JP2017194551A - Coloring composition for color filters and color filter - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a coloring composition for color filters having excellent storage stability, and a color filter that prevents foreign matter from occurring on a coating, has strong adhesion with a transparent substrate such as glass, has high heat resistance and solvent resistance, and has excellent alkali solubility.SOLUTION: The problem is solved by a coloring composition for color filters that contains an anionic dye (C) having a specific structure, the coloring composition having high storage stability, preventing foreign matter from occurring on a coating, having strong adhesion, and showing high heat resistance in a heat resistance test.SELECTED DRAWING: None

Description

The present invention relates to a colored composition for a color filter used for manufacturing a color filter used for a color liquid crystal display device, a color image pickup tube element, and the like, and a color filter including a filter segment formed using the same. is there.

In recent years, liquid crystal display devices have been evaluated for space saving, light weight, power saving, and the like due to their thinness, and recently they have been rapidly spread to television applications. For television applications, it is required to further improve the performance such as brightness and contrast, and further improvement of the transmittance and enhancement of the contrast are desired for the color filter which is a member of the color liquid crystal display device. ing.

As a method for producing the color filter, after forming a pattern with a photoresist, a dyeing method for dyeing the pattern, or by forming a transparent electrode of a predetermined pattern in advance, and using a pigment-containing resin dissolved and dispersed in a solvent by voltage application Electrodeposition method for ionization and pattern formation, printing method such as offset printing using ink containing thermosetting resin or ultraviolet curable resin, pigment dispersion using color resist agent in which colorant such as pigment is dispersed in photoresist material Recently, the pigment dispersion method has become mainstream. However, a color filter using a pigment as a colorant disturbs the degree of polarization controlled by the liquid crystal due to light scattering by the pigment particles, resulting in a decrease in brightness and contrast of the color liquid crystal display device. There is a problem that it is easy.

As a technique for solving this problem, the practical application of a dye-based curable composition using a dye that can exist in a dissolved state in a medium of the curable composition as a colorant has been studied and proposed (for example, patents). Reference 1). However, the dye used for the color resist agent has problems of heat resistance, light resistance, and solubility in the resin and the organic solvent used for the resin.

Therefore, in order to increase solubility, a color filter using a salt of an anionic dye and a cationic surfactant as a colorant has been proposed (for example, see Patent Documents 2 and 3). Generally, it is known that the solubility of an anionic dye in an organic solvent is increased by changing the sodium sulfonate group (—SO ₃ Na) of the anionic dye into an organic amine salt. It has been found that the above colorants increase the solubility of the anionic dye in organic solvents by changing the sodium sulfonate group of the anionic dye to the base salt of the cationic surfactant.

Further, as salt forming compounds of anionic dyes, those using a cationic resin as a counter have been studied as crystalline aqueous coloring materials (see, for example, Patent Document 4). In color filter applications that require use in a dissolved state, detailed studies have not been made.

On the other hand, a colored resin composition in which an anionic dye is added to a copolymer solution obtained by copolymerizing a monomer having an amide structure has also been proposed (see, for example, Patent Document 5). This is because the amide structure acts as a dyeing point with the anionic dye, thereby stabilizing the dye in the coating film and improving the resistance. However, the method disclosed here has a problem in that since a copolymer and an anionic dye are mixed in an organic solvent, a highly polar dye is not sufficiently dissolved and foreign matter is generated.

On the other hand, in order to improve heat resistance and light resistance, a coloring composition in which a dye is chemically bonded to a polymer has been proposed (for example, see Patent Document 6). However, the solvent resistance and resistance are insufficient only by simply combining the polymer and the dye, and the recent required level of alkali developability could not be satisfied.

On the other hand, the coloring composition for color filters containing a salt-forming compound obtained by reacting a resin having a cationic group in the side chain with an anionic dye has high storage stability and foreign matter to the coating film. It is known that there is no occurrence and excellent adhesion.

However, in recent color filters, higher heat resistance has been demanded, and although the solubility can be improved by the above method, the heat resistance of the anionic dye itself is greatly improved as long as the heat resistance of the anionic dye itself is not improved. It was difficult to improve.

JP 1994-75375 A JP 1993-333207 JP 2004-307391 A JP-A-2005-350648 JP 2000-352819 A JP 2000-162429 A JP 2011-242752 A JP 2013-33194 A

The object of the present invention is a color filter coloring composition having excellent storage stability, as well as no foreign matter generated on the coating film, and has strong adhesion with a transparent substrate such as glass, heat resistance, The object is to provide a color filter having high solvent resistance and excellent alkali solubility.

As a result of intensive studies to solve the above problems, the present inventors have found that a coloring composition for a color filter containing an anionic dye (C) represented by the general formula (11) has high storage stability. In addition, the present invention has been made based on this finding, and it has been found that no foreign matter is generated on the coating film, has excellent adhesion, and exhibits high heat resistance in a heat resistance test.

That is, the present invention is a color filter coloring composition comprising at least a colorant (A), a binder resin, and an organic solvent,
The colorant (A) is selected from the group consisting of an anionic dye (C) represented by the general formula (11), a quaternary ammonium salt compound, an amine, and a resin having a cationic group in the side chain. The present invention relates to a coloring composition for a color filter comprising a salt-forming compound (D) with a compound (B) having a cationic group.

Formula (11)

[X ₁ and X ₃ represent a monovalent aliphatic hydrocarbon group having 1 to 20 carbon atoms which may have a substituent.
X ₂ and X ₄ each represents a monovalent aromatic hydrocarbon group which may have a substituent, and at least one of them has a sulfo group. ]

Furthermore, the present invention relates to the coloring composition for a color filter, wherein the compound (B) having a cationic group contains a quaternary ammonium salt compound represented by the following general formula (2).
General formula (1)
[In General Formula (1), R _{1 to} R ₄ each independently represents an alkyl group having 1 to 20 carbon atoms or a benzyl group, and at least two of R ₁ , R ₂ , R ₃ , or R ₄ Is an alkyl group having 5 to 20 carbon atoms or a benzyl group. Y- represents an inorganic or organic anion. ]

Further, in the present invention, the compound (B) having a cationic group contains an amine, and the amine is at least one selected from the group consisting of a primary amine, a secondary amine, and a tertiary amine. It is related with the coloring composition for said color filters.

Further, in the present invention, the compound (B) having a cationic group includes a resin having a cationic group in a side chain, and the resin having a cationic group in the side chain is represented by the following general formula (2). It is related with the said coloring composition for color filters which is acrylic resin containing a structural unit.
General formula (2):

[In General Formula (2), R ₅ represents a hydrogen atom or a substituted or unsubstituted alkyl group. R _{6 to} R ₈ each independently represents a hydrogen atom, an optionally substituted alkyl group, an optionally substituted alkenyl group, or an optionally substituted aryl group, and R _{6 to} R ₈ Two of them may be bonded to each other to form a ring. Q represents an alkylene group, an arylene group, —CONH—R ₉ —, or —COO—R ₉ —, and R ₉ represents an alkylene group. Y- represents an inorganic or organic anion. ]

Furthermore, the present invention provides the colored composition for a color filter, wherein the acrylic resin containing the structural unit represented by the general formula (2) has a thermally crosslinkable functional group. Related to things.

Furthermore, the present invention relates to the coloring composition for a color filter, wherein the thermally crosslinkable functional group is a hydroxyl group or a carboxyl group.

  Furthermore, this invention relates to the coloring composition for said color filters characterized by the ammonium salt value of acrylic resin containing the structural unit represented by the said General formula (2) being 10-200 mgKOH / g.

Furthermore, the present invention relates to the coloring composition for a color filter, wherein the organic solvent contains propylene glycol monomethyl ether acetate as a main component.

Furthermore, the present invention relates to the color filter coloring composition, wherein the colorant (A) further contains a pigment.

Furthermore, this invention relates to the coloring composition for said color filters characterized by containing a photopolymerizable monomer and / or a photoinitiator further.

Moreover, this invention relates to the color filter formed with the said coloring composition for color filters.

Furthermore, the present invention provides a color filter coloring composition comprising at least a colorant (A), a binder resin, and an organic solvent, wherein the colorant (A) is an anion represented by the general formula (11). A salt-forming compound (D) comprising a cationic dye (C) and a compound (B) having a cationic group selected from the group consisting of a quaternary ammonium salt compound, an amine, and a resin having a cationic group in the side chain The salt-forming compound (D) is a mixture of a compound (B) having a cationic group and an anionic dye (C) in an aqueous solution, and a counter anion and an anionic dye of the compound (B) having a cationic group. It is related with the manufacturing method of the coloring composition for color filters characterized by removing the salt which consists of a counter cation of (C).

In the present invention, a cationic property selected from the group consisting of the anionic dye (C) represented by the general formula (11), a quaternary ammonium salt compound, an amine, and a resin having a cationic group in the side chain. By using the salt-forming compound (D) with the group-containing compound (B), it has high storage stability, no foreign matter is generated at the time of coating film formation, excellent adhesion, and higher heat resistance and solvent resistance And a color filter exhibiting excellent alkali development can be obtained.

Hereinafter, the present invention will be described in detail.
The coloring composition for a color filter of the present invention is composed of an anionic dye (C) represented by the general formula (11), a quaternary ammonium salt compound, an amine, and a resin having a cationic group in a side chain. It is a coloring composition for color filters containing the salt-forming compound (D) with the compound (B) which has a selected cationic group.

<Anionic Dye (C) Represented by General Formula (11)>
First, the anionic dye (C) represented by the general formula (11) will be described.
Formula (11)

[X ₁ and X ₃ represent a monovalent aliphatic hydrocarbon group having 1 to 20 carbon atoms which may have a substituent.
X ₂ and X ₄ each represents a monovalent aromatic hydrocarbon group which may have a substituent, and at least one of them has a sulfo group. ]
X < ₁ >, X < ₃ > represents the monovalent | monohydric C1-C20 aliphatic hydrocarbon group which may have a substituent.
Examples of the aliphatic hydrocarbon group having 1 to 20 carbon atoms include a methyl group, an ethyl group, an n-propyl group, an n-butyl group, an n-pentyl group, an n-hexyl group, an n-heptyl group, and an n-octyl group. N-nonyl group, n-decyl group, n-undecyl group, n-dodecyl group, n-tridecyl group, n-tetradecyl group, n-pentadecyl group, n-hexadecyl group, n-heptadecyl group, n-octadecyl group, etc. A linear aliphatic hydrocarbon group of a group, n-octadecyl group, n-nonadecyl group, n-icosanyl group;
Isopropyl group, isobutyl group, sec-butyl group, isopentyl group, 1-methylpentyl group, 2-methylpentyl group, 3-methylpentyl group, 4-methylpentyl group, 1-ethylbutyl group, 2-ethylbutyl group, 1- Methylhexyl group, 2-methylhexyl group, 3
-Methylhexyl group, 4-methylhexyl group, 5-methylhexyl group, 1-ethylpentyl group, 2-ethylpentyl group, 3-ethylpentyl group, 1-propylbutyl group, 1- (1
-Methylethyl) butyl group, 1- (1-methylethyl) -2-methylpropyl group, 1-methylheptyl group, 2-methylheptyl group, 3-methylheptyl group, 4-methylheptyl group, 5-methylheptyl group Group, 6-methylheptyl group, 1-ethylhexyl group, 2-ethylhexyl group, 3-ethylhexyl group, 4-ethylhexyl group, 1-n-propylpentyl group, 2-propylpentyl group, 1- (1-methylethyl) Pentyl group, 1-butylbutyl group, tert-butyl group, 1,1-dimethylpropyl group, 1,1-dimethylbutyl group, 1,
2-dimethylbutyl group, 1,3-dimethylbutyl group, 2,3-dimethylbutyl group, 1-ethyl-2-methylpropyl group, 1,1-dimethylpentyl group, 1,2-dimethylpentyl group, 1, 3-dimethylpentyl group, 1,4-dimethylpentyl group, 2,2-dimethylpentyl group, 2,3-dimethylpentyl group, 2,4-dimethylpentyl group, 3,3-dimethylpentyl group, 3,4- Dimethylpentyl group, 1-ethyl-1-methylbutyl group, 1-ethyl-2-methylbutyl group, 1-ethyl-3-methylbutyl group, 2-ethyl-1-methylbutyl group, 2-ethyl-3-methylbutyl group, 1 , 1-dimethylhexyl group, 1,2-dimethylhexyl group, 1,3-dimethylhexyl group, 1,4-dimethylhexyl group, 1,5-dimethylhexyl group
Dimethylhexyl group, 2,2-dimethylhexyl group, 2,3-dimethylhexyl group, 2,
4-dimethylhexyl group, 2,5-dimethylhexyl group, 3,3-dimethylhexyl group,
3,4-dimethylhexyl group, 3,5-dimethylhexyl group, 4,4-dimethylhexyl group, 4,5-dimethylhexyl group, 1-ethyl-2-methylpentyl group, 1-ethyl-3
-Methylpentyl group, 1-ethyl-4-methylpentyl group, 2-ethyl-1-methylpentyl group, 2-ethyl-2-methylpentyl group, 2-ethyl-3-methylpentyl group, 2-
Ethyl-4-methylpentyl group, 3-ethyl-1-methylpentyl group, 3-ethyl-2-
Methylpentyl group, 3-ethyl-3-methylpentyl group, 3-ethyl-4-methylpentyl group, 1-propyl-1-methylbutyl group, 1-propyl-2-methylbutyl group, 1-propyl-3-methylbutyl group 1- (1-methylethyl) -1-methylbutyl group, 1- (
1-methylethyl) -2-methylbutyl group, 1- (1-methylethyl) -3-methylbutyl group, 1,1-diethylbutyl group, 1,2-diethylbutyl group, stearyl group, etc. Group hydrocarbon group; and the like.
Examples of the substituent for the monovalent aliphatic hydrocarbon group having 1 to 20 carbon atoms include a carboxyl group, a sulfo group, an amino group, an acryloyl group, a methacryloyl group, an alkoxy group, a phenyl group, a chloro group, a bromo group, and an iodo group. Is mentioned. These may further have a substituent.
X ₂ and X ₄ each represents a monovalent aromatic hydrocarbon group which may have a substituent, and at least one of them has a sulfo group.
Examples of the monovalent aromatic hydrocarbon group include a phenyl group, a monomethylphenyl group, a dimethylphenyl group, a trimethylphenyl group, a naphthyl group, a monomethylnaphthyl group, a dimethylnaphthyl group, a trimethylnaphthyl group, and a tetramethylnaphthyl group.
X2 and X4 each have a sulfo group, and are phenyl group, monomethylphenyl group, dimethylphenyl group, trimethylphenyl group, naphthyl group, monomethylnaphthyl group, dimethylnaphthyl group, trimethylnaphthyl group, tetramethyl group. Examples include those in which hydrogen such as a naphthyl group is substituted with a sulfo group.
Examples of the sulfo group include a sulfo group or a salt of the sulfo group.
Examples of the substituent for the monovalent aromatic hydrocarbon group include a carboxyl group, a sulfo group, an amino group, an acryloyl group, a methacryloyl group, an alkoxy group, a phenyl group, a chloro group, a bromo group, and an iodo group. These may further have a substituent.
X ₂ and X ₄ may be ones in which one of them is a 2,6-dimethylphenyl group and the other is a group in which hydrogen on a phenyl group of a 2,6-dimethylphenyl group is substituted with a sulfo group. ,preferable.

Next, the compound (B) having a cationic group will be described.
The compound (B) having a cationic group is selected from the group consisting of a quaternary ammonium salt compound, an amine, and a resin having a cationic group in the side chain.

(Quaternary ammonium salt compound)
The molecular weight of the cation moiety serving as a counter in the quaternary ammonium salt compound is preferably in the range of 190 to 900. Here, the cation moiety corresponds to the (NR ₁ R ₂ R ₃ R ₄ ) + moiety in the following general formula (1). When the molecular weight is smaller than 190, light resistance and heat resistance are lowered, and the solubility in a solvent may be further lowered. On the other hand, when the molecular weight is larger than 900, the ratio of the coloring component in the molecule is lowered, so that the color developability is lowered and the lightness is also lowered. More preferably, the molecular weight of the cation moiety is in the range of 240 to 850, and particularly preferably in the range of 350 to 800.
Here, the molecular weight was calculated based on the structural formula. The atomic weight of C was 12, the atomic weight of H was 1, and the atomic weight of N was 14.

  Moreover, the compound represented by following General formula (1) can be used as a quaternary ammonium salt compound.

General formula (1)
[In General Formula (1), R _{1 to} R ₄ each independently represents an alkyl group having 1 to 20 carbon atoms or a benzyl group, and at least two of R ₁ , R ₂ , R ₃ , or R ₄ Is an alkyl group having 5 to 20 carbon atoms or a benzyl group. Y- represents an inorganic or organic anion. ]

R ₁ to R ₄ in by the a 5 to 20 the number of at least two and C, solubility in solvents is improved. When the number of alkyl groups having C less than 5 is 3 or more, the solubility in a solvent is deteriorated, and coating film foreign matter is likely to be generated. Moreover, when the alkyl group in which the number of C exceeds 20 exists, the coloring property of a salt-formation product may be impaired.

  The Y-component constituting the anion of the quaternary ammonium salt compound may be an inorganic or organic anion, but is preferably a halogen, usually chlorine.

