JP2016188993A - Colored composition for color filter, and color filter - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a colored composition for a color filter, which excels in dispersibility, a contrast ratio, lightness and heat resistance, excels in developability with an alkali aqueous solution, and achieves high resolution, and a color filter using the colored composition.SOLUTION: The colored composition for a color filter comprises: an acidic dispersant having a main chain that is a polyester having a carboxyl group derived from a tricarboxylic acid anhydride and/or tetracarboxylic acid dianhydride, and having a side chain that is a vinyl polymer having a vinyl polymer structure having at least one structure selected from the group represented by general formula (1) to general formula (4) below; and a basic dispersant that is a random copolymer having an amine value of 90-320 mgKOH/g, produced by radical polymerization of an ethylenically unsaturated monomer (d) comprising an ethylenically unsaturated monomer having an amino group.SELECTED DRAWING: None

Description

  The present invention is a color liquid crystal display device, a color filter coloring composition used for the production of a color filter used for a color image pickup tube element, and the like, a photosensitive color composition for a color filter, and formed using the same. The present invention relates to a color filter having a filter segment.

  Generally, in a color liquid crystal display device, a transparent electrode for driving a liquid crystal is formed on a color filter by vapor deposition or sputtering, and an alignment film for aligning the liquid crystal in a certain direction is further formed thereon. Yes. In order to sufficiently obtain the performance of these transparent electrodes and alignment films, the formation thereof must generally be performed at a high temperature of 200 ° C. or higher, preferably 230 ° C. or higher. For this reason, at present, as a method for producing a color filter, a method called a pigment dispersion method using a pigment having excellent heat resistance and light resistance as a colorant is mainly used.

In general, when producing a pigment composition, it is known that it is difficult to stably disperse the pigment at a high concentration, which causes various problems to the production process and the product itself.

  Therefore, in general, a dispersant is used in order to keep the dispersion state good. The dispersant has a structure of a site that adsorbs to the pigment and a site that has a high affinity for the solvent that is the dispersion medium, and the performance of the dispersant is determined by the balance of these two functional sites.

  Pigment composition with excellent dispersibility, fluidity, and storage stability, used in combination with acidic resin dispersants with aromatic carboxyl groups and vinyl resins (dispersants) with tertiary amino groups for color filter applications The thing is proposed (refer patent document 1). However, the aromatic carboxyl group described here has good dispersibility, but has a problem of low brightness after the heat treatment step. There is also a problem that the developability is poor and the resolution is poor. There is such a problem that there has been a problem that it has not been possible to achieve a high brightness color filter which has been increasingly demanded in recent years.

JP 2009-185277 A JP 2010-54808 A

An object of the present invention is to provide a color filter dispersant and a color filter coloring composition that have excellent dispersibility, contrast ratio, lightness, and heat resistance, and further have excellent developability in an alkaline aqueous solution and achieve high resolution. It is providing the photosensitive coloring composition for color filters, and a color filter using the same.

  As a result of intensive studies to solve the above problems, the present inventors have developed a specific basic dispersant and a specific acidic dispersant as a color filter coloring composition and a color filter photosensitive coloring composition. As a result, it was found that a color filter having excellent dispersibility, contrast ratio, brightness, and heat resistance, and also having excellent developability and resolution for an alkaline aqueous solution can be produced, and the present invention has been achieved.

That is, the present invention is a color filter coloring composition comprising a pigment, a basic dispersant, an acidic dispersant, a binder resin, and a solvent,
The acidic dispersant is a main chain which is a polyester having a carboxyl group derived from tricarboxylic anhydride and / or tetracarboxylic dianhydride, and from the group represented by the following general formula (1) to general formula (4). An acidic dispersant characterized by having a side chain that is a vinyl polymer having at least one selected structure;
A random copolymer having an amine value of 90 to 320 mgKOH / g, wherein the basic dispersant is a radical polymerization of an ethylenically unsaturated monomer (d) containing an ethylenically unsaturated monomer having an amino group. It is related with the coloring composition for color filters characterized by these.

General formula (1):



(In the general formula (1), n is an integer of 1 to 4, R ₁ represents hydrogen or a methyl group, X is a direct bond or -CR ₆ R ₇ -Z-, and Z is a direct bond or -CR ₈ R ₉ - is represented _by, R 2 to R ₉ is a hydrogen atom, a halogen atom, a phthalimido _group, -CH ₂ CH 2 COOH, substituted or unsubstituted alkenyl group having 2 to 20 carbon atoms, a substituted or unsubstituted A substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, or a substituted or unsubstituted aryl group having 6 to 10 carbon atoms, and —CH ₂ — contained in these groups is —O—, —CO—, or — May be substituted with OCO-,
R ₂ and R ₄ may combine to form an unsaturated double bond, R ₂ and R ₃ and / or R ₄ and R ₅ together form ═CH ₂ , R ₂ and R ₆ and R ₄ and R ₈ may be bonded to each other to form a ring having 6 to 10 carbon atoms, and “*” represents a bond. )
General formula (2):



(In General Formula (2), n represents an integer of 1 to 4, W ₁ represents CR ₁₁ or a nitrogen atom, W ₂ represents CR ₁₄ or a nitrogen atom, Y represents —COOH, —SO ₃ H, R ₁₀ represents hydrogen or a methyl group, and R _{11 to} R ₁₄ represent a hydrogen atom, a halogen atom, a nitro group, an ethynyl group, —SO ₃ H, —COOH, —COCl, —NHCOCH ₃ , substituted or unsubstituted carbon. Represents an alkyl group having 1 to 20, R ₁₁ and R ₁₂ , R ₁₂ and R ₁₃ , R ₁₃ and R ₁₄ may be bonded to each other to form a ring having 6 to 10 carbon atoms; Indicates a bond.)

General formula (3):



(In General Formula (3), n represents an integer of 1 to 3, R ₁₅ represents hydrogen or a methyl group, and R _{16 to} R ₂₅ represent a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms. R ₁₇ and R ₁₉ and / or R ₂₃ and R ₂₅ may be bonded to each other to form a ring containing an unsaturated double bond, and R ₁₇ and R ₂₃ may be bonded to each other to form a ring. ("*" Indicates a bond)

General formula (4):



(In General Formula (4), n represents an integer of 1 to 3, R ₂₆ represents hydrogen or a methyl group, R ₃₁ represents a hydrogen atom or a methyl group, R _{27 to} R ₃₀ represent a hydrogen atom, a halogen atom, A nitro group, —COOH, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, and “*” represents a bond.)

In the color filter according to the invention, the ethylenically unsaturated monomer having an amino group is an ethylenically unsaturated monomer (d1) having an N, N-dialkylamino group. The present invention relates to a coloring composition.

Further, the present invention is characterized in that the ethylenically unsaturated monomer having an amino group is an ethylenically unsaturated monomer (d2) having a hindered amine skeleton represented by the following general formula (10). The present invention relates to a coloring composition for a color filter.
General formula (10):



(In the general formula (10), R ₃₂ is a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aralkyl group having 7 to 12 carbon atoms, an acyl group, an oxy radical group, or OR. represents _35, R ₃₅ represents a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aralkyl group or an acyl group, having 7 to 12 carbon atoms, R _33, and R ₃₄ Each independently represents a methyl group, an ethyl group, or a phenyl group, and “*” represents a bond.)

Moreover, this invention relates to the coloring composition for color filters in any one of Claims 1-3 whose acid values of the said vinyl polymer (a) are 10-100 mgKOH / g.

In the present invention, the side chain of the acidic dispersant has a structure represented by the general formula (1) and / or the general formula (2), and R _{2 to} R _{5 in the} general formula (1). Is a hydrogen composition, and R _{11 to} R ₁₄ in the general formula (2) are hydrogen.

The present invention also relates to the coloring composition for a color filter, wherein the binder resin has at least one structure selected from the group represented by the general formulas (1) to (4).

In the present invention, the pigment may be a halogenated zinc phthalocyanine pigment, an aluminum phthalocyanine pigment, C.I. I. Pigment Yellow 138, C.I. I. Pigment Y
yellow 139, C.I. I. Pigment Yellow 150, and C.I. I. P
It is at least 1 sort (s) of pigments chosen from pigment Yellow 185, It is related with the said coloring composition for color filters characterized by the above-mentioned.

In addition, the present invention relates to the color composition for color filters, further comprising an active energy ray-curable monomer and / or an active energy ray polymerization initiator.

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

According to the present invention, dispersibility, contrast ratio, brightness, heat resistance can be obtained by using a specific basic dispersant and a specific acidic dispersant as a color filter coloring composition and a color filter photosensitive coloring composition. In addition, it is possible to provide a color filter coloring composition and a color filter that are very excellent in properties and have both excellent developability and resolution for an alkaline aqueous solution.

Hereinafter, the present invention will be described in detail.
In the present application, when “(meth) acryloyl”, “(meth) acryl”, “(meth) acrylic acid”, “(meth) acrylate”, or “(meth) acrylamide” is particularly described, Unless otherwise indicated, “acryloyl and / or methacryloyl”, “acrylic and / or methacrylic”, “acrylic acid and / or methacrylic acid”, “acrylate and / or methacrylate”, or “acrylamide and / or methacrylamide”, respectively. It shall represent.
Further, “CI” mentioned in the present specification means a color index (CI).

The present invention relates to a coloring composition containing a pigment, a basic dispersant, an acidic dispersant, a binder resin, and a solvent, wherein the acidic dispersant is derived from a tricarboxylic acid anhydride and / or a tetracarboxylic acid dianhydride. A side which is a vinyl polymer having a main chain which is a polyester having a carboxyl group, and a vinyl polymer structure having at least one structure selected from the group represented by the following general formulas (1) to (4) And the basic dispersant is a radical polymerization of an ethylenically unsaturated monomer (d) containing an ethylenically unsaturated monomer having an amino group and has an amine value of 90 to 320 mgKOH / g. It is characterized by being a random copolymer. Thereby, it has excellent developability while having excellent dispersibility, contrast ratio, brightness, and heat resistance.
<Acid dispersant (X)>
The acidic dispersant (X) is represented by a main chain which is a polyester having a carboxyl group derived from tricarboxylic acid anhydride and / or tetracarboxylic dianhydride, and the following general formulas (1) to (4). It has the side chain which is a vinyl polymer which has a structure, It is characterized by the above-mentioned.
[Structure represented by general formula (1) to general formula (4)]
The greatest feature of the present invention is that a specific acidic structure which is a structure represented by the general formula (1) to the general formula (4) is introduced into the side chain which is a vinyl polymer of the acidic dispersant (X). is there. By using these, it is possible to provide a color filter coloring composition and a color filter that are excellent in dispersibility, contrast ratio, lightness, heat resistance, and developability. In general formulas (1) to (4), n is independently an integer of 1 to 4, and may be the same or different.

General formula (1):



(In the general formula (1), n is an integer of 1 to 4, R ₁ represents hydrogen or a methyl group, X is a direct bond or -CR ₆ R ₇ -Z-, and Z is a direct bond or -CR ₈ R ₉ - is represented _by, R 2 to R ₉ is a hydrogen atom, a halogen atom, a phthalimido _group, -CH ₂ CH 2 COOH, substituted or unsubstituted alkenyl group having 2 to 20 carbon atoms, a substituted or unsubstituted A substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, or a substituted or unsubstituted aryl group having 6 to 10 carbon atoms, and —CH ₂ — contained in these groups is —O—, —CO—, or — May be substituted with OCO-,
R ₂ and R ₄ may combine to form an unsaturated double bond, R ₂ and R ₃ and / or R ₄ and R ₅ together form ═CH ₂ , R ₂ and R ₆ and R ₄ and R ₈ may be bonded to each other to form a ring having 6 to 10 carbon atoms, and “*” represents a bond. )

Examples of the substituted or unsubstituted alkenyl group having 2 to 20 carbon atoms represented by R _{2 to} R _{9 in} the general formula (1) include a vinyl group, an allyl group, a butenyl group, a pentenyl group, a hexenyl group, a cyclohexenyl group, Propenyl group, 4-pentenyl group, 5-hexenyl group, 1-methyl-vinyl group, 2-methyl-vinyl group, n-2-propenyl group, 1,2-dimethyl-vinyl group, 1-methyl-propenyl group, Examples include 2-methyl-propenyl group, n-1-butenyl group, n-2-butenyl group, n-3-butenyl group, 2-octenyl group, 3-dodecenyl group, vinyl group, allyl group, 2- A methyl-propenyl group, 2-octenyl group, and 3-dodecenyl group are particularly preferable.

Examples of the substituted or unsubstituted alkyl group having 1 to 20 carbon atoms of R _{2 to} R _{9 in} the general formula (1) include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, and an isobutyl group. , Sec-butyl group, tert-butyl group, pentyl group, hexyl group, octyl group, and the like, and a methyl group is particularly preferable.

Examples of the substituted or unsubstituted aryl group having 6 to 10 carbon atoms of R _{2 to} R _{9 in} the general formula (1) include a phenyl group and a naphthyl group, and a phenyl group is particularly preferable.

In the general formula (1), X is a direct _{bond, -CH 2 -, - CR 6} R 7 -CR 8 R 9 - _preferably, R 2 to R ₅ is a hydrogen atom, the number of carbon atoms of the substituted or unsubstituted 1 to 20 An alkyl group, a halogen atom, or a phthalimide group, or R ₂ and R _6, and R ₄ and R ₈ may form a ring having 6 to 10 carbon atoms together with the carbon atom to which they are bonded. preferable.

The structure represented by the general formula (1) is preferably derived from a (meth) acrylate monomer. For example, 2- (meth) acryloyloxyethyl hexahydrophthalic acid, 2- (meth) acryloyloxy Examples thereof include ethyl succinic acid and 2- (meth) acryloyloxyethyl phthalic acid. 2- (Meth) acryloyloxyethyl succinic acid is preferable because it is more excellent in developability and brightness.
The structure represented by the general formula (1) can also be obtained by reacting an ethylenically unsaturated monomer containing a hydroxyl group with an acid anhydride represented by the following general formula (6).

Examples of the ethylenically unsaturated monomer containing 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 methacrylates such as (meth) acrylate or cyclohexanedimethanol mono (meth) acrylate. Preferred are 2-hydroxyethyl (meth) acrylate, 2- or 3-hydroxypropyl (meth) acrylate, and 2- or 3- or 4-hydroxybutyl (meth) acrylate.

General formula (6):


(In formula (6), X is a direct bond or is _represented by -CR ₆ R 7 -Z-, Z is a direct bond or _-CR 8 _{R 9} - is represented by,
R _{2 to} R ₉ are a hydrogen atom, a halogen atom, a phthalimide group, —CH ₂ CH ₂ COOH, a substituted or unsubstituted alkenyl group having 2 to 20 carbon atoms, and a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms. Or a substituted or unsubstituted aryl group having 6 to 10 carbon atoms, and —CH ₂ — contained in these groups may be substituted with —O—, —CO— or —OCO—,
R ₂ and R ₄ may combine to form an unsaturated double bond, R ₂ and R ₃ and / or R ₄ and R ₅ together form ═CH ₂ , R ₂ and R ₆ and R ₄ and R ₈ may be bonded to each other to form a ring having 6 to 10 carbon atoms. )

R _{2 to} R ₉ in the general formula (6) are the same as those in the general formula (1). X is preferably a direct bond, —CH ₂ —, —CR ₆ R ₇ —CR ₈ R ₉ —, wherein R _{2 to} R ₅ are a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a halogen atom It is preferably an atom or a phthalimide group, and R ₂ and R ₆ and R ₄ and R ₈ are preferably combined with the carbon atom to which they are bonded to form a ring having 6 to 10 carbon atoms.

As preferable examples of the acid anhydride represented by the general formula (6), the following compounds can be exemplified. M-1, M-15, and M-18 are preferable from the viewpoint of developability.

General formula (2):



(In General Formula (2), n represents an integer of 1 to 4, W ₁ represents CR ₁₁ or a nitrogen atom, W ₂ represents CR ₁₄ or a nitrogen atom, Y represents —COOH, —SO ₃ H, R _10. Represents hydrogen or a methyl group, and R _{11 to} R ₁₄ are a hydrogen atom, a halogen atom, a nitro group, an ethynyl group, —SO ₃ H, —COOH, —COCl, —NHCOCH ₃ , a substituted or unsubstituted carbon number of 1 Represents an alkyl group of ˜20, R ₁₁ and R ₁₂ , R ₁₂ and R ₁₃ , R ₁₃ and R ₁₄ may be bonded to each other to form a ring having 6 to 10 carbon atoms, and “*” represents a bond Indicates that it is a hand.)

The general formula (2) halogen atom R ₁₁ to R ₁₄ in, fluorine atom, chlorine atom, bromine atom, an iodine atom, a bromine atom, a chlorine atom are particularly preferred.

Examples of the substituted or unsubstituted alkyl group having 1 to 20 carbon atoms of R _{11 to} R _{14 in} the general formula (2) include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, and an isobutyl group. , Sec-butyl group, tert-butyl group, pentyl group, hexyl group, octyl group, dodecyl group, decyl group, tetradecyl group, octadecyl group, hexadecyl group and the like, and methyl group, n-butyl group, octyl group Particularly preferred.

In General Formula (2), R _{11 to} R ₁₄ are preferably a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, and a halogen atom.

The structure represented by the general formula (2) is preferably derived from a (meth) acrylate monomer, and examples thereof include 2- (meth) acryloyloxyethylphthalic acid.
The structure represented by the general formula (2) is obtained by reacting an ethylenically unsaturated monomer containing a hydroxyl group with an acid anhydride represented by the following general formula (7) or an acid anhydride represented by M-16. Can also be obtained.

General formula (7):

(In General Formula (7), W 1 represents CR ₁₁ or a nitrogen atom, W 2 represents CR ₁₄ or a nitrogen atom, and R _{11 to} R ₁₄ represent a hydrogen atom, a halogen atom, a nitro group, an ethynyl group, —SO _3. H, —COOH, —COCl, —NHCOCH ₃ , a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, and R ₁₁ and R ₁₂ , R ₁₂ and R ₁₃ , R ₁₃ and R ₁₄ are bonded to each other. And may form a ring having 6 to 10 carbon atoms.)

_R 11 in the general formula (7) _{to R 14} are the same as _R 11 _{to R 14} in the general formula (2). R _{11 to} R ₁₄ are preferably a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, and a halogen atom.

As preferable examples of the acid anhydride represented by the general formula (7), the following compounds M3 to M8 and M17 can be exemplified. M-3 and M-16 are preferable from the viewpoint of developability.

General formula (3):



(In General Formula (3), n represents an integer of 1 to 3, R ₁₅ represents hydrogen or a methyl group, and R _{16 to} R ₂₅ represent a hydrogen atom, a substituent, or an unsubstituted alkyl group having 1 to 20 carbon atoms. R ₁₇ and R ₁₉ and / or R ₂₃ and R ₂₅ may be combined to form an unsaturated double bond, and R ₁₇ and R ₂₃ may be combined with the carbon atom to which they are bonded. And may form a ring, and “*” indicates a bond.)

