JP2015007802A - Coloring composition for color filter, and color filter - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a coloring composition for a color filter which is excellent in dispersibility, flowability, storage stability, and developability.SOLUTION: A coloring composition for a color filter contains a polyester dispersant (X), a pigment, a binder resin, an active energy ray curable monomer, an active energy ray polymerization initiator, and a solvent. The polyester dispersant (X) is obtained by reacting a hydroxyl group in polyol, which is obtained by radical polymerization of an ethylenically unsaturated monomer containing an ethylenically unsaturated monomer having an ether group in the presence of a compound having two hydroxyl groups and one thiol group in the molecule, and contains a vinyl polymer having two hydroxyl groups in one terminal region, with an acid anhydride group of a tricarboxylic acid anhydride and/or a tetracarboxylic acid anhydride.

Description

  TECHNICAL FIELD The present invention relates to a color filter coloring composition used for forming a filter segment constituting a color filter used in a color liquid crystal display device and a solid-state imaging device, and a color filter obtained using the color filter coloring composition. .

  In the liquid crystal display device, a liquid crystal layer sandwiched between two polarizing plates controls the amount of light passing through the first polarizing plate by controlling the degree of polarization of light passing through the first polarizing plate. Is a display device that performs display. By providing a color filter between these two polarizing plates, color display is possible, and in recent years it has come to be used in televisions, personal computer monitors, etc., so there is a demand for higher brightness and higher contrast for color filters. Is growing.

  A color filter has two or more kinds of fine band (striped) filter segments arranged in parallel or intersecting with each other on the surface of a transparent substrate such as glass, or the fine filter segments are arranged in a fixed arrangement. It is made up of arranged ones. The filter segments are as fine as several microns to several hundreds of microns, and are regularly arranged in a predetermined arrangement for each hue.

  In general, in a color liquid crystal display device, a transparent electrode for driving liquid crystal is formed on a color filter by vapor deposition or sputtering, and an alignment film for aligning 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 light resistance and heat resistance as a colorant is mainly used.

  In general, however, it is difficult to obtain a stable dispersion by dispersing fine pigment particles in a pigment carrier such as a varnish, and the dispersion often increases in viscosity due to aggregation of the pigment particles over time, resulting in thixotropic properties. As shown. Such an increase in viscosity and poor fluidity of the composition cause various problems in manufacturing operations and product value. For example, the filter segment of a color filter is generally formed by applying a colored composition in which a pigment is dispersed in a carrier containing a monomer and a resin on a transparent substrate such as glass. If a coloring composition with poor coating properties is used, a coating film having a uniform film thickness cannot be obtained due to poor coating properties, poor leveling, or the like.

  Therefore, as a method for stabilizing a dispersion using a pigment, many proposals have been made so far. For example, a method using a surfactant (see Patent Document 1) or a method using a resin-type dispersant ( Improvement by a dispersing agent such as a method using a polymer dispersing agent in which an organic dye and a polymer are bonded (see Patent Document 3) has been proposed.

  The present inventors have also provided a coloring composition for a color filter which is excellent in dispersibility and storage stability and has a high contrast ratio by applying a polyester dispersant having a specific structure (Patent Document 4). reference).

  Here, the colored filter segments constituting the color filter are coated with a photosensitive material on a glass substrate and the like, and after removing excess solvent by drying, proximity exposure (ultraviolet light source exposure) is performed through a photomask for forming the filter segment. ) And the like, and a portion to be a filter segment is cured, and an unexposed portion is dissolved and removed (developed) with a solvent, an alkaline solution or the like. By repeating this for each color, a color filter is produced. Recently, however, a coloring composition for a color filter having a higher development speed has been demanded in order to improve productivity.

JP 2000-98608 A JP 2000-95992 A JP-A-4-139262 JP 2008-298967 A

  An object of the present invention is to provide a color composition color filter for a color filter that is excellent in dispersibility, fluidity, and storage stability, and further excellent in developability.

The subject is a coloring composition for a color filter comprising a pigment, a dispersant, a binder resin, an active energy ray-curable monomer, an active energy ray polymerization initiator, and a solvent,
The dispersant is
Ethylenic unsaturation comprising an ethylenically unsaturated monomer (b1) having an ether group represented by the following general formula (1) in the presence of a compound (a1) having two hydroxyl groups and one thiol group in the molecule A hydroxyl group in the polyol (a) comprising a vinyl polymer (a2) having two hydroxyl groups in one terminal region, obtained by radical polymerization of the monomer (b);
An acid anhydride group of tricarboxylic anhydride (c1) and / or tetracarboxylic dianhydride (c2);
It is solved by the coloring composition for color filters characterized by being polyester dispersing agent (X) formed by making this react.

  General formula (1):

(In the general formula (1), R ¹ is a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms which may have a substituent, and 1 carbon atom which may have a substituent. -20 alkenyl group or a phenyl group which may have a substituent, R ² is a linear or branched alkylene group having 1 to 8 carbon atoms, R ³ is a hydrogen atom, Or a methyl group, and n is an integer of 1 to 30.)

  Further, the present invention is characterized in that the ethylenically unsaturated monomer (b1) having an ether group is 20 to 100% by weight based on the total weight of the ethylenically unsaturated monomer (b). It is related with the coloring composition for said color filters.

  The present invention also relates to the colored composition for a color filter, wherein the ethylenically unsaturated monomer (b1) having an ether group is 2-methoxyethyl (meth) acrylate.

  Moreover, this invention relates to the said coloring composition for color filters formed by containing a pigment derivative.

  Furthermore, this invention relates to the color filter characterized by including the filter segment formed using the said coloring composition for color filters.

  The coloring composition for a color filter of the present invention can provide a coloring composition for a color filter that suppresses the aggregation of the pigment and is excellent in the stability of the dispersion and also has excellent developability.

  First, the coloring composition for a color filter of the present invention will be described.

The color filter coloring composition of the present invention is a color filter coloring composition comprising a pigment, a dispersant, a binder resin, an active energy ray-curable monomer, an active energy ray polymerization initiator, and a solvent. And
The dispersant is
Ethylenic unsaturation comprising an ethylenically unsaturated monomer (b1) having an ether group represented by the following general formula (1) in the presence of a compound (a1) having two hydroxyl groups and one thiol group in the molecule A hydroxyl group in the polyol (a) comprising a vinyl polymer (a2) having two hydroxyl groups in one terminal region, obtained by radical polymerization of the monomer (b);
An acid anhydride group of tricarboxylic anhydride (c1) and / or tetracarboxylic dianhydride (c2);
The greatest feature is that it is a polyester dispersant (X) obtained by reacting.

  General formula (1):

(In the general formula (1), R ¹ is a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms which may have a substituent, and 1 carbon atom which may have a substituent. -20 alkenyl group or a phenyl group which may have a substituent, R ² is a linear or branched alkylene group having 1 to 8 carbon atoms, R ³ is a hydrogen atom, Or a methyl group, and n is an integer of 1 to 30.)

  In general, a pigment dispersant has a structure of a part that adsorbs to a pigment and a part that has a high affinity for a pigment carrier and a solvent that is a dispersion medium, and the performance of the dispersant is determined by the balance of these two parts. That is, in order to develop dispersibility, both the ability of the dispersant to adsorb to the pigment and the affinity to the pigment carrier and the solvent as the dispersion medium are very important. The pigment carrier referred to here comprises a resin and its precursor or a mixture thereof obtained by removing the pigment component and the dispersant from the solid content.

  <Polyester dispersant (X)> The polyester dispersant (X) used in the present invention comprises a main chain polycarboxylic acid site (C) as a pigment adsorbing group and a side chain vinyl polymer site (B) as a pigment carrier. By acting as an affinity group, the dispersion of the pigment is suppressed and the stability of the dispersion is excellent, and the vinyl polymer portion (B) in the side chain has an ether group as shown in the general formula (1). By copolymerizing the ethylenically unsaturated monomer (b1), it is possible to provide a color filter coloring composition having excellent developability. First, each component of the polyester dispersant (X) of the present invention will be described.

[Compound (a1) having two hydroxyl groups and one thiol group in the molecule] As the compound (a1) having two hydroxyl groups and one thiol group in the molecule used in the present invention, 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-2-methyl-1, Examples include 3-propanediol, 2-mercaptoethyl-2-ethyl-1,3-propanediol, and the like.

  [Ethylenically Unsaturated Monomer (b1) Having Ether Group] The ethylenically unsaturated monomer (b1) is a monomer represented by the following general formula (1).

  General formula (1):

(In the general formula (1), R ¹ is a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms which may have a substituent, and 1 carbon atom which may have a substituent. -20 alkenyl group or a phenyl group which may have a substituent, R ² is a linear or branched alkylene group having 1 to 8 carbon atoms, R ³ is a hydrogen atom, Or a methyl group, and n is an integer of 1 to 30.)

In the general formula (1), specific examples of R ¹ include methyl group, ethyl group, n-butyl group, 2-ethylhexyl group, lauryl group (dodecyl group), palmityl group (hexadecyl group), stearyl group (octadecyl group). ), An isostearyl group, an undecenyl group, an oleyl group, a cyclohexyl group, a dicyclohexyl group, a dicyclohexyl group, a phenyl group, a nonylphenyl group, or a paracumylphenyl group, but is not limited thereto.

In the general formula (1), specific examples of R ² include ethylene group, ethylene group and propylene group, propylene group, ethylene group and tetramethylene group, tetramethylene group, hexamethylene group, and octamethylene group. However, it is not limited to these.

In the general formula (1), specific examples of R ³ include a hydrogen atom or a methyl group.

As an example of the ethylenically unsaturated monomer (b1) having an ether group represented by the general formula (1), when R ¹ is methyl, methoxyethyl (meth) acrylate, methoxypolyethylene glycol (meta ) Acrylate, methoxypolypropylene glycol (meth) acrylate, methoxypolytetramethylene glycol (meth) acrylate, or methoxypolyethylene glycol polypropylene glycol (meth) acrylate, and the like may be commercially available, or synthesized as appropriate. It may be what you did.

As a commercial product made by NOF Corporation, the brand name Blemmer,
PME-100 (n≈2), 200 (n≈4), 400 (n≈9), 550 (n≈12), or 100 (n≈23) or the like methoxypolyethylene glycol monomethacrylate [also known as polyethylene glycol monomethyl ether Methacrylate]; octoxy polyethylene glycol polypropylene glycol monomethacrylate such as 50POEP-800B (n≈8, 6) [also known as polyethylene glycol polypropylene glycol mono 2-ethylhexyl ether methacrylate];
Lauroxy polyethylene glycol monomethacrylate [also known as polyethylene glycol monolauryl ether methacrylate] such as PLE-200 (n≈4);
Stearoxy polyethylene glycol monomethacrylate [also known as polyethylene glycol monostearyl ether methacrylate] such as PSE-400 (n≈9) or PSE-1300 (n≈30);
Phenoxy polyethylene glycol monomethacrylate [also known as polyethylene glycol monophenyl ether methacrylate] such as PAE-50 (n≈1) or PAE-100 (n≈2);
Phenoxy polyethylene glycol polypropylene glycol monomethacrylate [also known as polyethylene glycol polypropylene glycol monophenyl ether methacrylate] such as 43PAPE-600B (n≈6, 6);
Polyethylene glycol monomethyl ether acrylate [also known as methoxypolyethylene glycol acrylate] such as AME-400 (n≈9);
Lauroxy polyethylene glycol monoacrylate [aka polyethylene glycol monolauryl ether acrylate] such as ALE series;
Nonylphenoxypolyethylene glycol monoacrylate [also known as polyethylene glycol monononylphenyl ether acrylate] such as AE-1300 (n≈30);
Nonylphenoxy polypropylene glycol monoacrylate such as ANP-300 (n≈5) [also known as polypropylene glycol monononyl phenyl ether acrylate];
Nonylphenoxy polyethylene glycol polypropylene glycol monoacrylate [also known as polyethylene glycol polypropylene glycol monononyl phenol ether acrylate] such as 75ANEP-600;
Phenoxy polyethylene glycol monoacrylate [also known as polyethylene glycol monophenyl ether acrylate] such as AAE-50 (n = 1) or AAE-300 (n≈5.5);
As a commercial product made by Shin-Nakamura Chemical Co., Ltd., the trade name NK ester,
Methoxypolyethylene glycol metallates [also known as polyethylene glycol monomethyl ether methacrylate] such as M-20G (n≈2), M-90G (n≈9), or M-230G (n≈23);
Phenoxyethylene glycol metallate such as PHE-G [also known as phenoxyethyl methacrylate];
Phenoxy (poly) ethylene glycol acrylate ([also known as (poly) ethylene glycol monophenyl ether acrylate] such as AMP-10G (n≈1) or AMP-20GY (n≈2);
Methoxy polyethylene glycol acrylate such as AM-30G (n≈3), AM-90G (n≈9), AM-130G (n≈13), or AM-230G (n≈23) [also known as polyethylene glycol monomethyl ether acrylate] Or
As a commercial product made by Toagosei Chemical Industry Co., Ltd., the trade name Aronix,
Phenol EO-modified acrylate such as M-101A (n≈2) or M-102 (n≈4) [also known as polyethylene glycol monophenyl ether acrylate];
Paracumylphenol EO-modified acrylates such as M-110 (n≈1) [also known as (poly) ethylene glycol monoparacumyl phenyl ether acrylate];
Nonylphenol EO-modified acrylate such as M-111 (n≈1) or M-113 (n≈4) [also known as polyethylene glycol monononyl phenyl ether acrylate];
Nonylphenol PO-modified acrylate [also known as polypropylene glycol monononylphenyl ether acrylate] such as M-117 (n≈2.5); or
2-ethylhexyl carbitol acrylate [also known as diethylene glycol mono 2-ethylhexyl ether acrylate] such as M-120 (n = 2);
Commercial products manufactured by Kyoeisha Chemical Co., Ltd.
BO (n-butoxyethyl methacrylate), BC (n-butoxydiethylene glycol methacrylate), MTG (methoxytriethylene glycol methacrylate), 130MA (methoxypolyethylene glycol methacrylate, n≈9), 041MA (methoxypolyethylene glycol methacrylate, n≈30) Or PO (2-phenoxyethyl methacrylate), or trade name light acrylate,
BO-A (n-butoxyethyl acrylate), EC-A (ethoxydiethylene glycol acrylate), MTG-A (methoxytriethylene glycol acrylate) 130A (methoxypolyethylene glycol acrylate, n≈9), DPM-A (methoxydipropylene glycol) Acrylate), PO-A (phenoxyethyl acrylate), P-200A (phenoxypolyethylene glycol acrylate), NP-4EA (nonylphenol EO adduct acrylate, also known as nonylphenoxypolyethylene glycol acrylate, n≈4), or NP-8EA (nonylphenol) EO adduct acrylate, also known as nonylphenoxypolyethylene glycol acrylate, n≈8), or
As a commercial product made by Osaka Organic Chemical Industry Co., Ltd.,
2-MTA (2-methoxyethyl acrylate), 2-ETA (2-ethoxyethyl acrylate), or the trade name biscoat,
MTG (methoxytriethylene glycol acrylate), # 190 (ethyl carbitol acrylate, also known as diethylene glycol monoethyl ether acrylate), or # 192 (phenoxyethyl acrylate), or
As a commercial product made by Sartomer,
SR-256 [2- (2-ethoxyethoxy) ethyl acrylate, also known as diethylene glycol monoethyl ether acrylate], SR-339A [2-phenoxyethyl acrylate], or SR-504 [ethoxylated nonylphenol acrylate, also known as nonylphenoxy polyethylene glycol acrylate ] Etc. are mentioned.