  Specific examples of such quaternary ammonium salt compounds include tetramethylammonium chloride (with a molecular weight of the cation moiety of 74), tetraethylammonium chloride (with a molecular weight of the cation moiety of 122), and monostearyltrimethylammonium chloride (with a molecular weight of the cation moiety). 312), distearyldimethylammonium chloride (cation part molecular weight 550), tristearyl monomethylammonium chloride (cation part molecular weight 788), cetyltrimethylammonium chloride (cation part molecular weight 284), trioctylmethylammonium chloride ( The molecular weight of the cation moiety is 368), dioctyldimethylammonium chloride (the molecular weight of the cation moiety is 270), monolauryltrimethyla Monium chloride (cation part molecular weight 228), dilauryldimethylammonium chloride (cation part molecular weight 382), trilaurylmethylammonium chloride (cation part molecular weight 536), triamylbenzylammonium chloride (cation part molecular weight 318), trihexylbenzylammonium chloride (cation part molecular weight 360), trioctylbenzylammonium chloride (cation part molecular weight 444), trilaurylbenzylammonium chloride (cation part molecular weight 612), benzyldimethylstearylammonium chloride (Molecular weight of the cation moiety is 388) and benzyldimethyloctyl ammonium chloride (molecular weight of the cation moiety is 248) , Or dialkyl (alkyl C14 -C18) dimethyl ammonium chloride (hydrogenated tallow) (molecular weight of the cationic portion 438 to 550) is preferably used.

  Examples of commercially available quaternary ammonium salt compounds include, for example, Cotamin 24P, Cotamin 86P Conch, Cotamin 60W, Cotamin 86W, Cotamin D86P, Sanizol C and Sanizole B-50 manufactured by Kao Corporation, and Arcade 210-80E manufactured by Lion Corporation, 2C-75, 2HT-75, 2HT flakes, 2O-75I, 2HP-75 and 2HP flakes are mentioned, among others, Cotamine D86P (distearyldimethylammonium chloride) and Arcard 2HT-75 (dialkyl (alkyl is C14 to C18) dimethyl) Ammonium chloride) is preferred.

(Resin having a cationic group in the side chain)
The resin having a cationic group in the side chain is preferably an acrylic resin containing a structural unit represented by the following general formula (2), and the cationic group in the general formula (2) is an anion of an anionic dye. A salt-forming compound can be obtained by forming a salt with a functional group. (See Reference 1)
(Reference 1) Japanese Patent Application No. 2011-261667
General formula (2):

(In general formula (2), R ₅ represents a hydrogen atom or a substituted or unsubstituted alkyl group. R _{6 to} R ₈ each independently represents a hydrogen atom, an optionally substituted alkyl group, or a substituted group. Represents an alkenyl group which may be substituted, or an aryl group which may be substituted, and two of R _{6 to} R ₈ may be bonded to each other to form a ring, Q is an alkylene group, an arylene group, —CONH _{-R 7 -, - COO-R} 7 - represents, R ₇ is .Y- represents an alkylene group represents an inorganic or organic anion).

In general formula (2), R ₅ represents a hydrogen atom or a substituted or unsubstituted alkyl group. Examples of the alkyl group for R ₅ include a methyl group, an ethyl group, a propyl group, an n-butyl group, an i-butyl group, a t-butyl group, an n-hexyl group, and a cyclohexyl group. As this alkyl group, a C1-C12 alkyl group is preferable, a C1-C8 alkyl group is more preferable, and a C1-C4 alkyl group is especially preferable.

When the alkyl group represented by R ₅ has a substituent, examples of the substituent include a hydroxyl group and an alkoxyl group.

Among the above, R ₅ is most preferably a hydrogen atom or a methyl group.

In general formula (2), each of R _{6 to} R ₈ is independently a hydrogen atom, an optionally substituted alkyl group, an optionally substituted alkenyl group, or an optionally substituted aryl group. Can be mentioned.

Here, as the alkyl group in R _{6 to} R ₈ , for example, a linear alkyl group (methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-octyl, n-decyl, n-dodecyl, n -Tetradecyl, n-hexadecyl, n-octadecyl, etc.), branched alkyl groups (isopropyl, isobutyl, sec-butyl, tert-butyl, isopentyl, neopentyl, tert-pentyl, isohexyl, 2-ethylhexyl and 1,1,3,3) -Tetramethylbutyl etc.), cycloalkyl groups (cyclopropyl, cyclobutyl, cyclopentyl and cyclohexyl etc.) and bridged cyclic alkyl groups (norbornyl, adamantyl and pinanyl etc.). As this alkyl group, a C1-C18 alkyl group is preferable, More preferably, it is a C1-C8 alkyl group.

Examples of the alkenyl group in R _{6 to} R ₈ include linear or branched alkenyl groups (vinyl, allyl, 1-propenyl, 2-propenyl, 1-butenyl, 2-butenyl, 3-butenyl, 1-methyl-1 -Propenyl, 1-methyl-2-propenyl, 2-methyl-1-propenyl, 2-methyl-2-propenyl and the like) and cycloalkenyl groups (such as 2-cyclohexenyl and 3-cyclohexenyl). As this alkenyl group, a C2-C18 alkenyl group is preferable, More preferably, it is a C2-C8 alkenyl group.

Examples of the aryl group in R _{6 to} R ₈ include monocyclic aryl groups (such as phenyl), condensed polycyclic aryl groups (such as naphthyl, anthracenyl, phenanthrenyl, anthraquinolyl, fluorenyl, and naphthoquinolyl) and aromatic heterocyclic hydrocarbons. Groups (thienyl (group derived from thiophene)), furyl (group derived from furan), pyranyl (group derived from pyran), pyridyl (group derived from pyridine), 9-oxoxanthenyl (from xanthone) Derived groups) and 9-oxothioxanthenyl (groups derived from thioxanthone) and the like.

When the alkyl group, alkenyl group, or aryl group represented by R _{6 to} R ₈ has a substituent, examples of the substituent include a halogen atom, a hydroxyl group, an alkoxyl group, an aryloxy group, an alkenyl group, an acyl group, Examples include a substituent selected from an alkoxycarbonyl group, a carboxyl group, a phenyl group, and the like. Among these substituents, a halogen atom, a hydroxyl group, an alkoxyl group, and a phenyl group are particularly preferable.

R _{6 to} R ₈ are preferably an alkyl group which may be substituted from the viewpoint of stability, and more preferably an unsubstituted alkyl group.

Two of R _{6 to} R ₈ may be bonded to each other to form a ring.

In general formula (2), the component of Q that connects the acrylic moiety and the ammonium base represents an alkylene group, an arylene group, —CONH—R ₇ —, —COO—R ₇ —, and R ₇ represents an alkylene group, Among these, —CONH—R ₇ — and —COO—R ₇ — are preferable because of polymerizability and availability. R ₇ is more preferably a methylene group, an ethylene group, a propylene group, or a butylene group, and particularly preferably an ethylene group.

  The Y- component in the general formula (2) constituting the counter anion of the resin may be an inorganic or organic anion. As the counter anion, known ones can be used without limitation. Specifically, hydroxide ions; halogen ions such as chloride ions, bromide ions, and iodide ions; carboxylate ions such as formate ions and acetate ions; Carbonate ions, bicarbonate ions, nitrate ions, sulfate ions, sulfite ions, chromate ions, dichromate ions, phosphate ions, cyanide ions, permanganate ions, and even hexacyanoferrate (III) ions And complex ions. From the viewpoint of synthesis suitability and stability, halogen ions and carboxylate ions are preferable, and halogen ions are most preferable. When the counter anion is an organic acid ion such as a carboxylate ion, the organic acid ion may be covalently bonded in the resin to form an inner salt.

  In order to obtain an acrylic resin containing the structural unit represented by the general formula (2), not only a method of copolymerizing an ethylenically unsaturated monomer having an ammonium base as a monomer component but also having an amino group After obtaining an acrylic resin having an amino group copolymerized with an ethylenically unsaturated monomer as a monomer component, it may be obtained by reacting an onium chlorinating agent and ammonium chloride.

  Specific examples of the ethylenically unsaturated monomer having an ammonium base, the ethylenically unsaturated monomer having an amino group, and an onium chlorinating agent are shown below. In addition, in this specification, when showing either or both of "acryl, methacryl", it may describe as "(meth) acryl". Similarly, when one or both of “acryloyl and methacryloyl” are indicated, it may be described as “(meth) acryloyl”.

  Examples of the ethylenically unsaturated monomer having an ammonium base include (meth) acryloyloxyethyltrimethylammonium chloride, (meth) acryloyloxyethyltriethylammonium chloride, (meth) acryloyloxyethyldimethylbenzylammonium chloride, and (meth) acryloyl. Alkyl (meth) acrylate quaternary ammonium salts such as oxyethylmethylmorpholino ammonium chloride, (meth) acryloylaminopropyltrimethylammonium chloride, (meth) acryloylaminoethyltriethylammonium chloride, (meth) acryloylaminoethyldimethylbenzylammonium chloride Alkyl (meth) acryloylamide quaternary ammonium salts such as dimethyl Allyl ammonium methyl sulfate, trimethyl vinyl phenyl ammonium chloride.

  Examples of the ethylenically unsaturated monomer having an amino group include dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, dipropylaminoethyl (meth) acrylate, diisopropylaminoethyl (meth) acrylate, and dibutylamino. Ethyl (meth) acrylate, diisobutylaminoethyl (meth) acrylate, di-t-butylaminoethyl (meth) acrylate, dimethylaminopropyl (meth) acrylamide, diethylaminopropyl (meth) acrylamide, dipropylaminopropyl (meth) acrylamide, diisopropyl Aminopropyl (meth) acrylamide, dibutylaminopropyl (meth) acrylamide, diisobutylaminopropyl (meth) acrylamide, di-t-butyl Examples include (meth) acrylic acid esters having a dialkylamino group such as minopropyl (meth) acrylamide or (meth) acrylamide, and styrenes having a dialkylamino group such as dimethylaminostyrene and dimethylaminomethylstyrene, diallylmethylamine, diallylamine And amino group-containing aromatic vinyl monomers such as N-vinylpyrrolidine, N-vinylpyrrolidone and N-vinylcarbazole.

  Examples of the onium chloride agent include alkyl sulfates such as dimethyl sulfate, diethyl sulfate, or dipropyl sulfate, sulfonate esters such as methyl p-toluenesulfonate, or methyl benzenesulfonate, methyl chloride, ethyl chloride, propyl chloride, or Examples thereof include alkyl chlorides such as octyl chloride, alkyl bromides such as methyl bromide, ethyl bromide, propyl bromide, and octyl chlorobromide, benzyl chloride, and benzyl bromide.

  The reaction between the ethylenically unsaturated monomer having an amino group and the onium chlorinating agent is usually performed by dropping an equimolar amount or less of the onium chlorinating agent into the amino group-containing ethylenically unsaturated monomer solution. Can be done. The temperature during the ammonium chlorination reaction is about 90 ° C. or less, and particularly when the vinyl monomer is ammonium chlorinated, it is preferably about 30 ° C. or less, and the reaction time is about 1 to 4 hours.

  Alternatively, an alkoxycarbonylalkyl halide can also be used as the onium chlorinating agent. The alkoxycarbonylalkyl halide is represented by the following general formula (21).

Z—R ₈ —COOR ₉ general formula (21)

(In the general formula (21), Z is a halogen such as chlorine or bromine, preferably bromine, and R ₈ is an alkylene group having 1 to 6 carbon atoms, preferably 1 to 5 carbon atoms, more preferably 1 to 3 carbon atoms. And R ₉ is a lower alkyl group having 1 to 6 carbon atoms, preferably 1 to 3 carbon atoms.)

Reaction of the ethylenically unsaturated monomer and alkoxycarbonylalkyl halide with an amino group, after equimolar following alkoxycarbonylalkyl halide was reacted in the same manner as in the above onium chloride agent to an amino group, a -COOR ₇ It is obtained by hydrolysis and conversion to carboxylate ions (—COO—). Thereby, an ethylenically unsaturated monomer having a carboxybetaine structure represented by the general formula (21) and having an ammonium base can be obtained.

  Other ethylenically unsaturated monomers that can be used other than the structural unit represented by the general formula (21) include, for example, (meth) acrylic acid esters, crotonic acid esters, vinyl esters, maleic acid Diesters, fumaric acid diesters, itaconic acid diesters, (meth) acrylamides, vinyl ethers, vinyl alcohol esters, styrenes, (meth) acrylonitrile and the like are preferable. Specific examples of such vinyl monomers include the following compounds.

  Examples of (meth) acrylic acid esters include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, and n-butyl (meth) acrylate. , Isobutyl (meth) acrylate, t-butyl (meth) acrylate, n-hexyl (meth) acrylate, cyclohexyl (meth) acrylate, t-butylcyclohexyl (meth) acrylate, (meth) acrylic acid 2- Ethylhexyl, t-octyl (meth) acrylate, dodecyl (meth) acrylate, octadecyl (meth) acrylate, acetoxyethyl (meth) acrylate, phenyl (meth) acrylate, 2-methoxyethyl (meth) acrylate, (Meth) acrylic acid 2-ethoxyethyl, (meth) acrylic acid 2- (2-methoxyethyl) Xyl) ethyl, benzyl (meth) acrylate, (meth) acrylic acid diethylene glycol monomethyl ether, (meth) acrylic acid diethylene glycol monoethyl ether, (meth) acrylic acid triethylene glycol monomethyl ether, (meth) acrylic acid triethylene glycol mono Ethyl ether, (meth) acrylic acid polyethylene glycol monomethyl ether, (meth) acrylic acid polyethylene glycol monoethyl ether, (meth) acrylic acid β-phenoxyethoxyethyl, (meth) acrylic acid nonylphenoxy polyethylene glycol, (meth) acrylic acid Dicyclopentenyl, dicyclopentenyloxyethyl (meth) acrylate, trifluoroethyl (meth) acrylate, octafluoropentyl (meth) acrylate , Perfluorooctylethyl (meth) acrylate, dicyclopentanyl (meth) acrylate, tribromophenyl (meth) acrylate, tribromophenyloxyethyl (meth) acrylate, and the like.

  Examples of crotonic acid esters include butyl crotonate and hexyl crotonate.

  Examples of vinyl esters include vinyl acetate, vinyl propionate, vinyl butyrate, vinyl methoxyacetate, vinyl benzoate, and the like. Examples of maleic acid diesters include dimethyl maleate, diethyl maleate, and dibutyl maleate.

  Examples of the fumaric acid diesters include dimethyl fumarate, diethyl fumarate, and dibutyl fumarate.

  Examples of itaconic acid diesters include dimethyl itaconate, diethyl itaconate, and dibutyl itaconate.

  Examples of (meth) acrylamides include (meth) acrylamide, N-methyl (meth) acrylamide, N-ethyl (meth) acrylamide, N-propyl (meth) acrylamide, N-isopropyl (meth) acrylamide, Nn -Butyl acryl (meth) amide, Nt-butyl (meth) acrylamide, N-cyclohexyl (meth) acrylamide, N- (2-methoxyethyl) (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N , N-diethyl (meth) acrylamide, N-phenyl (meth) acrylamide, N-benzyl (meth) acrylamide, (meth) acryloylmorpholine, diacetone acrylamide and the like.

  Examples of vinyl ethers include methyl vinyl ether, butyl vinyl ether, hexyl vinyl ether, and methoxyethyl vinyl ether. Examples of styrenes include styrene, methyl styrene, dimethyl styrene, trimethyl styrene, ethyl styrene, isopropyl styrene, butyl styrene, hydroxy styrene, methoxy styrene, butoxy styrene, acetoxy styrene, chlorostyrene, dichlorostyrene, bromostyrene, chloromethyl Examples thereof include styrene, hydroxystyrene protected with a group that can be deprotected by an acidic substance (for example, t-Boc and the like), methyl vinylbenzoate, and α-methylstyrene.

The acrylic resin containing the structural unit represented by the general formula (2) preferably has a thermally crosslinkable functional group.

The acrylic resin having a thermally crosslinkable functional group forms a crosslink between the acrylic resins having a thermal crosslinkable functional group or a binder resin in the heating step in the production of the color filter. Thereby, a strong film is formed, color change of the film can be prevented, that is, heat resistance can be improved, and solvent resistance is also improved.

The preferred structure of the thermally crosslinkable functional group is not particularly limited, and examples thereof include a hydroxyl group, a carboxyl group, a carboxylic anhydride, a primary or secondary amino group, an imino group, an oxetanyl group, a t-butyl group, and an epoxy. Group, mercapto group, isocyanate group, allyl group, (meth) acryl group and the like.
Among these, from the viewpoint of storage stability and reactivity with other materials in the use of a coloring composition for a color filter, a hydroxyl group, a carboxyl group, an oxetanyl group, a t-butyl group, an isocyanate group, and a (meth) acryl group are preferable. In particular, it preferably has a hydroxyl group.
Moreover, it is preferable to have a carboxyl group from a viewpoint of alkali developability.

  One method for introducing a heat-crosslinkable functional group in the resin (B) having a cationic group in the side chain used in the present invention into an acrylic resin is to use an ethylenically unsaturated monomer having a heat-crosslinkable functional group. And a method of copolymerizing with an ethylenically unsaturated monomer corresponding to the cationic group represented by the general formula (1).

