JP4687835B2 - Pigment dispersion composition for color filter and color filter - Google Patents

Description

  The present invention relates to a pigment dispersion composition for a color filter using a pigment as a coloring material.

  In general, the color filter is a reflective type so that the three primary colors of red, green, and blue light are selectively transmitted on a substrate provided with a mesh-like light-shielding thin film layer called a black matrix. In the black matrix, a colored cured coating layer corresponding to each color is formed in each mesh of the black matrix so that the three primary colors of cyan, magenta, and yellow are selectively reflected, and the mesh of each color is regular. Are arranged. The “mesh” of the black matrix is referred to as “pixel”.

  The color filter is used for a color solid-state imaging device, a liquid crystal color display, a color display such as a color CRT or the like. In recent years, high contrast has been demanded from the demand for higher image quality of color filters.

  The color filter manufacturing method was initially dyed using a dye as a colorant, but recently, pigments with excellent heat resistance, light resistance, chemical resistance, etc. have been used to meet the above requirements. The pigment dispersion method has become mainstream. In this pigment dispersion method, a pigment dispersion resist in which a photopolymerizable monomer and a photopolymerization initiator are added to a pigment dispersion composition in which a pigment is dispersed using a dispersant in a binder resin is applied onto a substrate. A “photolithography method” in which a cured coating film layer of a pigment-dispersed resist is formed on a pixel portion by drying and exposing through a photomask, followed by development and thermosetting is generally widely performed.

  As a method for producing a color filter by this “photolithography method”, for example, a pigment, a coupling agent, an acrylic copolymer having an N, N-disubstituted amino group and an acidic group in the main chain or side chain, and There has been proposed a pigment dispersion composition for a color filter which contains a solvent and is excellent in transparency, developability, light resistance and storage stability (see, for example, Patent Document 1). However, even this method is not always satisfactory with respect to the recent required properties such as higher dispersion stability, long-term storage stability, and transparency.

In contrast, when kneading a general-purpose pigment, resin, and organic solvent as raw materials, the solid content ratio (in terms of mass) of the pigment and the resin is set to a specific ratio, and the organic solvent is removed by evaporation. There is known a method of obtaining a pigment dispersion for a color filter excellent in dispersion stability, long-term storage stability, transparency, and the like by kneading the raw materials with a planetary mixer. (For example, refer to Patent Document 2). However, this method is not a simple kneading method because it involves kneading while constantly monitoring the solid content ratio, or requires kneading for a long time because it is solid kneading.

JP 2003-64293 A (paragraphs [0002] to [0008]) JP 2006-111752 A

  An object of the present invention is to provide a pigment dispersion composition for a color filter that uses a general-purpose pigment and provides a color filter having excellent dispersion stability and excellent contrast.

The present inventor previously has at least one type of polymerization which is soluble in a non-aqueous solvent and insoluble or hardly soluble after polymerization, on the pigment surface, containing a polymer containing a polymerizable unsaturated group soluble in the non-aqueous solvent. Invented a pigment characterized by having a polymer obtained by polymerizing a polymerizable unsaturated monomer (Japanese Patent Laid-Open No. 2008-88211), and prepared as a pigment dispersion composition for a color filter using the pigment It has been found that the dispersion stability is excellent (Japanese Patent Application No. 2009-529445).
The present inventors further applied a modified pigment using a polymer having a specific structure to a pigment dispersion composition for a color filter instead of a polymer containing a polymerizable unsaturated group soluble in a non-aqueous solvent. As a result, it was found that a color filter having excellent dispersion stability and excellent contrast of the color filter pixel portion was obtained, and the present invention was completed.

That is, the present invention is a pigment dispersion composition for a color filter containing a colorant, a resin, and an organic solvent capable of dissolving the resin,
On the surface of the pigment (A),
A modified polyamine (B) obtained by reacting a vinyl copolymer (B-1) having a functional group that reacts with an amino group to form an amide bond at one end with an amino group of the polyamine;
Polymer (P) obtained by polymerizing at least one polymerizable unsaturated monomer (C) that is soluble in a non-aqueous solvent and becomes insoluble or hardly soluble after polymerization
There is provided a pigment dispersion composition for a color filter using a modified pigment (D) having

The present invention also provides a color filter using the above-described pigment dispersion composition for a color filter.

  According to the present invention, it is possible to provide a pigment dispersion composition for a color filter that uses a general-purpose pigment and gives a color filter having excellent dispersion stability and excellent contrast.

(Modified pigment (D))
The modified pigment (D) used as a colorant in the present invention is a general purpose pigment (A), a non-aqueous solvent, and a vinyl copolymer (B) having a functional group at one end which reacts with an amino group to form an amide bond. -1) at least one polymerizable unsaturated monomer that is soluble in the non-aqueous solvent and insoluble or hardly soluble after polymerization in the presence of the modified polyamine (B) obtained by reacting the amino group of the polyamine It can be obtained by so-called in-situ polymerization in which (C) is polymerized.

(Pigment (A))
The pigment (A) used in the present invention is at least one pigment selected from known and commonly used organic pigments or inorganic pigments. In the present invention, either an untreated pigment or a treated pigment can be applied.