Examples of the substituted or unsubstituted alkyl group having 1 to 20 carbon atoms of R _{16 to} R _{25 in} the general formula (3) include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, and an isobutyl group. , Sec-butyl group, tert-butyl group, pentyl group, hexyl group, octyl group and the like, and methyl group and tert-butyl group are particularly preferable.

The structure represented by the general formula (3) is preferably derived from a (meth) acrylate monomer, and examples thereof include 2- (meth) acryloyloxyethyl tetrahydrophthalic acid.
The structure represented by the general formula (3) can also be obtained by reacting an ethylenically unsaturated monomer containing a hydroxyl group with an acid anhydride represented by the following general formula (8).

General formula (8):



(In the general formula (8), R _{16 to} R ₂₅ represent a hydrogen atom, a substituent, or an unsubstituted alkyl group having 1 to 20 carbon atoms, and R ₁₇ and R ₁₉ and / or R ₂₃ and R ₂₅ May be bonded to form a ring containing an unsaturated double bond, and R ₁₇ and R ₂₃ may be bonded to each other to form a ring.)

_R 16 in the general formula (8) _{to R 25} are the same as _R 16 _{to R 25} in the general formula (3). Preferable examples of the acid anhydride represented by the general formula (8) include the following compounds.

General formula (4):



(In General Formula (4), n represents an integer of 1 to 3, R ₂₆ represents hydrogen or a methyl group, R ₃₁ represents a hydrogen atom or a methyl group, R _{27 to} R ₃₀ represent a hydrogen atom, a halogen atom, Represents a nitro group, —COOH, a substituent or an unsubstituted alkyl group having 1 to 20 carbon atoms, and “*” represents a bond.)

As a halogen atom of R < ₂₇ > -R < ₃₀ > in General formula (4), a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom are mentioned, A bromine atom and a chlorine atom are especially preferable.

Examples of the substituted or unsubstituted alkyl group having 1 to 20 carbon atoms of R _{27 to} R _{30 in} the general formula (4) include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, and an isobutyl group. , Sec-butyl group, tert-butyl group, pentyl group, hexyl group, octyl group, and the like, and a methyl group is particularly preferable.

The structure represented by the general formula (4) is preferably derived from a (meth) acrylate monomer, and is represented by, for example, an ethylenically unsaturated monomer containing a hydroxyl group and the following general formula (9). It can also be obtained by reacting with an acid anhydride.

General formula (9):


(In General Formula (9), R ₃₁ represents a hydrogen atom or a methyl group, and R _{27 to} R ₃₀ represent a hydrogen atom, a halogen atom, a nitro group, —COOH, a substituent, or an unsubstituted C 1-20. Represents an alkyl group.)

R < ₂₇ > -R < ₃₁ > in General formula (9) is the same as R < ₂₇ > -R < ₃₁ > in General formula (4). Preferable examples of the acid anhydride represented by the general formula (9) include the following compounds.

The side chain of the acidic dispersant (X) has a structure represented by the general formula (1) and / or the general formula (2), and R _{2 to} R _{5 in} the general formula (1) are hydrogen. In addition, it is preferable from the viewpoint of developability and brightness that R _{11 to} R ₁₄ in the general formula (2) are hydrogen. More preferably, the side chain of the acidic dispersant (X) has a structure represented by the general formula (1), and R _{1 to} R _{5 in} the general formula (1) are hydrogen.

[Structure and synthesis method of acidic dispersant (X)]
The acidic dispersant (X) used in the present invention acts as a pigment adsorbing group in which a main chain which is a polyester having a carboxyl group derived from a tricarboxylic anhydride and / or a tetracarboxylic dianhydride directly acts on the pigment surface. (Alternatively, the basic dispersant described later acts directly on the pigment and acts as an indirect pigment adsorbing group that interacts with the basic dispersant.) The side chain vinyl polymer moiety serves as the pigment carrier affinity group. By acting, it suppresses the aggregation of the pigment and is excellent in dispersibility, and the pigment can be sufficiently miniaturized, thereby contributing to the development of an excellent contrast ratio and transmittance (lightness). Furthermore, the coloring composition for color filters excellent in developability by providing the specific acidic structure represented by the general formula (1) to the general formula (4) in the vinyl polymer portion of the side chain, and the color filter The photosensitive coloring composition can be provided.

The acidic dispersant (X) is a polyester having a carboxyl group derived from a tricarboxylic anhydride and / or a tetracarboxylic dianhydride, a vinyl polymer moiety in a side chain, and the general formula in the side chain. If it has the specific acidic structure represented by General formula (4) from (1), there will be no restriction | limiting in particular.
The acidic dispersant (X) is preferably formed by radical polymerization of an ethylenically unsaturated monomer (b) in the presence of a compound (a1) having two hydroxyl groups and one thiol group in the molecule, for example. The hydroxyl group of the vinyl polymer (a2) having two hydroxyl groups in one end region is reacted with the acid anhydride group of the tricarboxylic acid anhydride (c1) and / or the tetracarboxylic acid dianhydride (c2) (hereinafter referred to as the following). This is abbreviated as manufacturing method (1), and the method described in Japanese Patent No. 4396777.
Preferably, the hydroxyl group in the compound (a1) having two hydroxyl groups and one thiol group in the molecule and the acid anhydride in the tricarboxylic anhydride (c1) and / or tetracarboxylic dianhydride (c2) The ethylenically unsaturated monomer (b) is radically polymerized in the presence of the polyester (c3) obtained by reacting with a group (hereinafter abbreviated as production method (2). Described in JP 2010-185934 A Method.) Can also be obtained.
These production methods will be described in detail including the method for introducing a specific acidic structure into the vinyl polymer site.

[Production method (1)]
Radical polymerization of an ethylenically unsaturated monomer (b) containing an ethylenically unsaturated monomer having a specific acidic structure in the presence of a compound (a1) having two hydroxyl groups and one thiol group in the molecule. To obtain a vinyl polymer (a2) having two hydroxyl groups in one terminal region, two hydroxyl groups in one terminal region of the vinyl polymer (a2), tricarboxylic acid anhydride (c1) and / or tetracarboxylic acid. By reacting with the acid anhydride group of the acid dianhydride (c2), a specific acidic structure can be introduced into the side chain that is the vinyl polymer of the acidic dispersant (X). In detail, it is compoundable by the method as described in patent 4396777 grade | etc.,.

[Ethylenically unsaturated monomer containing specific acidic structure]
Although it will not specifically limit if it is an ethylenically unsaturated monomer which has a specific acidic structure, It is preferable that it is a (meth) acrylate monomer, for example, 2- (meth) acryloyloxyethyl hexahydrophthalic acid, 2- (Meth) acryloyloxyethyl succinic acid, 2- (meth) acryloyloxyethyl phthalic acid, etc. are mentioned. 2- (Meth) acryloyloxyethyl succinic acid is preferable because it is more excellent in developability and brightness.
An ethylenically unsaturated monomer having a specific acidic structure is obtained by reacting an ethylenically unsaturated monomer containing a hydroxyl group with an acid anhydride represented by the general formula (6) to the general formula (9). It can also be obtained.
[Production method (2)]
First, the hydroxyl group in the compound (a1) having two hydroxyl groups and one thiol group in the molecule and the acid anhydride group in the tricarboxylic anhydride (c1) and / or tetracarboxylic dianhydride (c2) To obtain a polyester (c3), and in the presence thereof, an ethylenically unsaturated monomer (b) containing an ethylenically unsaturated monomer containing a specific acidic structure is radically polymerized to produce an acidic dispersion. A specific acidic structure can be introduced into the side chain which is a vinyl polymer of the agent (X).

Alternatively, first, the hydroxyl group in the compound (a1) having two hydroxyl groups and one thiol group in the molecule, and the acid anhydride in the tricarboxylic acid anhydride (c1) and / or the tetracarboxylic acid dianhydride (c2). A polyester (c3) is obtained by reacting with a physical group, and in the presence thereof, an ethylenically unsaturated monomer (b) containing an ethylenically unsaturated monomer containing a hydroxyl group is subjected to radical polymerization, thereby causing acidic dispersion. It can also be obtained by introducing a hydroxyl group into the side chain which is a vinyl polymer of the agent (X) and adding an acid anhydride represented by the general formula (6) to the general formula (9) to the hydroxyl group. Details are described in JP 2010-185934 A.

[Compound having two hydroxyl groups and one thiol group in the molecule (a1)]
The compound (a1) having two hydroxyl groups and one thiol group in the molecule (hereinafter sometimes referred to as compound (a1)) includes two hydroxyl groups and one thiol group in the molecule. Is not particularly limited as long as it functions as a chain transfer agent in vinyl polymerization, but a trivalent residue excluding two hydroxyl groups and one thiol group,
What is a C1-C20 hydrocarbon group is preferable, More preferably, it is a C1-C4 hydrocarbon group. Specific examples include, for example, 1-mercapto-1,1-methanediol, 1-mercapto-1,1-ethanediol, 3-mercapto-1,2-propanediol (thioglycerin), 2-mercapto-1,2 -Propanediol, 2-mercapto-2-methyl-1,3-propanediol, 2-mercapto-2-ethyl-1,3-propanediol, 1-mercapto-2,2-propanediol, 2-mercaptoethyl- Examples include 2-methyl-1,3-propanediol, 2-mercaptoethyl-2-ethyl-1,3-propanediol, and the like.

[Ethylenically unsaturated monomer (b)]
Examples of those other than the ethylenically unsaturated monomer having a specific acidic structure 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, esters of vinyl alcohol, styrenes, (meth) acrylonitrile and the like.

Specific examples of such a monomer include the following compounds.
Methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth), tertiary butyl (meth) acrylate, isoamyl (meth) acrylate, octyl (Meth) acrylate, isooctyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, cetyl (meth) acrylate, decyl (meth) acrylate, isodecyl (meth) acrylate, lauryl (meth) acrylate, tridecyl (meth) acrylate, iso Linear or branched alkyl (meth) acrylates such as myristyl (meth) acrylate, stearyl (meth) acrylate, and isostearyl (meth) acrylate;
Cyclic alkyl (meth) acrylates such as cyclohexyl (meth) acrylate, tertiarybutylcyclohexyl (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentenyl (meth) acrylate, and isobornyl (meth) acrylate;
(Meth) acrylates having a heterocyclic ring such as tetrahydrofurfuryl (meth) acrylate and 3-methyl-3-oxetanyl (meth) acrylate;
(Meth) acrylates having an aromatic ring of benzyl (meth) acrylate and phenoxyethyl (meth) acrylate;
2-methoxyethyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, 2-methoxypropyl (meth) acrylate, diethylene glycol monomethyl ether (meth) acrylate, diethylene glycol monoethyl ether (meth) acrylate, diethylene glycol mono-2-ethylhexyl Ether (meth) acrylate, dipropylene glycol monomethyl ether (meth) acrylate, triethylene glycol monomethyl ether (meth) acrylate, triethylene glycol monoethyl ether (meth) acrylate, tripropylene glycol monomethyl ether (meth) acrylate, tetraethylene glycol Monomethyl ether (meth) acrylate, polyethylene glycol monomethyl ether (Meth) acrylate, polypropylene glycol monomethyl ether (meth) acrylate, polyethylene glycol monolauryl ether (meth) acrylate, polyethylene glycol monostearyl ether (meth) acrylate, and octoxypolyethylene glycol-polypropylene glycol (meth) acrylate, (Poly) alkylene glycol monoalkyl ether (meth) acrylates;
Phenoxyethyl (meth) acrylate, phenoxydiethylene glycol (meth) acrylate, phenoxytetraethylene glycol (meth) acrylate, phenoxyhexaethylene glycol (meth) acrylate, phenoxypolyethylene glycol (meth) acrylate, paracumylphenoxyethyl (meth) acrylate, parac Milphenoxyethylene glycol (meth) acrylate, paracumylphenoxypolyethylene glycol (meth) acrylate, nonylphenoxypolyethylene glycol (meth) acrylate, nonylphenoxypolypropylene glycol (meth) acrylate, and nonylphenoxypoly (ethylene glycol-propylene glycol) (meth) ) Having an aromatic ring such as acrylate (poly) Ruki glycol (meth) acrylates;
Fluoroalkyl (meth) acrylates such as trifluoroethyl (meth) acrylate, octafluoropentyl (meth) acrylate, perfluorooctylethyl (meth) acrylate, and tetrafluoropropyl (meth) acrylate;
(Meth) acryloxy-modified polydimethylsiloxanes (silicone macromers);
N-substituted (meth) acrylamides such as (meth) acrylamide, dimethyl (meth) acrylamide, N, N-diethyl (meth) acrylamide, N-isopropyl (meth) acrylamide, diacetone (meth) acrylamide, and acryloylmorpholine;
Nitriles such as (meth) acrylonitrile are exemplified.
Styrenes such as styrene and α-methylstyrene;
Macromonomers having a mono (meth) acryloyl group at the end of the polymer molecular chain, such as polystyrene, polymethyl (meth) acrylate, poly-n-butyl (meth) acrylate, polysiloxane;
Vinyl ethers such as ethyl vinyl ether, n-propyl vinyl ether, isopropyl vinyl ether, n-butyl vinyl ether, and isobutyl vinyl ether;
Fatty acid vinyls such as vinyl acetate and vinyl propionate;

Furthermore, a carboxyl group-containing ethylenically unsaturated monomer can be used in combination. Examples of the carboxyl group-containing ethylenically unsaturated monomer include (meth) acrylic acid, (meth) acrylic acid dimer, itaconic acid, maleic acid, fumaric acid, crotonic acid, β-carboxyethyl (meth) acrylate, and ω- Examples include carboxypolycaprolactone (meth) acrylate.

In the case of the production method (1), it is preferable that the ethylenically unsaturated monomer (b) does not contain an ethylenically unsaturated monomer containing a hydroxyl group. This is because, when an ethylenically unsaturated monomer containing a hydroxyl group is used, a hydroxyl group is present in addition to the one terminal region of the vinyl polymer (a2), and the tricarboxylic acid anhydride (c1) and / or tetracarboxylic dianhydride is present. This is because the acid anhydride group of the product (c2) reacts with other than the one end region of the vinyl polymer (a2). When using the ethylenically unsaturated monomer containing a hydroxyl group in the ethylenically unsaturated monomer (b), it is preferable to select the production method (2). Moreover, it is most preferable to use an ethylenically unsaturated monomer having a specific structure represented by the general formulas (1) to (4).

Two or more types can be selected from the ethylenically unsaturated monomers mentioned above, and at least methyl (meth) acrylate is preferably used. Ethylenically unsaturated monomer (b) 100 weight % Of methyl methacrylate is preferable in terms of heat resistance and developability. More preferably, it is 50 to 80% by weight. Since methyl methacrylate has a high glass transition temperature of about 105 ° C. for homopolymer, the glass transition temperature Tg of the vinyl polymer (a2) is increased, and as a result, heat resistance and lightness are improved. However, when Tg is high, developability is lowered, but having a specific acidic site can achieve both heat resistance, lightness, and developability.

[Tricarboxylic anhydride (c1), tetracarboxylic dianhydride (c2)]
By using tricarboxylic acid anhydride (c1) and tetracarboxylic acid dianhydride (c2), a plurality of carboxyl groups can be introduced into the main chain of the dispersant, and function as a pigment adsorbing group. Examples of the tricarboxylic acid anhydride (c1) include aliphatic tricarboxylic acid anhydrides and aromatic tricarboxylic acid anhydrides.

Examples of the aliphatic tricarboxylic acid anhydride include 3-carboxymethylglutaric acid anhydride, 1,2,4-butanetricarboxylic acid-1,2-anhydride, cis-propene-1,2,3-tricarboxylic acid- 1,2-anhydride, 1,3,4-cyclopentanetricarboxylic acid anhydride, etc. are mentioned.

Examples of the aromatic tricarboxylic acid include benzenetricarboxylic acid anhydride (1,2,3-benzenetricarboxylic acid anhydride, trimellitic acid anhydride [1,2,4-benzenetricarboxylic acid anhydride], etc.), naphthalenetricarboxylic acid, and the like. Acid anhydride (1,2,4-naphthalenetricarboxylic acid anhydride, 1,4,5-naphthalenetricarboxylic acid anhydride, 2,3,6-naphthalenetricarboxylic acid anhydride, 1,2,8-naphthalenetricarboxylic acid anhydride Products), 3,4,4′-benzophenone tricarboxylic acid anhydride, 3,4,4′-biphenyl ether tricarboxylic acid anhydride, 3,4,4′-biphenyl tricarboxylic acid anhydride, 2,3,2 ′ -Biphenyltricarboxylic acid anhydride, 3,4,4'-biphenylmethanetricarboxylic acid anhydride, 3,4,4'-biphenyl Sulfonic tricarboxylic acid anhydrides. When tricarboxylic acid anhydride is used, aromatic tricarboxylic acid anhydride is particularly preferable among the above, and trimellitic acid anhydride is more preferable.

As tetracarboxylic dianhydride (c2) used in the present invention,
1,2,3,4-butanetetracarboxylic dianhydride, 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,3-dimethyl-1,2,3,4-cyclobutanetetracarboxylic acid Dianhydride, 1,2,3,4-cyclopentanetetracarboxylic dianhydride, 2,3,5-tricarboxycyclopentylacetic acid dianhydride, 3,5,6-tricarboxynorbornane-2-acetic acid dianhydride 2,3,4,5-tetrahydrofurantetracarboxylic dianhydride, 5- (2,5-dioxotetrahydrofural) -3-methyl-3-cyclohexene-1,2-dicarboxylic dianhydride, or Aliphatic tetracarboxylic dianhydrides such as bicyclo [2,2,2] -oct-7-ene-2,3,5,6-tetracarboxylic dianhydride, pyromellitic dianhydride, Lenglycol ditrimellitic anhydride ester, propylene glycol ditrimellitic anhydride ester, butylene glycol ditrimellitic anhydride ester, 3,3 ′, 4,4′-benzophenone tetracarboxylic dianhydride, 3,3 ′, 4,4′-biphenylsulfonetetracarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 3,3 ′ , 4,4'-biphenyl ether tetracarboxylic dianhydride, 3,3 ', 4,4'-dimethyldiphenylsilane tetracarboxylic dianhydride, 3,3', 4,4'-tetraphenylsilane tetracarboxylic Acid dianhydride, 1,2,3,4-furantetracarboxylic dianhydride, 4,4′-bis (3,4-dicarboxyphenoxy) diphenylsulfuric acid Fido dianhydride, 4,4′-bis (3,4-dicarboxyphenoxy) diphenylsulfone dianhydride, 4,4′-bis (3,4-dicarboxyphenoxy) diphenylpropane dianhydride, 3,3 ', 4,4'-perfluoroisopropylidenediphthalic dianhydride, 3,3', 4,4'-biphenyltetracarboxylic dianhydride, bis (phthalic acid) phenylphosphine oxide dianhydride, p- Phenylene-bis (triphenylphthalic acid) dianhydride, m-phenylene-bis (triphenylphthalic acid) dianhydride, bis (triphenylphthalic acid) -4,4′-diphenyl ether dianhydride, bis (triphenyl) Phthalic acid) -4,4′-diphenylmethane dianhydride, 9,9-bis (3,4-dicarboxyphenyl) fluorene dianhydride, 9,9-bis [4- (3,4) Dicarboxyphenoxy) phenyl] fluorene dianhydride, 3,4-dicarboxy-1,2,3,4-tetrahydro-1-naphthalene succinic dianhydride, or 3,4-dicarboxy-1,2,3 Aromatic tetracarboxylic dianhydrides such as 1,4-tetrahydro-6-methyl-1-naphthalene succinic dianhydride.