  Examples of the ethylenically unsaturated monomer having a hydroxyl group are not particularly limited. For example, 2-hydroxyethyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, Examples thereof include glycerol mono (meth) acrylate, 4-hydroxyvinylbenzene, 2-hydroxy-3-phenoxypropyl acrylate or caprolactone adducts of these monomers (addition mole number is preferably 1 to 5).

  Examples of the ethylenically unsaturated monomer having a carboxyl group include acrylic acid, methacrylic acid, itaconic acid, maleic acid, fumaric acid, crotonic acid, etc., and ethylenic having a carboxylic anhydride group. Examples of the unsaturated monomer include maleic anhydride and itaconic anhydride.

  Examples of the ethylenically unsaturated monomer having an oxetanyl group include 3- (acryloyloxymethyl) 3-methyloxetane, 3- (methacryloyloxymethyl) 3-methyloxetane, 3- (acryloyloxymethyl) 3-ethyloxetane, 3- (methacryloyloxymethyl) 3-ethyloxetane, 3- (acryloyloxymethyl) 3-butyloxetane, 3- (methacryloyloxymethyl) 3-butyloxetane, 3- (acryloyloxymethyl) 3-hexyloxetane and 3- (Methacryloyloxymethyl) 3-hexyloxetane and the like.

  Examples of the ethylenically unsaturated monomer having a t-butyl group include t-butyl acrylate and t-butyl methacrylate.

  Examples of the ethylenically unsaturated monomer having an isocyanate group include 2-isocyanate ethyl methacrylate, 2-isocyanate ethyl acrylate, 4-isocyanate butyl methacrylate, 4-isocyanate butyl acrylate, and the like.

  The isocyanate group in the present invention includes a blocked isocyanate group and can be preferably used. Under normal conditions, the blocked isocyanate group can protect the isocyanate group with other functional groups to suppress the reactivity of the isocyanate group, and can be deprotected by heating to regenerate the active isocyanate group. The isocyanate block body is shown.

  Examples of commercially available ethylenically unsaturated monomers having such a blocked isocyanate group include 2-[(3,5-dimethylpyrazolyl) carboxyamino] ethyl methacrylate (Karenz MOI-BP, Showa Denko); Examples include 2- (0- [1′methylpropylideneamino] carboxyamino) ethyl methacrylate (Karenz MOI-BM, manufactured by Showa Denko).

  Moreover, as an ethylenically unsaturated monomer which has a block isocyanate group, a commercial item can be used, and it can also prepare and use by a well-known method. For example, an isocyanate compound having an ethylenically unsaturated bond and a blocking agent are stirred in a solvent at a temperature of about 0 to 200 ° C., and known separation and purification means such as concentration, filtration, extraction, crystallization and distillation are performed. It can obtain by separating using.

  Another method for introducing the thermally crosslinkable functional group in the resin (B) having a cationic group in the side chain used in the present invention into the acrylic resin is to obtain the acrylic resin, In this method, a functional group capable of reacting with the functional group is reacted with a compound having a thermally crosslinkable functional group. For example, by reacting a glycidyl group of an ethylenically unsaturated monomer having a glycidyl group with a carboxyl group in an acrylic resin having a carboxyl group, an acrylic resin having a (meth) acryloyl group as a thermally crosslinkable functional group is obtained. Can be obtained.

  At least one kind of the heat-crosslinkable functional group needs to be contained in the resin, and two or more kinds may be contained.

  Furthermore, when two or more types of thermally crosslinkable functional groups are contained, there is a preferable combination among the thermally crosslinkable functional groups. This is a combination in which heat-crosslinkable functional groups are more likely to react with each other when heated. In this case, the effect of crosslinking is improved. For example, it is effective to use an oxetanyl group and a carboxyl group at the same time. Similarly, since a t-butyl group becomes a carboxyl group when heated, a combination of an oxetanyl group and a t-butyl group is also effective. A combination of a hydroxyl group, a blocked isocyanate group and an isocyanate group is also effective. In particular, the combination of a hydroxyl group and a carboxyl group is most preferable because not only a strong film can be obtained by thermal crosslinking, but also in the alkali development step before thermal crosslinking, alkali developability is improved by the presence of carboxyl groups.

The acrylic resin containing the structural unit represented by the general formula (2) preferably has a glass transition temperature (hereinafter abbreviated as Tg) of 50 ° C. or higher.
An acrylic resin having a glass transition temperature (hereinafter abbreviated as Tg) of 50 ° C. or higher forms a stronger film in the heating process in the production of a color filter and prevents color change of the film, that is, improves heat resistance. In addition, the solvent resistance is improved.

When synthesizing the resin (B) having a cationic group in the side chain used in the present invention, an acrylic resin having a Tg of 50 ° C. or higher can be obtained by selecting an ethylenically unsaturated monomer to be used. it can. It is possible to control the Tg of the acrylic resin by appropriately selecting the ethylenically unsaturated monomer to be used within a range that does not affect other physical properties.

Considering use in the electronics field such as a color filter having a heating step of 200 ° C. or higher, the Tg of the acrylic part is more preferably 70 ° C. or higher. The upper limit of Tg is not particularly limited, but if it exceeds 150 ° C., there may be practical problems in workability and film-forming properties, so that it is preferably less than 150 ° C.

The Tg of the acrylic resin of the present invention indicates a value calculated by the Fox formula shown below from the Tg of each homopolymer of the ethylenically unsaturated monomer to be copolymerized.
Fox formula 1 / Tg = W1 / Tg1 + W2 / Tg2 +... + Wn / Tgn
W1 to Wn represent the weight fraction of the monomer used, and Tg1 to Tgn represent the glass transition temperature of the monomer homopolymer (unit is absolute temperature “K”).
Tg (glass transition temperature) of the homopolymer of the main monomer used for calculation is illustrated below.
Ethyl acrylate: -22 ° C (251K)
Butyl acrylate: -54 ° C (219K)
Benzyl methacrylate: 55 ° C (328K)
Acrylic acid: 106 ° C (379K)
Methyl methacrylate: 105 ° C (378K)
n-Butyl methacrylate: 20 ° C. (293K)
2-Ethylhexyl methacrylate: -10 ° C (263K)
Hydroxyethyl methacrylate: 55 ° C (328K)
Methacrylic acid: 130 ° C (403K)
3- (Methacryloyloxymethyl) 3-ethyloxetane: 105 ° C (378K)
2-isocyanatoethyl methacrylate: 60 ° C. (333 K)
t-Butyl methacrylate: 107 ° C (380K)
Dimethylaminoethylmethyl chloride methacrylate salt: 58 ° C (331K)

For example, when the calculation is performed by the above method, the glass transition temperature of the vinyl polymer portion obtained by radical polymerization of an ethylenically unsaturated monomer synthesized using 90 parts by weight of methyl methacrylate and 10 parts by weight of ethyl acrylate is 86.8. It becomes ℃.

In order to increase Tg, it is necessary to contain an ethylenically unsaturated monomer having a high Tg of the homopolymer in the copolymer composition. Among the ethylenically unsaturated monomers, the following are high in Tg and are effective for increasing the Tg of the acrylic resin.
Monomers with relatively high Tg of homopolymer are listed.
Methyl methacrylate: 105 ° C (378K)
t-Butyl methacrylate: 107 ° C (380K)
Methacrylic acid: 130 ° C (403K)
Acrylic acid: 106 ° C (379K)
3- (Methacryloyloxymethyl) 3-ethyloxetane: 105 ° C (378K)
Isobornyl acrylate: 94 ° C (367K)
Isobornyl methacrylate: 180 ° C (453K)
Dicyclopentanyl acrylate: 120 ° C (393K)
Dicyclopentanyl methacrylate: 175 ° C (448K)
Adamantyl acrylate: 153 ° C (426K)
Adamantyl methacrylate: 250 ° C (523K)
Among these, t-butyl methacrylate and methacrylic acid are particularly preferable because they can increase the Tg and introduce a thermally crosslinkable functional group. Further, methyl methacrylate is preferable from the viewpoint of versatility.

  As a method for obtaining a resin having a cationic group in the side chain, known methods such as anion polymerization, living anion polymerization, cation polymerization, living cation polymerization, free radical polymerization, and living radical polymerization can be used. Of these, free radical polymerization or living radical polymerization is preferred.

  In the case of the free radical polymerization method, it is preferable to use a polymerization initiator. As the polymerization initiator, for example, an azo compound and an organic peroxide can be used. Examples of the azo compounds include 2,2′-azobisisobutyronitrile, 2,2′-azobis (2-methylbutyronitrile), 1,1′-azobis (cyclohexane 1-carbonitrile), 2 , 2′-azobis (2,4-dimethylvaleronitrile), 2,2′-azobis (2,4-dimethyl-4-methoxyvaleronitrile), dimethyl 2,2′-azobis (2-methylpropionate) 4,4′-azobis (4-cyanovaleric acid), 2,2′-azobis (2-hydroxymethylpropionitrile), or 2,2′-azobis [2- (2-imidazolin-2-yl ) Propane] and the like. Examples of organic peroxides include benzoyl peroxide, t-butyl perbenzoate, cumene hydroperoxide, diisopropyl peroxydicarbonate, di-n-propyl peroxydicarbonate, di (2-ethoxyethyl) peroxy Examples thereof include dicarbonate, t-butyl peroxyneodecanoate, t-butyl peroxybivalate, (3,5,5-trimethylhexanoyl) peroxide, dipropionyl peroxide, and diacetyl peroxide. These polymerization initiators can be used alone or in combination of two or more. The reaction temperature is preferably 40 to 150 ° C., more preferably 50 to 110 ° C., and the reaction time is preferably 3 to 30 hours, more preferably 5 to 20 hours.

  In the living radical polymerization method, side reactions that occur in general radical polymerization are suppressed, and further, since the growth of polymerization occurs uniformly, it is possible to easily synthesize block polymers and resins with uniform molecular weight.

  Among them, the atom transfer radical polymerization method using an organic halide or a sulfonyl halide compound as an initiator and a transition metal complex as a catalyst is applicable to a wide range of monomers, and has a polymerization temperature applicable to existing equipment. It is preferable in that it can be adopted. The atom transfer radical polymerization method can be carried out by the methods described in the following references 1 to 8 and the like.

(Reference 1) Fukuda et al., Prog. Polym. Sci. 2004, 29, 329
(Reference 2) Matyjaszewski et al., Chem. Rev. 2001, 101, 2921
(Reference 3) Matyjaszewski et al. Am. Chem. Soc. 1995, 117, 5614
(Reference 4) Macromolecules 1995, 28, 7901, Science, 1996, 272, 866
(Reference 5) WO96 / 030421
(Reference 6) WO97 / 018247
(Reference 7) JP-A-9-208616 (Reference 8) JP-A-8-41117

  It is preferable to use an organic solvent for the polymerization. The organic solvent is not particularly limited, but for example, ethyl acetate, n-butyl acetate, isobutyl acetate, toluene, xylene, acetone, hexane, methyl ethyl ketone, cyclohexanone, propylene glycol monomethyl ether acetate, dipropylene glycol monomethyl ether Acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, or the like is used. Two or more kinds of these polymerization solvents may be mixed and used.

The amount of the ammonium base present in the resin having a cationic group in the side chain is not particularly limited, but the ammonium salt value of the resin is preferably 10 to 200 mgKOH / g, and 20 to 130 mgKOH / g. It is more preferable that When the ammonium salt value is less than 10 mgKOH / g, the ratio of the anionic dye (a1) to be reacted is reduced, so that the coloring power is lowered, and more salt-forming compound (a3) is required in the resist material. Therefore, the binder resin, the curable resin, or the like originally added to the resist material is reduced, and the glass adhesion of the resist film may be deteriorated or the coating film resistance of the resist film may be deteriorated. On the other hand, when it exceeds 200 mgKOH / g, the solvent solubility of the salt-forming compound (a3) is deteriorated and may be deposited as a foreign substance in the resist material.
In order for the ammonium salt value of the resin to satisfy the above range, the preferred content of the structural unit having a quaternary ammonium base is 4 to 74% by weight in a total of 100% by weight of the structural units constituting the resin, A more preferred range is 8 to 48% by weight.

  The molecular weight of the resin having a cationic group in the side chain used in the present invention is not particularly limited, but the weight average molecular weight in terms of polystyrene measured by gel permeation chromatography (GPC) is 1,000 to 500. Is preferably 3,000, more preferably 3,000 to 15,000.

  In the resin having a cationic group in the side chain, the total content of the structural unit represented by the general formula (2) is not particularly limited, but the entire structure contained in the resin having a cationic group in the side chain When the unit is 100 parts by mass, the total content of the structural unit represented by the general formula (2) is 5 parts by mass or more from the viewpoint of solvent solubility and coloring power of the salt-formation product. Is preferable, and it is more preferable that it is 10-50 mass parts.

(Amine)
Examples of the amine of the present invention include primary amine compounds, secondary amine compounds, and tertiary amine compounds.

  Primary amine compounds include methylamine, ethylamine, propylamine, isopropylamine, butylamine, amylamine, hexylamine, heptylamine, octylamine, nonylamine, decylamine, undecylamine, dodecylamine (laurylamine), tridodecylamine, tetra Examples include aliphatic unsaturated primary amines such as decylamine (myristylamine), pentadecylamine, cetylamine, stearylamine, oleylamine, cocoalkylamine, beef tallow alkylamine, cured tallow alkylamine, allylamine, aniline, and benzylamine. .

  Secondary amine compounds include aliphatic unsaturated secondary amines such as dimethylamine, diethylamine, dipropylamine, diisopropylamine, dibutylamine, diamylamine, diallylamine, methylaniline, ethylaniline, dibenzylamine, diphenylamine, dicocoalkyl. Amine, di-cured tallow alkylamine, distearylamine, etc.

  Examples of the tertiary amine compound include trimethylamine, triethylamine, tripropylamine, tributylamine, triamylamine, dimethylaniline, diethylaniline, tribenzylamine and the like.

(Salt formation)
The salt-forming compound (D) of the present invention is prepared by stirring or vibrating an aqueous solution in which a compound (B) having a cationic group and an anionic dye (C) are dissolved, or a compound having a cationic group (B ) And an aqueous solution of the anionic dye (C) can be easily obtained by mixing under stirring or vibration. In the aqueous solution, the cationic group of the compound and the anionic group of the dye are ionized, these are ionically bonded, and the ion-bonded portion becomes water-insoluble and precipitates. On the contrary, the salt composed of the counter anion of the compound and the counter cation of the acidic dye is water-soluble, and can be removed by washing with water. As the compound (B) having a cationic group and the anionic dye (C) to be used, only a single type or a plurality of types having different structures may be used.

As an aqueous solution used at the time of salt formation, a mixed solution of water and a water-soluble organic solvent may be used in order to dissolve the compound (B) having a cationic group in the side chain and an anionic dye. Examples of the water-soluble organic solvent include methanol, ethanol, n-propanol, isopropanol, 1-methoxy-2-propanol, 1-ethoxy-2-propanol, n-butanol, isobutanol, 2- (methoxymethoxy) ethanol, 2- Butoxyethanol, 2- (isopentyloxy) ethanol, 2- (hexyloxy) ethanol, ethylene glycol, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene Glycol, propylene glycolic monomethyl ether acetate, dipropylene glycol, dipropylene glycol Monomethyl ether, dipropylene glycol monoethyl ether, triethylene glycol, triethylene glycol monomethyl ether, polyethylene glycol, glycerin, tetraethylene glycol, dipropylene glycol, acetone, diacetone alcohol, aniline, pyridine, ethyl acetate, isopropyl acetate, methyl ethyl ketone , N, N-dimethylformamide, dimethyl sulfoxide, tetrahydrofuran (THF), dioxane, 2-pyrrolidone, 2-methylpyrrolidone, N-methyl-2-pyrrolidone, 1,2-hexanediol, 2,4,6-hexanetriol , Tetrafurfuryl alcohol, 4-methoxy-4-methylpentanone and the like. These water-soluble organic solvents are preferably used in an amount of 5 to 50% by weight, and most preferably 5 to 20% by weight, based on the total weight of the aqueous solution (100% by weight).

The ratio of the compound (B) having a cationic group to the anionic dye (C) is such that the molar ratio of the total cationic unit of the resin to the total anionic group of the anionic dye (C) is 10/1 to 1 / If it is in the range of 4, the salt-forming compound (D) of the present invention can be suitably adjusted, and the range of 2/1 to 1/2 is more preferable.

[Pigment]
The colorant (A) used in the photosensitive coloring composition for a color filter of the present invention can be used by further adding a pigment and using it in combination.
As the pigment, organic or inorganic pigments can be used alone or in admixture of two or more. The pigment is preferably a pigment having a high color developability and a high heat resistance, particularly a pigment having a high heat decomposition resistance, and an organic pigment is usually used. Below, the specific example of the organic pigment which can be used for a coloring agent (A) is shown by a color index number.