As the pigment (A), commercially available pigments conventionally used in color filters, and “Color Index Handbook” (edited by the Japan Pigment Technical Association, 1977) “Latest Pigment Applied Technology” (CMC Publishing, 1986) “Printing Ink Technology” (CMC Publishing Co., Ltd. published in 1984) and the like.
Specifically, as a pigment generally used in color filters, for example, C.I. I. Pigment red 254 and C.I. I. Pigment red 177 and C.I. I. Red pigments such as CI Pigment Orange 71; I. Pigment green 36, C.I. I. Pigment green 58 and C.I. I. Pigment Green 7 and other green pigments, C.I. I. Pigment blue 15: 6 and C.I. I. Blue pigments such as CI Pigment Blue 22; I. Pigment violet 23 and C.I. I. Violet pigments such as CI Pigment Violet 50, C.I. I. Pigment yellow 138, C.I. I. Pigment yellow 150 and C.I. I. Yellow pigments such as CI Pigment Yellow 20 and the like; I. Examples thereof include CI pigment black 7 and black pigments such as carbon black and titanium black, but these pigments can be used alone or in combination of two or more as required.
In general, the transparency of a cured coating film of a pigment dispersion for a color filter increases as the particle diameter of the pigment to be contained decreases, but the primary particle diameter is preferably in the range of 10 to 80 nm, preferably 30 to 50 nm. The range is particularly preferable. If the primary particle size is less than 10 nm, the cohesiveness of the pigment is increased, making it difficult to disperse, and if it exceeds 80 nm, the transparency is lowered.
Among these, since the effect of the present invention is exhibited to the maximum, C.I. I. Pigment Green 58 is preferably used.

(Non-aqueous solvent)
The non-aqueous solvent used in the present invention is an organic solvent in which an aliphatic and / or alicyclic hydrocarbon solvent is essential. Examples of the aliphatic and / or alicyclic hydrocarbon solvents include n-hexane, n-heptane, n-octane, “Loose” or “Mineral Split EC” manufactured by Shell Chemicals, and ExxonMobil Chemical manufactured by ExxonMobil Chemical. “Isopar C”, “Isopar E”, “Isopar G”, “Isopar H”, “Isopar L”, “Isopar M”, “Naphtha 3”, “Naphtha 5” or “Naphtha 6”, Idemitsu Oil “Solvent 7”, “IP Solvent 1016”, “IP Solvent 1620”, “IP Solvent 2028” or “IP Solvent 2835” of Chemical Co., Ltd., “Whitesol” of Japan Energy Products, Maruzen Petrochemical Co., Ltd. The company product “Marcazole 8” and the like can be mentioned.

Moreover, you may mix and use another organic solvent in the range which does not impair the effect of this invention. Specific examples of such organic solvents include “Swazole 100 or 150” manufactured by Maruzen Petrochemical Co., Ltd., aromatic hydrocarbon solvents such as toluene or xylene; methyl acetate, ethyl acetate, acetic acid- esters such as n-butyl or amyl acetate; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, methyl amyl ketone or cyclohexanone; or such as methanol, ethanol, n-propanol, i-propanol or n-butanol Examples include alcohols.
When mixed and used, the amount of the aliphatic and / or alicyclic hydrocarbon solvent used is preferably 50% by mass or more, and more preferably 60% by mass or more.

(Modified polyamine (B))
The modified polyamine (B) used in the present invention is a vinyl copolymer (B-1) having a functional group that reacts with an amino group to form an amide bond at one end (hereinafter referred to as “reacting with an amino group to form an amide bond. The vinyl copolymer (B-1) having a functional group to be formed at one end is simply referred to as vinyl copolymer (B-1)) and is a modified polyamine (B) obtained by reacting the amino group of the polyamine. . Polyamines are generally known to have high adsorptivity to pigments, and the modified polyamine (B) of the present invention improves the dispersion stability of pigments in a hydrophobic solvent. As a result, it is considered preferable because the dispersed particle diameter of the modified pigment (D) obtained by polymerizing the polymerizable unsaturated monomer (C) described later on the pigment surface becomes finer.

(Polyamine)
The polyamine used in the present invention is a polymer having a repeating unit having a primary or secondary amino group. Such a polyamine is preferably at least one selected from the group consisting of polyallylamine, polyvinylamine and polyethyleneimine. Further, it may be a copolymer of polyallylamine, polyvinylamine, or polyethyleneimine and another polymerizable monomer.
When polyallylamine, polyvinylamine, or a copolymer of polyethyleneimine and another polymerizable monomer is used, the amine value of the polyamine of the present invention is preferably 50 or more, more preferably 300 or more. When the amine value is less than 50, the dispersibility of the modified pigment obtained due to insufficient adsorbing power to the pigment may be lowered. These polyamines may be used alone or in combination. Among these, from the viewpoint of industrial availability, polyallylamine or polyethyleneimine is preferable. Among them, polyallylamine is most preferable. The reason for this is that polyethyleneimine generally has a branched polymer structure, whereas polyallylamine has a linear polymer structure, so the amine has a high anchoring effect on the pigment. ing.
The number average molecular weight of the polyamine in the present invention is preferably 150 to 100,000, more preferably 600 to 20,000. If the number average molecular weight of the polyamine used in the present invention is less than 150, there is a risk that the pigment will be difficult to disperse due to insufficient adsorptive power to the pigment, whereas if it exceeds 100,000, the viscosity during reaction with the vinyl polymer may be increased. May increase or the gelation of the polymer, and the molecular weight of the polymer becomes too large, and the dispersibility may be lowered due to aggregation of the pigments.

(Polyallylamine)
The polyallylamine used in the present invention may be obtained by polymerizing allylamine in the presence of a polymerization initiator, optionally in the presence of a chain transfer catalyst, by a known method, or a commercially available product may be used. As a commercial item, it sells as polyallylamine series, such as PAA-01, PAA-03, PAA-05, PAA-15, PAA-10C, from Nitto Boseki Co., Ltd., for example.

(Polyvinylamine)
The polyvinylamine used in the present invention is, for example, a variety of known polymers such as N-vinylformamide polymerized by a known method in the presence of a polymerization initiator, optionally in the presence of a chain transfer catalyst, and then subjected to a hydrolysis reaction. It can be obtained by the method.

