyl ether as a solvent were mixed to prepare a dye solution A.

Modulation example 6

10 parts by mass of C.I. Basic Blue 11 (triarylmethane-based basic dye) as a coloring agent, and 90 parts by mass of propylene glycol monomethyl ether as a solvent were mixed to prepare a dye solution B.

Modulation example 7

10 parts by mass of C.I. Basic Violet 16 (methine-based basic dye) and 90 parts by mass of propylene glycol monomethyl ether as a solvent were mixed to prepare a dye solution C.

Modulation example 8

10 parts by mass of C.I. Basic Blue 41 (azo basic dye) and 90 parts by mass of propylene glycol monomethyl ether as a solvent were mixed to prepare a dye solution D.

Modulation example 9

Mixing 10 parts by mass of CI Basic Blue 3 as a coloring agent ( A basic dye), 90 parts by mass of propylene glycol monomethyl ether as a solvent to prepare a dye solution E.

Modulation example 10

10 parts by mass of C.I. Basic Blue 22 (anthraquinone basic dye) and 90 parts by mass of propylene glycol monomethyl ether as a solvent were mixed to prepare a dye solution F.

Modulation example 11

10 parts by mass of C.I. Basic Red 1 (xanthene-based basic dye) as a coloring agent and 90 parts by mass of propylene glycol monomethyl ether as a solvent were mixed to prepare a dye solution G.

Modulation example 12

10 parts by mass of C.I. Basic Red 13 (methine-based basic dye) as a coloring agent and 90 parts by mass of propylene glycol monomethyl ether as a solvent were mixed to prepare a dye solution H.

Modulation example 13

10 parts by mass of a yellow dye represented by the following formula and 90 parts by mass of cyclohexanone as a solvent were mixed to prepare a dye solution I.

<Synthesis of binder resin> Synthesis Example 3

To a flask equipped with a cooling tube and a stirrer, 100 parts by mass of propylene glycol monomethyl ether acetate was added to carry out nitrogen substitution. The mixture was heated to 80 ° C, and 100 parts by mass of propylene glycol monomethyl ether acetate, 20 parts by mass of methacrylic acid, 10 parts by mass of styrene, and 5 parts by mass of benzyl methacrylate were added dropwise at the same temperature for 1 hour. Ester, 15 parts by mass of 2-hydroxyethyl methacrylate, 23 parts by mass of 2-ethylhexyl methacrylate, 12 parts by mass of N-phenylmaleimide, 15 parts by mass of succinic acid A mixed solution of (2-propenyloxyethyl)ester and 6 parts by mass of 2,2'-azobis(2,4-dimethylvaleronitrile) was maintained at this temperature for 2 hours. Then, 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 binder resin was Mw = 12,200 and Mn = 6,500. This binder resin is referred to as "adhesive resin (b)".

<Modulation and evaluation of coloring composition> Example 1

13.6 parts by mass of the pigment dispersion liquid (A-1), 27.2 parts by mass of the dye solution A, 16.1 parts by mass of the binder resin (b) solution as the binder resin, 5.5 parts by mass of the specific polymer (B1) solution, 9.2 parts by mass of a copolymer of M-402 (a mixture of dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate) as a crosslinking agent, and 2.2 parts by mass of 2-benzyl-2-di which is a photopolymerization initiator Methylamino-1-(4- Phenylphenyl)butan-1-one (trade name: IRGACURE 369, manufactured by CIBA Specialty Chemicals Co., Ltd.), 0.2 parts by mass of DIC (product) Megafac F-554 as a fluorine-based surfactant, and propylene glycol monomethyl as a solvent Ether acetate was prepared to prepare a colored composition having a solid content concentration of 20% by mass.

The obtained coloring composition was applied onto a glass substrate using a spin coater, and then prebaked on a hot plate at 80 ° C for 10 minutes to form a coating film having a film thickness of about 2.5 μm.

Next, after the substrate was cooled to room temperature, radiation of respective wavelengths of 365 nm, 405 nm, and 436 nm was exposed to each of the coating films without using a mask at a exposure amount of 2,000 J/m ² using a high-pressure mercury lamp. In this manner, a blue evaluation cured film was formed on the substrate.