The tetracarboxylic dianhydride used in the present invention is not limited to the compounds exemplified above, and may have any structure as long as it has two carboxylic anhydride groups. These may be used alone or in combination. Tetracarboxylic dianhydride is preferable as a component of the dispersant of the present invention from the viewpoint of pigment adsorptivity because it forms a dispersant having two carboxyl groups in one unit of polyester by reaction with a polyol. .

Furthermore, what is preferably used in the present invention is an aromatic tetracarboxylic dianhydride, and pyromellitic dianhydride is preferable from the viewpoint of adsorptivity to the pigment. Aromatic carboxylic acids have higher pigment adsorption capacity than aliphatic carboxylic acids.

Specific examples include aromatic tetracarboxylic dianhydrides represented by the following general formula (13) or general formula (14).

General formula (13):

[In General Formula (13), k is 1 or 2. ]

General formula (14):

[In General Formula (14), Q ₁ represents a direct bond, —O—, —CO—, —COOCH ₂ CH ₂ OCO
_{-, - SO 2 -, -} C (CF 3) 2 -, the formula (15):

Or a group represented by the general formula (16):

It is group represented by these. ]

Furthermore, a compound having one carboxylic anhydride group in the molecule or a compound having three or more can be used in combination.

[Vinyl polymer (a2)]
The vinyl polymer (a2) which is a side chain of the dispersant is obtained by changing the compound (a1) having two hydroxyl groups and one thiol group in the molecule according to the molecular weight of the target vinyl polymer (a2). It can be obtained by mixing and heating the ethylenically unsaturated monomer (b) and, optionally, a polymerization initiator. (Manufacturing method (1))
Alternatively, a hydroxyl group in the compound (a1) having two hydroxyl groups and one thiol group in the molecule, and an acid anhydride group in the tricarboxylic acid anhydride (c1) and / or tetracarboxylic dianhydride (c2) In accordance with the molecular weight of the target vinyl polymer (a2), the ethylenically unsaturated monomer (b) and, optionally, a polymerization initiator are mixed and heated to the polyester (c3) obtained by reacting Can be obtained. (Manufacturing method (2))
The compound (a1) having two hydroxyl groups and one thiol group is used in a bulk polymerization, using 0.5 to 10% by weight based on the total weight of monomers obtained by adding the weights of ethylenically unsaturated monomers. Alternatively, solution polymerization is preferably performed, and more preferably 0.8 to 6% by weight. If it is less than 0.5% by weight, the molecular weight of the vinyl polymer part (a2) is too high, and its absolute amount increases as an affinity part for the pigment carrier and the solvent, and the dispersibility effect itself decreases. If the amount exceeds 10% by weight, the molecular weight of the vinyl polymer part (a2) is too low, and the effect of steric repulsion is lost as an affinity site for the pigment carrier and solvent, and the aggregation of the pigment is suppressed. May be difficult. Further, since the glass transition temperature Tg of the vinyl polymerized portion (a2) is also lowered, the heat resistance is insufficient, so that the recently required physical properties cannot be satisfied.

As for the acid value of the vinyl polymer part of a side chain, 10-100 are preferable. When the acid value is 10 or more, the developability is excellent even when the vinyl polymer part (a2) has a high molecular weight and a high Tg in order to increase heat resistance. If it is less than 100, it is preferable because it is excellent in dispersibility, brightness, and CR. From the above viewpoint, it is more preferably 25 to 70.

  The reaction temperature is 40 to 150 ° C, preferably 50 to 110 ° C. When the temperature is lower than 40 ° C., the polymerization does not proceed sufficiently, and when the temperature is higher than 150 ° C., the molecular weight may be difficult to control.

The weight average molecular weight of the vinyl polymer (a2) is preferably 2,000 to 40,000, more preferably 2000 to 30,000, still more preferably 2,200 to 25,000. This site becomes an affinity site for the pigment carrier and the solvent. When the weight average molecular weight of the vinyl polymer part (a2) is less than 2,000, the steric repulsion effect is lost as an affinity part for the pigment carrier and the solvent, and it may be difficult to suppress the aggregation of the pigment. . Further, since the glass transition temperature Tg of the vinyl polymerized portion (a2) is also lowered, the heat resistance is insufficient, so that the recently required physical properties cannot be satisfied. Moreover, when it exceeds 40,000, the absolute amount will increase as an affinity site | part with respect to a pigment carrier and a solvent, and the dispersibility effect itself may fall. Further, the viscosity of the dispersion may increase. The vinyl polymer (a2) can easily adjust the molecular weight to the above range, and also has good affinity for the solvent.

In the polymerization, 0.001 to 5% by weight of a polymerization initiator can be arbitrarily used on the basis of the total monomer weight obtained by adding the weights of the ethylenically unsaturated monomers. As the polymerization initiator, an azo compound and an organic peroxide can be used.

Examples of 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), 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) peroxydicarbonate, t-butylperoxyneo Examples include decanoate, 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.

In the case of solution polymerization, the polymerization solvents are 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 mono Ethyl ether acetate, ethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, or the like is used, but is not particularly limited thereto. These polymerization solvents may be used as a mixture of two or more. After completion of the reaction, the solvent used in the polymerization reaction can be removed by an operation such as distillation, or can be used as it is as a solvent for the next step or as part of a product.

[Reaction catalyst]
As the catalyst used for the production of the polyester and acidic dispersant (X) of the present invention, a known catalyst can be used. The catalyst is preferably a tertiary amine compound, for example,
Triethylamine, triethylenediamine, N, N-dimethylbenzylamine, N-methylmorpholine, 1,8-diazabicyclo- [5.4.0] -7-undecene, or 1,5-diazabicyclo- [4.3.0] -5-nonene and the like.

[Reaction solvent]
The polyester and acidic dispersant (X) of the present invention can be produced using only the raw materials listed above, but a solvent is used to avoid problems such as high viscosity and non-uniform reaction. Is preferred. There is no limitation in particular as a solvent used, A well-known thing can be used. Examples include acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, ethyl acetate, butyl acetate, toluene, xylene, acetonitrile, and propylene glycol monomethyl ether acetate. After completion of the reaction, the solvent used in the reaction can be removed by an operation such as distillation, or can be used as it is as a solvent for the next step or as part of a product.

[Reaction conditions]
The reaction temperature for polyester synthesis is 50 ° C to 180 ° C, preferably 80 ° C to 140 ° C. When the reaction temperature is 50 ° C. or lower, the reaction rate is slow, and when the reaction temperature is 180 ° C. or higher, the carboxyl group and the hydroxyl group may undergo an esterification reaction, resulting in a decrease in acid value or gelation. Ideally, the reaction is stopped until the absorption of the acid anhydride is eliminated by infrared absorption, but the reaction may be stopped when the acid value of the polyester falls within the range of 5 to 200.

[Molecular weight]
The number average molecular weight of the obtained acidic dispersant (X) is preferably 2,000 to 35,000, more preferably 4,000 to 30,000, and still more preferably 6,000 to 20,000. If the number average molecular weight is less than 2,000, the stability of the colored composition may be lowered. is there.

[Acid value]
The acid value of the obtained acidic dispersant (X) is preferably 7 to 200. More preferably, it is 10-150, More preferably, it is 15-130. When the acid value is less than 7, the pigment adsorbing ability may be lowered and the pigment dispersibility may be problematic. When the acid value exceeds 200, the interaction between the resins becomes strong, the viscosity of the pigment dispersion composition is increased, and the brightness is increased. May be lower.

[Basic dispersant]
The basic dispersant used in the present invention is obtained by radical polymerization of an ethylenically unsaturated monomer (d) containing an ethylenically unsaturated monomer having an amino group, and has an amine value of 90 to 320 mgKOH / g. It is characterized by being a random copolymer.
The amine value of the basic dispersant is more preferably 110 to 220 mgKOH / g. Within the above range, heat resistance and brightness are excellent. If the amine value is less than 90 mgKOH / g, it will not be sufficiently adsorbed by the pigment, etc., resulting in poor dispersion. It becomes a poor distribution.

The basic dispersant of the present invention can be obtained by radical polymerization of an ethylenically unsaturated monomer having an amino group and, if necessary, another ethylenically unsaturated monomer.
In the present specification, an amino group means —NH ₂ , —NHR, and —NR ₂ (R represents a carbon radical such as a hydrocarbon group or another organic residue), but ethylene having an amino group As the ethylenically unsaturated monomer, an ethylenically unsaturated monomer (d1) having an N, N-dialkylamino group and an ethylenically unsaturated monomer having a hindered amine skeleton represented by the general formula (10) are preferable. .
Examples of the ethylenically unsaturated monomer (d1) having an N, N-dialkylamino group include:
N, such as N, N-dimethylaminoethyl (meth) acrylate, N, N-diethylaminoethyl (meth) acrylate, N, N-dimethylaminopropyl (meth) acrylate, or N, N-diethylaminopropyl (meth) acrylate N-dialkylamino group-containing (meth) acrylates;
N, such as N, N-dimethylaminoethyl (meth) acrylamide, N, N-diethylaminoethyl (meth) acrylamide, N, N-dimethylaminopropyl (meth) acrylamide, or N, N-diethylaminopropyl (meth) acrylamide And N-dialkylamino group-containing (meth) acrylamides.

Of these, N, N-dialkylamino group-containing (meth) acrylates are preferable, and N, N-dimethylaminoethyl (meth) acrylate is more preferable.

As the ethylenically unsaturated monomer having an amino group, an ethylenically unsaturated monomer having a hindered amine skeleton represented by the general formula (10) described in detail below is most preferable.

[An ethylenically unsaturated monomer having a hindered amine skeleton represented by the general formula (10)]
As the ethylenically unsaturated monomer having an amino group in the basic dispersant of the present invention, an ethylenically unsaturated monomer having a hindered amine skeleton represented by the following general formula (10) is excellent in lightness and heat resistance. Therefore, it is most preferable.

General formula (10)

(In the formula (10), R ₃₂ is a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aralkyl group having 7 to 12 carbon atoms, an acyl group, an oxy radical group, or OR _35. R ₃₅ represents a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aralkyl group having 7 to 12 carbon atoms, or an acyl group, and R ₃₃ and R ₃₄ are Each independently represents a methyl group, an ethyl group, or a phenyl group, and “*” represents a bond.)

In the above general formula (10), examples of the alkyl group having 1 to 18 carbon atoms of R ₃₂ and R ₃₅ include linear, branched, and cyclic alkyl groups. Group, normal propyl group, isopropyl group, n-butyl group, t-butyl group, n-hexyl group, cyclohexyl group, n-octyl group, hexadecyl group and the like.

In the general formula (10), examples of the aryl group having 6 to 20 carbon atoms of R ₃₂ and R ₃₅ include a phenyl group, a 1-naphthyl group, and a 2-naphthyl group.

In the general formula (10), the aralkyl group having 7 to 12 carbon atoms of the R ₃₂ and R _35, for example, an alkyl group having 1 to 8 carbon atoms attached to an aryl group having 6 to 10 carbon atoms Specific examples include benzyl group, phenethyl group, α-methylbenzyl group, 2-phenylpropan-2-yl group and the like.

In the general formula (10), examples of the acyl group of R ₃₂ and R ₃₅ include alkanoyl groups having 2 to 8 carbon atoms and aroyl groups, and specific examples include acetyl groups and benzoyl groups. I can do it.
In the present invention, R ₃₂ is preferably a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or an oxy radical group, more preferably a hydrogen atom or a methyl group, and particularly preferably a methyl group.

Specific examples of the ethylenically unsaturated monomer having a group represented by the general formula (10) include, for example, a compound represented by the following general formula (11-1), and the following general formula (11-2). ) And the like.

General formula (11-1), (11-2)

[In General Formula (11-1) and General Formula (11-2), R ₃₆ and R ₃₈ each represent a hydrogen atom or a methyl group, R ₃₇ represents an alkylene group having 1 to 5 carbon atoms, X represents a group represented by the general formula (10), and Y represents —CONH— *, —SO ₂ —, —SO ₂ NH— * (provided that the bond marked with “*” is X and And n represents an integer of 0 to 9. ]

R ₃₇ is preferably an ethylene group or a propylene group, and particularly preferably an ethylene group. n is preferably an integer of 0 to 8, particularly preferably an integer of 0 to 6.

Specific examples of the monomer represented by the general formula (11-1) include compounds represented by the following general formulas (12-1) to (12-7).

General formula (12-1) to general formula (12-7)

(Formula (12-1) to the general formula (12-7), R ₃₆ has the same meaning as R ₃₆ in the general formula (11-1).)

Specific examples of the monomer represented by the general formula (11-2) include compounds represented by the following general formulas (13-1) to (13-4).

General formula (13-1)-general formula (13-4)

[Formula (13-1) - general formula (13-4), R ₃₈ has the same meaning as R ₃₈ in the general formula (11-2). ]

Of these, general formula (12-1) and general formula (12-2) are preferable, and 2,2,6,6-tetramethylpiperidyl methacrylate (in the general formula (12-1), R ³⁶ represents a methyl group). And 1,2,2,6,6-pentamethylpiperidyl methacrylate (a compound in which R ₃₆ is a methyl group in the above general formula (12-2)) is more preferable, and 1,2,2,6 is particularly preferable. , 6-pentamethylpiperidyl methacrylate (the above general formula (12-2)) is preferable.

[Other ethylenically unsaturated monomers]
The other ethylenically unsaturated monomer is not particularly limited as long as it is a monomer copolymerizable with an ethylenically unsaturated monomer having an amino group, and can be appropriately selected according to the use. 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, styrene And (meth) acrylonitrile.

Specific examples of such monomers include linear or branched alkyl (meth) acrylates, cyclic alkyl (meth) acrylates, (meth) acrylates having a heterocyclic ring, and aromatic rings mentioned for the acidic dispersant. (Meth) acrylates, hydroxyalkyl methacrylates, (poly) alkylene glycol monoalkyl ether (meth) acrylates, (poly) alkylene glycol (meth) acrylates having an aromatic ring, fluoroalkyl (meth) acrylates, (Meth) acryloxy-modified polydimethylsiloxane (silicone macromers), N-substituted (meth) acrylamides, and nitriles can be raised, and styrenes have a mono (meth) acryloyl group at the end of the polymer molecular chain Macromonomer, vinyl ester Ethers, carboxyl group-containing ethylenically unsaturated monomer, and can also be used fatty acid vinyls.

One or two or more types can be selected from the ethylenically unsaturated monomers listed above, and at least a linear or branched alkyl (meth) acrylate having 1 to 4 carbon atoms, an aromatic ring It is preferable to use an ethylenically unsaturated monomer selected from the group consisting of (meth) acrylates, hydroxyalkyl methacrylates, and alkylene glycol (meth) acrylates having at least benzyl (meth) acrylate, It is preferred to use an ethylenically unsaturated monomer selected from the group consisting of methyl (meth) acrylate, ethyl (meth) acrylate, methoxyethyl (meth) acrylate, and hydroxyethyl (meth) acrylate.

[About polymerization method]
(Random polymerization)
The basic dispersant of the present invention is a random copolymer, and a free radical polymerization method can be suitably used. 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 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-methylpropio) Nate), 4,4′-azobis (4-cyanovaleric acid), 2,2′-azobis (2-hydroxymethylpropionitrile), or 2,2′-azobis [2- (2-imidazoline-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. When using this polymerization initiator, 0.01-20 weight part is preferable with respect to 100 weight part of ethylenically unsaturated monomers.

  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.

From the viewpoint of viscosity and viscosity stability of the pigment dispersion, the basic dispersant contains 1% to 100% by weight of the ethylenically unsaturated monomer having an amino group based on the solid content of the ethylenically unsaturated monomer. It is preferably contained, more preferably 25 to 100% by weight, and particularly preferably 40 to 100% by weight. Especially, since group represented by General formula (10) has an antioxidant function, it can prevent the oxidation of a color filter material by including even a small quantity, and can prevent the fall of the brightness more as a result.

  The number average molecular weight of the basic dispersant is preferably 500 to 30,000. If it is less than 500 or exceeds 30,000, the viscosity and viscosity stability of the pigment dispersion may be deteriorated.

  In the step of producing the basic dispersant, as in the step of producing the polymer represented by the acidic dispersant, a solvent-free or optionally solvent can be used.

  The amount of the solvent used is preferably 0 to 300 parts by weight, more preferably 0 to 100 parts by weight, based on 100 parts by weight of the ethylenically unsaturated monomer. The solvent used can be removed by an operation such as distillation after completion of the reaction, or can be used as it is as a part of the product of the dispersant.

Moreover, it is desirable to use the acidic dispersant and the basic dispersant when dispersing the pigment. By using it at the time of pigment dispersion, the dispersant is more easily adsorbed on the pigment surface, and the interaction with the pigment becomes stronger, thereby improving the dispersibility.
<Pigment>
The pigment that can be used in the coloring composition of the present invention can be arbitrarily selected from conventionally known various pigments. The following are typical pigments that can be used in the present invention. The pigment can be used in combination with a plurality of pigments, and can be used in combination with various conventionally known dyes. The dyes are also listed below.

  Examples of red pigments that can be used in the present invention include C.I. I. Pigment Red 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 14, 17, 22, 23, 31, 38, 41, 48: 1, 48: 2, 48: 3, 48: 4, 49, 49: 1, 49: 2, 57: 1, 81, 81: 1, 81: 2, 81: 3, 81: 4, 83, 88, 90, 105, 112, 119, 122, 123, 144, 146, 149, 150, 155, 166, 168, 169, 170, 171, 172, 175, 176, 177, 178, 179, 184, 185, 187, 188, 190, 200, 202, 206, 207, 208,209,210,216,220,221,224,226,242,246,254,255,264,269,270,272,273,274,276,277,278,279,280,2 1,282,283,284,285,286,287 or diketopyrrolopyrrole pigment described in JP-T 2011-523433 discloses the like, but not particularly limited thereto. Also, red dyes such as xanthene, azo, disazo, and anthraquinone can be used. Specifically, C.I. I. Examples thereof include salt-forming compounds of xanthene acid dyes such as Acid Red 52, 87, 92, 289 and 338.

  Examples of the orange pigment that can be used in the present invention include C.I. I. Pigment Orange 38, 43, 71, 73, etc. are mentioned, but it is not particularly limited to these.