  Examples of the red pigment for forming the red filter segment include C.I. I. Pigment Red 7, 9, 14, 41, 48: 1, 48: 2, 48: 3, 48: 4, 57: 1, 81, 81: 1, 81: 2, 81: 3, 81: 4, 122, 123, 146, 150, 168, 169, 176, 177, 178, 180, 184, 185, 187, 192, 200, 202, 208, 210, 215, 216, 217, 220, 223, 224, 226, 227, 228, 240, 242, 246, 254, 255, 264, 268, 270, 272, 273, 274, 276, 277, 278, 279, 280, 281, 282, 283, 284, 285, 286, or 287, etc. Red pigments can be used. In addition to these red pigments, C.I. I. Pigment Orange 38, 43, 71, or 73, and / or C.I. I. Pigment Yellow 1, 2, 3, 4, 5, 6, 10, 12, 13, 14, 15, 16, 17, 18, 24, 31, 32, 34, 35, 35: 1, 36, 36: 1, 37, 37: 1, 40, 42, 43, 53, 55, 60, 61, 62, 63, 65, 73, 74, 77, 81, 83, 93, 94, 95, 97, 98, 100, 101, 104, 106, 108, 109, 110, 113, 114, 115, 116, 117, 118, 119, 120, 123, 126, 127, 128, 129, 138, 139, 147, 150, 151, 152, 153, 154, 155, 156, 161, 162, 164, 166, 167, 168, 169, 170, 171, 172, 173, 174, 175, 176, 177, 179, 180, 181 , 182, 185, 187, 188, 193, 194, 198, 199, 213, 214, 218, 219, 220, or 221 can be used in combination.

Examples of the green pigment for forming the green filter segment include C.I. I. Green pigments such as CI Pigment Green 7, 10, 36, 37, 58 can be used. In addition to these green pigments, C.I. I. Pigment Yellow 1, 2, 3, 4, 5, 6, 10, 12, 13, 14, 15, 16, 17, 18, 24, 31, 32, 34, 35, 35: 1, 36, 36: 1, 37, 37: 1, 40, 42, 43, 53, 55, 60, 61, 62, 63, 65, 73, 74, 77, 81, 83, 93, 94, 95, 97, 98, 100, 101, 104, 106, 108, 109, 110, 113, 114, 115, 116, 117, 118, 119, 120, 123, 126, 127, 128, 129, 138, 139, 147, 150, 151, 152, 153, 154, 155, 156, 161, 162, 164, 166, 167, 168, 169, 170, 171, 172, 173, 174, 175, 176, 177, 179, 180, 181 182,185,187,188,193,194,198,199,213,214,218,219,220, or a yellow pigment 221 and the like can be used in combination.
It is also preferable to use an aluminum phthalocyanine pigment, and aluminum phthalocyanine pigments described in JP-A No. 2004-333817, Japanese Patent No. 4893859 and the like can also be used.

  Examples of the blue pigment for forming the blue filter segment include C.I. I. Pigment Blue 1, 1: 2, 1: 3, 2, 2: 1, 2: 2, 3, 8, 9, 10, 10: 1, 11, 12, 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, 16, 18, 19, 22, 24, 24: 1, 53, 56, 56: 1, 57, 58, 59, 60, 61, 62, 64, etc. Can be used. In addition to these blue pigments, C.I. I. Purple violet pigments such as CI Pigment Violet 1, 19, 23, 27, 29, 30, 32, 37, 40, 42, and 50 can be used in combination.

  Examples of cyan pigments for forming a cyan filter segment include C.I. I. Blue pigments for cyan such as CI Pigment Blue 15: 1, 15: 2, 15: 4, 15: 3, 15: 6, 16, and 81 can be used alone or in combination.

  Examples of the magenta pigment for forming the magenta color filter segment include C.I. I. Pigment violet 1, 19, C.I. I. Purple pigments such as CI Pigment Red 144, 146, 177, 169, 81, and red pigments can be used alone or in combination. As these magenta pigments, yellow pigments can be used in combination with the magenta red and purple pigments.

  In addition, inorganic pigments include titanium oxide, barium sulfate, zinc white, lead sulfate, yellow lead, zinc yellow, red bean (red iron oxide (III)), cadmium red, ultramarine blue, bitumen, chromium oxide green, cobalt green, amber And synthetic iron black. Inorganic pigments are used in combination with organic pigments in order to ensure good coatability, sensitivity, developability and the like while maintaining a balance between saturation and lightness.

  The use ratio of the pigment and the salt-forming compound (D) is preferably 1 to 800 parts by weight of the salt-forming compound (D) with respect to 100 parts by weight of the pigment. More preferably, it is 5 to 400 parts by weight. If the addition amount of the salt-forming compound (D) is less than 1 part by weight, the reproducible chromaticity region becomes narrow, and if it exceeds 800 parts by weight, the hue changes, which is not preferable.

  Further, when converted in consideration of the color composition, when the pigment and the salt-forming compound (D) are salt-forming compounds, the blending ratio with the content of the effective pigment component in the anionic dye in the salt-forming compound is 100% of the pigment. The effective pigment component in the dye is preferably 1 to 400 parts by weight with respect to parts by weight. More preferably, the effective pigment component in the dye is in the range of 5 to 300 parts by weight with respect to 100 parts by weight of the pigment.

(Miniaturization of pigment)
The pigment added to the colorant (A) used in the present invention is preferably refined by a salt milling process or the like in order to correspond to high transmittance and high contrast. The primary particle diameter of the pigment is preferably 10 nm or more because of good dispersion in the colorant carrier. Moreover, since a filter segment with high contrast can be formed, it is preferable that it is 80 nm or less. A particularly preferred range is 20 to 60 nm.

  Salt milling is a process in which a mixture of pigment, water-soluble inorganic salt and water-soluble organic solvent is heated using a kneader such as a kneader, two-roll mill, three-roll mill, ball mill, attritor, or sand mill. After kneading, the water-soluble inorganic salt and the water-soluble organic solvent are removed by washing with water. The water-soluble inorganic salt serves as a crushing aid, and the pigment is crushed using the high hardness of the inorganic salt during salt milling. By optimizing the conditions for salt milling the pigment, it is possible to obtain a pigment having a sharp particle size distribution with a very fine primary particle diameter and a wide distribution range.

  As the water-soluble inorganic salt, sodium chloride, barium chloride, potassium chloride, sodium sulfate and the like can be used, but sodium chloride (salt) is preferably used from the viewpoint of cost. The water-soluble inorganic salt is preferably used in an amount of 50 to 2000 parts by weight, and most preferably 300 to 1000 parts by weight with respect to 100 parts by weight of the pigment, from the viewpoint of both processing efficiency and production efficiency.

  The water-soluble organic solvent functions to wet the pigment and the water-soluble inorganic salt, and is not particularly limited as long as it dissolves (mixes) in water and does not substantially dissolve the inorganic salt to be used. However, a high boiling point solvent having a boiling point of 120 ° C. or higher is preferable from the viewpoint of safety because the temperature rises during salt milling and the solvent is easily evaporated. For example, 2-methoxyethanol, 2-butoxyethanol, 2- (isopentyloxy) ethanol, 2- (hexyloxy) ethanol, diethylene glycol, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, triethylene glycol, triethylene glycol monomethyl ether, Liquid polyethylene glycol, 1-methoxy-2-propanol, 1-ethoxy-2-propanol, dipropylene glycol, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, liquid polypropylene glycol and the like are used. The water-soluble organic solvent is preferably used in an amount of 5 to 1000 parts by weight, and most preferably 50 to 500 parts by weight, based on 100 parts by weight of the pigment.

  When the salt is milled, a resin may be added as necessary. The type of resin used is not particularly limited, and natural resins, modified natural resins, synthetic resins, synthetic resins modified with natural resins, and the like can be used. The resin used is solid at room temperature, preferably insoluble in water, and more preferably partially soluble in the organic solvent. The amount of the resin used is preferably in the range of 5 to 200 parts by weight with respect to 100 parts by weight of the pigment.

<Binder resin>
The binder resin is one that disperses a colorant, particularly a salt-forming compound (D) and a pigment, or one that dyes and penetrates a salt-forming compound, and examples thereof include thermoplastic resins and thermosetting resins.

  Examples of the thermoplastic resin include acrylic resin, butyral resin, styrene-maleic acid copolymer, chlorinated polyethylene, chlorinated polypropylene, polyvinyl chloride, vinyl chloride-vinyl acetate copolymer, polyvinyl acetate, and polyurethane resin. Polyester resins, vinyl resins, alkyd resins, polystyrene resins, polyamide resins, rubber resins, cyclized rubber resins, celluloses, polyethylene (HDPE, LDPE), polybutadiene, polyimide resins, and the like.

  Examples of the thermosetting resin include epoxy resins, benzoguanamine resins, rosin-modified maleic acid resins, rosin-modified fumaric acid resins, melamine resins, urea resins, and phenol resins.

  The binder resin is preferably a resin having a spectral transmittance of preferably 80% or more, more preferably 95% or more in the entire wavelength region of 400 to 700 nm in the visible light region. Moreover, since the coloring composition for color filters of the present invention is in the form of an alkali development type colored resist material, it is preferable to use an alkali-soluble vinyl resin obtained by copolymerizing an acidic group-containing ethylenically unsaturated monomer.

  Examples of the alkali-soluble resin obtained by copolymerizing an acidic group-containing ethylenically unsaturated monomer include resins having an acidic group such as a carboxyl group and a sulfone group. Specific examples of the alkali-soluble resin include an acrylic resin having an acidic group, an α-olefin / (anhydrous) maleic acid copolymer, a styrene / styrene sulfonic acid copolymer, an ethylene / (meth) acrylic acid copolymer, or Examples include isobutylene / (anhydrous) maleic acid copolymer. Among these, at least one resin selected from an acrylic resin having an acidic group and a styrene / styrene sulfonic acid copolymer, particularly an acrylic resin having an acidic group, is preferably used because of its high heat resistance and transparency.

  In order to improve the photosensitivity of the alkali-soluble resin copolymerized with the acidic group-containing ethylenic non-monomer, an energy beam curable resin having an ethylenically unsaturated active double bond can also be used. In addition, it is preferable to use an active energy ray-curable resin having an ethylenically unsaturated double bond in the side chain because it has an effect of improving the solvent resistance of the resist material.

  Examples of the active energy ray-curable resin having an ethylenically unsaturated double bond include resins having an unsaturated ethylenic double bond introduced by the following methods (a) and (b).

[Method (a)]
As the method (a), for example, a side chain epoxy group of a copolymer obtained by copolymerizing an unsaturated ethylenic monomer having an epoxy group and one or more other monomers is used. Then, the carboxyl group of the unsaturated monobasic acid having an unsaturated ethylenic double bond is subjected to an addition reaction, and the resulting hydroxyl group is reacted with a polybasic acid anhydride to convert the unsaturated ethylenic double bond and the carboxyl group into There is a way to introduce.

  Examples of the unsaturated ethylenic monomer having an epoxy group include glycidyl (meth) acrylate, methyl glycidyl (meth) acrylate, 2-glycidoxyethyl (meth) acrylate, 3,4 epoxybutyl (meth) acrylate, And 3,4 epoxy cyclohexyl (meth) acrylates, and these may be used alone or in combination of two or more. From the viewpoint of reactivity with the unsaturated monobasic acid in the next step, glycidyl (meth) acrylate is preferred.

  Examples of unsaturated monobasic acids include (meth) acrylic acid, crotonic acid, o-, m-, p-vinylbenzoic acid, α-haloalkyl of (meth) acrylic acid, alkoxyl, halogen, nitro, cyano substituted products, etc. Monocarboxylic acid etc. are mentioned, These may be used independently or may use 2 or more types together.

  Examples of polybasic acid anhydrides include tetrahydrophthalic anhydride, phthalic anhydride, hexahydrophthalic anhydride, succinic anhydride, maleic anhydride, etc., and these may be used alone or in combination of two or more. It doesn't matter. If necessary, use a tricarboxylic anhydride such as trimellitic anhydride or a tetracarboxylic dianhydride such as pyromellitic dianhydride to increase the number of carboxyl groups. The group can also be hydrolyzed. Moreover, when an etrahydrophthalic anhydride or maleic anhydride having an unsaturated ethylenic double bond is used as the polybasic acid anhydride, the number of unsaturated ethylenic double bonds can be increased.

  As a method similar to the method (a), for example, a side chain of a copolymer obtained by copolymerizing an unsaturated ethylenic monomer having a carboxyl group and one or more other monomers. There is a method in which an unsaturated ethylenic monomer having an epoxy group is added to a part of a carboxyl group to introduce an unsaturated ethylenic double bond and a carboxyl group.

[Method (b)]
As the method (b), an unsaturated ethylenic monomer having a hydroxyl group is used, and an unsaturated monobasic acid monomer having another carboxyl group or another monomer is copolymerized. There is a method of reacting an isocyanate group of an unsaturated ethylenic monomer having an isocyanate group with a side chain hydroxyl group of the obtained copolymer.

  Examples of the unsaturated ethylenic monomer having a hydroxyl group include 2-hydroxyethyl (meth) acrylate, 2- or 3-hydroxypropyl (meth) acrylate, 2- or 3- or 4-hydroxybutyl (meth) acrylate, and glycerol Examples thereof include hydroxyalkyl (meth) acrylates such as (meth) acrylate or cyclohexanedimethanol mono (meth) acrylate, and these may be used alone or in combination of two or more. Further, polyether mono (meth) acrylate obtained by addition polymerization of ethylene oxide, propylene oxide, and / or butylene oxide to the above hydroxyalkyl (meth) acrylate, (poly) γ-valerolactone, (poly) ε-caprolactone And / or (poly) 12-hydroxystearic acid added (poly) ester mono (meth) acrylate can also be used. From the viewpoint of suppressing foreign matter on the coating film, 2-hydroxyethyl (meth) acrylate or glycerol (meth) acrylate is preferable.

  Examples of the unsaturated ethylenic monomer having an isocyanate group include 2- (meth) acryloyloxyethyl isocyanate, 1,1-bis [(meth) acryloyloxy] ethyl isocyanate, and the like. In addition, two or more types can be used in combination.

  The weight average molecular weight (Mw) of the binder resin is preferably in the range of 10,000 to 100,000, more preferably in the range of 10,000 to 80,000 in order to disperse the colorant preferably. The number average molecular weight (Mn) is preferably in the range of 5,000 to 50,000, and the value of Mw / Mn is preferably 10 or less.

  The binder resin has an affinity for a colorant adsorbing group and a carboxyl group acting as an alkali-soluble group during development, a colorant carrier, and a solvent from the viewpoints of dispersibility, penetrability, developability, and heat resistance of the pigment and salt-forming compound. The balance between the aliphatic group and aromatic group acting as a functional group is important for the dispersibility, penetrability, developability and durability of the pigment and salt-forming compound, and a resin having an acid value of 20 to 300 mgKOH / g is used. It is preferable. When the acid value is less than 20 mgKOH / g, the solubility in the developing solution is poor and it is difficult to form a fine pattern. When it exceeds 300 mgKOH / g, no fine pattern remains.

  The binder resin is preferably used in an amount of 30% by weight or more based on the total weight of the colorant (100% by weight) because the film formability and various resistances are good, and the colorant concentration is high and good. Since color characteristics can be expressed, it is preferably used in an amount of 500 wt% or less.

<Organic solvent>
In the photosensitive color composition for color filter of the present invention, the colorant (A) is sufficiently dispersed and penetrated in the colorant carrier, and the dry film thickness becomes 0.2 to 5 μm on a substrate such as a glass substrate. In order to make it easy to apply and form a filter segment, an organic solvent can be included.

  Examples of the organic solvent include ethyl lactate, benzyl alcohol, 1,2,3-trichloropropane, 1,3-butanediol, 1,3-butylene glycol, 1,3-butylene glycol diacetate, 1,4-dioxane, 2-heptanone, 2-methyl-1,3-propanediol, 3,5,5-trimethyl-2-cyclohexen-1-one, 3,3,5-trimethylcyclohexanone, ethyl 3-ethoxypropionate, 3-methyl -1,3-butanediol, 3-methoxy-3-methyl-1-butanol, 3-methoxy-3-methylbutyl acetate, 3-methoxybutanol, 3-methoxybutyl acetate, 4-heptanone, m-xylene, m -Diethylbenzene, m-dichlorobenzene, N, N-dimethylacetamide, N, N- Methylformamide, n-butyl alcohol, n-butylbenzene, n-propyl acetate, o-xylene, o-chlorotoluene, o-diethylbenzene, o-dichlorobenzene, p-chlorotoluene, p-diethylbenzene, sec-butylbenzene, tert-butylbenzene, γ-butyrolactone, isobutyl alcohol, isophorone, ethylene glycol diethyl ether, ethylene glycol dibutyl ether, ethylene glycol monoisopropyl ether, ethylene glycol monoethyl ether, ethylene glycol monoethyl ether acetate, ethylene glycol monotertiary butyl ether, Ethylene glycol monobutyl ether, ethylene glycol monobutyl ether acetate, ethylene glycol Monopropyl ether, ethylene glycol monohexyl ether, ethylene glycol monomethyl ether, ethylene glycol monomethyl ether acetate, diisobutyl ketone, diethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol monoisopropyl ether, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether, diethylene glycol monobutyl ether acetate , Diethylene glycol monomethyl ether, cyclohexanol, cyclohexanol acetate, cyclohexanone, dipropylene glycol dimethyl ether, dipropylene glycol methyl ether acetate, dipropylene glycol monoethyl ether Dipropylene glycol monobutyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monomethyl ether, diacetone alcohol, triacetin, tripropylene glycol monobutyl ether, tripropylene glycol monomethyl ether, propylene glycol diacetate, propylene glycol phenyl ether, propylene glycol mono Ethyl ether, propylene glycol monoethyl ether acetate, propylene glycol monobutyl ether, propylene glycol monopropyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether propionate, benzyl alcohol, Louis Seo ketone, methyl cyclohexanol, acetic acid n- amyl acetate n- butyl, isoamyl acetate, isobutyl acetate, propyl acetate, and dibasic acid esters.