  These ethylenically unsaturated monomers (b1) having an ether group may be only one type or two or more types.

  Of these, methoxyethyl (meth) acrylate is particularly preferred from the viewpoint of developability.

[Ethylenically unsaturated monomer having no ether group (b2)]
Examples of the ethylenically unsaturated monomer (b2) having no ether group include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, Isobutyl (meth) acrylate, 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, isomyristyl (meth) acrylate, stearyl (meth) acrylate, or isostearyl (meth) Linear or branched alkyl (meth) acrylates such as acrylate;
Cyclohexyl (meth) acrylate, Tertiarybutylcyclohexyl (meth) acrylate, Dicyclopentanyl (meth) acrylate, Dicyclopentanyloxyethyl (meth) acrylate, Dicyclopentenyl (meth) acrylate, Dicyclopentenyloxyethyl (meth) ) Acrylates or cyclic alkyl (meth) acrylates such as isobornyl (meth) acrylate;
Fluoroalkyl (meth) acrylates such as trifluoroethyl (meth) acrylate, octafluoropentyl (meth) acrylate, perfluorooctylethyl (meth) acrylate, or tetrafluoropropyl (meth) acrylate;
(Meth) acryloxy-modified polydimethylsiloxanes (silicone macromers);
(Meth) acrylates having a heterocyclic ring such as tetrahydrofurfuryl (meth) acrylate or 3-methyl-3-oxetanyl (meth) acrylate;
Benzyl (meth) acrylate, phenoxyethyl (meth) acrylate, phenoxypolyethylene glycol (meth) acrylate, paracumylphenoxyethyl (meth) acrylate, paracumylphenoxypolyethylene glycol (meth) acrylate, or nonylphenoxypolyethylene glycol (meth) acrylate, etc. (Meth) acrylates having the following aromatic ring;
(Meth) acrylic acid, acrylic acid dimer, 2- (meth) acryloyloxyethyl phthalate, 2- (meth) acryloyloxypropyl phthalate, 2- (meth) acryloyloxyethyl hexahydrophthalate, 2- (meth) (Meth) acrylates having a carboxyl group such as acryloyloxypropyl hexahydrophthalate, ethylene oxide-modified succinic acid (meth) acrylate, β-carboxyethyl (meth) acrylate, or ω-carboxypolycaprolactone (meth) acrylate;
Vinyls such as styrene, α-methylstyrene, vinyl acetate, vinyl (meth) acrylate, or allyl (meth) acrylate;
N-substituted types such as (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N, N-diethyl (meth) acrylamide, N-isopropyl (meth) acrylamide, diacetone (meth) acrylamide, or acryloylmorpholine ) Acrylamides;
Amino group-containing (meth) acrylates such as N, N-dimethylaminoethyl (meth) acrylate or N, N-diethylaminoethyl (meth) acrylate;
Nitriles such as (meth) acrylonitrile; or a mixture thereof.

  Other than ethylenically unsaturated monomers (b1) having an ether group represented by the general formula (1) such as vinyl ethers such as ethyl vinyl ether, n-propyl vinyl ether, isopropyl vinyl ether, n-butyl vinyl ether, and isobutyl vinyl ether The ethylenically unsaturated monomer having an ether group can also be copolymerized with the monomer (b1).

[Vinyl polymer (a2)]
The vinyl polymer (a2) having two hydroxyl groups at one end used in the present invention is obtained by converting a compound (a1) having two hydroxyl groups and one thiol group in the molecule into a target vinyl polymer (a2). The ethylenically unsaturated monomer (b1) having an ether group and the ethylenically unsaturated monomer (b2) having no ether group and a polymerization initiator are optionally mixed and heated in accordance with the molecular weight of Can be obtained. The compound (a1) having two hydroxyl groups and one thiol group includes the weight of the ethylenically unsaturated monomer (b1) having an ether group and the ethylenically unsaturated monomer (b2) having no ether group. ) Is preferably used for bulk polymerization or solution polymerization, more preferably 2 to 9% by weight, still more preferably 3 to 8% by weight based on the total monomer weight of the total weight of %. If it is less than 1% 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 may decrease. Yes, if it 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 it is difficult to suppress the aggregation of the pigment It may become.

  The ethylenically unsaturated monomer (b1) having an ether group is preferably 20 wt% to 100 wt%, more preferably 35 wt% to 80 wt%, based on the weight of the total ethylenically unsaturated monomer (b). % By weight. When it is 20% by weight or more, the developability is remarkably improved.

  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 1,000 to 15,000, more preferably 2000 to 13,000, and still more preferably 3,000 to 12,000. This site becomes an affinity site for the pigment carrier and the solvent. If the weight average molecular weight of the vinyl polymer part (a2) is less than 1,000, the steric repulsion effect may be lost as an affinity part for the pigment carrier and the solvent, and it may be difficult to suppress pigment aggregation. . On the other hand, if it exceeds 15,000, the absolute amount increases as an affinity site for the pigment carrier and the solvent, and the dispersibility effect itself may decrease. 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.

  At the time of polymerization, the total monomer weight, which is the sum of the weight of the ethylenically unsaturated monomer (b1) having an ether group and the weight of the ethylenically unsaturated monomer (b2) having no ether group, As a standard, 0.001 to 5% by weight of a polymerization initiator can be arbitrarily used. 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.

[Other polyols]
In the present invention, an ethylenically unsaturated monomer (b1) having an ether group and an ethylenically unsaturated monomer having no ether group in the presence of a compound (a1) having two hydroxyl groups and one thiol group in the molecule. A polyol other than the vinyl polymer (a2) having two hydroxyl groups at one end formed by radical polymerization of the monomer (b2) can be used in any proportion.

  As such a polyol, it is possible to use a well-known thing, and if only a typical thing is illustrated especially among them, it will belong to the following groups (1)-(7). There is something. By using a polyol compound other than the vinyl polymer (a2) in combination, it becomes easy to adjust the density of the carboxylic acid group and the ratio of the solvent dissolving part.

  (1) ethylene glycol, propylene glycol, 1,3-propanediol, 1,4-butanediol, 1,3-butanediol, 1,5-pentanediol, neopentyl glycol, 1,6-hexanediol, 1, 4-bis (hydroxymethyl) cyclohesan, bisphenol A, hydrogenated bisphenol A, hydroxypivalylhydroxypivalate, trimethylolethane, trimethylolpropane, 2,2,4-trimethyl-1,3-pentanediol, glycerin, or Polyhydric alcohols such as hexanetriol;

  (2) Various polyethers such as polyoxyethylene glycol, polyoxypropylene glycol, polyoxyethylene polyoxytetramethylene glycol, polyoxypropylene polyoxytetramethylene glycol, or polyoxyethylene polyoxypropylene polyoxytetramethylene glycol Glycols;

  (3) Various polyhydric alcohols and various (cyclic) ether bonds such as ethylene oxide, propylene oxide, tetrahydrofuran, ethyl glycidyl ether, propyl glycidyl ether, butyl glycidyl ether, phenyl glycidyl ether, or allyl glycidyl ether Modified polyether polyols obtained by ring-opening polymerization with compounds;

  (4) Polyester polyols obtained by co-condensation with one or more of the various polyhydric alcohols described above and polycarboxylic acids, wherein the polycarboxylic acids are succinic acid, adipic acid, sebacic acid, Azelaic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, maleic acid, fumaric acid, citraconic acid, itaconic acid, glutaconic acid, 1,2,5-hexanetricarboxylic acid, 1,4-cyclohexanehycarboxylic acid, 1 , 2,4-benzenetricarboxylic acid, 1,2,5-benzenetricarboxylic acid, 1,2,4-cyclohexatricarboxylic acid, 2,5,7-naphthalenetricarboxylic acid, etc. Resulting polyols;

  (5) A lactone obtained by a polycondensation reaction between one or more of the various polyhydric alcohols described above and various lactones such as ε-caprolactone, δ-valerolactone, or 3-methyl-δ-valerolactone. Lactone-based polyester polyols, or lactone-modified polyester polyols obtained by polycondensation reaction of the above-described various polyhydric alcohols with polyvalent carboxylic acids or various lactones; or

  (6) Various epoxy compounds such as bisphenol A type epoxy compounds, hydrogenated bisphenol A type epoxy compounds, glycidyl ethers of monohydric and / or polyhydric alcohols, or glycidyl esters of monobasic acids and / or polybasic acids. , Epoxy-modified polyester polyols obtained by using one or more in combination during the synthesis of the polyester polyol;

  (7) Polyester polyamide polyol, polycarbonate polyol, polybutadiene polyol, polypentadiene polyol, castor oil, castor oil derivative, hydrogenated castor oil, hydrogenated castor oil derivative, hydroxyl group-containing acrylic copolymer, hydroxyl group-containing fluorine-containing compound, or hydroxyl group-containing silicon resin Etc.

  The other polyols optionally added shown in (1) to (7) may be used alone or in combination of two or more, but the weight average molecular weight is compatible or dispersed. From the viewpoint of stability, it is preferably 40 to 10,000, more preferably 100 to 2,000, and still more preferably 100 to 1,000. When the weight average molecular weight is less than 40, there is no effect of improving the compatibility and dispersion stability, and when the weight average molecular weight is 10,000 or more, the compatibility may be deteriorated.

  The number of hydroxyl groups in one molecule of other polyol is not particularly limited as long as the intended dispersant can be synthesized, but diol (a3) is preferred. In particular, by reacting with tetracarboxylic dianhydride (c1), carboxyl groups serving as pigment adsorbing groups can be regularly arranged in the main chain, which is advantageous for pigment dispersion. If a polyol having more than two hydroxyl groups is used in a large amount, the main chain of the polyester will be branched to increase the complexity and shade, making it difficult to obtain a dispersion effect. It should be kept to a minimum from the viewpoint of design, for example, for adjusting the molecular weight of the polyester dispersant and adjusting the viscosity of the dispersion. The blending amount will be described later.

[Tetracarboxylic acid anhydride (c2)]
The two anhydride groups of the tetracarboxylic dianhydride (c1) used in the present invention react with the hydroxyl groups of the polyol (a), thereby regulating the carboxyl groups that serve as pigment adsorbing groups in the main chain of the polyester dispersant. This is advantageous for pigment dispersion.