  Yellow dyes include azo dyes, azo metal complex dyes, anthraquinone dyes, indigo dyes, thioindigo dyes, phthalocyanine dyes, diphenylmethane dyes, triphenylmethane dyes, xanthene dyes, thiazine dyes, cationic dyes, cyanine dyes, nitro dyes, quinoline dyes , Naphthoquinone dyes and oxazine dyes.

  Therefore, specific examples of yellow dyes include C.I. I. Acid Yellow 2,3, 4, 5, 6, 7, 8, 9, 9: 1, 10, 11, 11: 1, 12, 13, 14, 15, 16, 17, 17: 1, 18, 20, 21, 22, 23, 25, 26, 27, 29, 30, 31, 33, 34, 36, 38, 39, 40, 40: 1, 41, 42, 42: 1, 43, 44, 46, 48, 51, 53, 55, 56, 60, 63, 65, 66, 67, 68, 69, 72, 76, 82, 83, 84, 86, 87, 90, 94, 105, 115, 117, 122, 127, 131, 132, 136, 141, 142, 143, 144, 145, 146, 149, 153, 159, 166, 168, 169, 172, 174, 175, 178, 180, 183, 187, 188, 189, 190, 191, 192, 199 Etc.

In addition, C.I. I. Direct yellow 1, 2, 4, 5, 12, 13, 15, 20, 2
4, 25, 26, 32, 33, 34, 35, 41, 42, 44, 44: 1, 45, 46, 48, 49, 50, 51, 61, 66, 67, 69, 70, 71, 72, 73, 74, 81, 84, 86, 90, 91, 92, 95, 107, 110, 117, 118, 119, 120, 121, 126, 127, 129, 132, 133, 134 and the like.

In addition, C.I. I. Basic yellow 1, 2, 5, 11, 13, 14, 15, 19,
21, 24, 25, 28, 29, 37, 40, 45, 49, 51, 57, 79, 87, 90, 96, 103, 105, 106 and the like.

In addition, C.I. I. Solvent Yellow 2, 3, 4, 7, 8, 10, 11, 12, 13
, 14, 15, 16, 18, 19, 21, 22, 25, 27, 28, 29, 30, 32, 33, 34, 40, 42, 43, 44, 45, 47, 48, 56, 62, 64 68, 69, 71, 72, 73, 77, 79, 81, 82, 83, 85, 88, 89, 90, 93, 94, 98, 104, 107, 114, 116, 117, 124, 130, 131 133, 135, 138, 141, 143, 145, 146, 147, 157, 160, 162, 163, 167, 172, 174, 175, 176, 177, 179, 181, 182, 183, 184, 185, 186 187, 188, 190, 191, 192, 194, 195 and the like.

In addition, C.I. I. Disperse Yellow 1, 2, 3, 5, 7, 8, 10, 11, 13
13, 23, 27, 33, 34, 42, 45, 48, 51, 54, 56, 59, 60, 63, 64, 67, 70, 77, 79, 82, 85, 88, 93, 99, 114 118, 119, 122, 123, 124, 126, 163, 184, 184: 1, 202, 211, 229, 231, 232, 233, 241, 245, 246, 247, 248, 249, 250, 251 etc. Can be mentioned.

  As the yellow pigment, organic or inorganic pigments can be used alone or in admixture of two or more, and pigments having high color development properties and high heat resistance, particularly pigments having high heat decomposition resistance are preferred. Organic pigments are used. As the organic pigment, commercially available ones can be used, and natural pigments and inorganic pigments can be used in combination according to the desired hue of the filter segment.

Below, the specific example of the yellow organic pigment which can be used for the said coloring composition is shown. Examples of yellow pigments include 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, Yellow pigments such as 182, 185, 187, 188, 192, 193, 194, 196, 198, 199, 213, 214 can be used. In particular, from the viewpoint of heat resistance, light resistance, and brightness of the filter segment, C.I. I. Pigment Yellow 138, 139, 150, and 185 are preferable.
These yellow pigments can be used alone or in combination of two or more depending on the desired color characteristics.

Examples of the green pigment that can be used in the present invention include C.I. I. Examples thereof include zinc phthalocyanine pigments described in CI Pigment Green 7, 10, 36, 37, 58, JP 2008-19383 A, JP 2007-320986 A, JP 2004-70342 A, and the like. It is not limited to.

  Examples of blue pigments that can be used in the present invention include C.I. I. Pigment Blue 1, 1: 2, 9, 14, 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, 16, 22, 60, 64, JP 2004-333817, Examples include aluminum phthalocyanine pigments described in Japanese Patent No. 4893859, but are not limited thereto.

  Examples of the pigment include zinc halide phthalocyanine pigment, aluminum phthalocyanine pigment, C.I. I. Pigment Yellow 138, C.I. I. Pigment Yellow 139, C.I. I. Pigment Yellow 150, and C.I. I. At least one pigment selected from Pigment Yellow 185 is preferred.

  The preferred pigment content in all the non-volatile components of the colored composition according to the present invention (corresponding to the total amount of the pigment obtained by adding the pigment component and the dye component when used in combination) is sufficient color reproducibility and stability. In view of the above, it is 10 to 90% by weight, more preferably 15 to 85% by weight, and most preferably 20 to 80% by weight.

(Miniaturization of pigment)
The pigment of the present invention can be refined by a salt milling process or the like. It is preferable that the average primary particle diameter calculated | required by TEM (transmission electron microscope) of a pigment is the range of 5-90 nm. When the thickness is smaller than 5 nm, dispersion in an organic solvent becomes difficult. When the thickness is larger than 90 nm, a sufficient contrast ratio cannot be obtained. For these reasons, a more preferable average primary particle size is in the range of 10 to 70 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.

<Dispersing aid>
When dispersing the pigment in the pigment carrier, a dispersion aid such as a dye derivative, a resin-type dispersant, or a surfactant may be appropriately contained. Since the dispersion aid has a great effect of preventing re-aggregation of the pigment after dispersion, the color composition obtained by dispersing the pigment in the pigment carrier using the dispersion aid has good brightness and viscosity stability. .

  Examples of the dye derivative include a compound obtained by introducing a basic substituent, an acidic substituent, or a phthalimidomethyl group which may have a substituent into an organic pigment, anthraquinone, acridone, or triazine. 63-305173, JP-B-57-15620, JP-B-59-40172, JP-B-63-17102, JP-B-5-9469, JP-A-2001-335717, JP-A-2003 128669, JP-A-2004-091497, JP-A-2007-156395, JP-A-2008-094773, JP-A-2008-094986, JP-A-2008-095007, JP-A-2008-195916 Gazette, Japanese Patent No. 4585781, Japanese Patent No. 5568804, etc. Can be used those which are mounting, it may be used alone or in combination of two or more. When using a pigment derivative, it is preferable to use a basic derivative from the viewpoint of dispersibility. Among these, among organic pigments, a phthalocyanine skeleton, anthraquinone, and triazine are preferable from the viewpoint of improving dispersibility.

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

  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 can be used alone or in admixture of two or more, but are not necessarily limited thereto.

  When the surfactant is 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 surfactant is less than 0.1 parts by weight, it is difficult to obtain the added effect. When the content is more than 55 parts by weight, the dispersion may be affected by an excessive dispersant. .

<Binder resin>
The binder resin that may be contained in the colored composition of the present invention is one that disperses a pigment, or one that allows dyeing or penetration, and includes conventionally known thermoplastic resins and thermosetting 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, it is preferable from a developable viewpoint that the specific structure represented by General formula (1) to General formula (4) is included from a developable viewpoint.

  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.

Moreover, when using with the form of an alkali image development type colored resist material, it is preferable to use the alkali-soluble resin which copolymerized the acidic group containing ethylenically unsaturated monomer. In that case, it is preferable from the viewpoint of developability to use an ethylenically unsaturated monomer containing the specific acidic group represented by the general formulas (1) to (4). In order to further improve the photosensitivity, an active energy ray-curable resin having an ethylenically unsaturated double bond can be used.
In particular, by using an active energy ray-curable resin having an ethylenically unsaturated double bond in the side chain as an alkali development type colored resist material, the resin is three-dimensionally crosslinked when exposed to active energy rays to form a coating film. As a result, the colorant is fixed, heat resistance is improved, and fading (lightness reduction) due to heat of the colorant can be suppressed. In addition, there is also an effect of suppressing aggregation and precipitation of the colorant component in the development process.

  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 or 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.

  Energy ray curable resins having an ethylenically unsaturated active double bond include polymers having reactive substituents such as hydroxy groups, carboxyl groups, amino groups, and reactive groups such as isocyanate groups, aldehyde groups, and epoxy groups. A resin in which a photo-crosslinkable group such as a (meth) acryloyl group or a styryl group is introduced into the polymer by reacting a (meth) acrylic compound having a substituent or cinnamic acid is used. Further, a polymer containing an acid anhydride such as a styrene-maleic anhydride copolymer or an α-olefin-maleic anhydride copolymer is half-esterified with a (meth) acrylic compound having a hydroxyl group such as hydroxyalkyl (meth) acrylate. A modified version is also used.

  Examples of the active energy ray-curable resin having an ethylenically unsaturated double bond include resins into which an ethylenically unsaturated double bond has been introduced by the following methods (i) and (ii).

[Method (i)]
As the method (i), for example, a side chain epoxy group of a copolymer obtained by copolymerizing an ethylenically unsaturated monomer having an epoxy group and one or more other monomers is used. Addition reaction of a carboxyl group of an unsaturated monobasic acid having an ethylenically unsaturated double bond, and further reacting a polybasic acid anhydride with the generated hydroxyl group to convert an ethylenically unsaturated double bond and a carboxyl group. There is a way to introduce.

  Examples of the ethylenically unsaturated monomer having an epoxy group include glycidyl (meth) acrylate, methyl glycidyl (meth) acrylate, 2-glycidoxyethyl (meth) acrylate, and 3,4-epoxybutyl (meth) acrylate. And 3,4-epoxycyclohexyl (meth) acrylate, which 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 be hydrolyzed. Further, when tetrahydrophthalic anhydride or maleic anhydride having an ethylenically unsaturated double bond is used as the polybasic acid anhydride, the ethylenically unsaturated double bonds can be further increased.

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

[Method (ii)]
As the method (ii), an ethylenically unsaturated 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 ethylenically unsaturated monomer having an isocyanate group with the side chain hydroxyl group of the obtained copolymer.

Examples of the ethylenically unsaturated 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 methacrylates 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 hydroxyalkyl (meth) acrylate, polyγ-valerolactone, polyε-caprolactone, and / or Polyester mono (meth) acrylate added with poly-12-hydroxystearic acid or the like can also be used. From the viewpoint of suppressing foreign matter on the coating film, 2-hydroxyethyl methacrylate or glycerol methacrylate is preferable.

  Examples of the ethylenically unsaturated monomer having an isocyanate group include 2- (meth) acryloyloxyethyl isocyanate or 1,1-bis [methacryloyloxy] ethyl isocyanate, but are not limited thereto. Two or more types can be used in combination.

  In addition, from the viewpoints of dispersibility, stability, developability, and heat resistance of the pigment, a carboxyl group that functions as a pigment adsorption group and an alkali-soluble group during development, an aliphatic group that functions as an affinity group for the pigment carrier and solvent, and an aromatic group. The balance of the group is important for the dispersibility of the pigment, the permeability of the developer in the coating film, the solubility of the developer in the uncured part, and the durability, and a resin having an acid value of 20 to 300 mgKOH / g should be used. 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. If it exceeds 300 mgKOH / g, a fine pattern may not remain.

  A thermoplastic resin having both alkali-soluble performance and energy ray curing performance is also preferred as the color filter coloring composition.

The following are mentioned as a monomer which comprises the said thermoplastic resin. For example, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, cyclohexyl (meth) acrylate, stearyl (meth) acrylate, lauryl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, isobornyl (meth) acrylate, phenyl (meth) acrylate, benzyl (meth) Acrylate, phenoxyethyl (meth) acrylate, phenoxydiethylene glycol (meth) acrylate, methoxypolypropylene glycol (meth) acrylate, or ethoxypoly Ji glycol (meth) acrylate of (meth) acrylates,
Alternatively, (meth) acrylamide (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N, N-diethyl (meth) acrylamide, N-isopropyl (meth) acrylamide, diacetone (meth) acrylamide, acryloylmorpholine, etc. Acrylamides, styrenes, styrenes such as α-methylstyrene, ethyl vinyl ethers, n-propyl vinyl ethers, isopropyl vinyl ethers, n-butyl vinyl ethers, vinyl ethers such as isobutyl vinyl ethers, fatty acid vinyls such as vinyl acetate or vinyl propionate Kind.

Alternatively, cyclohexylmaleimide, phenylmaleimide, methylmaleimide, ethylmaleimide, 1,2-bismaleimide ethane 1,6-bismaleimidehexane, 3-maleimidopropionic acid, 6,7-methylenedioxy-4-methyl-3-maleimide Coumarin, 4,4′-bismaleimide diphenylmethane, bis (3-ethyl-5-methyl-4-maleimidophenyl) methane, N, N′-1,3-phenylenedimaleimide, N, N′-1,4- Phenylene dimaleimide, N- (1-pyrenyl) maleimide, N- (2,4,6-trichlorophenyl) maleimide, N- (4-aminophenyl) maleimide, N- (4-nitrophenyl) maleimide, N-benzyl Maleimide, N-bromomethyl-2,3-dichloromaleimide, N-succin Midyl-3-maleimidobenzoate, N-succinimidyl-3-maleimidopropionate, N-succinimidyl-4-maleimidobutyrate, N-succinimidyl-6-maleimidohexanoate, N- [4- (2-benzimidazolyl) phenyl N-substituted maleimides such as maleimide and 9-maleimide acridine.

  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. Especially, an epoxy resin and a melamine resin are used more suitably from a viewpoint of heat resistance improvement.

  The weight average molecular weight (Mw) of the binder resin is preferably in the range of 5,000 to 80,000, more preferably in the range of 7,000 to 50,000 in order to disperse the colorant preferably. The number average molecular weight (Mn) is preferably in the range of 2,500 to 40,000, and the value of Mw / Mn is preferably 10 or less.

  Here, the weight average molecular weight (Mw) and the number average molecular weight (Mn) are HLC-8220GPC (manufactured by Tosoh Corporation) as a device, and TSK-GEL SUPER HZM-N is connected in series as a column. Is a molecular weight in terms of polystyrene measured using THF.

  When the binder resin is used as a coloring composition for a color filter, a colorant adsorbing group and a carboxyl group that acts as an alkali-soluble group during development, an aliphatic group that acts as an affinity group for the colorant carrier and solvent, and an aromatic group The balance of groups is important for the dispersibility, penetrability, developability, and durability of the colorant, and it is preferable to use a resin having an acid value of 20 to 300 mgKOH / g. 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. If it exceeds 300 mgKOH / g, the fine pattern may not remain in the development or the brightness may be lowered.

  The acid value is a value obtained by converting the measured acid value (mgKOH / g) into a solid content according to the potentiometric titration method of JIS K 0070.

  The binder resin is preferably used in an amount of 20 to 500 parts by weight with respect to 100 parts by weight of the colorant. If it is less than 20 parts by weight, the film formability and various resistances are insufficient, and if it is more than 500 parts by weight, the concentration of the colorant becomes low and color characteristics cannot be expressed.

<Organic solvent>
In the colored composition of the present invention, the pigment is sufficiently dispersed and permeated in the pigment carrier, and applied to a substrate such as a glass substrate so that the dry film thickness is 0.2 to 5 μm to form a filter segment. In order to facilitate this, an organic solvent is included. The organic solvent is selected in consideration of good applicability of the coloring composition, solubility of each component of the coloring composition, and safety.

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-dimethylformamide, 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 Ter, 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 Propylene glycol monomethyl ether, propylene glycol diacetate, propylene glycol phenyl ether, propylene glycol monoethyl ether, propylene glycol monoethyl ether acetate, propylene glycol monobutyl ether, propylene glycol monopropyl ether, propylene glycol monomethyl ether, propylene glycol Examples include rumonomethyl ether acetate, propylene glycol monomethyl ether propionate, benzyl alcohol, methyl isobutyl ketone, methylcyclohexanol, n-amyl acetate, n-butyl acetate, isoamyl acetate, isobutyl acetate, propyl acetate, dibasic acid ester, etc. It is done.
These solvents can be used alone or in admixture of two or more at any ratio as required.

  Among these, since the dispersibility of the pigment, the penetrability, and the coating property of the coloring composition are good, ethyl lactate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether It is preferable to use glycol acetates such as acetate, alcohols such as benzyl alcohol and diacetone alcohol, and ketones such as cyclohexanone.

  The organic solvent can be used in an amount of 500 to 4000 parts by weight with respect to 100 parts by weight of the pigment because the colored composition can be adjusted to an appropriate viscosity to form a filter segment with a desired uniform film thickness. preferable.

<Photopolymerizable monomer>
Photopolymerizable monomers that may be added to the colored composition of the present invention include monomers or oligomers that are cured by ultraviolet rays or heat to produce a transparent resin.

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 Ether 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, (meth) acrylic acid ester of methylolated melamine, epoxy (meth) acrylate, various acrylic acid esters such as urethane acrylate, methacrylic acid ester, (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.
These photopolymerizable compounds can be used singly or in combination of two or more at any ratio as required.

  The blending amount of the photopolymerizable monomer is preferably 5 to 400 parts by weight with respect to 100 parts by weight of the pigment, and more preferably 10 to 300 parts by weight from the viewpoint of photocurability and developability.

<Photopolymerization initiator>
In the colored composition of the present invention, a photopolymerization initiator is added to form a filter segment by photolithography by curing the composition by ultraviolet irradiation, and a solvent development type or alkali development type photosensitive coloring composition is added. It can be prepared in the form of

Examples of the photopolymerization initiator include 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] -1 − [
Acetophenone compounds such as 4- (4-morpholinyl) phenyl] -1-butanone or 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one; benzoin, benzoin methyl ether Benzoin compounds such as benzoin ethyl ether, benzoin isopropyl ether or benzyldimethyl ketal; benzophenone, benzoylbenzoic acid, methyl benzoylbenzoate, 4-phenylbenzophenone, hydroxybenzophenone, acrylated benzophenone, 4-benzoyl-4'-methyl Benzophenone compounds such as diphenyl sulfide or 3,3 ′, 4,4′-tetra (t-butylperoxycarbonyl) benzophenone; thioxanthone, 2-chlorothioxanthone, 2-methyl Thioxanthone compounds such as thioxanthone, isopropylthioxanthone, 2,4-diisopropylthioxanthone, or 2,4-diethylthioxanthone; 2,4,6-trichloro-s-triazine, 2-phenyl-4,6-bis (trichloromethyl) -S-triazine, 2- (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 (trick Triazine compounds such as (romethyl) -s-triazine, 2,4-trichloromethyl- (piperonyl) -6-triazine, or 2,4-trichloromethyl- (4′-methoxystyryl) -6-triazine; -Octanedione, 1- [4- (phenylthio)-, 2- (O-benzoyloxime)], or O- (acetyl) -N- (1-phenyl-2-oxo-2- (4'-methoxy- Oxime ester compounds such as naphthyl) ethylidene) hydroxylamine; phosphine compounds such as bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide or 2,4,6-trimethylbenzoyldiphenylphosphine oxide; 9,10- Quinone compounds such as phenanthrenequinone, camphorquinone and ethylanthraquinone Borate compounds; carbazole compounds; imidazole compounds; or titanocene compounds.
These photoinitiators can be used individually by 1 type or in mixture of 2 or more types by arbitrary ratios as needed.