  Among them, glycol acetates such as ethyl lactate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate and the like because of good dispersion and dissolution of the colorant (A) It is preferable to use aromatic alcohols such as benzyl alcohol and ketones such as cyclohexanone.

  These organic solvents can be used individually by 1 type or in mixture of 2 or more types. When using 2 or more types of mixed solvents, it is preferable that said preferable organic solvent is contained 65 to 95 weight% on the basis (100 weight%) of organic solvent whole quantity.

  Among these, propylene glycol monomethyl ether acetate is more preferable from the viewpoint of safety and health and low viscosity, and it is preferable that propylene glycol monomethyl ether acetate is a main component. In the present invention, the main component is a solvent having the largest percentage by weight in the total solvent.

  Moreover, since the organic solvent can adjust a coloring composition to appropriate viscosity and can form the filter segment of the target uniform film thickness, it is the quantity of 800-4000 weight part with respect to 100 weight part of coloring agents (A). It is preferable to use it.

<Photopolymerizable monomer>
The coloring composition for a color filter of the present invention is used after adding a photopolymerizable monomer.
The photopolymerizable monomer used in the present invention includes monomers or oligomers that are cured by ultraviolet rays or heat to produce a transparent resin, and these can be used alone or in admixture of two or more. The blending amount of the photopolymerizable monomer is preferably 5 to 400 parts by weight with respect to 100 parts by weight of the colorant (A), and 10 to 300 parts by weight from the viewpoint of photocurability and developability. Is more preferable.

  Examples of monomers and oligomers that are cured by ultraviolet rays or heat to produce a transparent resin include methyl (meth) acrylate, ethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, and 2-hydroxypropyl (meth) acrylate. , Cyclohexyl (meth) acrylate, β-carboxyethyl (meth) acrylate, polyethylene glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, triethylene glycol di (meth) acrylate, tripropylene glycol di ( (Meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, 1,6-hexanediol diglycy Luether di (meth) acrylate, bisphenol A diglycidyl ether di (meth) acrylate, neopentyl glycol diglycidyl ether di (meth) acrylate, dipentaerythritol hexa (meth) acrylate, dipentaerythritol penta (meth) acrylate, tricyclodeca Nyl (meth) acrylate, ester acrylate, methylolated melamine (meth) acrylate ester, epoxy (meth) acrylate, urethane acrylate and other acrylic esters and methacrylate esters, (meth) acrylic acid, styrene, vinyl acetate, Hydroxyethyl vinyl ether, ethylene glycol divinyl ether, pentaerythritol trivinyl ether, (meth) acrylamide, N-hydroxymethyl Examples include, but are not necessarily limited to, til (meth) acrylamide, N-vinylformamide, acrylonitrile and the like.

<Photopolymerization initiator>
The coloring composition for a color filter of the present invention is used after adding a photopolymerization initiator.
The colored composition for a color filter of the present invention is obtained by curing the composition by ultraviolet irradiation and adding a photopolymerization initiator when forming a filter segment by a photolithographic method. It is prepared in the form of The amount of the photopolymerization initiator used is preferably 5 to 200 parts by weight with respect to 100 parts by weight of the colorant (A), and 10 to 150 parts by weight from the viewpoint of photocurability and developability. More preferably.

  As the photopolymerization initiator (F), 4-phenoxydichloroacetophenone, 4-t-butyl-dichloroacetophenone, diethoxyacetophenone, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one, 2- (dimethylamino) -2-[(4-methylphenyl) methyl Acetophenone compounds such as 1- [4- (4-morpholinyl) phenyl] -1-butanone or 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one; Benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether Benzoin compounds such as tereline or benzyldimethyl ketal; benzophenone, benzoylbenzoic acid, methyl benzoylbenzoate, 4-phenylbenzophenone, hydroxybenzophenone, acrylated benzophenone, 4-benzoyl-4'-methyldiphenyl sulfide, or 3,3 Benzophenone compounds such as', 4,4'-tetra (t-butylperoxycarbonyl) benzophenone; thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, isopropylthioxanthone, 2,4-diisopropylthioxanthone, or 2,4- Thioxanthone compounds such as diethyl thioxanthone; 2,4,6-trichloro-s-triazine, 2-phenyl-4,6-bis (trichloromethyl) -s-triazine, -(P-methoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (p-tolyl) -4,6-bis (trichloromethyl) -s-triazine, 2-piperonyl-4, 6-bis (trichloromethyl) -s-triazine, 2,4-bis (trichloromethyl) -6-styryl-s-triazine, 2- (naphth-1-yl) -4,6-bis (trichloromethyl)- s-triazine, 2- (4-methoxy-naphth-1-yl) -4,6-bis (trichloromethyl) -s-triazine, 2,4-trichloromethyl- (piperonyl) -6-triazine, or 2, Triazine compounds such as 4-trichloromethyl- (4′-methoxystyryl) -6-triazine; 1,2-octanedione, 1- [4- (phenylthio)-, 2- (O-benzene) Nzoyloxime)], or oxime ester compounds such as O- (acetyl) -N- (1-phenyl-2-oxo-2- (4′-methoxy-naphthyl) ethylidene) hydroxylamine; bis (2,4 , 6-trimethylbenzoyl) phenylphosphine oxide or phosphine compounds such as 2,4,6-trimethylbenzoyldiphenylphosphine oxide; quinone compounds such as 9,10-phenanthrenequinone, camphorquinone and ethylanthraquinone; A compound; a carbazole compound; an imidazole compound; or a titanocene compound is used.

  These photopolymerization initiators can be used alone or in combination of two or more at any ratio as required.

<Sensitizer>
Furthermore, the photosensitive coloring composition for a color filter of the present invention can contain a sensitizer.

  Sensitizers include chalcone derivatives, unsaturated ketones such as dibenzalacetone, 1,2-diketone derivatives such as benzyl and camphorquinone, benzoin derivatives, fluorene derivatives, naphthoquinone derivatives, anthraquinone derivatives , Xanthene derivatives, thioxanthene derivatives, xanthone derivatives, thioxanthone derivatives, coumarin derivatives, ketocoumarin derivatives, cyanine derivatives, merocyanine derivatives, oxonol derivatives, and other polymethine dyes, acridine derivatives, azine derivatives, thiazine derivatives, oxazine derivatives, indoline derivatives, Azulene derivatives, azurenium derivatives, squarylium derivatives, porphyrin derivatives, tetraphenylporphyrin derivatives, triarylmethane derivatives, tetrabenzoporphyrin derivatives, Trapirazinoporphyrazine derivatives, phthalocyanine derivatives, tetraazaporphyrazine derivatives, tetraquinoxalyloporphyrazine derivatives, naphthalocyanine derivatives, subphthalocyanine derivatives, pyrylium derivatives, thiopyrylium derivatives, tetraphyrin derivatives, annulene derivatives, spiropyran derivatives, spirooxazine Derivatives, thiospiropyran derivatives, metal arene complexes, organoruthenium complexes, or Michler's ketone derivatives, α-acyloxy esters, acylphosphine oxides, methylphenylglyoxylate, benzyl, 9,10-phenanthrenequinone, camphorquinone, ethyl Anthraquinone, 4,4'-diethylisophthalophenone, 3,3 'or 4,4'-tetra (t-butylperoxycarbonyl) benzo Phenone, 4,4'-diethylaminobenzophenone, etc. are mentioned.

  More specifically, edited by Shin Okawara et al., “Dye Handbook” (1986, Kodansha), edited by Shin Okawara et al., “Chemistry of Functional Dye” (1981, CMC), edited by Tadasaburo Ikemori et al. Examples include, but are not limited to, sensitizers described in "Special Functional Materials" (1986, CMC). In addition, a sensitizer that absorbs light from the ultraviolet region to the near infrared region can also be contained.

  Two or more kinds of sensitizers may be used in any ratio as required. It is preferable that the compounding quantity at the time of using a sensitizer is 3-60 weight part with respect to 100 weight part of photoinitiators contained in a coloring composition, and 5 from a viewpoint of photocurability and developability. More preferably, it is -50 weight part.

<Antioxidant>
In order to increase the transmittance of the coating film, it is preferable that the photosensitive coloring composition for a color filter of this embodiment further contains an antioxidant.
The antioxidant is oxidized by heat treatment performed by the photopolymerization initiator and the thermosetting resin contained in the photosensitive coloring composition in the thermosetting step and the ITO (indium tin oxide) annealing step, and as a result, Can prevent yellowing. Therefore, when the coloring composition contains an antioxidant, the transmittance of the coating film can be increased.

  As the antioxidant, for example, a hindered phenol antioxidant, a hindered amine antioxidant, a phosphorus antioxidant or a sulfide antioxidant is preferably used, and a hindered phenol antioxidant, a hindered amine It is more preferable to use an antioxidant or a phosphorus antioxidant. These may be used alone or in combination of two or more.

  Examples of the hindered phenol antioxidant include pentaerythritol-tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], 2,4-bis [(laurylthio) methyl]- o-cresol, 1,3,5-tris (3,5-di-tert-butyl-4-hydroxybenzyl), 1,3,5-tris (4-tert-butyl-3-hydroxy-2,6- Dimethylbenzyl), and 2,4-bis- (n-octylthio) -6- (4-hydroxy-3,5-di-t-butylanilino) -1,3,5-triazine.

  Examples of the hindered amine antioxidant include bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate and bis (N-methyl-2,2,6,6-tetramethyl-4-piperidyl). Sebacate, N, N′-bis (2,2,6,6-tetramethyl-4-piperidyl) -1,6-hexamethylenediamine, 2-methyl-2- (2,2,6,6-tetramethyl) -4-piperidyl) amino-N- (2,2,6,6-tetramethyl-4-piperidyl) propionamide, tetrakis (2,2,6,6-tetramethyl-4-piperidyl) (1,2, 3,4-butanetetracarboxylate, poly [{6- (1,1,3,3-tetramethylbutyl) imino-1,3,5-triazine-2,4-diyl} {(2,2,6 , 6-Tetramethyl-4- Peridyl) imino} hexamethyl {(2,2,6,6-tetramethyl-4-piperidyl) imino}], poly [(6-morpholino-1,3,5-triazine-2,4-diyl) {(2 , 2,6,6-tetramethyl-4-piperidyl) imino} hexamethine {(2,2,6,6-tetramethyl-4-piperidyl) imino}], dimethyl succinate and 1- (2-hydroxyethyl) Polycondensates with -4-hydroxy-2,2,6,6-tetramethylpiperidine, and N, N′-4,7-tetrakis [4,6-bis {N-butyl-N- (1,2 , 2,6,6-pentamethyl-4-piperidyl) amino} -1,3,5-triazin-2-yl] -4,7-diazadecane-1,10-diamine.

  Examples of the phosphorus-based antioxidant include tris [2-[[2,4,8,10-tetrakis (1,1-dimethylethyl) dibenzo [d, f] [1,3,2] dioxaphosphine. Pin-6-yl] oxy] ethyl] amine, tris [2-[(4,6,9,11-tetra-tert-butyldibenzo [d, f] [1,3,2] dioxaphosphine- 2-yl) oxy] ethyl] amine, ethylbisphosphite (2,4-ditert-butyl-6-methylphenyl), and the like.

  Examples of sulfide antioxidants include 2,2-thio-diethylenebis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], 2,4-bis [(octylthio) methyl. ] -O-cresol and 2,4-bis [(laurylthio) methyl] -o-cresol.

  The antioxidant is preferably used in an amount of 0.1 to 5% by weight in a total of 100% by weight of the solid content of the photosensitive coloring composition for color filter.

<Amine compound>
Moreover, the photosensitive coloring composition for color filters of this invention can be made to contain the amine compound which has a function which reduces the dissolved oxygen.

  Such amine compounds include triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, 2-dimethylaminobenzoate. Examples include ethyl, 2-ethylhexyl 4-dimethylaminobenzoate, and N, N-dimethylparatoluidine.

<Leveling agent>
In order to improve the leveling property of the composition on the transparent substrate, a leveling agent can be added to the photosensitive coloring composition for a color filter of the present invention. As the leveling agent, dimethylsiloxane having a polyether structure or a polyester structure in the main chain is preferable. Specific examples of dimethylsiloxane having a polyether structure in the main chain include FZ-2122 manufactured by Toray Dow Corning, BYK-333 manufactured by Big Chemie. Specific examples of dimethylsiloxane having a polyester structure in the main chain include BYK-310 and BYK-370 manufactured by BYK Chemie. Dimethylsiloxane having a polyether structure in the main chain and dimethylsiloxane having a polyester structure in the main chain can be used in combination. In general, the leveling agent content is preferably 0.003 to 0.5% by weight based on the total weight of the coloring composition (100% by weight).

  Particularly preferred as a leveling agent is a kind of so-called surfactant having a hydrophobic group and a hydrophilic group in the molecule, having a hydrophilic group but low solubility in water, and when added to a coloring composition, It has the characteristics of low surface tension reduction ability, and it is useful to have good wettability to the glass plate despite its low surface tension reduction ability. Those that can sufficiently suppress the chargeability can be preferably used. As a leveling agent having such preferable characteristics, dimethylpolysiloxane having a polyalkylene oxide unit can be preferably used. Examples of the polyalkylene oxide unit include a polyethylene oxide unit and a polypropylene oxide unit, and dimethylpolysiloxane may have both a polyethylene oxide unit and a polypropylene oxide unit.

  In addition, the bonding form of the polyalkylene oxide unit with dimethylpolysiloxane includes a pendant type in which the polyalkylene oxide unit is bonded in the repeating unit of dimethylpolysiloxane, a terminal-modified type in which the end of dimethylpolysiloxane is bonded, and dimethylpolysiloxane. Any of linear block copolymer types in which they are alternately and repeatedly bonded may be used. Dimethylpolysiloxane having a polyalkylene oxide unit is commercially available from Toray Dow Corning Co., Ltd., for example, FZ-2110, FZ-2122, FZ-2130, FZ-2166, FZ-2191, FZ-2203, FZ. -2207, but is not limited thereto.

  An anionic, cationic, nonionic or amphoteric surfactant can be supplementarily added to the leveling agent. Two or more kinds of surfactants may be mixed and used.

  Anionic surfactants added to the leveling agent as auxiliary agents include polyoxyethylene alkyl ether sulfate, sodium dodecylbenzene sulfonate, alkali salt of styrene-acrylic acid copolymer, sodium alkyl naphthalene sulfonate, alkyl diphenyl ether disulfonic acid Sodium, lauryl sulfate monoethanolamine, lauryl sulfate triethanolamine, ammonium lauryl sulfate, monoethanolamine stearate, sodium stearate, sodium lauryl sulfate, monoethanolamine of styrene-acrylic acid copolymer, polyoxyethylene alkyl ether phosphate Examples include esters.

  Examples of the chaotic surfactant that is supplementarily added to the leveling agent include alkyl quaternary ammonium salts and their ethylene oxide adducts. Nonionic surfactants added to the leveling agent as auxiliary agents include polyoxyethylene oleyl ether, polyoxyethylene lauryl ether, polyoxyethylene nonylphenyl ether, polyoxyethylene alkyl ether phosphate ester, polyoxyethylene sorbitan monostearate And amphoteric surfactants such as alkyl dimethylamino acetic acid betaine and alkylimidazolines, and fluorine-based and silicone-based surfactants.

<Curing agent, curing accelerator>
Moreover, in order to assist hardening of a thermosetting resin, the photosensitive coloring composition for color filters of this invention may contain the hardening | curing agent, the hardening accelerator, etc. as needed. As the curing agent, phenolic resins, amine compounds, acid anhydrides, active esters, carboxylic acid compounds, sulfonic acid compounds and the like are effective, but are not particularly limited to these, and thermosetting resins. Any curing agent may be used as long as it can react with the. Among these, a compound having two or more phenolic hydroxyl groups in one molecule and an amine curing agent are preferable. Examples of the curing accelerator include amine compounds (for example, dicyandiamide, benzyldimethylamine, 4- (dimethylamino) -N, N-dimethylbenzylamine, 4-methoxy-N, N-dimethylbenzylamine, 4-methyl). -N, N-dimethylbenzylamine etc.), quaternary ammonium salt compounds (eg triethylbenzylammonium chloride etc.), blocked isocyanate compounds (eg dimethylamine etc.), imidazole derivative bicyclic amidine compounds and salts thereof (eg Imidazole, 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 4-phenylimidazole, 1-cyanoethyl-2-phenylimidazole, 1- (2-cyanoethyl) -2- D Ru-4-methylimidazole, etc.), phosphorus compounds (eg, triphenylphosphine, etc.), guanamine compounds (eg, melamine, guanamine, acetoguanamine, benzoguanamine, etc.), S-triazine derivatives (eg, 2,4-diamino-6) -Methacryloyloxyethyl-S-triazine, 2-vinyl-2,4-diamino-S-triazine, 2-vinyl-4,6-diamino-S-triazine isocyanuric acid adduct, 2,4-diamino-6 Methacryloyloxyethyl-S-triazine / isocyanuric acid adduct, etc.) can be used. These may be used alone or in combination of two or more. As content of the said hardening accelerator, 0.01-15 weight part is preferable with respect to 100 weight part of thermosetting resins.