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 An aliphatic tetracarboxylic dianhydride such as bicyclo [2,2,2] -oct-7-ene-2,3,5,6-tetracarboxylic dianhydride, or
Pyromellitic dianhydride, ethylene glycol 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 Anhydride, 3,3 ′, 4,4′-biphenyl ether tetracarboxylic dianhydride, 3,3 ′, 4,4′-dimethyldiphenylsilane tetracarboxylic dianhydride, 3,3 ′, 4,4 '-Tetraphenylsilanetetracarboxylic dianhydride, 1,2,3,4-furantetracarboxylic dianhydride, 4,4'-bis (3,4-dicarboxyl) Phenoxy) diphenyl sulfide 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 (Triphenylphthalic acid) -4,4′-diphenylmethane dianhydride, 9,9-bis (3,4-dicarboxyphenyl) fluorene dianhydride 9,9-bis [4- (3,4-dicarboxyphenoxy) f · BR> Fnyl] fluorene dianhydride, 3,4-dicarboxy-1,2,3,4-tetrahydro-1-naphthalene succinate Examples include acid dianhydrides or aromatic tetracarboxylic dianhydrides such as 3,4-dicarboxy-1,2,3,4-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 forms a dispersant having two carboxyl groups in one unit of polyester by reaction with a polyol. From the viewpoint of pigment adsorptivity, the component of the polyester dispersant of the present invention is as follows. preferable.

  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 (2) or general formula (3).

  General formula (2):

[In general formula (2), k is 1 or 2. ]

  General formula (3):

[In General Formula (3), Q ₁ is a direct bond, —O—, —CO—, —COOCH ₂ CH ₂ OCO—, —SO ₂ —, —C (CF ₃ ) ₂ —, General Formula (4) :

Or a group represented by the general formula (5):

It is group represented by these. ]

  Further, a compound having one carboxylic anhydride group in the molecule or a compound having three or more carboxylic acid anhydride groups is used in combination, that is, tetracarboxylic dianhydride (c) contained in the polycarboxylic acid anhydride (c) used in the present invention ( Polycarboxylic acid anhydrides (c) other than c2) can also be used.

  Polycarboxylic acid anhydrides other than tetracarboxylic dianhydride (c2) contained in polycarboxylic acid anhydride (c) used in the present invention are dicarboxylic acid anhydride (c3) and tricarboxylic acid anhydride (c1). An anhydride (c4) of a compound having 5 or more carboxylic acids can be mentioned. From the viewpoint of adsorptivity to pigments, two carboxyl groups are formed in one unit of the polyester dispersant by reaction with a polyol in the design of the polyester dispersant. The tricarboxylic acid anhydride (c1) from which the group is formed is preferred.

  Examples of the tricarboxylic acid anhydride (c1) include an aliphatic tricarboxylic acid anhydride or an aromatic tricarboxylic acid anhydride.

  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 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, or 3,4,4'-biphenyl Sulfonic tricarboxylic acid anhydride and the like.

  Of these, aromatic tricarboxylic acid anhydrides are preferably used in the present invention from the viewpoint of adsorptivity to pigments.

[Synthesis of polyester]
First, the process of synthesizing the polyester of the polyester dispersant of the present invention will be described by taking the reaction of diol (a3) and tetracarboxylic dianhydride (c2) as an example.

The tetracarboxylic dianhydride (c2) used in the present invention can react with a hydroxyl group to form an ester bond and leave a pendant carboxyl group on the resulting polyester main chain. When the molar amount of the diol (a3) having two hydroxyl groups is a, the molar amount of the tetracarboxylic dianhydride is c, i) a> c, ii) a = c, and iii) a <c Reactions of tetracarboxylic dianhydride (c2) and diol (a3) are shown in the following general formulas (6), (7), and (8). If the acid anhydride group remaining in the products of the following general formulas (6) to (8) is hydrolyzed, the product of this reaction will have two or three carboxyl groups in the X ₁ moiety in the structural formula. The plurality of carboxyl groups are effective as pigment adsorption sites.

  i) a> c

  General formula (6):

  ii) a = c

  General formula (7):

  iii) a <c

  General formula (8):

However, when only one carboxyl group is bonded to X ₁ (outside the scope of the present invention), high dispersibility, fluidity, and storage stability are not exhibited, which is not preferable.

In the present invention, X ₁ is a reaction residue after the tetracarboxylic dianhydride has reacted with a hydroxyl group, and Y is a reaction residue after the polyol compound has reacted with an acid anhydride group. The form of X ₁ is preferably a reaction residue after the tetracarboxylic dianhydride represented by the following general formula (9) or general formula (10) has reacted with the polyol compound.

  General formula (9):

[In General Formula (9), k is 1 or 2. ]

  General formula (10):

[In General Formula (10), Q ₁ represents a direct bond, —O—, —CO—, —COOCH ₂ CH ₂ OCO—, —SO ₂ —, —C (CF ₃ ) ₂ —, General Formula (11) :

Or a group represented by the general formula (12):

It is group represented by these. ]

[Synthesis of the polyester dispersant of the present invention]
In the polyester dispersant of the present invention, the vinyl polymer (a2) is introduced into Y in the diol (a3) via an S atom in the description of the synthesis of the polyester represented by the general formulas (6) to (8). It is a thing.

  Here, five main synthesis patterns are shown.

Synthesis pattern 1)
In the following general formula (13), an ethylenically unsaturated monomer (b1) having an ether group and an ethylene having no ether group are present in the presence of a compound (a1) having two hydroxyl groups and one thiol group at one end. Synthetic Pattern 1 by Radical Polymerization of the Polyunsaturated Unsaturated Monomer (b2) to Generate a Vinyl Polymer (a2) Having Two Hydroxyl Groups at One End and Reaction with Tetracarboxylic Acid Dianhydride (c2) It is. Theoretically, the molar ratio of (a2) is a (integer), the molar ratio of (c2) is c (integer), and c = a-1, so that no acid anhydride group remains from the viewpoint of stability. This is the case where the terminal is a hydroxyl group. The molecular weight is adjusted by changing a.

  General formula (13):

  In actual synthesis, a is often excessive from the theoretical value so that no acid anhydride remains. When c> a and the acidic group is increased, the anhydride group is hydrolyzed with a necessary amount of water and used. The molar ratio of the hydroxyl group of the vinyl polymer (a2) having two hydroxyl groups at one end to the acid anhydride group of the tetracarboxylic dianhydride (c2) is 2c / 2a = c / a = 0.3 to 1.2 is preferred. If it is less than 0.3, the number of acid anhydride residues in one molecule decreases and adsorption to the pigment becomes insufficient, and if it exceeds 1.2, an acid anhydride group remains, which causes a problem in storage stability. In many cases, even when hydrolyzed, the acidic group becomes excessive and the compatibility with the pigment carrier or solvent is deteriorated. From the viewpoint of pigment dispersibility and stability, c / a = 0.4 to 0.8 is more preferable.

Synthesis pattern 2)
In the following general formula (14), an ethylenically unsaturated monomer (b1) having an ether group and ethylene having no ether group in the presence of a compound (a1) having two hydroxyl groups and one thiol group at one end Is a synthetic pattern 2 in which a vinyl polymer (a2) having two hydroxyl groups at one end is produced by radical polymerization of the unsaturated monomer (b2), and this is reacted with a tricarboxylic acid anhydride (c1). . Theoretically, the molar ratio of (a2) is a (integer), the molar ratio of (c1) is β (integer), β = a, and a hydroxyl group is left at the terminal. The molecular weight is adjusted by changing a.

  General formula (14):

  The molar ratio between the hydroxyl group of the vinyl polymer (a2) having two hydroxyl groups at one end and the acid anhydride group of the tricarboxylic anhydride (c1) is preferably β / 2a = 0.3-1. If it is less than 0.3, there will be less acid anhydride residues in one molecule and adsorption to the pigment will be insufficient, and if it exceeds 1, acid anhydride groups will remain, causing problems in storage stability. However, even when hydrolyzed, the acidic group becomes excessive and the compatibility with the pigment carrier and the solvent deteriorates. From the viewpoint of pigment dispersibility and stability, β / 2a = 0.4 to 0.8 is more preferable.

Synthesis pattern 3)
In the following general formula (15), an ethylenically unsaturated monomer (b1) having an ether group and an ethylene having no ether group are present in the presence of a compound (a1) having two hydroxyl groups and one thiol group at one end. The radically unsaturated monomer (b2) is radically polymerized to form a vinyl polymer (a2) having two hydroxyl groups at one end, and this, other diol (a3), and tetracarboxylic dianhydride (c2 Is a synthesis pattern 3 obtained by reacting an acid anhydride group of From the viewpoint of stability, the molar amount of (a2) is a (integer), the molar amount of (a3) is α (integer), the molar amount of (c2) is c (integer), and c = a + α−1. This is a case where the terminal is a hydroxyl group so that no anhydride group remains. The molecular weight, solubility, and carboxyl group density are adjusted by changing the type of other diol (a3) and the ratio of a and α.

  General formula (15):

  When actually synthesizing, (a + α) is often excessive from the theoretical value so that no acid anhydride remains. When c> (a + α) and the acidic group is increased, the anhydride group is hydrolyzed with a necessary amount of water and used. The molar ratio of the hydroxyl group of the vinyl polymer (a2) and other diol (a3) having two hydroxyl groups at one end to the acid anhydride group of the tetracarboxylic dianhydride (c2) is 2c / 2 (a + α ) = C / (a + α) = 0.3 to 1.2. If it is less than 0.3, the number of acid anhydride residues in one molecule decreases and adsorption to the pigment becomes insufficient, and if it exceeds 1.2, an acid anhydride group remains, which causes a problem in storage stability. In many cases, even when hydrolyzed, the acidic group becomes excessive and the compatibility with the pigment carrier or solvent is deteriorated. From the viewpoint of pigment dispersibility and stability, c / (a + α) = 0.4 to 0.8 is more preferable.

  a = 0 is outside the scope of the present invention because there is no vinyl polymer part (a2). The other diol (a3) is used to adjust the molecular weight, viscosity, or compatibility of the polyester dispersant. When another diol (a3) is used as in (Synthesis pattern 3), the molar ratio between the other diol (a3) and the vinyl polymer (a2) having two hydroxyl groups at one end is α / a = 0.1-2.0 are preferable. If it is less than 0.1, there is no effect of using the diol (a3), and if it exceeds 2.0, the density of the vinyl polymer portion (a2) becomes low, which adversely affects the dispersibility.

Synthesis pattern 4)
In the following general formula (16), an ethylenically unsaturated monomer (b1) having an ether group and ethylene having no ether group are present in the presence of a compound (a1) having two hydroxyl groups and one thiol group at one end. The radically unsaturated monomer (b2) is radically polymerized to form a vinyl polymer (a2) having two hydroxyl groups at one end, and this is mixed with a tricarboxylic acid anhydride (c1) and a tetracarboxylic acid dianhydride ( It is the synthetic pattern 4 which made the acid anhydride group of c2) react. In this case, the molar amount of (a2) is a, the molar amount of (c2) is c, the molar amount of (c1) is β, c = a−1, and β = 1. The molecular weight of the main chain is adjusted by changing a, and one end becomes a polycarboxylic acid site by tricarboxylic acid (c1).

  General formula (16):

  When c ≠ 0 and β = 2, both ends are polycarboxylic acid sites. Further, a = 0 is outside the scope of the present invention because there is no vinyl polymer part.

  In actual synthesis, a is often excessive from the theoretical value so that no acid anhydride remains. When (2c + β)> 2a and the acidic group is increased, the anhydride group is used after being hydrolyzed with a necessary amount of water. However, since the tricarboxylic acid anhydride (c1) is monofunctional, in theory, when a = c + 1 and β ≦ 2, the polyester terminal reaction is stopped by (c1), so that no acid anhydride group remains. The molar ratio of the hydroxyl group of the vinyl polymer (a2) having two hydroxyl groups at one end to the acid anhydride groups of tetracarboxylic dianhydride (c2) and tricarboxylic acid (c1) is (2c + β) / 2a = 0.3-1.2 are preferable. If it is less than 0.3, the number of acid anhydride residues in one molecule decreases and adsorption to the pigment becomes insufficient, and if it exceeds 1.2, an acid anhydride group remains, which causes a problem in storage stability. In many cases, even when hydrolyzed, the acidic group becomes excessive and the compatibility with the pigment carrier or solvent is deteriorated. From the viewpoint of pigment dispersibility and stability, (2c + β) /2a=0.4 to 0.8 is more preferable.

  The tricarboxylic acid anhydride (c1) is used for adjusting the molecular weight of the polyester dispersant and the absolute amount of the polycarboxylic acid site, such as making the terminal of the polyester dispersant a polycarboxylic acid site. When tricarboxylic acid anhydride (c1) is used as in (Synthesis pattern 4), the molar ratio of tricarboxylic acid anhydride (c1) to tetracarboxylic acid dianhydride (c2) is β / c = 0.1. To 10 is preferred. If it is less than 0.1, there are few polyesters which have a polycarboxylic acid site | part at the terminal, and the effect of using a tricarboxylic acid anhydride (c1) together is not acquired. When it exceeds 10, the balance between the length of the polyester main chain, the number of polycarboxylic acid sites, and the number of vinyl polymer sites is deteriorated, and the dispersion stability is often deteriorated. β / c = 0.5-3 is preferable.

Synthesis pattern 5)
In the following general formula (17), an ethylenically unsaturated monomer (b1) having an ether group and an ethylene having no ether group are present in the presence of a compound (a1) having two hydroxyl groups and one thiol group at one end. Radically polymerizing the unsaturated monomer (b2) to produce a vinyl polymer (a2) having two hydroxyl groups at one end, and this and the other diol (a3), tricarboxylic acid anhydride (c1), and It is the synthetic pattern 5 which made the acid anhydride group of tetracarboxylic dianhydride (c2) react. The molar amount of (a2) is a (integer), the molar ratio of (a3) is α (integer), the molar ratio of (c2) is c, the molar ratio of (c1) is β, c = a + α-1, β = 1, when a> c. The molecular weight and properties of the main chain are adjusted by changing the ratio of a and α, and the end of the main chain becomes a polycarboxylic acid site by the tricarboxylic acid anhydride (c1).