The resulting substrate was post-baked in a clean oven at 230 ° C for 1 hour. The color difference (ΔEab*) was measured for the substrate before and after the post-baking. Further, the case where ΔEab* is less than 3.0 is evaluated as ○, the case where 3.0 or more and less than 5.0 is evaluated as Δ, and the case where 5.0 or more is evaluated as ×. The evaluation results are shown in Table 1.

Examples 2 to 12 and Comparative Examples 1 to 10

The coloring composition was prepared in the same manner as in Example 1 except that the type and amount of the pigment dispersion liquid, the dye solution, and the specific polymer solution, and the amount of the binder resin (b) solution in Example 1 were changed as shown in Table 1. . Further, the obtained colored composition was evaluated in the same manner as in Example 1. The evaluation results are shown in Table 1.

Example 13 and Comparative Example 11

In addition to the type and amount of the pigment dispersion liquid, the dye solution, and the specific polymer solution, the amount of the binder resin (b) solution, and the type and amount of the photopolymerization initiator, in Example 1, as shown in Table 1, In Example 1, the coloring composition was prepared in the same manner. Further, the obtained colored composition was evaluated in the same manner as in Example 1. The evaluation results are shown in Table 1.

In Table 1, each component is as follows.

D1: 2-benzyl-2-dimethylamino-1-(4- Polinylphenyl)butan-1-one (manufactured by CIBA Specialty Chemicals, trade name IRGACURE 369)

D2: ADEKA (share), trade name NCI-930

Claims (7)

A coloring composition comprising (A) a dye-containing coloring agent, (B) having a repetition of at least one selected from the group consisting of ethylenically unsaturated monomers having a sulfo group and salts thereof a polymer of the unit, and (C) a crosslinking agent, the coloring agent further containing a pigment other than the lake pigment. The coloring composition of claim 1, wherein (B) the copolymer is selected from a copolymerization ratio of at least one selected from the group consisting of ethylenically unsaturated monomers having a sulfo group and salts thereof It is 1 to 30% by mass. A coloring composition comprising (A) a dye-containing coloring agent, (B) having an ethylenically unsaturated monomer selected from the group consisting of ethylenically unsaturated monomers having a sulfo group and having a phosphinomethoxy group And a polymer of the repeating unit of at least one of the group of salts thereof, and (C) a crosslinking agent, further comprising (F) not having an ethylenically unsaturated monomer selected from the group consisting of having a sulfo group, a repeating unit having at least one of a group of ethylenically unsaturated monomers having a phosphinomethoxy group and a salt thereof, and a polymer having a carboxyl group, and the content of the (F) polymer is colored relative to (A) The agent is 10 to 1,000 parts by mass in 100 parts by mass. The colored composition of claim 3, wherein the (B) polymer is selected from the group consisting of ethylenically unsaturated monomers having a sulfo group, and having a phosphine fluorene The copolymerization ratio of the repeating unit derived from at least one of the group of the ethylenically unsaturated monomer of the oxy group and the salt thereof is from 1 to 30% by mass. A color filter comprising a colored layer comprising: (A) a coloring agent containing a dye other than a dye and a lake pigment, and (B) having an ethylenic group selected from the group consisting of having a sulfo group A polymer of repeating units derived from at least one of the group of unsaturated monomers and salts thereof. A color filter comprising a colored layer containing: (A) a dye-containing coloring agent, and (B) having an ethylenically unsaturated monomer selected from the group consisting of having a sulfo group, having a phosphine fluorene a polymer of a repeating unit derived from at least one of a group of an ethylenically unsaturated monomer of an oxy group and a salt thereof, and (F) having no ethylenically unsaturated monomer selected from the group consisting of having a sulfo group, a repeating unit having at least one of a group of ethylenically unsaturated monomers having a phosphinomethoxy group and a salt thereof, and a polymer having a carboxyl group, and the content of the (F) polymer is colored relative to (A) The agent is 10 to 1,000 parts by mass in 100 parts by mass. A display element comprising a color filter as in item 5 or 6 of the patent application.