(Polyethyleneimine)
The polyethyleneimine used in the present invention may be obtained by polymerizing ethyleneimine by a known method, or a commercially available product may be used. As a commercial item, it is marketed as a polyethyleneimine series, such as SP-003, SP-006, SP-012, SP-018, SP-200, and P-1000, from Nippon Shokubai Co., Ltd., for example.

(Vinyl copolymer (B-1))
In the vinyl copolymer (B-1) used in the present invention, functional groups that react with amino groups to form amide bonds include carboxyl groups, haloformyl groups such as chloroformyl groups, and oxycarbonyl groups such as methoxycarbonyl groups. Is mentioned. Among these, a carboxyl group is preferable because it can be easily introduced into a vinyl copolymer.
In order to obtain a vinyl copolymer having a carboxyl group at one end, for example, a method of coexisting a chain transfer agent having a carboxyl group at the time of polymerization can be mentioned. Examples of the chain transfer agent having a carboxyl group include thiocarboxylic acids such as mercaptoacetic acid, 2-mercaptopropionic acid, and 3-mercaptopropionic acid. It can also be obtained by a method of synthesizing a polymerizable monomer by a living radical polymerization method using a polymerization initiator having a carboxyl group such as 4,4′-azobis-4-cyanopentanoic acid.

Examples of the polymerizable monomer used as a raw material for the vinyl copolymer (B-1) include methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, and 2-ethylhexyl (meth) acrylate. Homopolymers of (meth) acrylic acid alkyl esters such as these, or between these esters or these esters, alkenyl benzenes such as styrene, α-methyl styrene, vinyl toluene, vinyl acetate, vinyl pyridine, acrylamide, methacryl Examples include amides, dimethylaminoethyl methacrylate, N-methylolacrylamide, N-butoxymethylacrylamide (meth) acrylic acid-2-hydroxyethyl, (meth) acrylic acid-2-hydroxypropyl, and the like. Among these, one kind or two or more kinds can be used.
However, it is preferable not to use a polymerizable monomer that has a functional group that reacts with an amino group to form an amide bond, for example, a functional group that is equivalent to or more highly reactive with an amino group than a carboxyl group. The vinyl polymer containing the polymerizable monomer as a raw material is not only the terminal of the vinyl copolymer but also the functional group is randomly grafted to the main chain of the copolymer, so that it reacts with polyallylamine. There is a possibility of gelling inside, and the performance of the resulting modified pigment may be deteriorated. Specifically, polymerizable monomers such as butadiene, isoprene, chloroprene, (meth) acrylic acid, itaconic acid, and maleic anhydride have groups that are highly reactive with amino groups. It is preferable not to use it as a raw material for the combined (B-1).

  Since liquid crystal display devices and the like are required to have higher display characteristics such as visibility, it may be required to control the retardation value of the colored pixel layer constituting the color filter. In such a case, the retardation value of the pixel can be controlled in the negative direction by the vinyl copolymer (B-1) containing an alkyl group having 10 to 24 carbon atoms. That is, a (meth) acrylic acid ester containing an alkyl group having 10 to 24 carbon atoms may be used as one of the raw materials. The (meth) acrylic acid ester containing an alkyl group having 10 to 24 carbon atoms may be either linear or branched, such as isodecyl (meth) acrylate, lauryl (meth) acrylate, (meth) acrylic acid. Examples include tridecyl, myristyl (meth) acrylate, cetyl (meth) acrylate, stearyl (meth) acrylate, behenyl (meth) acrylate, and the like. As a quantity which mix | blends such a (meth) acrylic acid ester containing a C4-C24 alkyl group with a vinyl copolymer (B-1), 10-100 mass% is preferable, and 20-100 mass is preferable. % Is more preferable. When the amount of the (meth) acrylic acid ester containing an alkyl group having 10 to 24 carbon atoms is less than 10% by mass, the desired retardation value adjusting ability may not be exhibited.

  The vinyl copolymer (B-1) can be obtained by heating the above various polymerizable monomers in a reaction vessel in the presence of a polymerization initiator and aging as necessary. The reaction conditions vary depending on, for example, the polymerization initiator and the solvent, but the reaction temperature is 30 to 150 ° C, preferably 60 to 120 ° C. The polymerization can be carried out in the presence of a non-reactive solvent.

  Examples of the polymerization initiator include peroxides such as t-butyl peroxybenzoate, di-t-butyl peroxide, cumene perhydroxide, acetyl peroxide, benzoyl peroxide, lauroyl peroxide; azobisisobutylnitrile, Examples thereof include azo compounds such as azobis-2,4-dimethylvaleronitrile and azobiscyclohexanecarbonitrile.

  Non-reactive solvents include, for example, aliphatic hydrocarbon solvents such as hexane and mineral spirits; aromatic hydrocarbon solvents such as benzene, toluene and xylene; ester solvents such as butyl acetate; methanol, butanol and the like And alcohol solvents such as: aprotic polar solvents such as dimethylformamide, dimethyl sulfoxide, N-methylpyrrolidone, and pyridine. These solvents may be used in combination. As these solvents, those capable of dissolving the obtained vinyl copolymer (B-1) can be appropriately selected and used.

  The molecular weight of the vinyl copolymer (B-1) used in the present invention is preferably in the range of number average molecular weight of 500 to 100,000, and more preferably in the range of 1000 to 20,000. If the number average molecular weight is less than 500, sufficient steric repulsion effect as a pigment dispersant may not be maintained, and if it exceeds 100,000, the viscosity of the vinyl polymer is increased and the solvent solubility is decreased. In some cases, the performance of the modified pigment is reduced.

  Further, the modified polyamine (B) in the present invention is one or more selected from the group consisting of the vinyl copolymer (B-1) and the following (B-2) to (B-5) as the polyamine. It is preferable that the above compound may be reacted.

  (B1) A vinyl copolymer having a functional group that reacts with an amino group at one end, wherein the amount of the functional group that reacts with an amino group, the copolymer composition, or the copolymer composition ratio is the vinyl copolymer (B A vinyl copolymer (B-2) different from -1).