  Formula (17):

  When c ≠ 0 and β = 2, both ends are polycarboxylic acid sites. Further, a = 0 is outside the scope of the present invention because there is no vinyl polymer part.

  When actually synthesizing, (a + α) is often excessive from the theoretical value so that no acid anhydride remains. When (2c + β)> (2a + 2α) and an acidic group is increased, an anhydride group is hydrolyzed with a necessary amount of water and used. However, since the tricarboxylic acid anhydride (c1) is monofunctional, in theory, when (a + α) = c + 1 and β ≦ 2, since the polyester terminal reaction is stopped by (c1), no acid anhydride group remains. Mole of hydroxyl group of vinyl polymer (a2) and other diol (a3) having two hydroxyl groups at one end and acid anhydride group of tetracarboxylic dianhydride (c2) and tricarboxylic anhydride (c1) The ratio is preferably (2c + β) / (2a + 2α) = 0.3 to 1.2. If it is less than 0.3, the number of acid anhydride residues in one molecule decreases and adsorption to the pigment becomes insufficient, and if it exceeds 1.2, an acid anhydride group remains, which causes a problem in storage stability. In many cases, even when hydrolyzed, the acidic group becomes excessive and the compatibility with the pigment carrier or solvent is deteriorated. From the viewpoint of pigment dispersibility and stability, (2c + β) / (2a + 2α) = 0.4 to 0.8 is more preferable.

  a = 0 is outside the scope of the present invention because there is no vinyl polymer part. The other diol (a3) is used to adjust the molecular weight, viscosity, or compatibility of the polyester dispersant. When another diol (a3) is used as in (Synthesis pattern 5), the molar ratio between the other diol (a3) and the vinyl polymer (a2) having two hydroxyl groups at one end is α / a = 0.1-2.0 are preferable. If it is less than 0.1, there is no effect of using the diol (a3), and if it exceeds 2.0, the density of the vinyl polymer portion (a2) becomes low, which adversely affects the dispersibility.

  The tricarboxylic acid anhydride (c1) is used for adjusting the molecular weight of the polyester dispersant and the absolute amount of the polycarboxylic acid site, such as making the terminal of the polyester dispersant a polycarboxylic acid site. When tricarboxylic anhydride (c1) is used as in (Synthesis pattern 5), the molar ratio of tricarboxylic anhydride (c1) to tetracarboxylic dianhydride (c2) is β / c = 0.1. To 10 is preferred. If it is less than 0.1, there are few polyesters which have a polycarboxylic acid site | part at the terminal, and the effect of using a tricarboxylic acid anhydride (c1) together is not acquired. When it exceeds 10, the balance between the length of the polyester main chain, the number of polycarboxylic acid sites, and the number of vinyl polymer sites is deteriorated, and the dispersion stability is often deteriorated. β / c = 0.5-3 is preferable.

[Reaction catalyst]
As the catalyst used for the production of the polyester and the polyester dispersant (X) of the present invention, known catalysts 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 the polyester dispersant (X) of the present invention can be produced using only the raw materials listed so far, 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 weight average molecular weight of the obtained polyester 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 weight average molecular weight is less than 2000, the stability of the pigment composition may be reduced, and if it exceeds 35,000, the interaction between the resins becomes strong and the viscosity of the color composition for color filter may increase. is there.

[Acid value]
As for the acid value of the obtained polyester dispersing agent (X), 5-200 are preferable. More preferably, it is 10-150, More preferably, it is 20-100. If the acid value is less than 5, the pigment adsorbing ability may be reduced and the pigment dispersibility may be problematic, and if it exceeds 200, the interaction between the resins may become strong and the viscosity of the pigment dispersion composition may be increased.

As above
In the presence of a compound (a1) having two hydroxyl groups and one thiol group in the molecule, an ethylenically unsaturated monomer (b1) having an ether group and an ethylenically unsaturated monomer having no ether group ( a hydroxyl group in the polyol (a) containing at least a vinyl polymer (a2) having two hydroxyl groups at one end formed by radical polymerization of b2);
An acid anhydride group of tricarboxylic anhydride (c1) and / or tetracarboxylic dianhydride (c2);
To obtain a polyester dispersant (X).

  As shown in the general formula (18), the polyester dispersant (X) of the present invention has a plurality of polycarboxylic acid sites serving as pigment adsorbing portions in the main chain and a plurality of solvents and pigment carriers having high affinity as side chains. Therefore, it is suitable for dispersing fine pigments. For this reason, it is suitably used in fields requiring high dispersibility such as color filters. Moreover, as an ethylenically unsaturated monomer which comprises a vinyl polymer (a2), the ethylenically unsaturated monomer (b1) which has an ether group, and the ethylenically unsaturated monomer (b2) which does not have an ether group By using this, aptitude excellent in developability can be exhibited.

  Formula (18):

  The content of the polyester dispersant (X) in the color filter coloring composition is preferably 0.01 to 100% by weight, more preferably 0.01 to 60% by weight, still more preferably, based on the weight of the pigment. 5 to 40% by weight. When the content of the polyester dispersant (X) is less than 0.01% by weight, the dispersion effect is insufficient, and when it exceeds 100% by weight, the dispersibility may be deteriorated.

<Pigment>
As a pigment contained in the coloring composition for a color filter of the present invention, organic or inorganic pigments can be used alone or in admixture of two or more. Among the pigments, pigments having high color developability and high heat resistance, particularly pigments having high heat decomposition resistance are preferred, and organic pigments are usually used.

  Below, the specific example of the organic pigment which can be used for the coloring composition for color filters of this invention is shown with a color index number.

  For example, CI Pigment Red 7, 9, 14, 41, 48: 1, 48: 2, 48: 3, 48: 4, 81: 1, may be used as a coloring composition for a red color filter to form a red filter segment. 81: 2, 81: 3, 97, 122, 123, 146, 149, 168, 177, 178, 179, 180, 184, 185, 187, 192, 200, 202, 208, 210, 215, 216, 217, Red pigments such as 220, 223, 224, 226, 227, 228, 240, 246, 254, 255, 264, 272, or 279 can be used. A yellow pigment and an orange pigment can be used in combination with the coloring composition for a red color filter.

  Examples of the coloring composition for yellow color filter for forming the yellow filter segment include CI Pigment Yellow 1, 2, 3, 4, 5, 6, 10, 12, 13, 14, 15, 16, 17, 18, 20, 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, 86, 93, 94, 95, 97, 98, 100, 101, 104, 106, 108, 109, 110, 113, 114, 115, 116, 117, 118, 119, 120, 123, 125, 126, 127, 128, 129, 137, 138, 139, 147, 148, 150, 151, 152, 153, 154, 155, 156, 161, 162, 16 166, 167, 168, 169, 170, 171, 172, 173, 174, 175, 176, 177, 179, 180, 181, 182, 185, 187, 188, 193, 194, 199, 213, 214, etc. The yellow pigment can be used.

  For example, an orange pigment such as CI Pigment orange 36, 43, 51, 55, 59, 61, 71, or 73 can be used as the coloring composition for the orange color filter for forming the orange filter segment. .

  As a coloring composition for a green color filter for forming a green filter segment, for example, a green pigment such as C.I. Pigment Green 7, 10, 36, 37, or 58 can be used. A yellow pigment can be used in combination with the coloring composition for a green color filter.

  Examples of the coloring composition for blue color filter for forming the blue filter segment include CI Pigment Blue 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, 16, 22, 60, Blue pigments such as 64 and 80 can be used. Among these, C.I. Pigment Blue 15, 15: 1, 15: 2, 15: 3, 15: 4, or 15: 6, which is a copper phthalocyanine-based blue pigment, is preferable. Purple pigments such as C.I. Pigment Violet 1, 19, 23, 27, 29, 30, 32, 37, 40, 42, or 50 can be used in combination with the coloring composition for the blue color filter.

  For example, CI Pigment Blue 15: 1, 15: 2, 15: 4, 15: 3, 15: 6, or 16, 81 or the like is used as a coloring composition for cyan color filter for forming a cyan filter segment. Pigments can be used.

  For the magenta color filter coloring composition for forming the magenta color filter segment, for example, a purple pigment and a red pigment such as CI Pigment Violet 1, 19, CI Pigment Red 81, 144, 146, 177, or 169 are used. Can do. A yellow pigment can be used in combination with the coloring composition for a magenta color filter.

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

  The coloring composition for a color filter of the present invention may contain a dye within a range that does not decrease heat resistance for color matching.

<Binder resin>
The binder resin is a resin having a 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. Examples of the resin include a thermoplastic resin, a thermosetting resin, and a photosensitive resin.

  Examples of the thermoplastic resin include butyral resin, styrene-maleic acid copolymer, chlorinated polyethylene, chlorinated polypropylene, polyvinyl chloride, vinyl chloride-vinyl acetate copolymer, polyvinyl acetate, polyurethane resin, and polyester resin. , Acrylic resins, alkyd resins, polystyrene, polyamide resins, rubber resins, cyclized rubber resins, celluloses, polyethylene, polybutadiene, or polyimide resins. 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.

  Examples of the photosensitive resin include (meth) acrylic compounds and silicate resins having a reactive substituent such as an isocyanate group, an aldehyde group, or an epoxy group in a polymer having a reactive substituent such as a hydroxyl group, a carboxyl group, or an amino group. A resin obtained by reacting an acid and introducing a photocrosslinkable group such as a (meth) acryloyl group or a styryl group into the polymer 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-treated with a (meth) acrylic compound having a hydroxyl group such as hydroxyalkyl (meth) acrylate. An esterified product is also used.

  The pigment carrier preferably contains an alkali-soluble non-photosensitive resin when a filter segment is formed by alkali development using the color filter coloring composition of the present invention. The alkali-soluble non-photosensitive resin is a resin that dissolves in an alkaline aqueous solution and does not crosslink with radicals. For example, a weight average molecular weight of 1,000 to 500,000 having an acidic functional group such as a carboxyl group or a sulfone group is preferable. May include 5,000-100,000 resins. Specific examples of the alkali-soluble non-photosensitive resin include an acrylic resin having an acidic functional group, an α-olefin / (anhydrous) maleic acid copolymer, a styrene / (anhydrous) maleic acid copolymer, and a styrene / styrene sulfone. Examples thereof include an acid copolymer, an ethylene / (meth) acrylic acid copolymer, and an isobutylene / (anhydrous) maleic acid copolymer. Among them, at least one selected from the group consisting of an acrylic resin having an acidic functional group, an α-olefin / (anhydrous) maleic acid copolymer, a styrene / (anhydrous) maleic acid copolymer, and a styrene / styrene sulfonic acid copolymer. A seed resin, particularly an acrylic resin having an acidic functional group, is preferably used because of its high heat resistance and transparency.

  <Active energy ray-curable monomer> The active energy ray-curable monomer contained in the color filter coloring composition of the present invention is an ethylenic resin that is cured by irradiation with active energy rays to form a resin. It means a compound having an unsaturated double bond, and the monomer includes a low polymer having an average molecular weight of less than 1000, generally called an oligomer, and having an ethylenically unsaturated double bond.