  The content of the photopolymerization initiator is preferably 2 to 200 parts by weight with respect to 100 parts by weight of the pigment, and more preferably 3 to 150 parts by weight from the viewpoint of photocurability and developability.

<Sensitizer>
Furthermore, the coloring composition 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, tetraphylline 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) benzopheno And 4,4′-diethylaminobenzophenone.
These sensitizers can be used singly or in combination of two or more at any ratio as necessary.

  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.

  The content of the sensitizer is preferably 3 to 60 parts by weight with respect to 100 parts by weight of the photopolymerization initiator contained in the colored composition, and 5 to 50 parts by weight from the viewpoint of photocurability and developability. It is more preferable that

<Antioxidant>
The coloring composition for a color filter of the present invention can contain an antioxidant. Antioxidants are used to prevent the photopolymerization initiators and thermosetting compounds contained in the color filter coloring composition from oxidizing and yellowing due to thermal processes during thermal curing and ITO annealing. Can be high. Therefore, by including an antioxidant, yellowing due to oxidation during the heating step can be prevented, and a high coating film transmittance can be obtained.

  The “antioxidant” in the present invention may be a compound having an ultraviolet absorbing function, a radical scavenging function, or a peroxide decomposing function. Specifically, as an antioxidant, a hindered phenol type, a hindered amine type are used. , Phosphorus-based, sulfur-based, benzotriazole-based, benzophenone-based, hydroxylamine-based, salicylate-based, and triazine-based compounds, and known ultraviolet absorbers, antioxidants, and the like can be used.

  Among these antioxidants, a hindered phenol antioxidant, a hindered amine antioxidant, a phosphorus antioxidant, or a sulfur antioxidant is preferable from the viewpoint of achieving both transmittance and sensitivity of the coating film. Agents. More preferably, they are hindered phenolic antioxidants, hindered amine antioxidants, or phosphorus antioxidants.

  As the hindered phenol-based antioxidant, 2,4-bis [(laurylthio) methyl] -o-cresol, 1,3,5-tris (3,5-di-t-butyl-4-hydroxybenzyl), 1,3,5-tris (4-t-butyl-3-hydroxy-2,6-dimethylbenzyl), 2,4-bis- (n-octylthio) -6- (4-hydroxy-3,5-di- -T-butylanilino) -1,3,5-triazine, pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate, 2,6-di-t-butyl-4- Nonylphenol, 2,2′-isobutylidene-bis- (4,6-dimethyl-phenol), 4,4′-butylidene-bis- (2-tert-butyl-5-methylphenol), 2,2′-thio -Bis- (6-tert-butyl-4-methylphenol), 2,5-di-tert-amyl-hydroquinone, 2,2'thiodiethylbis- (3,5-di-tert-butyl-4-hydroxy Phenyl) -propionate, 1,1,3-tris- (2′-methyl-4′-hydroxy-5′-t-butylphenyl) -butane, 2,2′-methylene-bis- (6- (1- Methyl-cyclohexyl) -p-cresol), 2,4-dimethyl-6- (1-methyl-cyclohexyl) -phenol, N, N-hexamethylenebis (3,5-di-t-butyl-4-hydroxy-) Hydrocinnamamide) and the like. In addition, oligomer-type and polymer-type compounds having a hindered phenol structure can also be used.

  Examples of hindered amine-based antioxidants include bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, 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-piperidi ) 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)- Polycondensate with 4-hydroxy-2,2,6,6-tetramethylpiperidine, 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, etc. Other oligomer type having a hindered amine structure as well as Rimmer type of compounds and the like can also be used.

  Phosphorous antioxidants include tris (isodecyl) phosphite, tris (tridecyl) phosphite, phenyl isooctyl phosphite, phenyl isodecyl phosphite, phenyl di (tridecyl) phosphite, diphenyl isooctyl phosphite, diphenyl isodecyl Phosphite, diphenyltridecyl phosphite, triphenyl phosphite, tris (nonylphenyl) phosphite, 4,4 ′ isopropylidenediphenol phosphite, trisnonylphenyl phosphite, trisdinonylphenyl phosphite, tris (2 , 4-di-t-butylphenyl) phosphite, tris (biphenyl) phosphite, distearyl pentaerythritol diphosphite, di ( , 4-Di-t-butylphenyl) pentaerythritol diphosphite, di (nonylphenyl) pentaerythritol diphosphite, phenylbisphenol A pentaerythritol diphosphite, tetratridecyl 4,4′-butylidenebis (3-methyl-) 6-t-butylphenol) diphosphite, hexatridecyl 1,1,3-tris (2-methyl-4-hydroxy-5-t-butylphenyl) butane triphosphite, 3,5-di-t-butyl -4-hydroxybenzyl phosphite diethyl ester, sodium bis (4-t-butylphenyl) phosphite, sodium-2,2-methylene-bis (4,6-di-t-butylphenyl) -phosphite, 1,3 -Bis (diphenoxyphosphonoxy)- Benzene, phosphorous acid ethyl bis (2,4-di-tert- butyl-6-methylphenyl), and the like. In addition, oligomer type and polymer type compounds having a phosphite structure can also be used.

  As sulfur-based antioxidants, 2,2-thio-diethylenebis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], 2,4-bis [(octylthio) methyl]- o-cresol, 2,4-bis [(laurylthio) methyl] -o-cresol and the like. In addition, oligomer type and polymer type compounds having a thioether structure can also be used.

  As the benzotriazole-based antioxidant, oligomer-type and polymer-type compounds having a benzotriazole structure can be used.

  Specific examples of the benzophenone antioxidant include 2-hydroxy-4-methoxybenzophenone, 2,4-dihydroxybenzophenone, 2-hydroxy-4-n-octoxybenzophenone, 4-dodecyloxy-2-hydroxybenzophenone, 2- Hydroxy-4-octadecyloxybenzophenone, 2,2′dihydroxy-4-methoxybenzophenone, 2,2′dihydroxy-4,4′-dimethoxybenzophenone, 2,2 ′, 4,4′-tetrahydroxybenzophenone, 2- Hydroxy-4-methoxy-5sulfobenzophenone, 2-hydroxy-4-methoxy-2′-carboxybenzophenone, 2-hydroxy-4-chlorobenzophenone and the like can be mentioned. In addition, oligomer type and polymer type compounds having a benzophenone structure can also be used.

  Examples of the triazine antioxidant include 2,4-bis (allyl) -6- (2-hydroxyphenyl) 1,3,5-triazine. In addition, oligomer-type and polymer-type compounds having a triazine structure can also be used.

  Examples of the salicylate ester antioxidant include phenyl salicylate, p-octylphenyl salicylate, p-tertbutylphenyl salicylate, and the like. In addition, oligomer-type and polymer-type compounds having a salicylate structure can also be used.

  These antioxidants can be used singly or in combination of two or more at any ratio as required.

  Further, the content of the antioxidant is more preferably 0.5 to 5.0% by weight based on the solid content weight of the color filter coloring composition because the brightness and sensitivity are good.

<Amine compound>
Moreover, the coloring composition 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, it is preferable to add a leveling agent to the colored composition 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 coloring composition 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- Til-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 coloring composition of the present invention may contain a storage stabilizer in order to stabilize the viscosity with time. 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 pigment.

  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 pigment in the coloring composition.

<Method for producing colored composition>
The coloring composition of the present invention comprises a pigment in a dye carrier such as a binder resin and / or a solvent, preferably together with a dispersion aid, a kneader, a two-roll mill, a three-roll mill, a ball mill, a horizontal sand mill, a vertical type. It can be produced by finely dispersing (pigment dispersion) using various dispersing means such as a sand mill, an annular bead mill, or an attritor. At this time, the specific quinophthalone compound, the aluminum phthalocyanine pigment, and a plurality of other pigments may be simultaneously dispersed in the pigment carrier, or those separately dispersed in the colorant carrier may be mixed. In addition, when the solubility of the pigment is high, specifically, it is highly soluble in the solvent to be used. Absent.

  Moreover, when using as a photosensitive coloring composition (resist material) for color filters, it can prepare as a solvent developing type or an alkali developing type coloring composition. The solvent development type or alkali development type coloring composition is a mixture of the pigment dispersion, a photopolymerizable monomer and / or a photopolymerization initiator, and, if necessary, a solvent, a dispersion aid, and an additive. Can be adjusted. The photopolymerization initiator may be added at the stage of preparing the colored composition, or may be added later to the prepared colored composition.

<Removal of coarse particles>
The colored composition of the present invention is prepared by means of centrifugal separation, filtration with a sintered filter or a membrane filter, and the like. Coarse particles of 5 μm or more, preferably 1 μm or more, more preferably 0.5 μm or more It is preferable to remove the mixed dust. Thus, it is preferable that a coloring composition does not contain a particle | grain of 0.5 micrometer or more substantially. 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 the present invention comprises a red filter segment, a green filter segment, and a blue filter segment, and the filter segment is formed from the colored composition of the present invention. The color filter may further include a magenta filter segment, a cyan filter segment, and a yellow filter segment.

  The red filter segment can be formed using a normal red coloring composition containing a red pigment and a pigment carrier. Examples of the red coloring composition include C.I. I. Pigment Red 7, 14, 41, 48: 1, 48: 2, 48: 3, 48: 4, 57: 1, 81, 81: 1, 81: 2, 81: 3, 81: 4, 122, 146, 168, 169, 176, 177, 178, 179, 184, 185, 187, 200, 202, 208, 210, 242, 246, 255, 264, 269, 270, 272, 273, 274, 276, 277, 278, Mention may be made of red pigments such as 279, 280, 281, 282, 283, 284, 285, 286 or 287. Also, red dyes such as xanthene, azo, disazo, and anthraquinone can be used. Specifically, C.I. I. Examples thereof include salt-forming compounds of xanthene acid dyes such as Acid Red 52, 87, 92, 289 and 338.

  In addition, red coloring compositions include C.I. I. Pigment orange 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, 82,185,187,188,193,194,198,199,213,214,218,219,220, or may be used in combination of a yellow pigment 221, and the like. Also, orange dyes and / or yellow dyes such as quinoline, azo, disazo, and methine dyes can be used.

  The blue filter segment can be formed using a normal blue coloring composition containing a blue pigment and a pigment carrier. Examples of blue pigments include C.I. I. Pigment Blue 1, 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, 16, 22, 60, 64, etc. are used. A purple pigment can be used in combination with the blue coloring composition. Examples of purple pigments that can be used in combination include C.I. I. And violet pigments such as CI Pigment Violet 1, 19, 23, 27, 29, 30, 32, 37, 40, 42, and 50. In addition, a basic dye or a salt-forming compound of an acid dye exhibiting blue or purple can be used. When the dye is used, a triarylmethane dye or a xanthene dye is preferable in terms of lightness.

<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 coloring composition prepared as the printing ink. Therefore, the color filter manufacturing method is low in cost and excellent in 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. Control of ink fluidity on a printing press is also important, and ink viscosity can be adjusted with a dispersant or extender pigment.

  When the filter segment is formed by photolithography, the colored composition prepared as a solvent developing type or alkali developing type colored resist material is applied on a transparent substrate by spray coating, spin coating, slit coating, roll coating or the like. By a method, it applies so that a dry film thickness may be set to 0.2-5 micrometers. 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, a water-soluble or alkaline water-soluble resin such as polyvinyl alcohol or a water-soluble acrylic resin is applied and dried to form a film that prevents polymerization inhibition by oxygen. Thereafter, ultraviolet exposure can also be performed.

  The color filter of the present invention can be produced by an electrodeposition method, a transfer method, an ink jet method or the like in addition to the above method, but the colored composition 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. Further, 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.

  The color filter is bonded to the counter substrate using a sealant, and after injecting liquid crystal from the injection port provided in the seal part, the injection port is sealed, and if necessary, a polarizing film or a retardation film is placed outside the substrate. A liquid crystal display panel is manufactured by bonding.

  Such liquid crystal display panels include twisted nematic (TN), super twisted nematic (STN), in-plane switching (IPS), vertical alignment (VA), and optically convented bend (OCB). It can be used in a liquid crystal display mode in which colorization is performed using a color filter such as

  Hereinafter, the present invention will be described based on examples, but the present invention is not limited thereto. In the examples, “parts” and “%” represent “parts by weight” and “% by weight”, respectively. “PGMAC” means propylene glycol monomethyl ether acetate.

(Average primary particle diameter of pigment)
The average primary particle diameter of the pigment was measured by a method of directly measuring the size of primary particles from an electron micrograph using a transmission (TEM) electron microscope. Specifically, the minor axis diameter and major axis diameter of the primary particles of each pigment were measured, and the average was taken as the particle diameter of the primary pigment particles. Next, for 100 or more pigment particles, the volume (weight) of each particle was obtained by approximating the obtained particle size cube, and the volume average particle size was defined as the average primary particle size.

[Average molecular weight of acrylic resin]
As for the weight average molecular weight (Mw) and number average molecular weight (Mn) of the acrylic resin used as the binder resin, HLC-8220GPC (manufactured by Tosoh Corporation) is used as a device, and TSK-GEL SUPER HZM-N is connected in series as a column. It is a polystyrene conversion molecular weight measured using THF as a solvent.

[Average molecular weight of acidic dispersant]
The number average molecular weight (Mn) and weight average molecular weight (Mw) of the acidic dispersant are GPC (manufactured by Tosoh Corp., HLC-8120GPC) equipped with a RI detector using a TSKgel column (Tosoh Corp.), and the developing solvent. It is the number average molecular weight (Mn) and weight average molecular weight (Mw) in terms of polystyrene measured using THF.

[Acid dispersant and acid value of acrylic resin]
The acid value of the acidic dispersant and the acrylic resin is a value obtained by converting the measured acid value (mgKOH / g) into a solid content according to the potentiometric titration method of JIS K0070.

[Average molecular weight of basic dispersant]
The number average molecular weight (Mn) and the weight average molecular weight (Mw) of the vinyl resin type dispersant are HLC-8320GPC (manufactured by Tosoh Corporation) as an apparatus, SUPER-AW3000 as a column, and 30 mM triethylamine as an eluent. And polystyrene-equivalent number average molecular weight (Mn) and weight average molecular weight (Mw) measured using an N, N-dimethylformamide solution of 10 mM LiBr.

[Amine number of basic dispersant]
The amine value of the vinyl resin type dispersant is a value obtained by converting the total amine value (mg KOH / g) measured according to the method of ASTM D 2074 into a solid content.

<Method for producing binder resin solution>
(Production Example 1)
[Production of binder resin (B1)]
Put 80 parts of propylene glycol monomethyl ether acetate in a reaction vessel, heat to 100 ° C. while injecting nitrogen gas into the vessel, and drop the mixture of the following monomers and thermal polymerization initiator at the same temperature over 1 hour to react. went.
-Methacrylic acid: 10.0 parts-Methyl methacrylate: 90.0 parts-Azobisisobutyronitrile: 4.0 parts After the dropwise addition, the mixture was further reacted at 100 ° C for 3 hours, and then azobisisobutyronitrile was added. A solution prepared by dissolving 8 parts in 20 parts of propylene glycol monomethyl ether acetate was added, and the reaction was further continued at 100 ° C. for 1 hour. 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. Propylene glycol monomethyl ether so that the nonvolatile content was 20% by mass in the previously synthesized resin solution. Acetate was added to obtain a binder resin (B1).

(Production Example 2)
[Production of Binder Resin (B2)] A binder resin (B2) was obtained in the same manner as in Production Example 1 except that the types and amounts of monomers shown in Table 2 were used.

(Production Example 3)
[Production of binder resin (B3)]
Put 80 parts of propylene glycol monomethyl ether acetate in a reaction vessel, heat to 100 ° C. while injecting nitrogen gas into the vessel, and drop the mixture of the following monomers and thermal polymerization initiator at the same temperature over 1 hour to react. went.
2-hydroxyethyl methacrylate: 9.6 parts Methyl methacrylate: 80.0 parts Azobisisobutyronitrile: 4.0 parts
After the addition, the mixture was further reacted at 100 ° C. for 3 hours, and then 0.8 part of azobisisobutyronitrile dissolved in 20 parts of propylene glycol monomethyl ether acetate was added, and the reaction was further continued at 100 ° C. for 1 hour. It was. After cooling to room temperature, 10.4 parts of 2-isocyanatoethyl acrylate (Karenz AOI manufactured by Showa Denko KK), 0.08 parts of dibutyltin laurate, 5.0 parts of propylene glycol monomethyl ether acetate, p-methoxyphenol 0 .05 parts was added and reacted at 70 ° C. for 4 hours in an air atmosphere. After cooling to room temperature, about 2 parts of the resin solution was sampled and heated and dried at 180 ° C. for 20 minutes to measure the non-volatile content. Ether acetate was added to prepare a resin solution (B3).

(Production Example 4)
[Production of Binder Resin (B4)] (Step 1: Polymerization of Resin Main Chain)
Place 100 parts of propylene glycol monomethyl ether acetate (PGMAC) in a reaction vessel equipped with a thermometer, cooling tube, nitrogen gas inlet tube, and stirrer in a separable four-necked flask, and heat to 120 ° C while injecting nitrogen gas into the vessel. Then, a mixture of 80.0 parts of methyl methacrylate, 7.5 parts of methacrylic acid, and 4.0 parts of azobisisobutyronitrile as a catalyst required for the reaction of the precursor at this stage from the dropping tube at the same temperature. The polymerization reaction was carried out dropwise over 5 hours. After the addition, the mixture was further reacted at 100 ° C. for 3 hours, and then 0.8 part of azobisisobutyronitrile dissolved in 20 parts of propylene glycol monomethyl ether acetate was added, and the reaction was further continued at 100 ° C. for 1 hour. It was.

(Step 2: Reaction to carboxyl group)
Next, the atmosphere in the flask was replaced with air, and 12.5 parts of glycidyl methacrylate and 0.3 part of trisdimethylaminomethylphenol and 0.3 part of hydroquinone were added as a catalyst required for this stage, and the reaction was performed at 120 ° C. for 5 hours. It was. After cooling to room temperature, about 2 parts of the resin solution was sampled and heated and dried at 180 ° C. for 20 minutes to measure the nonvolatile content. Propylene glycol monomethyl was added to the previously synthesized resin solution so that the nonvolatile content was 20% by weight. Ether acetate was added to prepare a resin solution (B4). Since the carboxyl group in the charged resin seed chain is ester-bonded with the epoxy group of glycidyl methacrylate, no carboxyl group is produced in the resin structure.