<Other additive components>
The photosensitive coloring composition for a color filter of the present invention can contain a storage stabilizer in order to stabilize the viscosity with time of the composition. Moreover, in order to improve adhesiveness with a transparent substrate, adhesion improving agents, such as a silane coupling agent, can also be contained.

  Examples of storage stabilizers include quaternary ammonium chlorides such as benzyltrimethyl chloride and diethylhydroxyamine, organic acids such as lactic acid and oxalic acid, and methyl ethers thereof, t-butylpyrocatechol, tetraethylphosphine, and tetraphenylphosphine. Organic phosphines, phosphites and the like can be mentioned. The storage stabilizer can be used in an amount of 0.1 to 10 parts by weight with respect to 100 parts by weight of the colorant (A).

  Examples of the adhesion improver include vinyl silanes such as vinyltris (β-methoxyethoxy) silane, vinylethoxysilane and vinyltrimethoxysilane, (meth) acrylsilanes such as γ-methacryloxypropyltrimethoxysilane, β- (3, 4-epoxycyclohexyl) ethyltrimethoxysilane, β- (3,4-epoxycyclohexyl) methyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltriethoxysilane, β- (3,4-epoxycyclohexyl) Epoxysilanes such as methyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, N-β (aminoethyl) γ-aminopropyltrimethoxysilane, N-β (amino Ethyl) γ-aminopropyltrie Xisilane, N-β (aminoethyl) γ-aminopropylmethyldiethoxysilane, γ-aminopropyltriethoxysilane, γ-aminopropyltrimethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, N-phenyl Examples include silane coupling agents such as aminosilanes such as -γ-aminopropyltriethoxysilane, and thiosilanes such as γ-mercaptopropyltrimethoxysilane and γ-mercaptopropyltriethoxysilane. The adhesion improver can be used in an amount of 0.01 to 10 parts by weight, preferably 0.05 to 5 parts by weight with respect to 100 parts by weight of the colorant (A).

<Method for producing colored composition for color filter>
The coloring composition for a color filter of the present invention is prepared by stirring a salt-forming compound (D) of an anionic dye (C) represented by the general formula (11) and a compound (B) having a cationic group in an organic solvent.・ After dissolution (colorant solution), resin, photopolymerizable monomer, photopolymerization initiator, and if necessary, further mixed with organic solvent (C) and other additives, solvent development type or alkali It can be adjusted as a development type coloring composition (resist material).

Formula (11)

[X ₁ and X ₃ represent a monovalent aliphatic hydrocarbon group having 1 to 20 carbon atoms which may have a substituent.
X ₂ and X ₄ each represents a monovalent aromatic hydrocarbon group which may have a substituent, and at least one of them has a sulfo group. ]

Also, after stirring and dissolving the salt-forming compound (D) of the anionic dye (C) represented by the general formula (11) and the compound (B) having a cationic group in an organic solvent (colorant solution), Resin is added and mixed, and then mixed with a photopolymerizable monomer, a photopolymerization initiator, and, if necessary, an organic solvent, other additives, etc., solvent development type or alkali development type A colored composition (resist material) can be obtained.

  When a pigment is further used as the colorant (A), a mixture containing at least a resin and a colorant component is kneaded with a two-roll mill or the like to obtain a sheet-like product, and then pulverized. The resulting chips are dissolved in an organic solvent with stirring and dispersed with a media dispersing machine such as a bead mill, or an intermediate of a colored composition (pigment dispersion) in which the above mixture is directly dispersed with a media dispersing machine such as a bead mill. And a photopolymerizable monomer, a photopolymerization initiator, an organic solvent, and the like.

  The coloring composition for a color filter can be prepared by mixing the salt-forming compound (D) and the pigment and dispersing them together. Alternatively, the colorant solution and the pigment dispersion can be produced separately and mixed for use. it can.

  The colorant (A) is preferably contained in the color filter coloring composition in a proportion of 0.5 to 10% by weight. Further, the colorant (A) is finally contained in the filter segment in a proportion of preferably 10 to 60% by weight, more preferably 20 to 50% by weight, and the remainder is the resin (B) or photopolymerizable monomer. It consists substantially of a monomer (E), a photoinitiator (F), etc.

(Dispersing aid)
When dispersing the pigment further contained in the colorant (A) in the colorant carrier, in addition to using the resin (B) in the form of a resin-type dispersant, a pigment derivative, other resin-type dispersant, A dispersion aid such as a surfactant can be further used. Since the dispersion aid is excellent in dispersion of the colorant and has a great effect of preventing reaggregation of the colorant after dispersion, a coloring composition obtained by dispersing the colorant in the pigment carrier using the dispersion aid is used. If so, a color filter with high spectral transmittance can be obtained.

Examples of the dye derivative include a compound obtained by introducing a basic substituent, an acidic substituent, or an optionally substituted phthalimidomethyl group into an organic pigment, anthraquinone, acridone, or triazine.
Of these, pigment derivatives are preferable, and the structure thereof is a compound represented by the following general formula (5).

P-Ln Formula (5)
(However,
P: organic pigment residue, anthraquinone residue, acridone residue or triazine residue L: basic substituent, acidic substituent, or optionally substituted phthalimidomethyl group n: an integer of 1 to 4 is there)
Examples of the organic pigment constituting the organic pigment residue of P include, for example, diketopyrrolopyrrole pigments; azo pigments such as azo, disazo and polyazo; phthalocyanine pigments such as copper phthalocyanine, halogenated copper phthalocyanine and metal-free phthalocyanine Anthraquinone pigments such as aminoanthraquinone, diaminodianthraquinone, anthrapyrimidine, flavantron, anthanthrone, indanthrone, pyranthrone, violanthrone; quinacridone pigments; dioxazine pigments; perinone pigments; perylene pigments; thioindigo pigments; Indoline pigments; isoindolinone pigments; quinophthalone pigments; selenium pigments; metal complex pigments.

  Examples of the dye derivative are described in JP-A-63-305173, JP-B-57-15620, JP-B-59-40172, JP-B-63-17102, JP-B-5-9469, and the like. What is currently used can be used, These can be used individually or in mixture of 2 or more types.

  The blending amount of the pigment derivative is preferably 0.5% by weight or more, more preferably 1% by weight or more, and most preferably 3% by weight or more based on 100 parts by weight of the pigment from the viewpoint of improving dispersibility. Further, from the viewpoint of heat resistance and light resistance, the amount is preferably 40% by weight or less, and most preferably 35% by weight or less with respect to 100 parts by weight of the pigment.

  The resin-type dispersant has a pigment-affinity part having a property of adsorbing to the colorant and a part compatible with the colorant carrier, and adsorbs to the colorant to disperse the colorant to the colorant carrier. It works to stabilize. Specific examples of resin-type dispersants include polycarboxylic acid esters such as polyurethane and polyacrylate, unsaturated polyamides, polycarboxylic acids, polycarboxylic acid (partial) amine salts, polycarboxylic acid ammonium salts, and polycarboxylic acid alkylamine salts. , Polysiloxane, long-chain polyaminoamide phosphate, hydroxyl group-containing polycarboxylic acid ester, modified products thereof, amides formed by reaction of poly (lower alkyleneimine) and polyester having a free carboxyl group, and salts thereof Oil-soluble dispersants such as, (meth) acrylic acid-styrene copolymer, (meth) acrylic acid- (meth) acrylic acid ester copolymer, styrene-maleic acid copolymer, polyvinyl alcohol, polyvinylpyrrolidone, etc. Resin, water-soluble polymer, polyester, modified poly Acrylate-based, ethylene oxide / propylene oxide addition compound, phosphate ester-based and the like are used, they can be used alone or in admixture of two or more, not necessarily limited thereto.

  Commercially available resin-type dispersants include Disperbyk-101, 103, 107, 108, 110, 111, 116, 130, 140, 154, 161, 162, 163, 164, 165, 166, and 170 manufactured by Big Chemie Japan. 171, 174, 180, 181, 182, 183, 184, 185, 190, 2000, 2001, 2020, 2025, 2050, 2070, 2095, 2150, 2155 or Anti-Terra-U, 203, 204, or BYK- P104, P104S, 220S, 6919, or SOLPERSE-3000, 9000, 13000, 13240, 13650, 13940, 1600 manufactured by Nihon Lubrizol Corporation, such as Lactimon, Lactimon-WS, or Bykumen. 17000, 18000, 20000, 21000, 24000, 26000, 27000, 28000, 31845, 32000, 32500, 32550, 33500, 32600, 34750, 35100, 36600, 38500, 41000, 41090, 53095, 55000, 76500, etc., BASF Japan EFKA-46, 47, 48, 452, 4008, 4009, 4010, 4015, 4020, 4047, 4050, 4055, 4060, 4080, 4400, 4401, 4402, 4403, 4406, 4408, 4300, 4310, 4320 , 4330, 4340, 450, 451, 453, 4540, 4550, 4560, 4800, 5010, 5065, 5066, 5070, 7500, 7 54,1101,120,150,1501,1502,1503, etc., Ajinomoto Fine-Techno Co., Ltd. of AJISPER PA111, PB711, PB821, PB822, PB824, and the like.

  Surfactants include sodium lauryl sulfate, polyoxyethylene alkyl ether sulfate, sodium dodecylbenzene sulfonate, alkali salt of styrene-acrylic acid copolymer, sodium stearate, sodium alkyl naphthalene sulfonate, sodium alkyl diphenyl ether disulfonate Anionic surfactants such as lauryl sulfate monoethanolamine, lauryl sulfate triethanolamine, ammonium lauryl sulfate, monoethanolamine stearate, monoethanolamine of styrene-acrylic acid copolymer, polyoxyethylene alkyl ether phosphate; Polyoxyethylene oleyl ether, polyoxyethylene lauryl ether, polyoxyethylene nonylphenyl ether, polyoxyethylene Nonionic surfactants such as alkyl ether phosphates, polyoxyethylene sorbitan monostearate and polyethylene glycol monolaurate; chaotic surfactants such as alkyl quaternary ammonium salts and their ethylene oxide adducts; alkyldimethylamino Examples include amphoteric surfactants such as alkylbetaines such as betaine acetate and alkylimidazolines, and these may be used alone or in admixture of two or more, but are not necessarily limited thereto.

  When a resin type dispersant and a surfactant are added, the amount is preferably 0.1 to 55 parts by weight, more preferably 0.1 to 45 parts by weight with respect to 100 parts by weight of the pigment. When the blending amount of the resin-type dispersant and the surfactant is less than 0.1 parts by weight, it is difficult to obtain the added effect. May affect.

<Removal of coarse particles>
The photosensitive coloring composition for color filter of the present invention is 5 μm or more coarse particles, preferably 1 μm or more coarse particles, more preferably 0.5 μm or more by means of centrifugation, sintered filter, membrane filter or the like. It is preferable to remove coarse particles and mixed dust.
Thus, it is preferable that the photosensitive coloring composition for color filters does not substantially contain particles of 0.5 μm or more. More preferably, it is 0.3 μm or less.

<Color filter>
Next, the color filter of the present invention will be described. The color filter of this invention comprises the filter segment formed using the photosensitive coloring composition for color filters of this invention. Examples of the color filter include those having a red filter segment, a green filter segment, and a blue filter segment, or those having a magenta filter segment, a cyan filter segment, and a yellow filter segment.

  As the transparent substrate, glass plates such as soda lime glass, low alkali borosilicate glass and non-alkali alumino borosilicate glass, and resin plates such as polycarbonate, polymethyl methacrylate, and polyethylene terephthalate are used. In addition, a transparent electrode made of indium oxide, tin oxide, or the like may be formed on the surface of the glass plate or the resin plate in order to drive the liquid crystal after forming the panel.

<Color filter manufacturing method>
The color filter of the present invention can be produced by a printing method or a photolithography method.

  The formation of the filter segment by the printing method can be patterned simply by repeating the printing and drying of the photosensitive coloring composition for a color filter prepared as a printing ink. Excellent mass productivity. Furthermore, it is possible to print a fine pattern having high dimensional accuracy and smoothness by the development of printing technology. In order to perform printing, it is preferable that the ink does not dry and solidify on the printing plate or on the blanket. Further, it is important to control the fluidity of the ink on the printing press, and the viscosity of the ink can be adjusted with a dispersant or extender pigment.

  When forming a filter segment by a photolithography method, the photosensitive coloring composition for a color filter prepared as the solvent developing type or alkali developing type coloring resist material is applied to a transparent substrate by spray coating, spin coating, slit coating, It applies so that a dry film thickness may be 0.2-5 micrometers by application | coating methods, such as a roll coat. If necessary, the dried film is exposed to ultraviolet light through a mask having a predetermined pattern provided in contact with or non-contact with the film. Then, after immersing in a solvent or alkali developer or spraying the developer by spraying or the like to remove the uncured portion to form a desired pattern, the same operation is repeated for other colors to produce a color filter. be able to. Furthermore, in order to accelerate the polymerization of the colored resist material, heating can be performed as necessary. According to the photolithography method, a color filter with higher accuracy than the above printing method can be manufactured.

In development, an aqueous solution such as sodium carbonate or sodium hydroxide is used as an alkali developer, and an organic alkali such as dimethylbenzylamine or triethanolamine can also be used. Moreover, an antifoamer and surfactant can also be added to a developing solution.
In order to increase the UV exposure sensitivity, after coating and drying the colored resist material, a water-soluble or alkaline water-soluble resin such as polyvinyl alcohol or water-soluble acrylic resin is applied and dried to form a film that prevents polymerization inhibition by oxygen. Then, ultraviolet exposure can be performed.

  The color filter of the present invention can be produced by an electrodeposition method, a transfer method or the like in addition to the above method, but the photosensitive coloring composition for a color filter of the present invention can be used in any method. The electrodeposition method is a method for producing a color filter by using a transparent conductive film formed on a substrate and forming each color filter segment on the transparent conductive film by electrophoresis of colloidal particles. . The transfer method is a method in which a filter segment is formed in advance on the surface of a peelable transfer base sheet, and this filter segment is transferred to a desired substrate.

  A black matrix can be formed in advance before forming each color filter segment on a transparent substrate or a reflective substrate. As the black matrix, a chromium, chromium / chromium oxide multilayer film, an inorganic film such as titanium nitride, or a resin film in which a light-shielding agent is dispersed is used, but is not limited thereto. In addition, a thin film transistor (TFT) may be formed in advance on the transparent substrate or the reflective substrate, and then each color filter segment may be formed. In addition, an overcoat film, a transparent conductive film, or the like is formed on the color filter of the present invention as necessary.

Hereinafter, the present invention will be described based on examples, but the present invention is not limited thereto. Unless otherwise specified, “parts” means “parts by weight”.

First, it demonstrates from the manufacturing method of the binder resin used for the Example and the comparative example, the refinement | purification pigment, the compound (B) which has a cationic group, and a salt-forming compound (D).

<Method for preparing binder resin solution>
(Preparation of binder resin solution 1)
A reaction vessel equipped with a separable four-necked flask equipped with a thermometer, a cooling tube, a nitrogen gas introduction tube, and a stirrer was charged with 70.0 parts of cyclohexanone, heated to 80 ° C., and the inside of the reaction vessel was purged with nitrogen. 13.3 parts of n-butyl methacrylate, 4.6 parts of 2-hydroxyethyl methacrylate, 4.3 parts of methacrylic acid, 7.4 parts of paracumylphenol ethylene oxide modified acrylate (“Aronix M110” manufactured by Toagosei Co., Ltd.), A mixture of 0.4 part of 2,2′-azobisisobutyronitrile was added dropwise over 2 hours. After completion of the dropwise addition, the reaction was further continued for 3 hours to obtain an acrylic resin solution having a weight average molecular weight of 26000. After cooling to room temperature, about 2 g of the resin solution was sampled and heated and dried at 180 ° C. for 20 minutes to measure the nonvolatile content. The methoxypropyl acetate was added to the previously synthesized resin solution so that the nonvolatile content was 20% by weight. The binder resin solution 1 was prepared by adding.
Here, the weight average molecular weight (Mw) of the binder resin was measured by gel permeation chromatography (GPC) using polystyrene as a standard substance.

(Preparation of binder resin solution 2)
207 parts of cyclohexanone was charged into a separable four-necked flask equipped with a thermometer, a cooling pipe, a nitrogen gas introduction pipe, a dropping pipe, and a stirring device, heated to 80 ° C., and the flask was purged with nitrogen. 20 parts of acid, 20 parts of paracumylphenol ethylene oxide modified acrylate (Aronix M110 manufactured by Toa Gosei Co., Ltd.), 45 parts of methyl methacrylate, 8.5 parts of 2-hydroxyethyl methacrylate, and 2,2′-azobisisobutyronitrile 1.33 parts of the mixture was added dropwise over 2 hours. After completion of the dropwise addition, the reaction was further continued for 3 hours to obtain a copolymer solution.
Next, after the nitrogen gas was stopped and stirred while injecting dry air for 1 hour with respect to the total amount of the copolymer solution obtained, the mixture was cooled to room temperature, and then 2-methacryloyloxyethyl isocyanate (Karenz manufactured by Showa Denko KK). MOI) A mixture of 6.5 parts, 0.08 part dibutyltin laurate and 26 parts cyclohexanone was added dropwise at 70 ° C. over 3 hours.
About 2 g of the resin solution was sampled and heated and dried at 180 ° C. for 20 minutes to measure the non-volatile content. Then, cyclohexanone was added to the previously synthesized resin solution so that the non-volatile content was 20% by weight. Prepared. The weight average molecular weight (Mw) was 18000.