As an active energy ray-curable monomer,
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, or isostearyl (meth) acrylate;
Cyclohexyl (meth) acrylate, Tertiarybutylcyclohexyl (meth) acrylate, Dicyclopentanyl (meth) acrylate, Dicyclopentanyloxyethyl (meth) acrylate, Dicyclopentenyl (meth) acrylate, Dicyclopentenyloxyethyl (meth) ) Acrylates or cyclic alkyl (meth) acrylates such as isobornyl (meth) acrylate;
Fluoroalkyl (meth) acrylates such as trifluoroethyl (meth) acrylate, octafluoropentyl (meth) acrylate, perfluorooctylethyl (meth) acrylate, or tetrafluoropropyl (meth) acrylate;
(Meth) acryloxy-modified polydimethylsiloxanes (silicone macromers);
(Meth) acrylates having a heterocyclic ring such as tetrahydrofurfuryl (meth) acrylate or 3-methyl-3-oxetanyl (meth) acrylate;
Benzyl (meth) acrylate, phenoxyethyl (meth) acrylate, phenoxypolyethylene glycol (meth) acrylate, paracumylphenoxyethyl (meth) acrylate, paracumylphenoxypolyethylene glycol (meth) acrylate, or nonylphenoxypolyethylene glycol (meth) acrylate, etc. (Meth) acrylates having the following aromatic ring;
2-methoxyethyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, 3-methoxybutyl (meth) acrylate, 2-methoxypropyl (meth) acrylate, diethylene glycol monomethyl ether (meth) acrylate, diethylene glycol monoethyl ether (meta ) Acrylate, triethylene glycol monomethyl ether (meth) acrylate, triethylene glycol monoethyl ether (meth) acrylate, diethylene glycol mono-2-ethylhexyl ether (meth) acrylate, dipropylene glycol monomethyl ether (meth) acrylate, tripropylene glycol mono (Meth) acrylate, polyethylene glycol monolauryl ether (meth) acrylate, or polyester Glycol monostearyl ether (meth) acrylate of (poly) alkylene glycol monoalkyl ether (meth) acrylates;
(Meth) acrylic acid, acrylic acid dimer, 2- (meth) acryloyloxyethyl phthalate, 2- (meth) acryloyloxypropyl phthalate, 2- (meth) acryloyloxyethyl hexahydrophthalate, 2- (meth) (Meth) acrylates having a carboxyl group such as acryloyloxypropyl hexahydrophthalate, ethylene oxide-modified succinic acid (meth) acrylate, β-carboxyethyl (meth) acrylate, or ω-carboxypolycaprolactone (meth) acrylate;
2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 2-acryloyloxyethyl-2-hydroxyethyl (meth) Phthalate, diethylene glycol mono (meth) acrylate, dipropylene glycol mono (meth) acrylate, polyethylene glycol mono (meth) acrylate, propylene glycol mono (meth) acrylate, polyp-BR> BRS lenglycol mono (meth) acrylate, polytetra Methylene glycol mono (meth) acrylate, poly (ethylene glycol-propylene glycol) mono (meth) acrylate, poly (ethylene glycol-tetramethylene glycol) mono (me (Meth) acrylates having a hydroxyl group such as acrylate), poly (propylene glycol-tetramethylene glycol) mono (meth) acrylate, or glycerol (meth) acrylate;
Ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate, tri Propylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, poly (ethylene glycol-propylene glycol) di (meth) acrylate, poly (ethylene glycol-tetramethylene glycol) di (meth) acrylate, poly (propylene glycol- Tetramethylene glycol) di (meth) acrylate, polytetramethylene glycol di (meth) acrylate, 1,3-butanediol di (Meth) acrylate, neopentyl glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate, or 2-ethyl, 2-butyl-propanediol di ( (Poly) alkylene glycol di (meth) acrylates such as (meth) acrylate; dimethylol dicyclopentane di (meth) acrylate, hydroxypivalic acid neopentyl glycol di (meth) acrylate, stearic acid-modified pentaerythritol di (meth) acrylate , Ethylene oxide modified bisphenol A di (meth) acrylate, propylene oxide modified bisphenol A di (meth) acrylate, tetramethylene oxide modified bisphenol A di (meth) acrylate, ethylene Xoxide modified bisphenol F di (meth) acrylate, propylene oxide modified bisphenol F di (meth) acrylate, tetramethylene oxide modified bisphenol F di (meth) acrylate, zinc diacrylate, ethylene oxide modified phosphate triacrylate, or glycerol di (meth) ) Di (meth) acrylates such as acrylate;
(Meth) acrylates having a tertiary amino group such as dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, dimethylaminopropyl (meth) acrylate, or diethylaminopropyl (meth) acrylate;
Glycerol tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, or dipentaerythritol hexa (meth) acrylate Trifunctional or higher polyfunctional (meth) acrylates such as
Glycerol triglycidyl ether- (meth) acrylic acid adduct, glycerol diglycidyl ether- (meth) acrylic acid adduct, polyglycerol polyglycidyl ether- (meth) acrylic acid adduct, 1,6-butanediol diglycidyl ether, Alkyl glycidyl ether- (meth) acrylic acid adduct, allyl glycidyl ether- (meth) acrylic acid adduct, phenyl glycidyl ether- (meth) acrylic acid adduct, styrene oxide- (meth) acrylic acid adduct, bisphenol A di Glycidyl ether- (meth) acrylic acid adduct, propylene oxide-modified bisphenol A diglycidyl ether- (meth) acrylic acid adduct, bisphenol F diglycidyl ether- (meth) acrylic acid adduct, epichlorohydride -Modified phthalic acid- (meth) acrylic acid adduct, epichlorohydrin-modified hexahydrophthalic acid- (meth) acrylic acid adduct, ethylene glycol diglycidyl ether- (meth) acrylic acid adduct, polyethylene glycol diglycidyl ether- (meta ) Acrylic acid adduct, propylene glycol diglycidyl ether- (meth) acrylic acid adduct, polypropylene glycol diglycidyl ether- (meth) acrylic acid adduct, phenol novolac type epoxy resin- (meth) acrylic acid adduct, cresol novolac Type epoxy resin- (meth) acrylic acid adducts, or other epoxy resins- (meth) acrylic acid adducts and other epoxy (meth) acrylates;
(Meth) acryloyl-modified isocyanurate, (meth) acryloyl-modified polyurethane, (meth) acryloyl-modified polyester, (meth) acryloyl-modified melamine, (meth) acryloyl-modified silicone, (meth) acryloyl-modified polybutadiene, or (meth) acryloyl-modified rosin (Meth) acryloyl-modified resin oligomers such as;
Vinyls such as styrene, α-methylstyrene, vinyl acetate, vinyl (meth) acrylate, or allyl (meth) acrylate;
Vinyl ethers such as hydroxyethyl vinyl ether, ethylene glycol divinyl ether, or pentaerythritol trivinyl ether;
Amides such as (meth) acrylamide, N-hydroxymethyl (meth) acrylamide, or N-vinylformamide; or
Examples include acrylonitrile. These can be used alone or in admixture of two or more.

<Active energy ray polymerization initiator>
As an active energy ray polymerization initiator contained in the coloring composition for a color filter of the present invention,
4-phenoxydichloroacetophenone, 4-t-butyl-dichloroacetophenone, diethoxyacetophenone, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, 1-hydroxycyclohexyl phenyl ketone, 2- Such as benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one or 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one An acetophenone-based active energy ray polymerization initiator;
Benzoin-based active energy ray polymerization initiators such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, or benzyldimethyl ketal;
Benzophenone-based active energy ray polymerization initiators such as benzophenone, benzoylbenzoic acid, methyl benzoylbenzoate, 4-phenylbenzophenone, hydroxybenzophenone, acrylated benzophenone, or 4-benzoyl-4′-methyldiphenyl sulfide;
Thioxanthone-based active energy ray polymerization initiators such as thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, isopropylthioxanthone, or 2,4-diisopropylthioxanthone,
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 (trichloro) Methyl) -6-styryl-s-triazine, 2- (naphth-1-yl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4-methoxy-naphth-1-yl) -4 , 6-Bis (trichloromethyl) -s-triazine, 2,4-trichloromethyl- (piperonyl) -6-triazine, or 2,4-trichloromethyl (4′-methoxystyryl) -6 Triazine-based active energy ray polymerization initiators such as triazine;
Borate-based active energy ray polymerization initiators;
A carbazole-based active energy ray polymerization initiator; or
An imidazole-based active energy ray polymerization initiator or the like is used.

  The active energy ray polymerization initiator can be used in an amount of 5 to 200% by weight, preferably 10 to 150% by weight, based on the weight of the pigment in the color filter coloring composition.

These active energy ray polymerization initiators are used alone or in combination of two or more, but as a sensitizer,
α-acyloxy ester, acylphosphine oxide, methylphenylglyoxylate, benzyl, 9,10-phenanthrenequinone, camphorquinone, ethylanthraquinone, 4,4′-diethylisophthalophenone, 3,3 ′, A compound such as 4,4′-tetra (t-butylperoxycarbonyl) benzophenone or 4,4′-diethylaminobenzophenone can also be used in combination.

  The content of the sensitizer can be used in an amount of 0.1 to 60% by weight based on the weight of the active energy ray polymerization initiator in the colored composition.

<Solvent>
In the coloring composition for a color filter of the present invention, a pigment is sufficiently dispersed in a pigment carrier and applied on a transparent substrate such as glass so that a dry film thickness is 0.2 to 5 μm to form a filter segment. A solvent can be included to facilitate the process.

As a solvent, for example,
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, N-methylpyrrolidone, o-xylene, o-chloro Ruene, o-diethylbenzene, o-dichlorobenzene, p-chlorotoluene, p-diethylbenzene, sec-butylbenzene, tert-butylbenzene, γ-butyrolactone, isobutyl alcohol, isophorone, ethylene glycol diethyl ether, ethylene glycol dibutyl ether, ethylene Glycol monoisopropyl ether, ethylene glycol monoethyl ether, ethylene glycol monoethyl ether acetate, ethylene glycol monotertiary butyl ether, ethylene glycol monobutyl ether, ethylene glycol monobutyl ether acetate, ethylene glycol monopropyl ether, ethylene glycol monohexyl ether, ethylene glycol Monomethyl ether, ethylene glycol Monoethyl 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, di Propylene glycol dimethyl ether, dipropylene glycol methyl ether acetate, dipropylene glycol monoethyl ether, dipropylene glycol monobutyl ether, dipropylene glycol monopropyl ether, dipropylene glycol Methyl ether, diacetone alcohol, triacetin, tripropylene glycol monobutyl ether, tripropylene 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 monomethyl ether acetate, propylene glycol monomethyl ether propionate, benzyl alcohol, methyl isobutyl ketone, methyl cyclohexanol, n-amyl acetate, n-butyl acetate, isoamyl acetate, isobutyl acetate , Acetic acid Propyl, or dibasic acid esters and the like, used alone or in combination.

  The coloring composition for a color filter of the present invention comprises a pigment or a pigment composition comprising two or more pigments in a transparent resin, a precursor thereof or a mixture thereof and a solvent together with the polyester dispersant (X). It can be produced by finely dispersing using various dispersing means such as a roll mill, a two-roll mill, a sand mill, a kneader, or an attritor. Moreover, the coloring composition for color filters containing 2 or more types of pigments can also be manufactured by mixing each pigment separately finely dispersed in a pigment carrier and a solvent. When the pigment is dispersed in the transparent resin, its precursor or a mixture thereof, and a solvent, in addition to the polyester dispersant (X), a resin type dispersant other than the polyester dispersant (X), surface activity A dispersing aid such as an agent and a pigment derivative can be contained. Since the dispersion aid is excellent in pigment dispersion and has a great effect of preventing re-aggregation of the pigment after dispersion, the coloring composition for a color filter obtained by dispersing the pigment in a pigment carrier and a solvent using the dispersion aid. When is used, a color filter excellent in transparency can be obtained.

<Other dispersants>
In order to improve the dispersibility of the pigment and the storage stability of the pigment composition or the pigment dispersion, the dispersant of the present invention is used in combination with a known resin type dispersion other than the dispersant of the present invention or a surfactant. You can also

Specifically, as such a known resin-type pigment dispersant,
Styrene-maleic anhydride copolymer, olefin-maleic anhydride copolymer, poly (meth) acrylate, styrene- (meth) acrylic acid copolymer, (meth) acrylic acid- (meth) acrylic acid alkyl ester Copolymer, (meth) acrylic acid-polyvinyl-based macromer copolymer, phosphoric ester group-containing acrylic resin, aromatic carboxyl group-containing acrylic resin, polystyrene sulfonate, acrylamide- (meth) acrylic acid copolymer, carboxymethylcellulose An anionic resin type pigment dispersant such as polyurethane having a carboxyl group, formalin condensate of naphthalene sulfonate, or sodium alginate;
Nonionic resin-type pigment dispersants such as polyvinyl alcohol, polyalkylene polyamine, polyacrylamide, or polymer starch; or
Polyethyleneimine, aminoalkyl (meth) acrylate copolymer, polyvinylimidazoline, polyurethane having amino group, reaction product of poly (lower alkyleneimine) and polyester having free carboxyl group, or cationic resin type pigment such as satkinsan A dispersing agent is mentioned, These can be used individually or in mixture of 2 or more types.

  Specific examples of the known dispersing agent include “Anti-Terra-U (polyaminoamide phosphate)”, “Anti-Terra-203 / 204 (high molecular weight polycarboxylate)” manufactured by BYK Chemie, “Disperbyk-101”. (Salts of long-chain polyaminoamide and polar acid ester), 107 (hydroxyl group-containing carboxylic acid ester), 110, 111 (copolymer containing an acid group), 130 (polyamide), 161, 162, 163, 164, 165 166, 170, 180, or 182 (high molecular weight copolymer) "," Bykumen (high molecular weight unsaturated acid ester) "," BYK-P104, or P105 (high molecular weight unsaturated acid polycarboxylic acid) "," P104S or 240S (high molecular weight unsaturated acid polycarboxylic acid and polysiloxane Mixture) ", or" Lactimon (a mixture of partial amides product and polysiloxanes with long chain amine and an unsaturated acid polycarboxylic acid) "can be mentioned.

  In addition, “Fuka 44, 46, 47, 48, 49, 54, 63, 64, 65, 66, 71, 701, 764, or 766” manufactured by Efka CHEMICALS, or “Efka Polymer 100 (modified polyacrylate), 150” (Aliphatic modified polymer), 400, 401, 402, 403, 450, 451, 452, 453 (modified polyacrylate), or 745 (copper phthalocyanine-based), “Kyoeisha Chemical Co., Ltd.” “Floren TG-710 (urethane oligomer) ) "," Flownon SH-290 or SP-1000 ", or" Polyflow No. 50E or No. 300 (acrylic copolymer) ", or" Disparon KS-860, 873SN, manufactured by Enomoto Kasei Co., Ltd. " 874 (polymer dispersant), # 2150 (aliphatic polyvalent polymer) Bonn acid), or # 7004 (polyether ester type) "can be mentioned.