(Production Example 5)
[Production of Binder Resin (B5)] (Step 1: Polymerization of Resin Main Chain)
Place 100 parts of propylene glycol monomethyl ether acetate (PGMAC) in a reaction vessel equipped with a thermometer, cooling tube, nitrogen gas inlet tube, and stirrer in a separable four-necked flask, and heat to 120 ° C while injecting nitrogen gas into the vessel. Then, a mixture of 80.0 parts of methyl methacrylate, 13.3 parts of glycidyl methacrylate, and 4.0 parts of azobisisobutyronitrile as a catalyst required for the reaction of the precursor at this stage is added from the dropping tube at the same temperature. The polymerization reaction was carried out dropwise over 5 hours. After the addition, the mixture was further reacted at 100 ° C. for 3 hours, and then 0.8 part of azobisisobutyronitrile dissolved in 20 parts of propylene glycol monomethyl ether acetate was added, and the reaction was further continued at 100 ° C. for 1 hour. It was.

(Step 2: Reaction to epoxy group)
Next, the inside of the flask was purged with air, and 6.7 parts of acrylic acid and 0.3 part of trisdimethylaminomethylphenol and 0.3 part of hydroquinone were added as a catalyst required for this stage and reacted at 120 ° C. for 5 hours. It was. After cooling to room temperature, about 2 parts of the resin solution was sampled and heated and dried at 180 ° C. for 20 minutes to measure the nonvolatile content. Propylene glycol monomethyl was added to the previously synthesized resin solution so that the nonvolatile content was 20% by weight. Ether acetate was added to prepare a resin solution (B5). Since the added acrylic acid is ester-bonded to the end of the epoxy group of the glycidyl methacrylate structural unit, no carboxyl group is generated in the resin structure.

(Production Example 6)
[Production of Binder Resin (B6)] (Step 1: Polymerization of Resin Main Chain)
Place 100 parts of propylene glycol monomethyl ether acetate (PGMAC) in a reaction vessel equipped with a thermometer, cooling tube, nitrogen gas inlet tube, and stirrer in a separable four-necked flask, and heat to 120 ° C while injecting nitrogen gas into the vessel. Then, a mixture of 80.0 parts of methyl methacrylate, 5.2 parts of methacrylic acid, and 4.0 parts of azobisisobutyronitrile as a catalyst required for the reaction of the precursor at this stage from the dropping tube at the same temperature. The polymerization reaction was carried out dropwise over 5 hours.

(Step 2: Reaction to carboxyl group)
Next, the inside of the flask was purged with air, and 8.7 parts of glycidyl methacrylate and 0.3 part of trisdimethylaminomethylphenol and 0.3 part of hydroquinone were added as a catalyst required for the reaction of the precursor at this stage. Reaction was performed for 5 hours, and the resin solution whose weight average molecular weight is about 12000 (measurement by GPC) was obtained. Since the carboxyl group of the resin main chain is ester-bonded to the end of the epoxy group of glycidyl methacrylate, no carboxyl group is generated in the resin structure.

(Step 3: Reaction to hydroxyl group)
Furthermore, as a catalyst required for the reaction of 6.1 parts of succinic anhydride and the precursor at this stage, 0.5 part of triethylamine was added and reacted at 120 ° C for 4 hours. In the added tetrahydrophthalic anhydride, one of two carboxyl groups generated by cleavage of the carboxylic anhydride moiety is ester-bonded to a hydroxyl group in the resin structure, and the other produces a carboxyl group terminal.

(Step 4: Adjustment of nonvolatile content)
Propylene glycol monomethyl ether acetate was added so that the nonvolatile content was 20% to obtain a resin solution (B6).

(Production Example 7)
[Production of Binder Resin (B7)] (Step 1: Polymerization of Resin Main Chain)
Place 100 parts of propylene glycol monomethyl ether acetate (PGMAC) in a reaction vessel equipped with a thermometer, cooling tube, nitrogen gas inlet tube, and stirrer in a separable four-necked flask, and heat to 120 ° C while injecting nitrogen gas into the vessel. Then, a mixture of 80.0 parts of methyl methacrylate, 9.0 parts of glycidyl methacrylate, and 4.0 parts of azobisisobutyronitrile as a catalyst required for the reaction of the precursor at this stage from the dropping tube at the same temperature. The polymerization reaction was carried out dropwise over 5 hours.

(Step 2: Reaction to epoxy group)
Next, the inside of the flask was purged with air, and 4.6 parts of acrylic acid and 0.3 parts of trisdimethylaminomethylphenol and 0.3 parts of hydroquinone were added as catalysts required for the reaction of the precursor at this stage, Reaction was performed for 5 hours, and the resin solution whose weight average molecular weight is about 12000 (measurement by GPC) was obtained. Since the added acrylic acid is ester-bonded to the end of the epoxy group of the glycidyl methacrylate structural unit, no carboxyl group is generated in the resin structure.

(Step 3: Reaction to hydroxyl group)
Further, 6.4 parts of succinic anhydride and 0.5 part of triethylamine as a catalyst required for the reaction of the precursor at this stage were added and reacted at 120 ° C. for 4 hours. In the added tetrahydrophthalic anhydride, one of two carboxyl groups generated by cleavage of the carboxylic anhydride moiety is ester-bonded to a hydroxyl group in the resin structure, and the other produces a carboxyl group terminal.

(Step 4: Adjustment of nonvolatile content)
Propylene glycol monomethyl ether acetate was added so that the nonvolatile content was 20% to obtain a resin solution (B7).

  Table 1 shows the composition and weight ratio of the obtained binder resins (B1) to (B7), the measured molecular weight, and the acid value.

The precursors of the structural units and the abbreviations of the structural units in Table 1 are described below.
MMA: methyl methacrylate MAA: methacrylic acid HOMS: 2-methacryloyloxyethyl succinic acid HEMA + AOI: AOI (2-isocyanatoethyl acrylate) added to the hydroxyl group of the structural unit (2-hydroxyethyl methacrylate) and bonded MAA- GMA: GMA added and reacted with carboxyl group of structural unit MAA (methacrylic acid) GMA-AA: Acrylic acid added and bonded with epoxy group of structural unit GMA (glycidyl methacrylate) MAA + GMA + succinic anhydride: GMA is added to the structural unit methacrylic acid and bonded to it, and succinic anhydride is esterified and bonded to the resulting OH group. GMA-AA + succinic anhydride: acrylic acid is added to the structural unit GMA and bonded. OH generated at that time That succinic anhydride was coupled by esterifying the

<Pigment production method>
(Green pigment (PG-1): PG58)
Phthalocyanine green pigment C.I. I. 100 parts of Pigment Green 58 (“FASTGEN GREEN A110” manufactured by DIC), 1200 parts of sodium chloride, and 120 parts of diethylene glycol were charged into a 1 gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 70 ° C. for 6 hours. The kneaded product is poured into 3000 parts of warm water, stirred for 1 hour while heating to 70 ° C. to form a slurry, filtered and washed repeatedly to remove sodium chloride and diethylene glycol, and then dried at 80 ° C. for a whole day and night. 97 parts of pigment (PG-1) were obtained. The average primary particle size was 28.2 nm.

(Green pigment (PG-2): Aluminum phthalocyanine)
In a reaction vessel, 225 parts of phthalodinitrile and 78 parts of anhydrous aluminum chloride were added to 1250 parts of n-amyl alcohol and stirred. To this, 266 parts of DBU (1,8-Diazabicyclo [5.4.0] undec-7-ene) was added, the temperature was raised, and the mixture was refluxed at 136 ° C. for 5 hours. The reaction solution cooled to 30 ° C. with stirring was poured into a mixed solvent of 5000 parts of methanol and 10000 parts of water with stirring to obtain a blue slurry. This slurry was filtered, washed with a mixed solvent of 2000 parts of methanol and 4000 parts of water, and dried to obtain 135 parts of chloroaluminum phthalocyanine. Further, 100 parts of chloroaluminum phthalocyanine was slowly added to 1200 parts of concentrated sulfuric acid at room temperature in a reaction vessel. The mixture was stirred at 40 ° C. for 3 hours, and the sulfuric acid solution was poured into 24000 parts of cold water at 3 ° C. The blue precipitate was filtered, washed with water and dried to obtain 102 parts of an aluminum phthalocyanine pigment represented by the following formula (17).
Next, 100 parts of methanol and 100 parts of the aluminum phthalocyanine pigment represented by the formula (17) and 49.5 parts of diphenyl phosphate were added to 1000 parts of methanol in a reaction vessel, heated to 40 ° C., and reacted for 8 hours. . After cooling this to room temperature, the product was filtered, washed with methanol, and dried to obtain 114 parts of an aluminum phthalocyanine pigment represented by the following formula (18).
A green pigment (PG-2) was obtained from the obtained aluminum phthalocyanine pigment represented by the formula (18) by the same salt milling method as that for the green pigment (PG-1). The average primary particle size was 31.2 nm.

Formula (17)

General formula (18)

(Green pigment (PG-3): Aluminum phthalocyanine)
In a reaction vessel, 100 parts of methanol and 100 parts of an aluminum phthalocyanine pigment represented by the formula (17) and 43.2 parts of diphenylphosphinic acid were added to 1000 parts of methanol, heated to 40 ° C., and reacted for 8 hours. After cooling this to room temperature, the product was filtered, washed with methanol, and dried to obtain 112 parts of an aluminum phthalocyanine pigment represented by the following formula (19).
A blue colorant (PG-3) was obtained from the obtained aluminum phthalocyanine pigment represented by the formula (19) by the same salt milling method as that for the blue colorant (PG-1). The average primary particle size was 29.5 nm.

General formula (19)

(Production of blue colorant (PG-4))
According to the synthesis method described in JP 2010-79247 A, an aluminum phthalocyanine pigment represented by the following formula (20) was obtained.
A blue colorant (PG-4) was obtained from the obtained aluminum phthalocyanine pigment represented by the formula (20) by the same salt milling method as that for the blue colorant (PB-1). The average primary particle size was 33.0 nm.

General formula (20)

(Production of blue colorant (PG-5))
To 100 parts of the aluminum phthalocyanine pigment represented by the formula (17), 200 parts of pyridine, 800 parts of xylene and 54.6 parts of phenylphosphonic acid were added, and heating and refluxing were continued for 8 hours. After filtration, washing with methanol, and drying, 110 parts of an aluminum phthalocyanine pigment represented by the following formula (21) was obtained.
Subsequently, a salt milling process was performed in the same manner as for the blue colorant (PG-1) to produce a blue colorant (PG-5). The obtained colorant had a volume average primary particle size of 37 nm.

Formula (21)


(Production of blue colorant (PG-6))
To a three-necked flask, 500 parts of 98% sulfuric acid, 50 parts of a phthalocyanine pigment represented by the formula (17), and 129.3 parts of 1,2-dibromo-5,5-dimethylhydantoin (DBDMH) were added and stirred. The reaction was carried out at 0 ° C. for 6 hours. Thereafter, the reaction mixture was poured into 5000 parts of ice water at 3 ° C., and the precipitated solid was collected by filtration and washed with water. To a beaker, 500 parts of a 2.5% aqueous sodium hydroxide solution and the residue collected by filtration were added and stirred at 80 ° C. for 1 hour. Thereafter, the mixture was collected by filtration, washed with water, and dried to obtain a pigment having an average of 10.1 bromine atoms substituted on the phthalocyanine ring.
Next, 500 parts of N-methylpyrrolidone, 50 parts of a pigment having an average of 10.1 bromine atoms substituted on the obtained phthalocyanine ring, and 13.9 parts of diphenyl phosphate were added to a three-necked flask. The mixture was heated to 0 ° C. and reacted for 8 hours. After cooling this to room temperature, the product was filtered, washed with methanol, and dried to obtain a phthalocyanine pigment (PG-6) represented by the following formula (23). The obtained colorant had a volume average primary particle size of 27 nm.

Formula (23)

(Yellow pigment (PY-1): PY138)
C. I. 100 parts of Pigment Yellow 138 (trade name Paliotor Yellow K0961HD, manufactured by BASF), 1200 parts of sodium chloride, and 120 parts of diethylene glycol were charged into a 1 gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 70 ° C. for 6 hours. The kneaded product was poured into 3000 parts of warm water, stirred for 1 hour while heating to 70 ° C. to form a slurry, filtered and washed repeatedly to remove sodium chloride and diethylene glycol, and then dried at 80 ° C. all day and night. 98 parts of pigment (PY-1) were obtained. The average primary particle size was 35.5 nm.

(Yellow pigment (PY-2): PY150)
C. I. 200 parts of Pigment Yellow 150 (“E-4GN” manufactured by LANXESS), 1400 parts of sodium chloride, and 360 parts of diethylene glycol were charged into a stainless gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 80 ° C. for 6 hours. Next, the kneaded product is put into 8000 parts of warm water, stirred for 2 hours while heating to 80 ° C. to form a slurry, filtered and washed with water repeatedly to remove sodium chloride and diethylene glycol, and then dried at 85 ° C. overnight. A fine yellow pigment (PY-2) was obtained.

(Red pigment (PR-1): PR254)
Diketopyrrolopyrrole red pigment C.I. I. 120 parts of Pigment Red 254 (“IRGAZIN RED 2030” manufactured by BASF), 1000 parts of ground sodium chloride, and 120 parts of diethylene glycol were charged into a stainless 1 gallon kneader (Inoue Seisakusho) and kneaded at 60 ° C. for 10 hours. The mixture was poured into 2000 parts of warm water and stirred for 1 hour while heating to 80 ° C. to form a slurry, filtered, washed with water repeatedly to remove salt and solvent, dried at 80 ° C. overnight, and 115 parts of red A pigment (PR-1) was obtained. The average primary particle size was 24.8 nm.

(Red pigment (PR-2): PR177)
Anthraquinone red pigment C.I. I. 200 parts of Pigment Red 177 (“chromophthaled red A2B” manufactured by BASF), 1400 parts of 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. Next, the kneaded product is put into 8000 parts of warm water, stirred for 2 hours while heating to 80 ° C. to form a slurry, filtered and washed with water repeatedly to remove sodium chloride and diethylene glycol, and then dried at 85 ° C. overnight. 190 parts of a red pigment (PR-2) were obtained. The average primary particle size was 27.6 nm.

(Red pigment (PR-3): brominated diketopyrrolopyrrole)

To a stainless steel reaction vessel equipped with a reflux tube, 200 parts of tert-amyl alcohol dehydrated with molecular sieves and 140 parts of sodium-tert-amyl alkoxide are added in a nitrogen atmosphere and heated to 100 ° C. with stirring to obtain an alcoholate solution. Prepared. On the other hand, 88 parts of diisopropyl succinate and 153.6 parts of 4-bromobenzonitrile were added to a glass flask and dissolved by heating to 90 ° C. with stirring to prepare a solution of these mixtures. The heated solution of the mixture was slowly dropped into the alcoholate solution heated to 100 ° C. at a constant rate over 2 hours with vigorous stirring. After completion of the dropwise addition, heating and stirring were continued for 2 hours at 90 ° C. to obtain an alkali metal salt of a diketopyrrolopyrrole compound. Furthermore, 600 parts of methanol, 600 parts of water and 304 parts of acetic acid were added to a reaction vessel with a glass jacket, and cooled to -10 ° C. This cooled mixture was cooled to 75 ° C. while rotating a shear disk having a diameter of 8 cm at 4,000 rpm using a high-speed stirring disperser, and the alkali metal of the diketopyrrolopyrrole compound obtained above was cooled to 75 ° C. The salt solution was added in small portions. At this time, the rate of addition of the alkali metal salt of the diketopyrrolopyrrole compound at 75 ° C. is adjusted while cooling so that the temperature of the mixture of methanol, acetic acid and water is always kept at −5 ° C. or lower. While being added in small portions over approximately 120 minutes. After addition of the alkali metal salt, red crystals were precipitated to form a red suspension. Subsequently, the obtained red suspension was washed with an ultrafiltration device at 5 ° C. and then filtered to obtain a red paste. This paste is re-dispersed in 3,500 parts of methanol cooled to 0 ° C. to make a suspension with a methanol concentration of about 90%, stirred at 5 ° C. for 3 hours, and subjected to particle sizing and washing with crystal transition. It was. Subsequently, the diketopyrrolopyrrole compound aqueous paste obtained by filtering with an ultrafilter was dried at 80 ° C. for 24 hours and pulverized to obtain 150.8 parts of a brominated diketopyrrolopyrrole pigment. Got. Next, 150 parts of the synthesized brominated diketopyrrolopyrrole pigment, 935 parts of sodium chloride, and 240 parts of diethylene glycol were charged into a stainless 1 gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 80 ° C. for 6 hours. Next, this kneaded product is put into 5300 parts of warm water, stirred for 2 hours while heating to 80 ° C. to form a slurry, filtered, washed with water repeatedly to remove sodium chloride and diethylene glycol, and then dried at 85 ° C. overnight. 127 parts of a red pigment (PR-3) were obtained. The average primary particle size was 27.6 nm.

(Red pigment (PR-4): PR269)
Naphtholazo red pigment C.I. I. 120 parts of Pigment Red 269 (“Permanent Carmine 3810” manufactured by Sanyo Color Co., Ltd.), 1000 parts of ground sodium chloride, and 120 parts of diethylene glycol were charged into a stainless steel 1 gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 60 ° C. for 10 hours. The mixture was added to 2000 parts of warm water, heated to about 80 ° C. and stirred with a high speed mixer for about 1 hour 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 the red pigment (PR-4) which is 115 parts of red refined pigments. The average primary particle diameter of the obtained pigment was 38.9 nm.

(Purple pigment (PV-1): PV23)
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 in a 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 for 1 hour while heating to 70 ° C. to form a slurry, filtered, washed with water repeatedly to remove salt and solvent, dried at 80 ° C. overnight, and 118 parts of purple A pigment (PV-1) was obtained. The average primary particle size was 26.4 nm.

(Blue pigment (PB-1) PB 15: 6)
Phthalocyanine blue pigment C.I. I. Pigment Blue 15: 6 (Toyocolor "Rionol 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 (PB-1). The average primary particle diameter of the obtained pigment was 28.3 nm.

(Production of blue colorant (PB-2))
Phthalocyanine blue pigment C.I. I. Pigment Blue 15: 3 (“LIONOL BLUE FG-7400-G” manufactured by Toyocolor Co., Ltd.), 800 parts of crushed salt and 100 parts of diethylene glycol were charged into a stainless steel 1 gallon kneader (manufactured by Inoue Seisakusho) at 70 ° C. Kneaded for 12 hours. 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 (PB-2). The average primary particle diameter of the obtained pigment was 31.5 nm.

Here, the average primary particle diameter of the pigment was determined by a transmission electron microscope (“JEM-1200 manufactured by JEOL Ltd.).
EX ”) was used to measure the primary particle diameter of all pigment particles in the observation sample at 50,000 times, and the average value was 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.

(Salt-forming dye compound (LM): AR52)

C. with reference to Production Example 50 of Patent Application 2011-261667. I. A salt-forming compound (LM) composed of Acid Red 52 and a resin having a cationic group in the side chain was produced.