  As the vinyl copolymer (B-2), a vinyl copolymer (B-2-1) is preferable. The vinyl copolymer (B-2-1) includes a weight% of a functional group that reacts with an amino group at one end of the vinyl copolymer (B-1), and the vinyl copolymer (B-2-1). 1) The ratio by weight of the functional group that reacts with the amino group at one end is in the range of 0.4 to 0.8, and the molar ratio (B) with the vinyl copolymer (B-1) -1) / (B-2-1) is preferably reacted with the modified polyamine so that (B-1) / (B-2-1) = 0.25 to 4.0. (Hereinafter referred to as vinyl copolymer (B-2-1))

  Moreover, as said vinyl copolymer (B-2), a vinyl copolymer (B-2-2) is preferable. The vinyl copolymer (B-2) is a vinyl copolymer obtained by polymerizing a plurality of vinyl monomers. The Tg of the vinyl copolymer (B-1) and the vinyl copolymer (B-2-2) ) Has a Tg difference of 20 ° C. or more, and a molar ratio (B-1) / (B-2) between the vinyl copolymer (B-1) and the vinyl copolymer (B-2-2). -2) is preferably reacted with the modified polyamine such that (B-1) / (B-2-2) = 0.25-4.0. (Hereinafter referred to as vinyl copolymer (B-2-2))

  (B2) (Meth) acrylate (B-3) having a polyalkylene glycol chain. (Hereinafter referred to as (meth) acrylate (B-3)). Among them, it is preferable that the polyalkylene glycol chain reacts with the modified polyamine so as to have a ratio of 1 to 30% by weight with respect to the whole molecule.

  (B3) Polyester having a functional group that reacts with an amino group at one end, Polyamide having a functional group that reacts with an amino group at one end, or Polyesteramide having a functional group that reacts with an amino group at one end (B-4) (Hereinafter referred to as polymer (B-4)). In particular, the modified polyamine is preferably reacted with the modified polyamine so that these residues have a ratio of 1 to 50% by weight based on the whole molecule.

  (B4) Monocarboxylic acid or (meth) acrylate (B-5). Among these, it is preferable to react with the modified polyamine so that these residues have a ratio of 1 to 30% by weight based on the whole molecule.

((B1) Vinyl copolymer (B-2-1))
The vinyl copolymer (B-2-1) is a copolymer having a functional group that reacts with an amino group at one end and is different from the vinyl copolymer (A). Weight% of functional group reacting with amino group at one end of compound (B-1), and weight% of functional group reacting with amino group at one end of vinyl copolymer (B-2-1) The molar ratio (B-1) / (B-2-1) with the vinyl copolymer (B-1) is (B-1). ) / (B-2-1) = 0.25-4.0 It is preferable that it reacts with the modified polyamine.
Specifically, the vinyl copolymer (B-2-1) is a vinyl copolymer having a carboxyl group, and a copolymer having a molecular weight different from that of the vinyl copolymer (B-1). The molecular weight is adjusted by the content of the carboxyl group at one end of the vinyl copolymer. The weight percentage of the carboxyl group in the vinyl copolymer is preferably in the range of 1 to 10, and the vinyl copolymer ( The ratio of the weight percent of the carboxyl group at one end of B-1) to the weight percent of the carboxyl group at one end of the vinyl copolymer (B-2-1) is 0.4 to 0.8. A range is preferred. (However, it is assumed that the vinyl copolymer (B-2-1) at this time has a higher molecular weight than the vinyl copolymer (B-1).)
In addition, the vinyl polymer (B-2-1) residual chain (the vinyl polymer (B-2-1) residual chain as used herein refers to the remaining portion reacted with the carboxyl group) and the vinyl copolymer (B -1) The ratio of the residual chain is such that the molar ratio (B-1) / (B-2-1) with the vinyl copolymer (B-1) is (B-1) / (B-2-1) = 0.25 to 4.0 is preferable.

((B1) Vinyl copolymer (B-2-2))
The vinyl copolymer (B-2-2) is obtained by polymerizing a plurality of vinyl monomers, and the difference between the Tg of the vinyl copolymer (B-1) and the Tg of the vinyl copolymer (B2) is It is a vinyl copolymer having a temperature of 20 ° C. or higher. Here, Tg is defined as a value measured by DSC (Differential Scanning Calorimetry) or tB-1nδ peak of dynamic viscoelasticity.
As described above, the molar ratio (B-1) / (B-2-2) between the vinyl copolymer (B-1) and the vinyl copolymer (B-2-2) is (B-1 ) / (B-2-2) = 0.25-4.0 It is preferable that it reacts with the modified polyamine.
Specifically, the Tg of the vinyl copolymer (B-2-2) is preferably 100 ° C. to −50 ° C., and it varies depending on the Tg of the vinyl copolymer (B-1). It is particularly preferred that the temperature is from -50 ° C to -50 ° C.

((B2) (Meth) acrylate (B-3))
In the (meth) acrylate (B-3), having a polyalkylene glycol chain means a state of polyalkylene glycol (meth) acrylate. Specific examples of the polyalkylene glycol include polyethylene glycol, polypropylene glycol, polybutylene glycol, and mixtures thereof. Among them, polyethylene glycol and polypropylene glycol are preferable.
The (meth) acrylate (B-3) is preferably reacted with the modified polyamine so that the polyalkylene glycol chain has a ratio of 1 to 30% by weight with respect to the whole molecule.