  Furthermore, “Demol RN, N (Naphthalenesulfonic acid formalin condensate sodium salt), MS, C, SN-B (aromatic sulfonic acid formalin condensate sodium salt) or EP” manufactured by Kao Corporation, “Homogenol L-18 ( Polycarboxylic acid type polymer) "," Emulgen 920, 930, 931, 935, 950, or 985 (polyoxyethylene nonylphenyl ether) "," Acetamine 24 (coconut amine acetate), or 86 (stearyl amine acetate) " "Solspers 5000 (phthalocyanine ammonium salt type), 13940 (polyesteramine type), 17000 (fatty acid amine type), or 24000" manufactured by Lubrizol, "Nikkor T106 (polyoxyethylene sorbitan mono) manufactured by Nikko Chemical Co., Ltd. Rate), MYS-IEX (polyoxyethylene monostearate), or Hexagline 4-0 (hexaglyceryl tetraoleate), or “Ajisper PB821 or PB822 (basic dispersant)” manufactured by Ajinomoto Fine Techno Co., Ltd. Can be mentioned.

Moreover, as a known surfactant,
Polyoxyethylene alkyl ether sulfate, sodium dodecylbenzenesulfonate, alkali salt of styrene-acrylic acid copolymer, sodium alkylnaphthalenesulfonate, sodium alkyldiphenylether disulfonate, lauryl sulfate monoethanolamine, lauryl sulfate triethanolamine, lauryl Anionic surfactants such as ammonium sulfate, monoethanolamine stearate, sodium stearate, sodium lauryl sulfate, monoethanolamine of styrene-acrylic acid copolymer, or polyoxyethylene alkyl ether phosphate;
Nonionic surfactants such as polyoxyethylene oleyl ether, polyoxyethylene lauryl ether, polyoxyethylene nonylphenyl ether, polyoxyethylene alkyl ether phosphate, polyoxyethylene sorbitan monostearate, or polyethylene glycol monolaurate;
Chaotic surfactants such as alkyl quaternary ammonium salts and their ethylene oxide adducts; or
Examples include alkylbetaines such as alkyldimethylaminoacetic acid betaines, and amphoteric surfactants such as alkylimidazolines, and these can be used alone or in admixture of two or more.

  When adding a resin-type pigment dispersant and a surfactant, the amount is preferably 0.1 to 40% by weight, more preferably 0.1 to 30% by weight, based on the weight of the pigment in the coloring composition. When the blending amount of the dispersion aid is less than 0.1% by weight, it is difficult to obtain the added effect. When the blending amount is more than 40% by weight, the dispersion aid is affected by an excessive dispersion aid. is there.

<Dye derivative>
In the coloring composition for a color filter of the present invention, a dye derivative can be used for the purpose of improving the dispersibility of the pigment. Examples of the dye derivative include a compound in which a basic substituent, an acidic substituent, or a phthalimidomethyl group which may have a substituent is introduced into an organic pigment, anthraquinone, acridone, or triazine.

In the present invention, a basic derivative is particularly preferable, and the basic derivative is a compound represented by the following general formula (18), which is a derivative having a specific parent skeleton having a basic group. The dye derivative is not particularly limited as long as it is a dye derivative having a basic group, but a dye derivative having a triazine ring skeleton having a basic group represented by the following general formula (18) can be preferably used.
Formula (19): P-Lm
(However, in general formula (19),
P is an m-valent organic pigment residue, an anthraquinone skeleton, an acridone skeleton, or a triazine skeleton,
m is an integer of 1 to 4,
L is a substituent selected from the group consisting of a substituent represented by the following general formula (20), a substituent represented by the following general formula (21), and a substituent represented by the following general formula (22). )

  Formula (20):

  Formula (21):

  General formula (22):

[However, in general formula (20)-(22),
X _{is, -SO 2 -, - CO -} , - CH 2 -, - CH 2 NHCOCH 2 -, - CH 2 NHSO 2 CH 2 -, or a direct bond,
Y is —NH—, —O—, or a direct bond;
n is an integer of 1 to 10,
Y ¹ is —NH—, —NR ⁵⁸ —Z—NR ⁵⁹ —, or a direct bond;
R ⁵⁸ and R ⁵⁹ are each independently a hydrogen bond, an optionally substituted alkyl group having 1 to 36 carbon atoms, an optionally substituted alkenyl group having 2 to 36 carbon atoms, or A phenyl group which may have a substituent,
Z is an alkylene group which may have a substituent, or an arylene group which may have a substituent,
R ⁵⁰ and R ⁵¹ are each independently a hydrogen atom, an optionally substituted alkyl group having 1 to 30 carbon atoms, an optionally substituted alkenyl group having 2 to 30 carbon atoms, or R ⁵⁰ and R ⁵¹ together are a heterocyclic ring which may further have a substituent containing a further nitrogen, oxygen or sulfur atom,
R ⁵² , R ⁵³ , R ⁵⁴ , and R ⁵⁵ are each independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms that may have a substituent, or 2 to carbon atoms that may have a substituent. 20 alkenyl group, an arylene group having 6 to 20 carbon atoms which may have a substituent,
R ⁵⁶ is a hydrogen atom, an optionally substituted alkyl group having 1 to 20 carbon atoms, an optionally substituted alkenyl group having 2 to 20 carbon atoms,
R ⁵⁷ is a substituent represented by the general formula (20) or a substituent represented by the general formula (21),
Q is a hydroxyl group, an alkoxyl group, a substituent represented by the general formula (20), or a substituent represented by the general formula (21). ]

  Examples of the amine component used to form the substituents represented by the general formulas (20) to (22) include dimethylamine, diethylamine, methylethylamine, N, N-ethylisopropylamine, N, N-ethyl. Propylamine, N, N-methylbutylamine, N, N-methylisobutylamine, N, N-butylethylamine, N, N-tert-butylethylamine, diisopropylamine, dipropylamine, N, N-sec-butylpropylamine , Dibutylamine, di-sec-butylamine, diisobutylamine, N, N-isobutyl-sec-butylamine, diamylamine, diisoamylamine, dihexylamine, dicyclohexylamine, di (2-ethylhexyl) amine, dioctylamine, N, N-methylocta Silamine, didecylamine, diallylamine, N, N-ethyl-1,2-dimethylpropylamine, N, N-methylhexylamine, dioleylamine, distearylamine, N, N-dimethylaminomethylamine, N, N-dimethylamino Ethylamine, N, N-dimethylaminoamylamine, N, N-dimethylaminobutylamine, N, N-diethylaminoethylamine, N, N-diethylaminopropylamine, N, N-diethylaminohexylamine, N, N-diethylaminobutylamine, N , N-diethylaminopentylamine, N, N-dipropylaminobutylamine, N, N-dibutylaminopropylamine, N, N-dibutylaminoethylamine, N, N-dibutylaminobutylamine, N, N-diisobutylamino Nthylamine, N, N-methyl-laurylaminopropylamine, N, N-ethyl-hexylaminoethylamine, N, N-distearylaminoethylamine, N, N-dioleylaminoethylamine, N, N-distearylaminobutylamine, Piperidine, 2-Pipecoline, 3-Pipecoline, 4-Pipecoline, 2,4-Lupetidine, 2,6-Lupetidine, 3,5-Lupetidine, 3-Piperidinmethanol, Pipecolic acid, Isonipecotic acid, Methyl isonipecotate, Isonipecotic acid Ethyl, 2-piperidineethanol, pyrrolidine, 3-hydroxypyrrolidine, N-aminoethylpiperidine, N-aminoethyl-4-pipecholine, N-aminoethylmorpholine, N-aminopropylpiperidine, N-aminopropyl-2-pipecoly N-aminopropyl-4-pipecoline, N-aminopropylmorpholine, N-methylpiperazine, N-butylpiperazine, N-methylhomopiperazine, 1-cyclopentylpiperazine, 1-amino-4-methylpiperazine, or 1-cyclopentyl And piperazine.

  The pigment derivative, anthraquinone derivative, and acridone derivative having a basic substituent of the present invention can be synthesized by various synthetic routes. For example, after introducing the substituents represented by the general formulas (23) to (26) into an organic dye, anthraquinone, or acridone, the substituents represented by the general formulas (20) to (22) react with the above substituents. For example, N, N-dimethylaminopropylamine, N-methylpiperazine, diethylamine, or 4- [4-hydroxy-6- [3- (dibutylamino) propylamino] -1,3. It can be obtained by reacting 5-triazin-2-ylamino] aniline or the like.

Formula (23): -SO ₂ Cl Formula (24): -COCl formula _{(25): -CH 2 NHCOCH 2} Cl Formula (26): -CH ₂ Cl

  In the reaction of the substituents of the general formulas (23) to (26) with the amine component, a part of the substituents of the general formulas (23) to (26) is hydrolyzed and chlorine is substituted with a hydroxyl group. It may be mixed. In that case, the general formula (23) and the general formula (24) are a sulfonic acid group and a carboxylic acid group, respectively, but any of them may be a free acid. Or a salt with a monoamine.

  When the organic dye is an azo dye, the substituent represented by the general formulas (20) to (22) is previously introduced into the diazo component or the coupling component, and then a coupling reaction is performed, thereby performing the azo pigment. Derivatives can also be produced.

  The triazine derivative having a basic group of the present invention can be synthesized by various synthetic routes. For example, starting from cyanuric chloride, an amine component that forms a substituent represented by general formulas (20) to (22) on at least one chlorine of cyanuric chloride, such as N, N-dimethylaminopropylamine or N- It can be obtained by reacting methylpiperazine or the like and then reacting the remaining chlorine of cyanuric chloride with various amines or alcohols.

  In the pigment composition of the present invention, the amount of the pigment derivative having a basic group is preferably 1 to 50% by weight, more preferably 3 to 30% by weight, most preferably 5 based on the weight of the pigment. ~ 25% by weight. If the pigment derivative having a basic group is less than 1% by weight, the effect of addition is difficult to obtain, and if it exceeds 50% by weight, heat resistance and light resistance may be deteriorated.

  Specific examples of the pigment derivative having a basic group of the present invention are shown below with compound numbers, but are not limited thereto.

・ Compound 1

    Formula (27):

[In general formula (27), CuPc is a copper phthalocyanine residue. ]

・ Compound 2
Formula (28):

・ Compound 3

  Formula (29):

Compound 4
Formula (30):

Compound 5

  Formula (31):

<Storage stabilizer>
Moreover, the coloring composition for color filters can contain a storage stabilizer in order to stabilize the viscosity with time of the coloring composition.

Examples of storage stabilizers include:
Quaternary ammonium chlorides such as benzyltrimethylammonium chloride or diethylhydroxyamine hydrochloride;
Organic acids such as lactic acid or oxalic acid;
Methyl ester of the organic acid;
pyrocatechol such as t-butyl pyrocatechol;
An organic phosphine such as tetraethylphosphine or tetraphenylphosphine; or
Examples thereof include phosphite.

<Coloring composition for color filter>
The coloring composition for a color filter of the present invention can be prepared as a coloring composition for a solvent developing type or alkali developing type color filter. The coloring composition for a solvent developing type or alkali developing type color filter generally comprises a thermoplastic resin, a thermosetting resin or a photosensitive resin, an ethylenically unsaturated monomer, a photopolymerization initiator, and an organic solvent. A pigment is dispersed in a composition containing.

  The coloring composition for a color filter of the present invention is mixed with various solvents, resins, additives, and the like as necessary, and dispersed with a horizontal sand mill, a vertical sand mill, an annular bead mill, an attritor, etc. A pigment dispersion obtained by dispersing in a varnish can be prepared. In particular, when a pigment derivative is used, the pigment, the polyester dispersant (X), the pigment derivative, other resins and additives in the present invention may be dispersed after mixing all the components. Disperse only the pigment and the dye derivative, or only the dye derivative and the polyester dispersant (X), or only the pigment, the dye derivative and the polyester dispersant (X), and then add other components. The dispersion may be performed again.

  It can also be produced by mixing several types of pigments separately dispersed on a pigment carrier. The photopolymerization initiator may be added at the stage of preparing the color filter coloring composition, or may be added later to the prepared color filter coloring composition.

  The coloring composition for a color filter of the present invention is a coarse particle of 5 μm or more, preferably a coarse particle of 1 μm or more, more preferably a coarse particle of 0.5 μm or more by means of centrifugation, sintered filter, membrane filter or the like. It is preferable to remove the mixed dust.

<Color filter>
Next, the color filter of the present invention will be described.

  The color filter of the present invention is provided with a filter segment or a black matrix formed from the coloring composition for a color filter of the present invention on a transparent substrate, and a general color filter includes at least one red filter segment, At least one green filter segment and at least one blue filter segment, or at least one magenta filter segment, at least one cyan filter segment, and at least one yellow filter segment.

  The color filter of this invention can be manufactured by forming the filter segment of each color on a board | substrate using the coloring composition of this invention by the photolithographic method. As the substrate, a glass plate having a high transmittance with respect to visible light, or a resin plate such as polycarbonate, polymethyl methacrylate, or polyethylene terephthalate is used.