<Preparation of acidic dispersant (X)>
(Production of Dispersant (X-1), Production Method (2))
In a reaction vessel equipped with a gas introduction tube, a condenser, a stirring blade, and a thermometer, 4.0 parts of 3-mercapto-1,2-propanediol, 24.4 parts of methoxypropyl acetate, 6.46 parts of pyromellitic anhydride Then, 0.005 part of monobutyltin (IV) oxide was added as a catalyst, and after substitution with nitrogen gas, the reaction was carried out at 130 ° C. for 2 hours and at 100 ° C. for 2 hours. It was confirmed by titration that 90% or more of the acid anhydride was half-esterified, and cooled to room temperature. (First step)
Methyl methacrylate 50 parts, t-butyl acrylate 6.1 parts, cyclohexyl acrylate 6.1 parts, methoxyethyl acrylate 6.1 parts, n-butyl methacrylate 6.1 parts, t-butyl methacrylate, benzyl methacrylate 6.1 parts, 7.6 parts of 2-hydroxyethyl methacrylate and 44 parts of methoxypropyl acetate were further charged into the reaction vessel and replaced with nitrogen gas. The reaction vessel was heated to 80 ° C., and 0.3 part of 2,2′-azobisisobutyronitrile dissolved in 24 parts of methoxypropyl acetate was added in 20 portions every 30 minutes. The reaction was carried out for 10 hours, and it was confirmed that 95% had reacted by measuring the solid content. (Second step)
Next, 5.8 parts of succinic anhydride and 0.2 part of 1,8-diazabicyclo- [5.4.0] -7-undecene as a catalyst were added and reacted at 120 ° C. for 2 hours and at 80 ° C. for 5 hours. I let you. It was confirmed by titration that 90% or more of the acid anhydride was half-esterified, and a dispersant (X-1) having an acid value of 31 mg KOH / g and a number average molecular weight (Mn) of 8,100 per solid content was obtained. . (Third process)
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. Propylene glycol monomethyl ether so that the nonvolatile content was 20% by mass in the previously synthesized resin solution. Acetate was added to obtain dispersant (X-1).

(Production of dispersants (X-2) to (X-30))
Dispersants (X-2) to (X-) are the same as the dispersant (X-1) except that the types, weight parts, acid anhydride types, and weight parts of the monomers shown in Tables 2 to 3 are changed. 30) was obtained.

(Production of Dispersant (X-31), Production Method (1))
In a reaction vessel equipped with a gas introduction tube, a condenser, a stirring blade and a thermometer, 50 parts of methyl methacrylate, 6.1 parts of t-butyl acrylate, 6.1 parts of cyclohexyl acrylate, 6.1 parts of methoxyethyl acrylate, n- 6.1 parts of butyl methacrylate, 6.1 parts of t-butyl methacrylate, 6.1 parts of benzyl methacrylate, 13.37 of 2-methacryloyloxyethyl succinic acid, and 44 parts of methoxypropyl acetate were charged and replaced with nitrogen gas. After heating the inside of the reaction vessel to 80 ° C. and adding 4.0 parts of 3-mercapto-1,2-propanediol, 0.3 parts of 2,2′-azobisisobutyronitrile was added to methoxypropyl acetate 24 What was melt | dissolved in the part was divided into 20 times and added every 30 minutes, it reacted for 12 hours with 80 degreeC, and it confirmed that 95% had reacted by solid content measurement. Next, 6.46 parts of pyromellitic anhydride and 0.2 part of 1,8-diazabicyclo- [5.4.0] -7-undecene as a catalyst were added, and 5 hours at 80 ° C. for 2 hours at 120 ° C. Reacted for hours. It was confirmed by titration that 90% or more of the acid anhydride was half-esterified, and a dispersant (X-31) having an acid value per solid content of 31 mg KOH / g and a number average molecular weight (Mn) of 8,000 was obtained. . 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. Propylene glycol monomethyl ether so that the nonvolatile content was 20% by mass in the previously synthesized resin solution. Acetate was added to obtain a dispersant (X-31).

(Production of dispersants (X-32) to (X-39))
Dispersants (X-32) to (X-39) were obtained in the same manner as in the polyester (X-31) except that the types of monomers shown in Table 4 were changed to parts by weight.

(Production of dispersant (X-40))
In a reaction vessel equipped with a gas introduction tube, a condenser, a stirring blade, and a thermometer, 0.3 parts of hydroquinone, 44 parts of methoxypropyl acetate, 5.8 parts of succinic anhydride, 2-hydroxyethyl methacrylate, 7. 6 parts and 0.2 part of 1,8-diazabicyclo- [5.4.0] -7-undecene as a catalyst were added and reacted at 120 ° C. for 2 hours and at 80 ° C. for 5 hours. It was confirmed by titration that 90% or more of the acid anhydride was half-esterified, allowed to cool to room temperature, and further 50 parts of methyl methacrylate, 6.1 parts of t-butyl acrylate, 6.1 parts of cyclohexyl acrylate, methoxyethyl 6.1 parts of acrylate, 6.1 parts of n-butyl methacrylate, 6.1 parts of t-butyl methacrylate and 6.1 parts of benzyl methacrylate were charged into the reaction vessel and replaced with nitrogen gas. The reaction vessel was heated to 80 ° C., and 0.3 part of 2,2′-azobisisobutyronitrile dissolved in 24 parts of methoxypropyl acetate was added in 20 portions every 30 minutes. It was confirmed that 95% had reacted by solid content measurement, and the dispersant (X-40) having an acid value per solid content of 31 mg KOH / g and a number average molecular weight (Mn) of 7,900 was measured. Obtained. 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. Propylene glycol monomethyl ether so that the nonvolatile content was 20% by mass in the previously synthesized resin solution. Acetate was added to obtain a dispersant (X-40).

(Production of Comparative Dispersants (X-41) to (X-42))
Dispersants (X-41) to (X-42) were obtained in the same manner as in the polyester (X-31) except that the types of monomers shown in Table 4 were changed to parts by weight.

Abbreviations in Tables 2 to 4 are described below.
MMA: methyl methacrylate t-BA: t-butyl acrylate CHA: cyclohexyl acrylate 2-MTA: 2-methoxyethyl acrylate n-BMA: n-butyl methacrylate t-BMA: t-butyl methacrylate BzMA: benzyl acrylate MAA: methacrylic acid HEMA : 2-hydroxyethyl methacrylate HPMA: 2-hydroxypropyl methacrylate HBMA: 2-hydroxybutyl methacrylate HEA: 2-hydroxyethyl acrylate HPA: 2-hydroxypropyl acrylate HBA: 2-hydroxybutyl acrylate HOMS: 2-methacryloyloxyethyl succinate Acid HOA: 2-acryloyloxyethyl succinic acid MMS: 2-methacryloyloxyethyl hexahydrophthalic acid MOA: 2 -Acryloyloxyethyl hexahydrophthalic acid

<Preparation of basic dispersant>
(Production of Basic Dispersant (DM-1)) A reaction vessel equipped with a random copolymer gas introduction tube, a condenser, a stirring blade, and a thermometer was charged with 133 parts of methoxypropyl acetate and 110 ° C. with nitrogen substitution. The temperature was raised to. In a dropping tank, 1,2,2,6,6-pentamethylpiperidyl methacrylate 177 parts, methyl acrylate 3 parts, 2-hydroxyethyl methacrylate 20 parts, methoxypropyl acetate 61 parts, and 2,2′-azobis (2,4 -Dimethylvaleronitrile) was charged in 6 parts and stirred until it was uniform, then dropped into the reaction vessel over 2 hours, and then the reaction was continued at the same temperature for 3 hours. In this manner, a basic dispersant (DM-1) having a hindered amine skeleton having an amine value per solid content of 208 mgKOH / g and a number average molecular weight of 3,800 (Mn) was obtained.
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. Then, propylene glycol monomethyl ether acetate was added so that the nonvolatile content was 20% by weight, and the hindered amine skeleton was added. A basic dispersant (DM-1) solution having

(Production of Basic Dispersant (DM-2)) Random Copolymer A reaction vessel equipped with a gas introduction tube, a condenser, a stirring blade, and a thermometer was charged with 133 parts of methoxypropyl acetate and 110 ° C. while substituting nitrogen. The temperature was raised to. In a dropping tank, 116 parts of dimethylaminoethyl methacrylate, 64 parts of methyl acrylate, 20 parts of 2-hydroxyethyl methacrylate, 61 parts of methoxypropyl acetate, and 6 parts of 2,2′-azobis (2,4-dimethylvaleronitrile) are charged. After stirring until uniform, it was added dropwise to the reaction vessel over 2 hours, and then the reaction was continued for 3 hours at the same temperature. In this manner, a basic dispersant (DM-2) having an amine value per solid content of 207 mgKOH / g and a number average molecular weight of 3,900 (Mn) was obtained.
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. Then, propylene glycol monomethyl ether acetate was added so that the nonvolatile content was 20% by weight, and the hindered amine skeleton was added. A basic dispersing agent (DM-2) solution having no water content was prepared.

(Production of Basic Dispersant (DM-3)) Random Copolymer A reaction vessel equipped with a gas introduction tube, a condenser, a stirring blade, and a thermometer was charged with 133 parts of methoxypropyl acetate and 110 ° C. while substituting nitrogen. The temperature was raised to. In a dropping tank, 177 parts of dimethylaminoethyl methacrylate, 3 parts of methyl acrylate, 20 parts of 2-hydroxyethyl methacrylate, 61 parts of methoxypropyl acetate, and 6 parts of 2,2′-azobis (2,4-dimethylvaleronitrile) are charged. After stirring until uniform, it was added dropwise to the reaction vessel over 2 hours, and then the reaction was continued for 3 hours at the same temperature. In this way, a basic dispersant (DM-3) having an amine value per solid content of 316 mg KOH / g and a number average molecular weight of 3,800 (Mn) was obtained.
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. Then, propylene glycol monomethyl ether acetate was added so that the nonvolatile content was 20% by weight, and the hindered amine skeleton was added. A basic dispersing agent (DM-3) solution having no water content was prepared.

(Production of basic dispersants (DM-4) to (DM-8))
The basic dispersant solutions (DM-4) to (DM-8) having a hindered amine skeleton were used in the same manner as the basic dispersant (DM-1) except that the types of monomers shown in Table 5 were changed to parts by weight. Obtained.

<Method for producing colored composition>
Next, it shows about the manufacturing method of coloring composition (P-1)-(P-69) which is an Example, and coloring composition (P-70) and (P-71) which are comparative examples.
[Production Example 1]
(Coloring composition (P-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 coloring composition (P-1).
Refined pigment (PB-1) 12.0 parts Basic dispersant (DM-1) 6.0 parts Dispersant (X-1) 12.0 parts Binder resin (B1) 22.0 parts PGMAC 48.0 parts

[Production Examples 2 to 71]
(Coloring compositions (P-2) to (P-73))
The refined pigment (PB-1), the basic dispersant (DM-1), the dispersant (X-1), and the binder resin (B1) are shown in Tables 6 and 7. The refined pigment, the basic dispersant, and the dispersion are shown in Tables 6 and 7. Colored compositions (P-2) to (P-73) were obtained in the same manner as the colored composition (P-1) except that the agent and the binder resin were changed.

[Production Example 220]
(Coloring composition (P-220))
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 the coloring composition (P-220) was produced.
Salt-forming dye compound (LM) 12.0 parts Binder resin (B1) 10.0 parts PGMAC 78.0 parts

Next, the colored compositions (P-74) to (P-144) prepared by using the colored compositions (P-1) to (P-73) and (P-220) will be described.
[Example 1]
(Coloring composition (P-74))
When the coloring composition (P-1) and the coloring composition (P-2) have a dried coating film having a chromaticity of x = 0. 0 in a microspectrophotometer ("OSP-SP100" C light source manufactured by Olympus Optical Co., Ltd.). 141, y = 0.084, and the mixture was stirred and mixed with a disper for 1 hour.

[Example 2]
(Coloring composition (P-75))
The colored composition (P-1) and the colored composition (P-2) were changed in the same manner as in Example 1 except that the colored compositions (P-2) were changed to the colored compositions shown in Tables 8 and 9. -75) was obtained.

[Example 3]
(Coloring composition (P-76))
The coloring composition (P-3) and the coloring composition (P-4) were dried at a coating film having a chromaticity of x = 0. 0 in a microspectrophotometer ("OSP-SP100" C light source manufactured by Olympus Optical Co., Ltd.). The blending ratio was adjusted to 655 and y = 0.325, and the mixture was stirred and mixed with a disper for 1 hour.

[Examples 4 to 6]
(Coloring compositions (P-77) to (P-79))
The colored composition (P-77) was changed in the same manner as in Example 3 except that the colored composition (P-3) and the colored composition (P-4) were changed to the colored compositions shown in Table 8. To (P-79) was obtained.

[Example 7]
(Coloring composition (P-80))
When the coloring composition (P-7) and the coloring composition (P-12) were dried, the chromaticity of the dried coating film was measured by a microspectrophotometer ("OSP-SP100" C light source manufactured by Olympus Optical Co., Ltd.). 600, x
The blending ratio was adjusted to 0.291, and the mixture was stirred and mixed with a disper for 1 hour.

[Examples 8-69, Comparative Examples 1-2]
(Coloring compositions (P-81) to (P-144))
The colored composition (P-7) and the colored composition (P-12) were changed in the same manner as in Example 7 except that the colored compositions (P-12) were changed to the colored compositions shown in Tables 8 and 9. -81) to (P-144) were obtained.

<Evaluation of coloring composition>
The viscosity, CR, brightness, and heat resistance of the obtained colored composition (P-74 to 144) were evaluated by the following methods. Tables 8 and 9 show the evaluation results.

(Evaluation of viscosity)
The viscosity of the colored composition after the initial viscosity η ₁ , accelerated by aging by keeping it constant at 40 ° C. for 4 weeks, is the viscosity η ₂ with time, and the E-type viscometer “ELD viscometer” ( Using Toki Sangyo Co., Ltd.) under the conditions of 25 ° C. and rotation speed 20 rpm. A lower initial viscosity means higher dispersion stability. The evaluation criteria for the viscosity were as follows. Further, the thickening ratio is obtained by dividing the difference between the initial viscosity and the viscosity with time by the value of the initial viscosity. X is a difficult level to use.
◎: Initial viscosity is within 7 and thickening rate is within ± 10% ◎: Initial viscosity is within 7 and thickening rate is over ± 10%, within ± 20% ○: Initial viscosity is over 7 and 10 The viscosity increase rate is within ± 10%. △: The initial viscosity is over 7 and less than 10. The viscosity increase rate is over ± 10% and within ± 20%. △: The initial viscosity is over 10 and within 20. Thickening rate is within ± 10% ×: Initial viscosity exceeds 20

(Evaluation of contrast ratio)
The film thickness after heat treatment at 230 ° C. was changed to about 1 by using the spin coater on the 100 mm × 100 mm, 1.1 mm thick glass substrate of the colored composition produced in the examples and comparative examples. The film was coated on three substrates so that the thickness was about 5 μm, then dried at 70 ° C. for 20 minutes, then heated at 220 ° C. for 60 minutes and allowed to cool. Was measured, and the contrast at a film thickness of 1.5 μm was determined from the data at three points by the primary correlation method. X is a difficult level to use.
◎: CR ≧ 14000 or more ○: CR = 12000 or more, less than 14,000 ○ Δ: CR = 8000 or more, less than 12000 Δ: CR = 3000 or more, less than 8000 ×: CR = less than 3000

(Evaluation of heat resistance of coating film)
The obtained colored composition was applied onto a 100 mm × 100 mm, 1.1 mm thick glass substrate using a spin coater, then dried at 70 ° C. for 20 minutes, and then heated at 220 ° C. for 120 minutes and allowed to cool. Thus, a coated substrate was produced. After the heat treatment at 220 ° C., the prepared coated substrate was C = 0.655 for the red colored composition, y = 0.600 for the green colored composition, and y = 0.084 for the blue colored composition. To match the chromaticity of.
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. After that, as a heat resistance test, it was heated at 230 ° C. for 1 hour, and the chromaticity ([L * (2), a * (2), b * (
2)]) was measured, and the color difference ΔEab * was determined by the following calculation formula and evaluated in the following four stages. X is a difficult level to use.
ΔEab * = √ ((L * (2)-L * (1)) ² + (a * (2)-a * (1)) ² + (b * (2)-b * (1)) ² )

A: ΔEab * is less than 1.0
A: ΔEab * is 1.5 or more and less than 1.0
○: ΔEab * is 3.0 or more and less than 1.5 ○ △: ΔEab * is 5.0 or more and less than 3.0 ×: ΔEab * is less than 5.0

(Lightness evaluation)
The coloring composition (P-74 to 144) was applied onto a 100 mm × 100 mm, 1.1 mm thick glass substrate using a spin coater, dried at 70 ° C. for 20 minutes, and then heated at 230 ° C. for 1 hour. The coating film substrate was produced by allowing to cool. The chromaticity of the obtained coating film was measured using a microspectrophotometer ("OSP-SP100" manufactured by Olympus Optical Co., Ltd.), and the chromaticity of the blue colored composition (P-74 to 75) substrate was a C light source. When the chromaticity of the green coloring composition (P-80 to 144) substrate is x = 0.291 and y = 0.600 with a C light source when x = 0.141 and y = 0.084 The brightness: Y (C) when the chromaticity of the red coloring composition (P-76 to 79) substrate was x = 0.655 and y = 0.325 with a C light source was measured. Judgment criteria are as follows. X is a difficult level to use.

(Blue coloring composition)
◎◎: 10.0 or more
A: 9.8 or more and less than 10.0 ○: 9.4 or more and less than 9.8 Δ: 8.9 or more and less than 9.4 ×: less than 8.9 (green coloring composition)
◎◎: 60.0 or more
A: 59.5 or more and less than 60.0 ○: 58.5 or more and less than 59.5 Δ: 58.0 or more and less than 58.5 ×: less than 58.0 (red coloring composition)
◎◎: 18.2 or higher
A: 18.0 or more to less than 18.2 B: 17.8 or more to less than 18.0 Δ: 17.6 or more to less than 17.8 ×: less than 17.6

As shown in Tables 8 and 9, a basic dispersant is used, an acidic dispersant is also used, and the acidic dispersant is a carboxyl group derived from tricarboxylic acid anhydride and / or tetracarboxylic dianhydride. When having a main chain that is a polyester having a side chain and a side chain that is a vinyl polymer having a specific structure represented by the general formulas (1) to (4), heat resistance, CR, and brightness Both the viscosity and the viscosity were good. When not used, the brightness, viscosity and CR were remarkably low.
Moreover, when Example 35 and Examples 57-58 are compared, Example 34 using the basic dispersing agent (DM-1) manufactured using 1,2,2,6,6-pentamethylpiperidyl methacrylate is as follows. Compared with Examples 53 and 54 using the basic dispersants (DM-2) and (DM-3) produced using dimethylaminoethyl methacrylate, this is superior in terms of brightness and heat resistance. In addition, Examples 59 to 61 having an amine value in the range of 110 to 220 gave better results than Examples 58 and 62 in terms of brightness, viscosity, heat resistance, and CR.