((B3) Polymer (B-4))
Specifically, the polymer (B-4) is any one of the following polymers (b3-1) to (b3-3).
(B3-1) polyester having a functional group that reacts with an amino group at one end;
(B3-2) Polyamide having a functional group that reacts with an amino group at one end (b3-3) Polyesteramide having a functional group that reacts with an amino group at one end

(B3-1) The polyester having a functional group that reacts with an amino group at one end is specifically a polyester having a carboxyl group at the end. This can be synthesized by various methods as follows.
(B-1) an addition reaction for adding a lactone compound to a monocarboxylic acid compound, (b) an addition reaction for adding a lactone compound to a hydroxycarboxylic acid compound, (c) a monocarboxylic acid compound, a hydroxycarboxylic acid compound, and a lactone compound Examples thereof include a condensation reaction in which three components are condensed.

  (B3-2) The polyamide having a functional group that reacts with an amino group at one end is specifically a polyamide having a carboxyl group at the end. This is prepared from lactams such as ε-caprolactam and ω-laurolactam, and aminocarboxylic acids such as aminocaproic acid and 11-aminoundecanoic acid.

  (B3-3) The polyesteramide having a functional group that reacts with an amino group at one end is specifically a co-condensate of an ester and an amide having a carboxyl group at the end. This can be prepared by co-condensing hydroxycarboxylic acid, lactone and the like used in the production of the polyester and polyamide with aminocarboxylic acid and lactam.

  The polymer (B-4) is preferably reacted with the modified polyamine so that these residues have a ratio of 1 to 50% by weight based on the whole molecule. Here, the residue represents the remaining polymer portion reacted with the carboxyl group.

((B4) monocarboxylic acid or (meth) acrylate (B-5))
The monocarboxylic acid is not particularly limited as long as it is a compound having one carboxylic acid group in one molecule, and specifically, acetic acid, propionic acid, caprylic acid, nonanoic acid, capric acid, octylic acid, lauric acid, Examples include aliphatic monocarboxylic acids such as myristic acid, palmitic acid, stearic acid, isononanoic acid, and arachidic acid, and aromatic monocarboxylic acids such as benzoic acid and p-butylbenzoic acid.

The (meth) acrylate used in the present invention is, for example, (meth) acrylic such as methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, etc. Homopolymers of acid alkyl esters, or between these esters or these esters with alkenylbenzene such as styrene, α-methylstyrene, vinyltoluene, and vinyl acetate, vinylpyridine, acrylamide, methacrylamide, dimethylamino methacrylate Examples thereof include copolymers with ethyl, N-methylolacrylamide, N-butoxymethylacrylamide, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, and the like.
It is preferable that the monocarboxylic acid and the (meth) acrylate react with the modified polyamine so as to have these residues in a proportion of 1 to 30% by weight with respect to the whole molecule. Here, the residue represents the remaining monocarboxylic acid or (meth) acrylate reacted with the carboxyl group.

(Reaction between polyamine and vinyl copolymer (B-1))
The reaction between the polyamine and the vinyl copolymer (B-1) or the mixture of the vinyl copolymer (B-1) to the compound (B-5) is, for example, 200 ° C. or less under a nitrogen gas stream. Can be done. For the reaction, a known polymerization catalyst such as tin-based or titanium-based may be used. If necessary, a non-reactive solvent such as toluene, xylene, or solvesso that does not participate in the reaction can be used. It is not always necessary to remove the solvent used.

  The graft ratio of the vinyl copolymer (B-1) to the polyamine is preferably in the range of about 20 to 95%, and in the range of 30 to 90%, the affinity with the diluting solvent and the film-forming resin. And is particularly preferred because of its excellent balance of affinity with the pigment. Here, the graft ratio represents the reaction amount of the carboxyl group of the vinyl copolymer (B-1) with respect to the total amount of amino groups of the polyamine, and is through the amide bond of the modified polyamine of the present invention. Vinyl copolymer (B-1) Remaining chain (here, vinyl copolymer (B-1) The remaining chain refers to the remaining portion where the carboxyl group reacted).

  When the residual chain of the vinyl copolymer (B-1) of the modified polyamine is less than 20%, the pigments are likely to aggregate with each other, and the insufficient viscosity reduction effect and the ink film may be affected. Further, when the residual chain of the vinyl copolymer (B-1) possessed by the modified polyamine exceeds 95%, the amino group which is a functional group that adsorbs to the pigment is insufficient, and dispersion stability tends to decrease depending on the pigment. In some cases, the effect of lowering the viscosity is insufficient and the ink film is defective.

(Reaction of polyamine with one or more compounds selected from the group consisting of (B-2) to (B-5))
The reaction between the polyamine and one or more compounds selected from the group consisting of (B-2) to (B-5) can be performed, for example, at 200 ° C. or lower under a nitrogen gas stream. For the reaction, a known polymerization catalyst such as tin-based or titanium-based may be used. If necessary, a non-reactive solvent such as toluene, xylene, or solvesso that does not participate in the reaction can be used. The solvent used is not necessarily removed and can be used as it is as one component of the pigment dispersant.
The reaction between the polyamine and one or more compounds selected from the group consisting of (B-2) to (B-5) is sequentially performed even at the same time as the vinyl copolymer (B-1). It doesn't matter.

(Other ingredients)
The modified polyamine (B) used in the present invention may contain a non-reactive solvent used in the production of the modified polyamine (B), and after the non-reactive solvent used in the production is distilled off, A new solvent may be added.

In order to give the modified polyamine (B) used in the present invention a crosslinking point with the polymer (P) obtained by polymerizing the polymerizable unsaturated monomer (C) described later, a polymerizable unsaturated group It is also preferable to introduce. This is because the surface of the pigment can be more firmly coated by crosslinking the polymer (P) and the modified polyamine (B). As a method for introducing a polymerizable unsaturated group into the modified polyamine (B), for example, after reacting a polyamine and a vinyl copolymer (B-1), a glycidyl methacrylate is added to introduce a polymerizable unsaturated group. There are ways to do it.