  The formation of each color filter segment by photolithography is performed by the following method. That is, the color composition for color filter prepared as a color composition for solvent development type or alkali development type color filter is applied to a transparent substrate such as glass by a coating method such as spray coating, spin coating, slit coating or roll coating. It is applied so that the dry film thickness is 0.2 to 10 μm, more preferably 0.2 to 5 μm. When drying the coating film, a vacuum dryer, a convection oven, an IR oven, a hot plate, or the like may be used. 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. Thereafter, the color filter can be manufactured by immersing in a solvent or an alkaline developer, or spraying the developer with a spray or the like to remove an uncured portion to form a desired pattern.

  Furthermore, in order to accelerate | stimulate superposition | polymerization of the coloring composition for color filters, it can also heat as needed. According to the photolithography method, a color filter with higher accuracy than the 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, a film that prevents the inhibition of polymerization by oxygen by applying and drying a water-soluble or alkali-soluble resin such as polyvinyl alcohol or a water-soluble acrylic resin after coating and drying the color filter coloring composition. After forming, UV exposure can also be performed.

  If a black matrix is formed in advance before forming each color filter segment on a transparent substrate or a reflective substrate, the contrast of the liquid crystal display panel can be further increased. As the black matrix, an inorganic film such as chromium, a chromium / chromium oxide multilayer film, titanium nitride, or a resin film in which a light-shielding agent is dispersed may be used. In addition, a thin film transistor (TFT) may be formed in advance on the transparent substrate or the reflective substrate, and then a filter segment may be formed. By forming the filter segment on the TFT substrate, the aperture ratio of the liquid crystal display panel can be increased and the luminance can be improved.

  On the color filter of the present invention, an overcoat film, a columnar spacer, a transparent conductive film, a liquid crystal alignment film, and the like are formed 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 the above.

  Hereinafter, the present invention will be described based on examples, but the present invention is not limited thereto. In the examples and comparative examples, “part” means “part by weight”.

[Manufacture of finer pigments]
(Refinement pigment production example 1)
120 parts of halogenated copper phthalocyanine-based green pigment PG36 (“Lionol Green 6YK” manufactured by Toyo Ink Co., Ltd.), 1500 parts of crushed salt, and 250 parts of diethylene glycol were charged into a 1 gallon kneader (manufactured by Inoue Seisakusho) at 60 ° C. And kneading for 15 hours. The mixture was put into 5000 parts of warm water, stirred at a high speed mixer for about 1 hour while being heated to about 70 ° C. to form a slurry, filtered and washed repeatedly to remove salt and solvent, and then at 80 ° C. for 24 hours. It dried and obtained 117 parts refined pigment (G-1).

(Refinement pigment production example 2)
100 parts of quinophthalone-based yellow pigment PY138 (“Pariotol Yellow K0961HD” manufactured by BASF), 3 parts of a dye derivative (compound 2), 800 parts of crushed salt and 180 parts of diethylene glycol are added to a 1 gallon kneader (manufactured by Inoue Seisakusho) made of stainless steel. The mixture was kneaded at 70 ° C. for 4 hours. The mixture was added to 3000 parts of warm water, stirred at a high speed mixer for about 1 hour while being heated to about 80 ° 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 refined pigment (Y-1).

(Refinement pigment production example 3)
100 parts of diketopyrrolopyrrole red pigment PR254 ("Irgafoa Red B-CF" manufactured by Ciba Specialty Chemicals), 10 parts of pigment derivative (Compound 5), 1000 parts of crushed salt, and 120 parts of diethylene glycol, 1 gallon made of stainless steel The mixture was charged into a kneader (manufactured by Inoue Seisakusho) and kneaded at 70 ° C. for 8 hours. The mixture was poured into 2000 parts of warm water, stirred at a high speed mixer for about 1 hour while being heated to about 80 ° 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 100 parts refined pigment (R-1).

(Fine refined pigment production example 4)
100 parts of anthraquinone red pigment PR177 (“Chromophthal Red A2B” manufactured by Ciba Specialty Chemicals), 5 parts of a pigment derivative (compound 4), 800 parts of crushed salt, and 180 parts of diethylene glycol are made of 1 gallon kneader made of stainless steel (manufactured by Inoue Seisakusho). And kneaded at 70 ° C. for 5 hours. The mixture was poured into 4000 parts of warm water, stirred at a high speed mixer for about 1 hour while being heated to about 80 ° 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 100 parts refined pigment (R-2).

(Fine refined pigment production example 5)
500 parts of a metal complex yellow pigment PY150 (“E4GN” manufactured by LANXESS), 2500 parts of sodium chloride, and 250 parts of diethylene glycol were charged into a stainless gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 100 ° C. for 6 hours. Next, the kneaded product is put into 5 liters 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 at 80 ° C. for 24 hours. It dried and obtained 98 parts of micronized pigment (Y-2).

(Fine refined pigment production example 6)
100 parts of copper phthalocyanine blue pigment PB15: 6 (“Lionol Blue ES” manufactured by Toyo Ink Co., Ltd.), 5 parts of a pigment derivative (Compound 1), 1000 parts of crushed salt, and 100 parts of diethylene glycol were added to a 1 gallon kneader made of stainless steel ( Prepared by Inoue Seisakusho) and kneaded at 50 ° C. for 12 hours. The mixture was added to 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 refined pigment (B-1).

(Refinement Pigment Production Example 7)
300 parts of dioxazine-based purple pigment PV23 (“Rionogen Violet RL” manufactured by Toyo Ink Manufacturing Co., Ltd.) was added to 3000 parts of 96% sulfuric acid, stirred for 1 hour, and poured into 5 ° C. water. After stirring for 1 hour, it was filtered, washed with warm water until the washing solution became neutral, and dried at 70 ° C. 120 parts of the obtained acid pasting pigment, 5 parts of a dye derivative (compound 3), 1500 parts of crushed salt and 100 parts of diethylene glycol were charged into a stainless steel 1 gallon kneader (Inoue Seisakusho) and kneaded at 70 ° C. for 20 hours. did. The mixture was poured into 5000 parts of warm water, stirred at a high-speed mixer for about 1 hour while being heated to about 70 ° C. to form a slurry, filtered and washed repeatedly to remove salt and solvent, and then at 80 ° C. for 24 hours. It dried and obtained 115 parts refined pigment (V-1).

[Manufacture of binder resin solution]
370 parts of propylene glycol monomethyl ether acetate (PGMAC) is placed in a reaction vessel, heated to 80 ° C. while injecting nitrogen gas into the vessel, and a mixture of the following monomer and thermal polymerization initiator is added dropwise at the same temperature over 1 hour. The polymerization reaction was carried out.

Methacrylic acid 13.0 parts
2-hydroxyethyl methacrylate 14.0 parts
Glycerol monomethacrylate 25.0 parts
Benzyl methacrylate 25.0 parts
Butyl methacrylate 23.0 parts
2,2'-azobisisobutyronitrile 4.0 parts

  After completion of the dropwise addition, the mixture was further reacted at 80 ° C. for 3 hours, and then 1.0 part of azobisisobutyronitrile dissolved in 50 parts of propylene glycol monomethyl ether acetate (PGMAC) was added. The reaction was continued for a time to obtain a copolymer solution. After cooling to room temperature, about 2 g of the alkali-soluble resin solution is sampled and heated and dried at 180 ° C. for 20 minutes to measure the non-volatile content, so that the non-volatile content in the previously synthesized alkali-soluble resin solution is 20 wt% Propylene glycol monomethyl ether acetate (PGMAC) was added. The obtained non-photosensitive transparent resin had a weight average molecular weight of 32,000 and an acid value of 78.

(Production Example 1 of polyester dispersant X1)
A reaction vessel equipped with a gas introduction tube, a thermometer, a condenser, and a stirrer was charged with 50.0 parts of methyl methacrylate and 50.0 parts of 2-methoxyethyl acrylate, and replaced with nitrogen gas. The inside of the reaction vessel was heated to 80 ° C., and 6.0 parts of 3-mercapto-1,2-propanediol and 0.1 part of 2,2′-azobisisobutyronitrile were added to propylene glycol monomethyl ether acetate 45. The solution dissolved in 4 parts was added and reacted for 10 hours. It was confirmed that 95% had reacted by solid content measurement. At this time, the weight average molecular weight was 4000. Next, 9.7 parts of pyromellitic dianhydride (manufactured by Daicel Chemical Industries, Ltd.), 31.7 parts of PGMAc, and 1,8-diazabicyclo- [5.4.0] -7-undecene 0.2 as a catalyst An additional portion was added and reacted at 120 ° C. for 7 hours. The reaction was terminated after confirming that 98% or more of the acid anhydride had been half-esterified by measuring the acid value. After completion of the reaction, propylene glycol monomethyl ether acetate was added so as to have a nonvolatile content of 60% by weight to obtain a solution of polyester dispersant X1 having an acid value of 43 mgKOH / g and a weight average molecular weight of 9,500.

The raw materials used in the examples are listed below.
[Ethylenically unsaturated monomer having ether group (b1)] 2-MTA: 2-methoxyethyl acrylate Blemmer PME100 (manufactured by NOF Corporation) BREMMER 50POEP-800B (manufactured by NOF Corporation)

  [Ethylenically unsaturated monomer having no ether group (b2)] MMA: methyl methacrylate EA: ethyl acrylate MAA: methacrylic acid n-BMA: n-butyl acrylate BzMA: benzyl methacrylate t-BMA : T-butyl acrylate

  [Compound having two hydroxyl groups and one thiol group in the molecule (a1)] thioglycerol: 3-mercapto-1,2-propanediol

  [Radical polymerization initiator] AIBN: 2,2'-azobisisobutyronitrile

[Organic solvent] ・ PGMAC: Propylene glycol monomethyl ether acetate [Tetracarboxylic acid dianhydride (c2)] ・ PMA: Pyromellitic dianhydride (manufactured by Daicel Chemical Industries) ・ TMA: Trimellitic anhydride

  [Esterification reaction catalyst] DBU: 1,8-diazabicyclo- [5.4.0] -7-undecene (manufactured by San Apro Co., Ltd.)

  [Active energy ray-curable monomer] M-402; Aronix M-402: Dipenter erythritol pentaacrylate / dipentaerythritol hexaacrylate (manufactured by Toagosei Co., Ltd.)

  [Active energy ray polymerization initiator] Irgacure 907: 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one (manufactured by Ciba Geigy)

[Sensitizer] EAB-F: 4,4′-bis (diethylamino) benzophenone (Hodogaya Chemical Co., Ltd.) (Production Examples 2 to 8 of polyester dispersant (X2 to X8))
The synthesis was carried out in the same manner as in Production Example 1 except that the raw materials and preparation amounts shown in Table 1 were used to obtain a propylene glycol monomethyl ether acetate solution of polyester dispersants X2 to X8.

(Production Example 9 for Comparative Dispersant 1)
A reaction vessel equipped with a gas introduction tube, a thermometer, a condenser, and a stirrer was charged with 50.0 parts of benzyl methacrylate and 50.0 parts of n-butyl methacrylate and replaced with nitrogen gas. The reaction vessel was heated to 80 ° C., 6 parts of 3-mercapto-1,2-propanediol, 0.1 part of 2,2′-azobisisobutyronitrile, 45.4 parts of propylene glycol monomethyl ether acetate The solution dissolved in was added and reacted for 10 hours. It was confirmed that 95% had reacted by solid content measurement. At this time, the weight average molecular weight was 4000. Next, 9.7 parts of pyromellitic dianhydride, 31.7 parts of propylene glycol monomethyl ether acetate and 0.2 part of 1,8-diazabicyclo- [5.4.0] -7-undecene as a catalyst were added. And reacted at 120 ° C. for 7 hours. The reaction was terminated after confirming that 98% or more of the acid anhydride had been half-esterified by measuring the acid value.

  After completion of the reaction, a solution of Comparative Dispersant 1 having an acid value of 43 mgKOH / g and a weight average molecular weight of 9500 was prepared by adding propylene glycol monomethyl ether acetate so that the nonvolatile content was 60% by weight (cyclohexanone =>). .

(Production Example 10 for Comparative Dispersant 2)
The synthesis was carried out in the same manner as in Production Example 9 except that the raw materials and preparation amounts shown in Table 1 were used, and a propylene glycol monomethyl ether acetate solution of Comparative Dispersant 2 was obtained.

[Example 1]
After the mixture having the following composition is uniformly stirred and mixed, the mixture is dispersed for 2 hours with an Eiger mill (“Mini Model M-250 MKII” manufactured by Eiger Japan) using zirconia beads having a diameter of 1 mm, and then filtered through a 5 μm filter. A green pigment dispersion (GD1) was prepared.

Refined pigment (G-1) 8.0 parts Refined pigment (Y-1) 6.0 parts Polyester dispersant X1 solution 6.0 parts Binder resin solution 16.0 parts Propylene glycol monomethyl ether acetate (PGMAC) 64. 0 copies

  Next, the mixture having the following composition was stirred and mixed to be uniform, and then filtered through a 1 μm filter to obtain a green coloring composition (GC1) for a green color filter.