(Preparation of binder resin solution 3)
A separable four-necked flask equipped with a thermometer, a cooling pipe, a nitrogen gas introduction pipe, a dropping pipe and a stirring device was charged with 370 parts of cyclohexanone, heated to 80 ° C., and the atmosphere in the flask was replaced with nitrogen. 18 parts of milphenol ethylene oxide modified acrylate (Aronix M110 manufactured by Toagosei Co., Ltd.), 10 parts of benzyl methacrylate, 18.2 parts of glycidyl methacrylate, 25 parts of methyl methacrylate, and 2,2′-azobisisobutyronitrile 2.0 Part of the mixture was added dropwise over 2 hours. After dropping, the reaction was further carried out at 100 ° C. for 3 hours, and then 1.0 part of azobisisobutyronitrile dissolved in 50 parts of cyclohexanone was added, and the reaction was further continued at 100 ° C. for 1 hour. Next, the inside of the container is replaced with air, and 0.5 part of trisdimethylaminophenol and 0.1 part of hydroquinone are put into 9.3 parts of acrylic acid (100% of glycidyl group) and the container is placed at 120 ° C. The reaction was continued for 6 hours, and the reaction was terminated when the solid content acid value reached 0.5 to obtain a copolymer solution. Further, 19.5 parts of tetrahydrophthalic anhydride (100% of the generated hydroxyl group) and 0.5 parts of triethylamine were added and reacted at 120 ° C. for 3.5 hours to obtain a carboxyl group and a copolymer solution.
After cooling to room temperature, about 2 g of the resin solution was sampled, heated and dried at 180 ° C. for 20 minutes to measure the nonvolatile content, and cyclohexanone was added to the previously synthesized resin solution so that the nonvolatile content was 20% by weight. Thus, a binder resin solution 3 was prepared. The weight average molecular weight (Mw) was 19000.

<Production method of fine pigment>
(Blue refined pigment (P-1))
Phthalocyanine blue pigment C.I. I. Pigment Blue 15: 6 (Toyocolor "Lionol Blue ES") 100 parts, ground salt 800 parts, and diethylene glycol 100 parts were charged into a stainless steel 1 gallon kneader (Inoue Seisakusho) and kneaded at 70 ° C for 12 hours. did. The mixture was poured into 3000 parts of warm water, stirred at a high speed mixer for about 1 hour while being heated to about 70 ° C. to form a slurry, filtered and washed repeatedly to remove salt and solvent, and then at 80 ° C. for 24 hours. It dried and obtained 98 parts of blue refinement | purification pigments (P-1). The average primary particle diameter of the obtained pigment was 28.3 nm.

Here, the average primary particle diameter of the pigment was measured using a transmission electron microscope (“JEM-1200EX” manufactured by JEOL Ltd.) by measuring the primary particle diameter of all pigment particles in the observation sample at 50,000 times. Average values were used. In addition, when the particle shape was not spherical, the major axis and the minor axis were measured, and the value obtained by (major axis + minor axis) / 2 was defined as the particle diameter.

(Purple refined pigment (P-2))
Dioxazine-based purple pigment C.I. I. 120 parts of Pigment Violet 23 (“Fast Violet RL” manufactured by Clariant), 1600 parts of ground sodium chloride, and 100 parts of diethylene glycol were charged into a stainless 1 gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 90 ° C. for 18 hours. The mixture was poured into 5000 parts of warm water, stirred at a high speed mixer for about 1 hour while being heated to about 70 ° C. to form a slurry, filtered and washed repeatedly to remove salt and solvent, and then at 80 ° C. for 24 hours. It dried and obtained 118 parts purple refinement | purification pigment (P-2). The average primary particle diameter of the obtained pigment was 26.4 nm.

(Red fine pigment (P-3))
Diketopyrrolopyrrole red pigment C.I. I. 200 parts of Pigment Red 254 (“IRGAZIN RED 2030” manufactured by BASF Japan Ltd.), 1400 parts of ground sodium chloride, and 360 parts of diethylene glycol were charged into a stainless steel 1 gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 80 ° C. for 6 hours. The mixture was poured into 8000 parts of warm water, heated to about 80 ° C., stirred with a high speed mixer for about 2 hours to form a slurry, filtered and washed repeatedly to remove salt and solvent, then at 85 ° C. for 24 hours. It dried and obtained 190 parts of red fine pigments (P-3). The average primary particle diameter of the obtained pigment was 24.8 nm.

(Red fine pigment (P-4))
Red pigment C.I. I. 200 parts of Pigment Red 242 (“NOVOPERM SCARLET 4RF” manufactured by Clariant), 1400 parts of ground sodium chloride, and 360 parts of diethylene glycol were charged into a 1 gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 80 ° C. for 6 hours. The mixture is poured into 8000 parts of warm water, stirred for 2 hours with a high speed mixer while being heated to about 80 ° C. to form a slurry, filtered and washed repeatedly to remove salt and solvent, and then dried at 85 ° C. for 24 hours. 190 parts of red fine pigment (P-4) were obtained. The average primary particle diameter of the obtained pigment was 28.5 nm.

<Method for adjusting pigment dispersion>
(Preparation of pigment dispersion (DP-1))
The following mixture was stirred and mixed so as to be uniform, and then dispersed with an Eiger mill (“Mini Model M-250 MKII” manufactured by Eiger Japan) using zirconia beads having a diameter of 0.5 mm, and then 5.0 μm. And a pigment dispersion (DP-1) was produced.
Refined pigment (P-1) 11.0 parts Binder resin solution 1 40.0 parts Cyclohexanone 10.0 parts Propylene glycol monomethyl ether acetate (PGMAC) 38.0 parts Resin-type dispersant ("EFKA4300" manufactured by BASF Japan) 1.0 part

(Preparation of pigment dispersion (DP-2-4))
Similarly to the pigment dispersion (DP-1), pigment dispersions (DP-2 to 4) were prepared as shown in Table 1.

<Method for preparing resin having cationic group in side chain>
(Cationic resin 1)
Into a four-necked separable flask equipped with a thermometer, a stirrer, a distillation tube, and a condenser, 75.1 parts of isopropyl alcohol was charged, and the temperature was raised to 75 ° C. under a nitrogen stream. Separately, 47.8 parts of methyl methacrylate, 20.0 parts of n-butyl methacrylate, 10.0 parts of 2-ethylhexyl methacrylate, 10.0 parts of 2-ethylhexyl acrylate, 12.2 parts of dimethylaminoethyl methyl chloride salt, and Separately, 7.0 parts of 2,2′-azobis (2,4-dimethylvaleronitrile) dissolved in 23.4 parts of methyl ethyl ketone was homogenized, charged into a dropping funnel, and attached to a four-necked separable flask. It was added dropwise over time. Two hours after the completion of dropping, it was confirmed that the polymerization yield was 98% or more from the solid content, and the weight average molecular weight (Mw) was 7330, and the mixture was cooled to 50 ° C. Thereafter, 14.3 parts of methanol was added to obtain a cationic resin 1 having a Tg of 37 ° C. having a cationic group in the side chain of 40% by weight of the resin component. The ammonium salt value of the obtained resin was 32 mgKOH / g.

Here, the weight average molecular weight (Mw) of the resin having a cationic group in the side chain was measured by gel permeation chromatography (GPC) using polystyrene as a standard substance. The ammonium salt value of the resin (B) having a cationic group in the side chain was determined by titrating with a 0.1N silver nitrate aqueous solution using 5% potassium chromate aqueous solution as an indicator, and then the equivalent of potassium hydroxide. It is the converted value and indicates the ammonium salt value of the solid content.

(Cationic resin 2-6)
Hereafter, except having changed the monomer, the polymerization initiator, and reaction temperature into the composition shown in Table 2, it carried out similarly to the cationic resin 1, and obtained the cationic resins 2-6.

The following monomers were used in Table 2. Shown with glass transition temperature.
Dimethylaminoethyl methyl chloride salt:
Light ester DQ-100 (manufactured by Kyoeisha Chemical Co., Ltd.) (58 ° C)
MMA: Methyl methacrylate (105 ° C)
n-BMA: n-butyl methacrylate (20 ° C.)
2-EHMA: 2-ethylhexyl methacrylate (−10 ° C.)
2-EHA: 2-ethylhexyl acrylate (-85 ° C)
HEMA: hydroxyethyl methacrylate (55 ° C)
MAA: Methacrylic acid (130 ° C)
t-BMA: t-butyl methacrylate (107 ° C.)
IBMA: Isobutyl methacrylate (67 ° C)
CHMA: cyclohexyl methacrylate (66 ° C)
IBX: Isobornyl methacrylate (180 ° C.)
MOI: 2-isocyanatoethyl methacrylate (60 ° C)
The value of Tg in Table 2 is a value calculated using the above formula.

<Production of anionic dye (C)>
(Anionic dye 1)
Anionic dyes 1 to 4 are compounds represented by the following general formula (12).

Formula (12)

In general formula (12), X _{1 to} X ₄ are shown in Table 3.


Here, * indicates a bond with N.

Anionic dyes 1-4 were synthesized by the following method.
(Synthesis of anionic dye 1)
C. I. 45.0 parts of Acid Red 289, 45.3 parts of 1-iodopropane and 36.8 parts of potassium carbonate were added to 280 parts of N-methylpyrrolidone and stirred at 90 ° C. for 6 hours. The resulting reaction solution was cooled to room temperature, then added to 3000 parts of ethyl acetate and stirred at room temperature for 1 hour, whereupon crystals precipitated. The precipitated crystals were collected by filtration, washed with 2500 parts of ethyl acetate, and then dried under reduced pressure at 60 ° C. overnight to obtain 47.6 parts of anionic dye 1.

(Synthesis of anionic dye 2)
C. I. 45.0 parts of Acid Red 289, 56.6 parts of 2-iodopropane, and 46.0 parts of potassium carbonate were added to 360 parts of N-methylpyrrolidone and stirred at 85 ° C. for 12 hours. The obtained reaction solution was cooled to room temperature, added to 3600 parts of ethyl acetate, and stirred at room temperature for 1 hour, whereby crystals were deposited. The precipitated crystals were collected by filtration, washed with 3000 parts of ethyl acetate, and dried overnight at 60 ° C. under reduced pressure to obtain 43.0 parts of anionic dye 2.

(Synthesis of anionic dye 3)
The same operation as the synthesis method of anionic dye 1 was performed except that 45.3 parts of 1-iodopropane was changed to 71.4 parts of 1-iododecane, to obtain 53.2 parts of anionic dye 3.

(Synthesis of anionic dye 4)
20.0 parts of the compound represented by the formula (20) and 8.5 parts of sulfanilic acid were added to 180 parts of N-methylpyrrolidone and stirred at 100 ° C. for 2 hours. Next, 10.0 parts of aniline was added and stirred at 120 degrees for 4 hours. After cooling the obtained reaction liquid to room temperature, 2000 parts of ethyl acetate was added and stirred at room temperature for 1 hour, whereby crystals were deposited. The precipitated crystals were separated by filtration and dried overnight under reduced pressure to obtain 25.7 parts of Intermediate 1.
25.0 parts of Intermediate 1, 28.2 parts of 1-iodopropane and 23.0 parts of potassium carbonate were added to 200 parts of N-methylpyrrolidone and stirred at 90 ° C. for 4 hours. The obtained reaction solution was cooled to room temperature, then added to 2000 parts of ethyl acetate and stirred at room temperature for 1 hour, whereby crystals were deposited. The precipitated crystals were collected by filtration, washed with 1500 parts of ethyl acetate, and then dried under reduced pressure at 60 ° C. overnight to obtain 26.7 parts of anionic dye 4.

Formula (20)

<Manufacture of salt-forming compounds>
(Salt-forming compound (DA-1))
A salt-forming compound (DA-1) comprising an anionic dye 1 and a cationic resin 1 was prepared by the following procedure.
51 parts of the cationic resin 1 is added to 2000 parts of water, and after sufficient stirring and mixing, the mixture is heated to 60 ° C. On the other hand, an aqueous solution in which 10 parts of the anionic dye 1 is dissolved in 90 parts of water is prepared and added dropwise little by little to the resin solution. After dropping, the mixture is stirred at 60 ° C. for 120 minutes to sufficiently react. In order to confirm the end point of the reaction, it was judged that a salt-forming compound was obtained with the reaction solution dropped onto the filter paper and the point where the bleeding disappeared as the end point. After cooling to room temperature with stirring, suction filtration is performed, and after washing with water, the salt-forming compound remaining on the filter paper is dried by removing moisture with a dryer, and 32 parts of anionic dye 1 and a cationic resin are obtained. A salt-forming compound (DA-1) with 1 was obtained. At this time, the content of the effective pigment component derived from the anionic dye 1 in the salt-forming compound (DA-1) was 29% by weight.

(Salt-forming compounds (DA-2) to (DA-9))
In the same manner as the salt-forming compound (DA-1), (DA-2) to (DA-9) were prepared as shown in Table 4.

(Salt-forming compound (DA-10))
A salt-forming compound (DA-10) composed of anionic dye 1 and distearyldimethylammonium chloride (Coatamine D86P) was prepared by the following procedure.
11.5 parts of Cotamine D86P is added to 2000 parts of a 10% aqueous sodium hydroxide solution, sufficiently stirred and mixed, and then heated to 60 ° C. On the other hand, 10 parts of C.I. in 90 parts of water. I. An aqueous solution in which Acid Red 289 is dissolved is prepared and added dropwise to the previous solution. After dropping, the mixture is stirred at 60 ° C. for 120 minutes to sufficiently react. In order to confirm the end point of the reaction, it was judged that a salt-forming compound was obtained with the reaction solution dropped onto the filter paper and the point where the bleeding disappeared as the end point. After cooling to room temperature with stirring, suction filtration is performed, and after washing with water, the salt-forming compound remaining on the filter paper is dried by removing moisture with a dryer, and 17 parts of anionic dye 1 and Coatamine D86P The salt-forming compound (DA-10) was obtained.
Here, distearyldimethylammonium chloride (Cotamine D86P) is a quaternary ammonium salt compound.

(Salt-forming compound (DA-11))
A salt formation product (DA-11) composed of anionic dye 1 and stearylamine (Kao Pharmin 80) (molecular weight: 269) was prepared by the following procedure.
Stearylamine was added to a 10-20% aqueous acetic acid solution and the solution was stirred well. The solution was heated to 60 ° C. and then C.I. I. Acid Red 289 was added dropwise little by little. C. I. Acid Red 289 may be used as an aqueous solution. After completion of the dropwise addition, this solution was stirred at 60 ° C. for 120 minutes for sufficient reaction. The end point of the reaction was the time when the reaction solution was dropped on the filter paper and no bleeding occurred. That is, it was judged that a salt-forming product was obtained when bleeding disappeared. The mixture was allowed to cool to room temperature with stirring, filtered with suction, and further washed with water. After washing with water, moisture was removed from the salt formation product remaining on the filter paper using a dryer to obtain a salt formation product (DA-11) which is a salt formation product of anionic dye 1 and stearylamine. .
Here, stearylamine (Kao Pharmin 80) is a tertiary amine.

(Salt-forming compounds (D-1) to (D-2))
In the same manner as the salt-forming compound (DA-1), (D-1) to (D-2) were produced as shown in Table 4.
Here, the anionic dye used is as follows.
AR52: Acid Red 52
AR289: Acid Red 289

<Preparation of dye solution>
(Preparation of dye solution (SDA-1))
Salt-forming compound (DA-1) 10 parts 3-methoxybutanol 40 parts In the above composition, the salt-forming compound (DA-1) was added little by little while stirring 3-methoxybutanol at room temperature, and then 60 ° C. The mixture was stirred and dissolved for 3 hours to obtain a dye solution (SDA-1).

(Preparation of dye solution (SDA-2 to 11, SD-1 and 2))
In the same manner as the salt-forming compound solution (SDA-1), salt-forming compound solutions (SDA-2 to 11) were prepared as shown in Table 5.

(Preparation of dye solution (SC-1))
Anionic dye 1 3 parts Binder resin solution 1 35 parts 3-Methoxybutanol 12 parts While stirring 3-methoxybutanol at room temperature, add binder resin solution 1 and add anionic dye 1 little by little. After the addition, the mixture was stirred and dissolved for 3 hours at 60 ° C. to obtain a dye solution (SC-1).

[Examples 1 to 34, Comparative Examples 1 to 16]
[Example 1]
The following mixture was stirred and mixed so as to be uniform to prepare a colored composition (DB-1).
Pigment dispersion (DP-1) 100 parts Salt-forming compound solution (SDA-1) 30 parts

[Examples 2 to 17, Comparative Examples 1 to 9]
In the same manner as the salt-forming compound solution (DB-1), colored compositions (DB-2 to 26) were prepared as shown in Table 6.

(Evaluation of coloring composition)
About the obtained coloring composition (DB-1-26), the heat resistance evaluation of a coating film, a foreign material test, and the test regarding the temporal storage stability of a coloring composition were done by the following method. The results of the test are shown in Table 6.