(Polymerizable unsaturated monomer (C) that is soluble in a non-aqueous solvent and becomes insoluble or hardly soluble after polymerization)
The polymerizable unsaturated monomer (C) used in the present invention that is soluble in the non-aqueous solvent and becomes insoluble or hardly soluble after polymerization is specifically exemplified by methyl (meth) acrylate, ethyl ( Such as olefins such as (meth) acrylate, n-propyl (meth) acrylate or i-propyl (meth) acrylate, or (meth) acrylonitrile, vinyl acetate, vinyl chloride, vinylidene chloride, vinyl fluoride or vinylidene fluoride, Vinyl monomers having no so-called reactive polar groups (functional groups); (meth) acrylamide, dimethyl (meth) acrylamide, Nt-butyl (meth) acrylamide, N-octyl (meth) acrylamide, diacetone acrylamide , Dimethylaminopropylacrylamide or alkoxylated N-methyl Amide bond-containing vinyl monomers such as rolled (meth) acrylamides; dialkyl [(meth) acryloyloxyalkyl] phosphates or (meth) acryloyloxyalkyl acid phosphates, or dialkyl [(meth) acryloyloxy Alkyl] phosphites or (meth) acryloyloxyalkyl acid phosphites; alkylene oxide adducts of the above (meth) acryloyloxyalkyl acid phosphates or acid phosphites, glycidyl (meth) acrylates and methylglycidyl (meta ) Ester compounds of epoxy group-containing vinyl monomers such as acrylate and phosphoric acid or phosphorous acid or their acidic esters, as well as 3-chloro-2-acid phosphoxypropipropylene Phosphorus atom-containing vinyl monomers such as (meth) acrylate; 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 3-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 3-chloro-2-hydroxypropyl (meth) acrylate, di-2-hydroxyethyl fumarate or mono-2-hydroxyethyl monobutyl fumarate Alternatively, polymerizable unsaturated carbo such as polypropylene glycol or polyethylene glycol mono (meth) acrylate, or “Placcel FM, FA monomer” (a caprolactone addition monomer manufactured by Daicel Chemical Industries, Ltd.) Hydroxyalkyl esters of acids or their adducts with ε-caprolactone, and unsaturated mono- or dicarboxylic acids such as (meth) acrylic acid, crotonic acid, maleic acid, fumaric acid, itaconic acid or citraconic acid In addition, polymerizable unsaturated carboxylic acids such as monoesters of these dicarboxylic acids and monohydric alcohols, or the above-mentioned polymerizable unsaturated carboxylic acid hydroxyalkyl esters and maleic acid, succinic acid, phthalic acid, hexa Various unsaturations such as adducts with anhydrides of polycarboxylic acids such as hydrophthalic acid, tetrahydrophthalic acid, hensentricarboxylic acid, benzenetetracarboxylic acid, "hymic acid", tetrachlorophthalic acid or dodecynyl succinic acid Carboxylic acids and “Cardura E”, palm oil fatty acid group Monoglycidyl esters of monovalent carboxylic acids such as sidyl esters or glycidyl octyl esters or adducts with monoepoxy compounds such as butyl glycidyl ether, ethylene oxide or propylene oxide, or adducts thereof with ε-caprolactone, or Hydroxyl-containing polymerizable unsaturated monomers such as hydroxy vinyl ether; Dialkylaminoalkyl (meth) acrylates such as dimethylaminoethyl (meth) acrylate and diethylaminoethyl (meth) acrylate; Glycidyl (meth) acrylate, (β- Methyl) glucidyl (meth) acrylate, (meth) allyl glycidyl ether or polymerizable unsaturated carboxylic acids or mono-2- (meth) acryloyloxymonoethyl phthalate, etc. Various unsaturated carboxylic acids such as an equimolar adduct of an acid group-containing vinyl monomer and the polycarboxylic acid anhydride are added to “Epicron 200”, “Epicron 400”, “Epicron 441”, “Epicron 850” or “Epicron”. "Epicron 1050" (epoxy resin manufactured by DIC Corporation), or "Epicoat 828", "Epicoat 1001" or "Epicoat 1004" (epoxy resin manufactured by Japan Epoxy Resin Co., Ltd.), "Araldite 6071" or "Araldite 6084" ( 1 such as “Chissonox 221” (epoxy compound manufactured by Chisso Corporation) or “Denacol EX-611” (epoxy compound manufactured by Nagase Kasei Co., Ltd.) Has at least two epoxy groups in the molecule Epoxy group-containing polymerizable unsaturated monomers such as an epoxy group-containing polymerizable compound obtained by addition reaction of various polyepoxy compounds at an equimolar ratio; 2-hydroxyethyl (meth) acrylate-hexamethylene diisocyanate, etc. Isocyanate group-containing α, β-ethylenically unsaturated monomers such as molar adducts and monomers having an isocyanate group and a vinyl group such as isocyanate ethyl (meth) acrylate; vinyl ethoxysilane, α-methacryloxypropyl Alkoxysilyl group-containing polymerizable unsaturated monomers such as silicon monomers such as trimethoxysilane, trimethylsiloxyethyl (meth) acrylate, “KR-215, X-22-5002” (product of Shin-Etsu Chemical Co., Ltd.) And (meth) acrylic acid, crotonic acid, maleic acid , Α, β-ethylenically unsaturated carboxylic acids such as unsaturated mono- or dicarboxylic acids such as fumaric acid, itaconic acid or citraconic acid, monoesters of these dicarboxylic acids with monohydric alcohols, or 2 -Hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 3-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meta ) Acrylate, such as 3-chloro-2-hydroxypropyl (meth) acrylate, di-2-hydroxyethyl fumarate, mono-2-hydroxyethyl-monobutyl fumarate or polyethylene glycol mono (meth) acrylate -Unsaturated cal Acid hydroalkyl esters and polyacids such as maleic acid, succinic acid, phthalic acid, hexahydrophthalic acid, tetrahydrophthalic acid, benzenetricarboxylic acid, benzenetetracarboxylic acid, "hymic acid", tetrachlorophthalic acid or dodecynyl succinic acid Examples include carboxyl group-containing α, β-ethylenically unsaturated monomers such as adducts of carboxylic acid anhydrides.
Of these, the use of C3 or lower alkyl (meth) acrylates such as methyl (meth) acrylate and ethyl (meth) acrylate is preferred. Furthermore, in order to change the surface characteristics of the pigment surface and enhance the interaction with the pigment dispersant or pigment dispersion resin, at least one kind of carboxyl group, sulfonic acid group, phosphoric acid group, hydroxyl group, dimethylamino group, etc. It is preferable to copolymerize a polymerizable unsaturated monomer containing a functional group.