Green pigment dispersion (GD1) 54.0 parts Binder resin solution 6.0 parts Active energy ray-curable monomer (M-402) 2.0 parts Active energy ray polymerization initiator (Irgacure 907) 1.8 parts Sensitizer (EAB-F) 0.2 part Propylene glycol monomethyl ether acetate (PGMAC) 37.0 parts

[Examples 2-8, Comparative Examples 1-2]
A green color filter coloring composition (GC2) was prepared in the same manner as in Example 1 except that the polyester dispersant solution was changed to the dispersant shown in Table 2 to prepare green pigment dispersions (GD2 to 10). To 10).

[Example 9]
After the mixture having the following composition is stirred and mixed uniformly, the mixture is dispersed for 2 hours with an Eiger mill (“Mini Model M-250 MKII” manufactured by Eiger Japan) using zirconia beads having a diameter of 1 mm, and then filtered through a 5 μm filter. A red pigment dispersion (RD1) was prepared.

Refined pigment (R-1) 5.0 parts Refined pigment (R-2) 4.0 parts Refined pigment (Y-2) 2.0 parts Polyester dispersant X2 solution 5.0 parts Binder resin solution 28. 0 parts 55.0 parts propylene glycol monomethyl ether acetate (PGMAC)

  Next, the mixture having the following composition was stirred and mixed to be uniform, and then filtered through a 1 μm filter to obtain a colored composition for a red color filter.

Red pigment dispersion (RD1) 44.0 parts Binder resin solution 13.0 parts Active energy ray-curable monomer (M402) 2.0 parts Active energy ray polymerization initiator (Irgacure 907) 1.8 parts Sensitization Agent (EAB-F) 0.2 parts Propylene glycol monomethyl ether acetate (PGMAC) 40.0 parts

[Examples 10 to 12, Comparative Example 3]
The polyester dispersant solution was changed to the dispersant shown in Table 2 and blended. Otherwise, a colored composition for a red color filter was obtained in the same manner as in Example 9.
A red pigment dispersion (RD2-4) was prepared by changing the polyester dispersant solution to the dispersant shown in Table 2, and a red color filter coloring composition (RC2) was used in the same manner as in Example 9 except that it was used. To 4).

[Example 13]
After the mixture having the following composition is uniformly stirred and mixed, the mixture is dispersed for 2 hours with an Eiger mill (“Mini Model M-250 MKII” manufactured by Eiger Japan) using zirconia beads having a diameter of 1 mm, and then filtered through a 5 μm filter. A blue pigment dispersion (BD1) was prepared.

Refined pigment (B-1) 13.0 parts Refined pigment (V-1) 1.0 part Polyester dispersant X2 solution 6.0 parts Binder resin solution 16.0 parts Propylene glycol monomethyl ether acetate (PGMAC) 64. 0 copies

  Next, the mixture having the following composition was stirred and mixed to be uniform, and then filtered through a 1 μm filter to obtain a colored composition for a blue color filter.

Blue pigment dispersion (BD1) 32.0 parts Binder resin solution 13.0 parts Active energy ray-curable monomer (M402) 5.0 parts Active energy ray polymerization initiator (Irgacure 907) 1.8 parts Sensitization Agent (EAB-F) 0.2 part Propylene glycol monomethyl ether acetate (PGMAC) 49.0 parts

[Examples 14 to 16, Comparative Example 4]
A blue pigment dispersion (BD2 to 4) was prepared by changing the polyester dispersant solution to the dispersant shown in Table 2, and a coloring composition for red color filter (BC2) was used in the same manner as in Example 9 except that it was used. To 4).

(Contrast ratio)
The coloring composition for a color filter obtained in Examples and Comparative Examples was applied on a glass substrate of 100 mm × 100 mm and 0.7 mm thickness using a spin coater at a rotation speed of 500 rpm, 1000 rpm, 1500 rpm, and a film thickness. Three types of coated substrates having different values were obtained. The coloring composition coated substrate for color filter was dried at 70 ° C. for 20 minutes, then exposed to ultraviolet light with an integrated light amount of 150 mJ using an ultra high pressure mercury lamp, heated at 230 ° C. for 1 hour, allowed to cool, and then measured for contrast ratio. . Next, the chromaticity (Y, x, y) of the coating film with a C light source was measured using a microspectrophotometer (“OSP-SP100” manufactured by Olympus Optical Co., Ltd.). From the three sets of contrast ratio and chromaticity measurement results, the color coating colored composition-coated substrate is y = 0.14 for the blue coating, y = 0.60 for the green coating, and x = for the red coating. The contrast ratio at 0.64 was determined using an approximation method.

(Viscosity stability)
About the coloring composition for color filters obtained by the Example and the comparative example, the viscosity stability was evaluated by the following method.
Using an E-type viscometer (“ELD-type viscometer” manufactured by Toki Sangyo Co., Ltd.), the initial viscosity of the next day after preparing the color filter coloring composition and the time-lapse viscosity accelerated at 40 ° C. for 1 week, The measurement was performed at 25 ° C. under the condition of a rotation speed of 50 rpm. From the values of the initial viscosity and the viscosity with time, the change rate with time was calculated by the following formula, and the viscosity stability was evaluated in three stages.

[Change in viscosity with time] = | ([initial viscosity] − [viscosity with time]) / [initial viscosity] | × 100
○: Change rate of less than 5% △: Change rate of 5% to 10% ×: Change rate of 10% or more

(Developability evaluation)
The coloring composition for a color filter obtained in Examples and Comparative Examples was applied on a 100 mm × 100 mm, 0.7 mm thick glass substrate using a spin coater at a rotation speed at which the film thickness after drying was 2 μm. The substrate was dried at 70 ° C. for 20 minutes and then developed with an alkaline developer composed of a 0.2 wt% sodium carbonate aqueous solution at 23 ° C., and the developability was evaluated in three stages.

Green color filter coloring composition coated substrate ○: Can be completely removed within 40 seconds. Δ: Can be completely removed within 40 to 60 seconds.

Red color filter coated substrate for color composition ○: Can be completely removed within 60 seconds Δ: Can be completely removed within 60 to 80 seconds ×: Cannot be completely removed even after 80 seconds

Blue color filter-coated substrate for colored composition ○: Those that can be completely removed within 20 seconds Δ: Those that can be completely removed within 20 to 40 seconds ×: Those that cannot be completely removed even after 40 seconds Is shown in Table 3.

  As shown in Table 3, the coloring composition for a color filter of the present invention using the polyester dispersants X1 to 8 is more developable while maintaining a high contrast ratio compared to those using the comparative dispersants 1 and 2. Was also excellent.

The subject is a coloring composition for a color filter comprising a pigment, a dispersant, a binder resin, an active energy ray-curable monomer, an active energy ray polymerization initiator, and a solvent,
The dispersant is
Ethylenic unsaturation comprising an ethylenically unsaturated monomer (b1) having an ether group represented by the following general formula (1) in the presence of a compound (a1) having two hydroxyl groups and one thiol group in the molecule A hydroxyl group in the polyol (a) comprising a vinyl polymer (a2) having two hydroxyl groups in one terminal region, obtained by radical polymerization of the monomer (b);
An acid anhydride group of tricarboxylic anhydride (c1) and / or tetracarboxylic dianhydride (c2);
Is a polyester dispersant (X) having an ether group in the side chain ,
Binder resin is an acrylic resin having an acidic functional group, α-olefin / (anhydrous) maleic acid copolymer, styrene / (anhydrous) maleic acid copolymer, styrene / styrene sulfonic acid copolymer, ethylene / (meth) It is at least one selected from an acrylic acid copolymer and an isobutylene / (anhydrous) maleic acid copolymer, and is solved by a coloring composition for a color filter characterized by having a weight average molecular weight of Mw 5,000 to 100,000. .

Further, the present invention is an ethylenically unsaturated monomer having an ether group (b1) is,
Main Tokishiechiru (meth) acrylate, methoxy polyethylene glycol (meth) acrylate, methoxy polypropylene glycol (meth) acrylate, methoxy polytetramethylene glycol (meth) acrylate, methoxy polyethylene glycol polypropylene glycol (meth) acrylate, octoxypolyethylene glycol polypropylene glycol mono Methacrylate, Lauroxypolyethylene glycol monomethacrylate, Stearoxypolyethylene glycol monomethacrylate, Phenoxypolyethyleneglycol mono (meth) acrylate, Phenoxypolyethyleneglycolpolypropyleneglycolmonomethacrylate, Nonylphenoxypolyethyleneglycolmonoacrylate, Nonylphenoxypo Propylene glycol monoacrylate, nonylphenoxy polyethylene glycol polypropylene glycol monoacrylate, phenoxyethylene glycol (meth) acrylate, (poly) ethylene glycol monoparacumyl phenyl ether acrylate, diethylene glycol mono 2-ethylhexyl ether acrylate, n-butoxyethyl (meth) acrylate , N-butoxydiethylene glycol methacrylate, ethoxydiethylene glycol acrylate, and 2-ethoxyethyl acrylate, at least one selected from the group consisting of the above.
Moreover, this invention relates to the coloring composition for said color filters in which polyester dispersing agent (X) has a carboxyl group in a side chain.
In addition, the present invention relates to the coloring composition for a color filter, wherein the (meth) acrylate having a carboxyl group is 0 to 5% by weight in 100% by weight of the ethylenically unsaturated monomer (b). .
The present invention also relates to the colored composition for a color filter, wherein the (meth) acrylate having a carboxyl group is methacrylic acid.

Moreover, this invention relates to the said coloring composition for color filters formed by containing a pigment derivative.
In the present invention, the coloring composition for a color filter according to any one of claims 1 to 8, wherein the pigment derivative is a basic derivative represented by the general formula (19):
General formula (19):
P-Lm
(However, in general formula (19),
P is an m-valent organic pigment residue, an anthraquinone skeleton, an acridone skeleton, or a triazine skeleton,
m is an integer of 1 to 4,
L is a substituent selected from the group consisting of a substituent represented by the following general formula (20), a substituent represented by the following general formula (21), and a substituent represented by the following general formula (22). )
Formula (20):

Formula (21):

Formula (22):

[However, in general formula (20)-(22),
X _{is, -SO 2 -, - CO -} , - CH 2 -, - CH 2 NHCOCH 2 -, - CH 2 NHSO 2 CH 2 -, or a direct bond,
Y is —NH—, —O—, or a direct bond;
n is an integer of 1 to 10,
Y ¹ is —NH—, —NR ⁵⁸ —Z—NR ⁵⁹ —, or a direct bond;
R ⁵⁸ and R ⁵⁹ are each independently a hydrogen bond, an optionally substituted alkyl group having 1 to 36 carbon atoms, an optionally substituted alkenyl group having 2 to 36 carbon atoms, or A phenyl group which may have a substituent,
Z is an alkylene group which may have a substituent, or an arylene group which may have a substituent,
R ⁵⁰ and R ⁵¹ are each independently a hydrogen atom, an optionally substituted alkyl group having 1 to 30 carbon atoms, an optionally substituted alkenyl group having 2 to 30 carbon atoms, or R ⁵⁰ and R ⁵¹ together are a heterocyclic ring which may further have a substituent containing a further nitrogen, oxygen or sulfur atom,
R ⁵² , R ⁵³ , R ⁵⁴ , and R ⁵⁵ are each independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms that may have a substituent, or 2 to carbon atoms that may have a substituent. 20 alkenyl group, an arylene group having 6 to 20 carbon atoms which may have a substituent,
R ⁵⁶ is a hydrogen atom, an optionally substituted alkyl group having 1 to 20 carbon atoms, an optionally substituted alkenyl group having 2 to 20 carbon atoms,
R ⁵⁷ is a substituent represented by the general formula (20) or a substituent represented by the general formula (21),
Q is a hydroxyl group, an alkoxyl group, a substituent represented by the general formula (20), or a substituent represented by the general formula (21). ]

Claims (5)

A coloring composition for a color filter comprising a pigment, a dispersant, a binder resin, an active energy ray-curable monomer, an active energy ray polymerization initiator, and a solvent,
The dispersant is
Ethylenic unsaturation comprising an ethylenically unsaturated monomer (b1) having an ether group represented by the following general formula (1) in the presence of a compound (a1) having two hydroxyl groups and one thiol group in the molecule A hydroxyl group of the polyol (a) comprising a vinyl polymer (a2) having two hydroxyl groups in one end region, which is obtained by radical polymerization of the monomer (b);
An acid anhydride group of tricarboxylic anhydride (c1) and / or tetracarboxylic dianhydride (c2);
A coloring composition for a color filter, which is a polyester dispersant (X) obtained by reacting the above.
General formula (1):
(In the general formula (1), R ¹ is a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms which may have a substituent, and 1 carbon atom which may have a substituent. -20 alkenyl group or a phenyl group which may have a substituent, R ² is a linear or branched alkylene group having 1 to 8 carbon atoms, R ³ is a hydrogen atom, Or a methyl group, and n is an integer of 1 to 30.)   The color according to claim 1, wherein the ethylenically unsaturated monomer (b1) having an ether group is 20 to 100% by weight based on the weight of the total ethylenically unsaturated monomer (b). Coloring composition for filters.   The coloring composition for a color filter according to claim 1 or 2, wherein the ethylenically unsaturated monomer (b1) having an ether group is 2-methoxyethyl (meth) acrylate.   Furthermore, the coloring composition for color filters in any one of Claims 1-3 containing a pigment derivative.   A color filter comprising a filter segment formed using the colored composition for a color filter according to claim 1.