<Method for producing photosensitive coloring composition>
Next, it shows about coloring composition (R-1)-(R-77) containing an active energy ray hardening monomer and / or an active energy ray polymerization initiator further.

[Example 70]
(Preparation of photosensitive coloring composition (R-1))
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 photosensitive coloring composition (R-1).
Coloring composition (P-74) 37.5 parts Binder resin (B1) 9.0 parts Photopolymerizable monomer ("Aronix M402" manufactured by Toagosei Co., Ltd. 3.0 parts Photopolymerization initiator ("IRGA" manufactured by BASF) Cure 907 ") 1.3 parts Sensitizer (" EAB-F "manufactured by Hodogaya Chemical Co., Ltd.) 0.2 parts PGMAC 49.0 parts

[Example 71]
(Photosensitive coloring composition (R-2)
A photosensitive colored composition (R-2) was obtained in the same manner as in Example 70 except that the colored composition (P-74) was changed to the colored compositions shown in Tables 10 and 11.

[Example 72]
(Preparation of red photosensitive coloring composition (R-3))
After stirring and mixing a mixture having the following composition to be uniform, it is filtered through a 1.0 μm filter,
A photosensitive coloring composition (R-3) was produced.
Colored composition (P-76) 37.5 parts Binder resin (B1) 9.0 parts Photopolymerizable monomer ("Aronix M402" manufactured by Toagosei Co., Ltd. 3.0 parts Photopolymerization initiator ("IRGA" manufactured by BASF Corporation) Cure 907 ") 1.3 parts Sensitizer (" EAB-F "manufactured by Hodogaya Chemical Co., Ltd.) 0.2 parts PGMAC 49.0 parts

[Examples 73 to 75]
(Photosensitive coloring composition (R-4 to 6)
A photosensitive colored composition (R-4 to 6) was obtained in the same manner as in Example 72 except that the colored composition (P-76) was changed to the colored composition shown in Table 10.

[Example 76]
(Photosensitive coloring composition (R-7))
A mixture having the following composition was stirred and mixed uniformly, and then filtered through a 1.0 μm filter to obtain a photosensitive colored composition (R-7).
Coloring composition (P-80) 37.5 parts Binder resin 1 9.0 parts Photopolymerizable monomer ("Aronix M402" manufactured by Toagosei Co., Ltd. 3.0 parts Photopolymerization initiator ("Irgacure 907 manufactured by BASF Corporation) ] 1.3 parts Sensitizer ("EAB-F" manufactured by Hodogaya Chemical Co., Ltd.) 0.2 parts PGMAC 49.0 parts

[Examples 77 to 144, Comparative Examples 3 to 4]
(Photosensitive coloring composition (R-8 to 77)
A photosensitive colored composition (R-8 to 77) was obtained in the same manner as in Example 76 except that the colored composition (P-80) was changed to the colored compositions shown in Tables 10 and 11.

<Preparation and evaluation of coating film of photosensitive coloring composition>
Evaluation of the developability, heat resistance, viscosity, lightness, and resolution of the coating film produced using the obtained photosensitive coloring composition (R-1 to 77) was performed by the following methods. Tables 10 and 11 show the evaluation results.

(Evaluation of viscosity)
The viscosity of the day after adjusting the photosensitive coloring composition is the initial viscosity η ₁ , and the viscosity after being accelerated by aging at 40 ° C. for 1 week is defined as the time-dependent viscosity η ₂ , and the E-type viscometer “ELD-type viscometer” ”(Manufactured by Toki Sangyo Co., Ltd.) was measured under the conditions of 25 ° C. and 20 rpm. A lower initial viscosity means higher dispersion stability. The evaluation criteria for the viscosity were as follows. Further, the thickening ratio is obtained by dividing the difference between the initial viscosity and the viscosity with time by the value of the initial viscosity. X is a difficult level to use.

◎: Initial viscosity is within 2.5 and viscosity increase rate is within ± 10% ◎: Initial viscosity is within 2.5, viscosity increase rate exceeds ± 10%, within ± 20% ○: Initial viscosity is More than 2.5 and less than 3.0, thickening rate is within ± 10% ○ △: Initial viscosity is over 3.0 and within 4.0, thickening rate is over ± 10%, within ± 20% Δ: Initial viscosity exceeds 4.0 and within 5.0, viscosity increase rate is within ± 10% ×: Initial viscosity exceeds 5.0

(Evaluation of contrast ratio)
The photosensitive coloring compositions (R-1 to 77) produced in the examples and comparative examples were placed on a glass substrate having a size of 100 mm × 100 mm and a thickness of 1.1 mm using a spin coater at 230 ° C. while changing the number of rotations. Is applied to three substrates so that the film thickness after the heat treatment is about 1.5 μm, and then dried at 70 ° C. for 20 minutes, and using an ultra-high pressure mercury lamp, ultraviolet light with an integrated light quantity of 150 mJ / cm ² It exposed and developed with the alkaline developing solution of 23 degreeC, and the coating-film board | substrate was obtained. Subsequently, after heating at 220 ° C. for 30 minutes and allowing to cool, the film thickness and contrast ratio of each of the obtained coating film substrates were measured, and the contrast at a film thickness of 1.5 μm was determined from the three points of data by the primary correlation method. X is a difficult level to use.

◎: CR ≧ 14000 or more ○: CR = 12000 or more, less than 14,000 ○ Δ: CR = 8000 or more, less than 12000 Δ: CR = 3000 or more, less than 8000 ×: CR = less than 3000

(Evaluation of heat resistance of coating film)
The obtained photosensitive coloring composition (R-1 to 77) was applied onto a glass substrate having a thickness 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. The coated substrate was prepared by heating at 220 ° C. for 30 minutes and allowing to cool. After the heat treatment at 220 ° C., the prepared coated substrate was C = 0.655 for the red colored composition, y = 0.600 for the green colored composition, and y = 0.084 for the blue colored composition. To match the chromaticity of.
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. After that, as a heat resistance test, it was heated at 230 ° C. for 1 hour, and the chromaticity ([L * (2), a * (2), b * (
2)]) was measured, and the color difference ΔEab * was determined by the following calculation formula and evaluated in the following four stages. X is a difficult level to use.
ΔEab * = √ ((L * (2)-L * (1)) ² + (a * (2)-a * (1)) ² + (b * (2)-b * (1)) ² )

A: ΔEab * is less than 1.0
A: ΔEab * is 1.5 or more and less than 1.0
○: ΔEab * is 3.0 or more and less than 1.5 ○ △: ΔEab * is 5.0 or more and less than 3.0 ×: ΔEab * is less than 5.0

(Lightness evaluation)
The photosensitive coloring composition (R-1 to 77) is applied onto a 100 mm × 100 mm, 1.1 mm thick glass substrate using a spin coater, dried at 70 ° C. for 20 minutes, and then using an ultrahigh pressure mercury lamp. Then, UV exposure was performed with an integrated light amount of 150 mJ / cm ² and development was performed with an alkaline developer at 23 ° C. to obtain a coated substrate. Subsequently, the coating-film board | substrate was produced by heating at 230 degreeC for 1 hour, and allowing to cool. The chromaticity of the obtained coating film was measured using a microspectrophotometer ("OSP-SP100" manufactured by Olympus Optical Co., Ltd.), and the chromaticity of the blue photosensitive coloring composition (R-1 to 2) substrate was C. Green photosensitive coloring composition (R-7 to 7) when x = 0.141 and y = 0.084 with a light source
7) When the chromaticity of the substrate is x = 0.291 and y = 0.600 with the C light source, the chromaticity of the red photosensitive coloring composition (R-3 to 6) is x = 0.2 with the C light source. Brightness when Y = 0.325, Y (C) was measured. In addition, as an alkaline developer, sodium carbonate 1.5% by weight, sodium hydrogen carbonate 0.5% by weight, an anionic surfactant (“PERILEX NBL” manufactured by Kao Corporation) 8.0% by weight and water 90% by weight. What was used. Judgment criteria are as follows. X is a difficult level to use.
(Blue photosensitive coloring composition)
◎◎: 10.0 or more
：: 9.8 or more and less than 10.0 ○: 9.4 or more and less than 9.8 Δ: 8.9 or more and less than 9.4 ×: less than 8.9 (green photosensitive coloring composition)
◎◎: 60.0 or more
A: 59.5 or more and less than 60.0 ○: 58.5 or more and less than 59.5 Δ: 58.0 or more and less than 58.5 ×: less than 58.0 (red photosensitive coloring composition)
◎◎: 18.2 or higher
A: 18.0 or more to less than 18.2 B: 17.8 or more to less than 18.0 Δ: 17.6 or more to less than 17.8 ×: less than 17.6

(Developability evaluation)
A substrate obtained by applying a photosensitive coloring composition (R-1 to 77) on a glass substrate of 100 mm × 100 mm, 1.1 mm thickness using a spin coater at a rotation speed at which the film thickness after drying becomes 2 μm, After drying at 70 ° C. for 20 minutes, spray development was performed using a sodium carbonate aqueous solution at 23 ° C., and the developability was evaluated in four stages. The alkali developer was 1.5% by weight of sodium carbonate, 0.5% by weight of sodium hydrogen carbonate, 8.0% by weight of an anionic surfactant (“Perex NBL” manufactured by Kao Corporation), and 90% by weight of water. The thing which consists of was used.
The developability evaluation was determined according to the following criteria. X is a difficult level to use.
◎ ◎ ◎: Can be completely removed within 10 seconds ◎ ◎: Over 10 seconds but can be completely removed within 12 seconds ◎: Over 12 seconds but can be completely removed within 15 seconds ○: 15 seconds That can be completely removed within 20 seconds ○ △: over 20 seconds but can be completely removed within 25 seconds Δ: over 25 seconds but can be completely removed within 30 seconds ×: 30 seconds What cannot be completely removed even if it exceeds

(Evaluation of heat resistance of coating film)
The obtained photosensitive coloring composition (R-1 to 77) was applied onto a 100 mm × 100 mm, 1.1 mm thick glass substrate using a spin coater, and then dried at 70 ° C. for 20 minutes. Using a high-pressure mercury lamp, UV exposure was performed with an integrated light amount of 150 mJ / cm ² and development was performed with an alkaline developer at 23 ° C. Subsequently, it was heated at 220 ° C. for 30 minutes and allowed to cool to obtain a coated substrate. After the heat treatment at 220 ° C., the prepared coated substrate was C = 0.640 for the red coloring composition, y = 0.600 for the green coloring composition, and y = 0.060 for the blue coloring composition. To match the chromaticity of.
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. After that, as a heat resistance test, it was heated at 230 ° C. for 1 hour, and the chromaticity ([L * (2), a * (2), b * (
2)]) was measured, and the color difference ΔEab * was determined by the following calculation formula and evaluated in the following four stages. X is a difficult level to use.
ΔEab * = √ ((L * (2)-L * (1)) ² + (a * (2)-a * (1)) ² + (b * (2)-b * (1)) ² )

A: ΔEab * is less than 1.5
○: ΔEab * is 1.5 or more and less than 3.0
Δ: ΔEab * is 3.0 or more and less than 5.0 ×: ΔEab * is 5.0 or more

As shown in Table 10 and Table 11, a basic dispersant and an acidic dispersant are used, and the acidic dispersant is a polyester having a carboxyl group derived from a tricarboxylic anhydride and / or a tetracarboxylic dianhydride. When it has a main chain and a side chain that is a vinyl polymer having a specific structure represented by the general formula (1) to the general formula (4), all of heat resistance, CR, lightness, and viscosity are good. In addition, the developability was remarkably good. When not used, the brightness, CR, and viscosity were extremely low, and the developability was poor. When Example 76 and Examples 101-109 are compared, since the glass transition temperature Tg of a dispersing agent becomes high, so that there is much MMA, it exists in the tendency for heat resistance and a brightness to be favorable. Example 71 and Examples 103 to 105 are preferable because they maintain both excellent heat resistance and lightness while also achieving developability. When Examples 116 to 121 are compared, the higher the acid value, the more the developability tends to be improved. However, Examples 116, 118, and 119 are preferable because they are excellent in all evaluation items. From the results of Examples 133 to 144, it is further preferable in terms of developability to use a resin having a specific structure represented by the general formula (1) to the general formula (4) as the binder resin or the post-addition resin. . Further, when a resin having a photofunctional double bond in the side chain is used as a binder resin or a post-addition resin, it is favorable from the viewpoint of heat resistance.
Moreover, when Example 104 and Examples 126-127 are compared, Example 104 using the basic dispersing agent (DM-1) manufactured using 1,2,2,6,6-pentamethylpiperidyl methacrylate is as follows. Compared to Examples 126 and 127 using basic dispersants (DM-2) and (DM-3) produced using dimethylaminoethyl methacrylate, the lightness and heat resistance are superior. In addition, Examples 128 to 130 having an amine value in the range of 110 to 220 gave better results than Examples 127 and 131 in terms of brightness, viscosity, heat resistance, and CR.
In comparison with these examples, the comparative examples were significantly inferior to the examples in terms of brightness, viscosity, CR, and developability.

<Production of color filter>
A black matrix is patterned on a glass substrate, and a red photosensitive coloring composition (R-6) is applied to the substrate with a spin coater in a C light source (hereinafter also used for green and blue) x = x = 0. 655, y = 0.325 was applied to form a colored film. The film was irradiated with ultraviolet rays of 150 mJ / cm ² 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 220 ° C. for 20 minutes to obtain a red filter segment. Formed. In the same manner, the blue photosensitive coloring composition (R-2) of the present invention was adjusted so that x = 0.291 and y = 0.600. A green filter segment and a blue filter segment were formed using x = 0.141 and y = 0.084 to obtain a color filter.

  By using the photosensitive coloring composition of the present invention, it is possible to produce a color filter with excellent resolution, heat resistance, lightness, and heat resistance without delaying the development speed, and there is no problem with other physical properties. It could be used suitably.

Claims (9)

A color filter coloring composition comprising a pigment, a basic dispersant, an acidic dispersant, a binder resin, and a solvent,
The acidic dispersant is a main chain which is a polyester having a carboxyl group derived from tricarboxylic anhydride and / or tetracarboxylic dianhydride, and from the group represented by the following general formula (1) to general formula (4). An acidic dispersant characterized by having a side chain that is a vinyl polymer having at least one selected structure;
The basic dispersant is a random copolymer having an amine value of 90 to 320 mgKOH / g, obtained by polymerizing an ethylenically unsaturated monomer (d) containing an ethylenically unsaturated monomer having an amino group. A coloring composition for a color filter, comprising:

General formula (1):

(In the general formula (1), n is an integer of 1 to 4, R ₁ represents hydrogen or a methyl group, X is a direct bond or -CR ₆ R ₇ -Z-, and Z is a direct bond or -CR ₈ R ₉ - is represented _by, R 2 to R ₉ is a hydrogen atom, a halogen atom, a phthalimido _group, -CH ₂ CH 2 COOH, substituted or unsubstituted alkenyl group having 2 to 20 carbon atoms, a substituted or unsubstituted A substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, or a substituted or unsubstituted aryl group having 6 to 10 carbon atoms, and —CH ₂ — contained in these groups is —O—, —CO—, or — May be substituted with OCO-,
R ₂ and R ₄ may combine to form an unsaturated double bond, R ₂ and R ₃ and / or R ₄ and R ₅ together form ═CH ₂ , R ₂ and R ₆ and R ₄ and R ₈ may be bonded to each other to form a ring having 6 to 10 carbon atoms, and “*” represents a bond. )

General formula (2):

(In General Formula (2), n represents an integer of 1 to 4, W ₁ represents CR ₁₁ or a nitrogen atom, W ₂ represents CR ₁₄ or a nitrogen atom, Y represents —COOH, —SO ₃ H, R ₁₀ represents hydrogen or a methyl group, and R _{11 to} R ₁₄ represent a hydrogen atom, a halogen atom, a nitro group, an ethynyl group, —SO ₃ H, —COOH, —COCl, —NHCOCH ₃ , substituted or unsubstituted carbon. Represents an alkyl group having 1 to 20, R ₁₁ and R ₁₂ , R ₁₂ and R ₁₃ , R ₁₃ and R ₁₄ may be bonded to each other to form a ring having 6 to 10 carbon atoms; Indicates a bond.)

General formula (3):


(In General Formula (3), n represents an integer of 1 to 3, R ₁₅ represents hydrogen or a methyl group, and R _{16 to} R ₂₅ represent a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms. R ₁₇ and R ₁₉ and / or R ₂₃ and R ₂₅ may combine with each other to form a ring containing an unsaturated double bond, and R ₁₇ and R ₂₃ combine with each other to form a ring. ("*" Indicates a bond)

General formula (4):

(In General Formula (4), n represents an integer of 1 to 3, R ₂₆ represents hydrogen or a methyl group, R ₃₁ represents a hydrogen atom or a methyl group, R _{27 to} R ₃₀ represent a hydrogen atom, a halogen atom, A nitro group, —COOH, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, and “*” represents a bond.) The coloring composition for a color filter according to claim 1, wherein the ethylenically unsaturated monomer having an amino group is an ethylenically unsaturated monomer (d1) having an N, N-dialkylamino group. object. The ethylenically unsaturated monomer having an amino group is an ethylenically unsaturated monomer (d2) having a hindered amine skeleton represented by the following general formula (10): The coloring composition for color filters as described.
General formula (10):

(In the general formula (10), R ₃₂ is a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aralkyl group having 7 to 12 carbon atoms, an acyl group, an oxy radical group, or OR. represents _35, R ₃₅ represents a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aralkyl group or an acyl group, having 7 to 12 carbon atoms, R _33, and R ₃₄ Each independently represents a methyl group, an ethyl group, or a phenyl group, and “*” represents a bond.) The colored composition for a color filter according to any one of claims 1 to 3, wherein the vinyl polymer (a) has an acid value of 10 to 100 mgKOH / g. The side chain of the acidic dispersant has a structure represented by the general formula (1) and / or the general formula (2), and R _{2 to} R _{5 in} the general formula (1) are hydrogen, The colored composition for a color filter according to claim 1, wherein R _{11 to} R _{14 in the} formula (2) are hydrogen. The colored composition for a color filter according to any one of claims 1 to 5, wherein the binder resin has at least one structure selected from the group represented by the general formula (1) to the general formula (4). . The pigment is a halogenated zinc phthalocyanine pigment, an aluminum phthalocyanine pigment, C.I. I. Pigment Yellow 138, C.I. I. Pigment Yellow 139, C.I. I. Pigment Yellow 150, and C.I. I. The coloring composition for a color filter according to any one of claims 1 to 6, wherein the coloring composition is at least one pigment selected from Pigment Yellow 185. The coloring composition for a color filter according to any one of claims 1 to 7, further comprising an active energy ray-curable monomer and / or an active energy ray polymerization initiator.   The color filter formed with the coloring composition for color filters in any one of Claims 1-8.