  In order to prevent the modified polyamine (B) and the polymer (P) from eluting from the pigment (A) when the modified pigment (D) is used, it is more preferable that the polymer (P) is crosslinked. Examples of the polyfunctional polymerizable unsaturated monomer used as the crosslinking component include divinylbenzene, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, polyethylene glycol di ( (Meth) acrylate, 1,3-butanediol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, neopentyl glycol dimethacrylate, trimethylolpropane tri Ethoxytri (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol Sa (meth) acrylate or allyl methacrylate, and the like.

  Further, in a use range in which a polymer having an essential component of a polymerizable unsaturated monomer (C) which is soluble in at least one non-aqueous solvent and becomes insoluble or hardly soluble after polymerization is not dissolved in the non-aqueous solvent system. Other polymerizable unsaturated monomers may be used. Examples of other polymerizable unsaturated monomers include polymerizable unsaturated monomers that can be used other than the alkyl (meth) acrylate having an alkyl group having 4 or more carbon atoms and the alkyl (meth) acrylate described above. A monomer is mentioned.

The modified pigment (D) used in the present invention is at least one polymer that is soluble in the non-aqueous solvent and insoluble or hardly soluble after polymerization in the presence of the pigment (A) and the modified polyamine (B). It is obtained by polymerizing the unsaturated monomer (C).
The pigment (A) and the modified polyamine (B) are preferably mixed before polymerization.
By mixing, the surface of the pigment (A) is wetted with the modified polyamine (B), and the interface formed by this (the pigment (A) and the modified polyamine (B)) is considered to be the place of polymerization. Then, after mixing the pigment (A) and the modified polyamine (B), the polymerizable unsaturated monomer (C) is further mixed and polymerized to obtain a modified pigment coated with the polymer (P). . In this method, that is, the case where the pigment (A) is finely and stably dispersed with the dispersion stabilizer is not essential, and therefore the surface treatment of the pigment (A) to form a finely dispersed state is always necessary. Rather, it can be applied to a wide variety of pigments.

As a mixing method, for example, a homogenizer, a disper, a bead mill, a paint shaker, a kneader, a roll mill, a ball mill, an attritor, a sand mill and the like can be used. In the present invention, the form of the pigment to be used is not limited, and any form of slurry, wet cake, and powder may be used. That is, in the production method of the present invention, even a pigment containing water such as a wet cake can be used.
After mixing the pigment (A) and the modified polyamine (B), the polymerizable unsaturated monomer (C) and a polymerization initiator described later are further mixed and polymerized to obtain the modified pigment (D).
At that time, the amount of the modified polyamine (B) is not particularly limited since it is appropriately optimized depending on the purpose, but usually 1 to 200 parts is used with respect to 100 parts of the pigment (A), more preferably. 2 to 50 parts, more preferably 3 to 30 parts.
Further, the amount of the polymerizable unsaturated monomer (C) used is not particularly limited because it is appropriately optimized depending on the purpose, but usually 1 to 200 parts per 100 parts of the pigment (A). More preferably 1 to 50 parts, still more preferably 1 to 30 parts.

  The amount of the modified polyamine (B) and polymer (P) finally coated on the pigment is preferably 2 to 400 parts, more preferably 3 to 100 parts, relative to 100 parts of the pigment (A). More preferably, it is 4-60 parts. In that case, it is preferable to use at least 1 sort of said polymerizable unsaturated monomer (C) normally in the ratio of 10-400 parts with respect to 100 parts of said modified polyamine (B), Preferably 30- 400 parts, more preferably 50 to 200 parts.

The method of polymerizing the polymerizable unsaturated monomer (C) in the presence of the pigment (A), the non-aqueous solvent, and the modified polyamine (B) may be performed by a known and conventional polymerization method. Usually, it is carried out in the presence of a polymerization initiator. Such polymerization initiators include azobisisobutyronitrile (AIBN), 2,2-azobis (2-methylbutyronitrile), benzoyl peroxide, t-butyl perbenzoate, t-butyl-2-ethylhexano A radical generating polymerization catalyst such as ate, t-butyl hydroperoxide, di-t-butyl peroxide, or cumene hydroperoxide may be used alone or in combination of two or more.
Since some polymerization initiators are difficult to dissolve in the non-aqueous solvent system, a method in which the polymerization initiator is dissolved in the polymerizable unsaturated monomer (C) and added to the mixed system of the pigment (A) and the modified polyamine (B) is preferable. .
The polymerizable unsaturated monomer (C) or the polymerizable unsaturated monomer (C) in which the polymerization initiator is dissolved can be added by a dropping method in a state where the polymerization temperature is reached. A method of adding the polymer at a normal temperature before warming, heating the polymer after sufficiently mixing, and polymerizing is stable and preferable.
The polymerization temperature is usually in the range of 60 ° C to 130 ° C. In addition, when the pigment (A) is an organic pigment, if the polymerization temperature is too high, the pigment may undergo significant changes in form such as alteration and crystal growth. In that case, it is preferable to polymerize at 70 to 100 ° C.