(Evaluation of heat resistance of coating film)
The coloring composition (DB-1 to 26) is applied on a glass substrate having a size of 100 mm × 100 mm and a thickness of 1.1 mm using a spin coater, and then dried at 70 ° C. for 20 minutes, and then at 220 ° C. for 30 minutes. The coated substrate was prepared by heating and allowing to cool. The coating film substrate thus prepared was subjected to heat treatment at 220 ° C., and the spin coater coating rotation speed was adjusted so that the film thickness was 2.0 μm. The chromaticity ([L * (1), a * (1), b * (1)]) of the obtained coating film with a C light source was measured with a microspectrophotometer ("OSP-SP100" manufactured by Olympus Optical Co., Ltd.). And measured. Further, as a heat resistance test, the sample was heated at 230 ° C. for 1 hour, and the chromaticity ([L * (2), a * (2), b * (2)]) with a C light source was measured. The color difference ΔEab * was determined.
ΔEab * = √ ((L * (2)-L * (1)) 2+ (a * (2)-a * (1)) 2+ (b * (2)-b * (1)) 2)
If ΔEab * is less than 2.0, there is no practical problem as a color filter, ΔEab is more preferably 1.5 or less, and most preferably 1.0 or less.

(Test on storage stability over time)
A colored composition (DB-1 to 26) stored for 6 months under a cold-reserving condition at 10 ° C. was applied onto a glass substrate of 100 mm × 100 mm, 1.1 mm thickness using a spin coater, and then 20 ° C. at 70 ° C. The film was dried for a while, then heated at 220 ° C. for 30 minutes and allowed to cool to produce a coated substrate, and this coated substrate was observed at 500 times using an optical microscope.
<Evaluation criteria>
◎: Generation of foreign matter is not recognized at all ○: Generation of foreign matter is recognized but allowable range ×: Generation of foreign matter is large and out of the allowable range

(Coating foreign material test method)
A test substrate was prepared with the colored composition (DB-1 to 26) immediately after preparation, and the evaluation was performed by counting the number of particles. First, a colored composition is applied on a 100 mm × 100 mm, 1.1 mm thick transparent glass substrate with a spin coater so that the film thickness after drying is about 2.0 μm, and heated in an oven at 230 ° C. for 20 minutes. A test substrate was obtained. Then, surface observation was performed using a metal microscope “BX60” manufactured by Olympus System (magnification is 500 times), and the number of particles that can be observed in any five visual fields by transmission was counted and evaluated according to the following criteria. did. In the evaluation results, ◎ and ○ are good with a small number of foreign matters, △ is a level where there is a large number of foreign matters, but there is no problem in use, and × is a state where it cannot be used because uneven coating due to foreign matters occurs. Equivalent to.
◎: Less than 5 ○: 5 or more, less than 20 Δ: 20 or more, less than 100 ×: 100 or more

AR289: C.I. I. Acid Red 289
AR52: C.I. I. Acid Red 52

In Examples 1 to 17, since the colorant contains an anionic dye represented by the general formula (11), all of them have good heat resistance, and ΔEab was 1.5 or less. Moreover, it was excellent in storage stability, and the coating film foreign matter was in a range that can be used as a color filter.
On the other hand, since Comparative Examples 1 to 9 did not have the anionic dye represented by the general formula (11), all of them had poor heat resistance and ΔEab exceeded 2.5.

[Example 18]
(Preparation of blue photosensitive coloring composition (R-1))
After stirring and mixing the following mixture uniformly, it is filtered through a 1.0 μm filter,
An alkali developing resist material R-1 was prepared.
Blue coloring composition (DB-1) 60.0 parts Binder resin solution 1 11.0 parts Trimethylolpropane triacrylate 4.2 parts ("NK ester ATMPT" manufactured by Shin-Nakamura Chemical Co., Ltd.)
Photopolymerization initiator ("Irgacure 907" manufactured by BASF Japan) 1.2 parts sensitizer ("EAB-F" manufactured by Hodogaya Chemical Co., Ltd.) 0.4 parts cyclohexanone 5.2 parts propylene glycol monomethyl ether acetate (PGMAC) 18.0 parts

[Examples 18 to 36, Comparative Examples 10 to 18]
(Blue photosensitive coloring composition (R-2 to 13, R-20 to 22), purple photosensitive coloring composition (R-14 to 15, R-23 to 24), red photosensitive coloring composition (R- 16-19, production of R-20-28))
Alkali development type photosensitive coloring compositions (R-2 to 28) were prepared in the same manner as in Example 18 except that the coloring composition and the binder resin solution were changed to the coloring compositions shown in Table 7.

(Evaluation of photosensitive coloring composition)
About the obtained photosensitive coloring composition (R-1 to 28), heat resistance evaluation of coating film, foreign matter test, storage stability with time, test on adhesion to transparent substrate such as glass, solvent resistance test An alkali developability test was conducted. A foreign matter test, an adhesion test with a transparent substrate such as glass, a solvent resistance test, and an alkali developability test method were performed by the following methods. About the method of evaluation / test other than that, it carried out similarly to the content described in Examples 1-17 and Comparative Examples 1-9. The test results are shown in Table 7.

(Coating foreign material test method)
A test substrate was prepared using the photosensitive coloring composition (R-1 to 28) immediately after preparation, and the number of particles was evaluated. First, a photosensitive coloring composition was applied on a 100 mm × 100 mm, 1.1 mm thick transparent glass substrate with a spin coater so that the film thickness after drying was about 2.0 μm, dried at 70 ° C. for 20 minutes, UV exposure is performed with an integrated light quantity of 150 mJ / cm @ 2 using an ultrahigh pressure mercury lamp through a photomask having a stripe-shaped opening having a width of 100 .mu.m, and the unexposed area with a 0.05% aqueous potassium hydroxide solution containing a surfactant. The substrate was washed and developed, and placed in a hot air oven at 230 ° C. for 20 minutes to form a stripe pattern having a width of 100 μm on the substrate to obtain a test substrate. Then, surface observation was performed using a metal microscope “BX60” manufactured by Olympus System (magnification is 500 times), and the number of particles that can be observed in any five visual fields by transmission was counted and evaluated according to the following criteria. did. In the evaluation results, ◎ and ○ are good with a small number of foreign matters, △ is a level where there is a large number of foreign matters, but there is no problem in use, and × is a state where it cannot be used because uneven coating due to foreign matters occurs. Equivalent to.
◎: Less than 5 ○: 5 or more, less than 20 Δ: 20 or more, less than 100 ×: 100 or more

(Glass adhesion test method)
Evaluation was performed by forming a test substrate in the same procedure as the coating film foreign matter test and confirming the chemical resistance. The obtained test substrate was immersed in a 5% aqueous sodium hydroxide solution at 25 ° C. for 30 minutes, and the adhesion to the glass before and after immersion was evaluated in three stages by visual observation.
◯: No peeling at all Δ: Slight peeling is observed ×: Peeling is recognized

(Solvent resistance test)
The test substrate obtained by the same procedure as the above-mentioned coating film foreign matter test was immersed in an N-methylpyrrolidone solution for 30 minutes, then washed with ion-exchanged water, air-dried, and the pattern on the 100 μm photomask portion was examined using an optical microscope. Evaluation was made by observation. The rank of evaluation is as follows.
◎: Appearance and color are good without change ○: Some wrinkles are generated, but color is good without change Δ: Slight color loss is generated ×: Peeling or color loss is generated

(Alkali developability test)
The photosensitive coloring composition (R-1 to 28) was applied on a 100 mm × 100 mm, 1.1 mm thick transparent glass substrate with a spin coater so that the film thickness after drying was about 2.0 μm, at 70 ° C. After drying for 20 minutes, UV exposure was performed with an integrated light quantity of 150 mJ / cm 2 using a super high pressure mercury lamp through a photomask having a stripe-shaped opening having a width of 100 μm. When developing with a 0.05% aqueous potassium hydroxide solution containing a surfactant, the unexposed area is washed away, the development is performed at an appropriate development time of +10 seconds and +20 seconds, and the developed glass surface is subjected to a microspectrophotometer ( Measured using “OSP-SP200” manufactured by Olympus Optical Co., Ltd., and alkali developability was determined by the presence or absence of residue.
◎: No residue at proper development time ○: No residue at proper development time + 10 seconds △: No residue at proper development time + 20 seconds ×: Residue at proper development time + 20 seconds

In Examples 18 to 36, since the colorant contains the anionic dye represented by the general formula (11), the heat resistance was good and ΔEab was 1.5 or less. Moreover, it was excellent in storage stability, the coating-film foreign material was in the range which can be used as a color filter, and it was a result with favorable glass adhesiveness, solvent resistance, and alkali developability.
On the other hand, since Comparative Examples 10-18 did not have an anionic dye represented by the general formula (11), the heat resistance was poor and ΔEab exceeded 2.5.

<Production of color filter>
In combination with the photosensitive coloring composition of the present invention, a red photosensitive coloring composition, a blue photosensitive coloring composition and a green photosensitive coloring composition used for the preparation of a color filter were prepared.

(Preparation of red photosensitive coloring composition (RR-1))
A mixture having the following composition was stirred and mixed so as to be uniform, and then dispersed with an Eiger mill (“Mini Model M-250 MKII” manufactured by Eiger Japan) for 5 hours using zirconia beads having a diameter of 0.5 mm. It filtered with a 0.0 micrometer filter, and produced the red coloring composition (DR-1).

Red pigment (CI Pigment Red 254) 9.6 parts Red Pigment (CI Pigment Red 177) 2.4 parts Resin Type Dispersant ("EFKA4300" manufactured by BASF Japan) 1.0 part binder resin solution 1 35.0 parts propylene glycol monomethyl ether acetate 52.0 parts

Subsequently, a mixture having the following composition was stirred and mixed so as to be uniform, and then filtered through a 1.0 μm filter to prepare a red photosensitive coloring composition (RR-1).

Red coloring composition (DR-1) 42.0 parts Binder resin solution 1 13.2 parts Photopolymerizable monomer (“Aronix M400” manufactured by Toagosei Co., Ltd.) 2.8 parts Photopolymerization initiator (manufactured by BASF Japan) "Irgacure 907") 2.0 parts sensitizer ("EAB-F" manufactured by Hodogaya Chemical Co., Ltd.) 0.4 parts ethylene glycol monomethyl ether acetate 39.6 parts

(Preparation of blue photosensitive coloring composition (RB-1))
A mixture having the following composition was stirred and mixed so as to be uniform, and then dispersed with an Eiger mill (“Mini Model M-250 MKII” manufactured by Eiger Japan) for 5 hours using zirconia beads having a diameter of 0.5 mm. A blue colored composition (DB-100) was produced by filtration through a 0.0 μm filter.

Blue pigment (CI Pigment Blue 15: 6) 7.2 parts purple pigment (CI Pigment Violet 23) 4.8 parts resin type dispersant ("EFKA4300" manufactured by BASF Japan Ltd.) 1.0 part binder Resin solution 1 17.5 parts Propylene glycol monomethyl ether acetate 69.5 parts

Then, after stirring and mixing the mixture of the following composition so that it might become uniform, it filtered with a 1.0 micrometer filter, and produced the blue photosensitive coloring composition (RB-1).

Blue coloring composition (DB-100) 34.0 parts Binder resin solution 1 7.6 parts Photopolymerizable monomer (“Aronix M400” manufactured by Toagosei Co., Ltd.) 3.3 parts Photopolymerization initiator (manufactured by BASF Japan) "Irgacure 907") 2.0 parts sensitizer ("EAB-F" manufactured by Hodogaya Chemical Co., Ltd.) 0.4 parts ethylene glycol monomethyl ether acetate 52.7 parts

(Preparation of green photosensitive coloring composition (RG-1))
A mixture having the following composition was stirred and mixed so as to be uniform, and then dispersed with an Eiger mill (“Mini Model M-250 MKII” manufactured by Eiger Japan) for 5 hours using zirconia beads having a diameter of 0.5 mm. It filtered with a 0.0 micrometer filter, and produced green coloring composition (DG-1).

Green pigment (CI Pigment Green 58) 12.0 parts Resin-type dispersant ("EFKA4300" manufactured by BASF Japan) 1.0 part Binder resin solution 1 35.0 parts Propylene glycol monomethyl ether acetate 52.0 parts

Subsequently, the mixture having the following composition was stirred and mixed so as to be uniform, and then filtered through a 1.0 μm filter to prepare a green photosensitive coloring composition (RG-1).
Green coloring composition (DG-1) 34.0 parts Binder resin solution 1 15.2 parts Photopolymerizable monomer (“Aronix M400” manufactured by Toagosei Co., Ltd.) 3.3 parts Photopolymerization initiator (manufactured by BASF Japan) "Irgacure 907" 2.0 parts sensitizer ("EAB-F" manufactured by Hodogaya Chemical Co., Ltd.) 0.4 parts ethylene glycol monomethyl ether acetate 45.1 parts

A black matrix was patterned on a glass substrate, and a red photosensitive coloring composition (RR-1) was applied on the substrate with a spin coater to a thickness of x = 0.640 to form a colored film. The coating was irradiated with 300 mJ / cm 2 of ultraviolet rays through a photomask using an ultrahigh pressure mercury lamp. Next, spray development was performed with an alkaline developer composed of a 0.2% by weight aqueous sodium carbonate solution to remove unexposed portions, followed by washing with ion-exchanged water. The substrate was heated at 230 ° C. for 20 minutes to obtain a red filter segment. Formed. By the same method, a blue filter segment is formed so that the film thickness of the blue photosensitive coloring composition (R-3) of the present invention is 2.0 μm, and then the green photosensitive coloring composition (RG-1) is formed. ) To form a green color filter segment to obtain a color filter.

Similarly, a color filter using the red photosensitive coloring composition (RR-1), the blue photosensitive coloring composition (R-3), and the green photosensitive coloring composition (RG-1) of the present invention. Got.

By using the photosensitive coloring composition of the present invention, the heat resistance of the color filter, the foreign matter test, the adhesion to a transparent substrate such as glass, the solvent resistance, and the alkali developability are improved and preferably used. I was able to.

Claims (12)

A color filter coloring composition comprising at least a colorant (A), a binder resin, and an organic solvent,
The colorant (A) is selected from the group consisting of an anionic dye (C) represented by the general formula (11), a quaternary ammonium salt compound, an amine, and a resin having a cationic group in the side chain. The coloring composition for color filters characterized by including the salt-forming compound (D) with the compound (B) which has a cationic group.

Formula (11)

[X ₁ and X ₃ represent a monovalent aliphatic hydrocarbon group having 1 to 20 carbon atoms which may have a substituent.
X ₂ and X ₄ each represents a monovalent aromatic hydrocarbon group which may have a substituent, and at least one of them has a sulfo group. ] The coloring composition for a color filter according to claim 1, wherein the compound (B) having a cationic group contains a quaternary ammonium salt compound represented by the following general formula (1).
General formula (1)
[In General Formula (1), R _{1 to} R ₄ each independently represents an alkyl group having 1 to 20 carbon atoms or a benzyl group, and at least two of R ₁ , R ₂ , R ₃ , or R ₄ Is an alkyl group having 5 to 20 carbon atoms or a benzyl group. Y- represents an inorganic or organic anion. ]   The compound (B) having a cationic group contains an amine, and the amine is at least one selected from the group consisting of a primary amine, a secondary amine, and a tertiary amine. Coloring composition for color filter. The compound (B) having a cationic group includes a resin having a cationic group in a side chain, and the resin having a cationic group in the side chain includes an acryl having a structural unit represented by the following general formula (2) The colored composition for a color filter according to claim 1, which is a resin based on color.
General formula (2):
[In General Formula (2), R ₅ represents a hydrogen atom or a substituted or unsubstituted alkyl group. R _{6 to} R ₈ each independently represents a hydrogen atom, an optionally substituted alkyl group, an optionally substituted alkenyl group, or an optionally substituted aryl group, and R _{6 to} R ₈ Two of them may be bonded to each other to form a ring. Q represents an alkylene group, an arylene group, —CONH—R ₉ —, or —COO—R ₉ —, and R ₉ represents an alkylene group. Y- represents an inorganic or organic anion. ] The colored composition for a color filter according to claim 4, wherein the acrylic resin containing the structural unit represented by the general formula (2) has a thermally crosslinkable functional group. The coloring composition for a color filter according to claim 5, wherein the thermally crosslinkable functional group is a hydroxyl group or a carboxyl group. The colored composition for a color filter according to any one of claims 4 to 6, wherein an ammonium salt value of the acrylic resin containing the structural unit represented by the general formula (2) is 10 to 200 mgKOH / g. .   The colored composition for a color filter according to any one of claims 1 to 7, wherein the organic solvent contains propylene glycol monomethyl ether acetate as a main component.   The coloring composition for a color filter according to any one of claims 1 to 8, wherein the colorant (A) further contains a pigment.   Furthermore, the coloring composition for color filters in any one of Claims 1-9 containing a photopolymerizable monomer and / or a photoinitiator. The color filter formed with the coloring composition for color filters in any one of Claims 1-10. A color filter coloring composition comprising at least a colorant (A), a binder resin, and an organic solvent,
The colorant (A) is selected from the group consisting of the anionic dye (C) represented by the general formula (11), a quaternary ammonium salt compound, an amine, and a resin having a cationic group in the side chain. A salt-forming compound (D) with a compound (B) having a cationic group
The salt-forming compound (D) is a mixture of a compound (B) having a cationic group and an anionic dye (C) in an aqueous solution, and a counter anion and an anionic dye (C) of the compound (B) having a cationic group. And a counter cation) is removed to produce a coloring composition for a color filter.