  After the polymerization, the nonaqueous solvent used for the polymerization is removed by filtration, followed by drying and pulverization to obtain a powdery polymer-coated pigment. Nutsche, filter press, etc. can be used for the filtration method. Moreover, it can dry with well-known drying apparatuses, such as a box-type dryer, a vacuum dryer, a band dryer, and a spray dryer. For the pulverization, a known pulverizer such as a mortar, a hammer mill, a disk mill, a pin mill, or a jet mill can be used.

(Pigment dispersion composition for color filter)
The pigment dispersion composition for a color filter of the present invention can be obtained by dispersing the modified pigment (D) in a resin solution in which a pigment dispersant such as a resin and an organic solvent are mixed. At that time, a publicly known and commonly used pigment dispersion method can be used, and the pigment dispersion is performed using a dispersing machine such as a ball mill, a sand mill, a bead mill, a three-roll mill, a paint conditioner, an attritor, a dispersion stirrer, or an ultrasonic wave. I can do things. Specific dispersing equipment includes super apex mill (manufactured by Kotobuki Giken Kogyo Co., Ltd.), ultra apex mill (manufactured by Kotobuki Giken Kogyo Co., Ltd.), dry swerke PM-DCP stirring bead mill device (manufactured by dry swerke), pico glen mill ( Asada Iron Works Co., Ltd.).

  Examples of the grinding medium used for pigment dispersion include a zirconia or steel grinding medium, and among these, a zirconia grinding medium having excellent wear resistance is particularly preferable. Further, the diameter of the grinding medium is preferably in the range of 0.01 to 3.0 mm, particularly preferably in the range of 0.05 to 0.5 mm. When the diameter of the grinding medium is larger than 3.0 mm, the wet pulverization becomes insufficient, which is not preferable.

As the pigment dispersant used in the pigment dispersion, a known pigment dispersant generally used for pigment dispersion can be used. Examples include surfactants, pigment intermediates or derivatives, dye intermediates or derivatives, or resin-type dispersants such as polyamide resins, polyurethane resins, polyester resins, and acrylic resins. Among the above various dispersants, it is preferable to use a polyester-based resin and an acrylic resin.
Examples of commercially available resin-type dispersants include, for example, “DISPERBYK-130”, “DISPERBYK-161”, “DISPERBYK-162”, “DISPERBYK-163”, “DISPERBYK-170”, and “DISPERBYK-171” manufactured by BYK Chemie. ”,“ DISPERBYK-174 ”,“ DISPERBYK-180 ”,“ DISPERBYK-182 ”,“ DISPERBYK-183 ”,“ DISPERBYK-184 ”,“ DISPERBYK-185 ”,“ DISPERBYK-2000 ”,“ DISPERBYK-2001 ”, “DISPERBYK-2020”, “DISPERBYK-2050”, “DISPERBYK-2070”, “DISPERBYK-2096”, “DISPERBYK” 2150 ”,“ EFKA1503 ”,“ EFKA4010 ”,“ EFKA4020 ”,“ EFKA4300 ”,“ EFKA4330 ”,“ EFKA4340 ”,“ EFKA4520 ”,“ EFKA4530 ”,“ EFKA5054 ”,“ EFK5054 ”,“ EFT50505 ” "EFKA7422", "EFKA7431", "EFKA7441", "EFKA7461", "EFKA7496", "EFKA7496", Lubrizol's "Solsparse 3000", "Solsparse 9000", "Solsparse 13240", "Solsparse 13650", ""Sol Sparse 13940", "Sol Sparse 17000", "Sol Sparse 18000", "Sol Sparse 20000", "Sol Sparse 210""0","Sol Sparse 20000", "Sol Sparse 24000", "Sol Sparse 26000", "Sol Sparse 27000", "Sol Sparse 28000", "Sol Sparse 32000", "Sol Sparse 36000", "Sol Sparse 37000", "Sol Sparse 38000", "Sol Sparse""41000","Solspers42000","Solspers43000","Solspers46000","Solspers54000","Solspers71000", Ajinomoto Fine Techno Co., Ltd. products Ajispar "PB-711", "Ajispur PB-821", " It is possible to use “Azisper PB-822”, “Azisper PB-814”, “Azisper PB-824”, and the like.
In addition, a leveling agent, a coupling agent, a cationic surfactant, and the like can be used together. In the present invention, these dispersants may be used in combination of two or more.

  Examples of organic solvents used for pigment dispersion include aromatic solvents such as toluene, xylene and methoxybenzene, ethyl acetate, propyl acetate and butyl acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate and the like. Acetic acid ester solvents, propionate solvents such as ethoxyethyl propionate, alcohol solvents such as methanol and ethanol, ether solvents such as butyl cellosolve, propylene glycol monomethyl ether, diethylene glycol ethyl ether, diethylene glycol dimethyl ether, methyl ethyl ketone, methyl isobutyl ketone, Ketone solvents such as cyclohexanone, aliphatic hydrocarbon solvents such as hexane, N, N-dimethylformamide, γ-butyrolac , N-methyl-2-pyrrolidone, nitrogen compounds such as aniline, pyridine, lactone solvents such as γ-butyrolactone, carbamic acid esters such as a 48:52 mixture of methyl carbamate and ethyl carbamate, water Etc. Of these, water-soluble polar solvents such as propionate, alcohol, ether, ketone, nitrogen compound, and lactone are particularly preferable. When a water-soluble organic solvent is used, water can be used in combination. In this invention, these solvents can also use 2 or more types together.

  Although there is no limitation in particular about each usage-ratio, generally 5-200 parts pigment dispersant with respect to 100 parts of modified pigment (D), Preferably, it is 10-100 pigment dispersant, More preferably Uses a pigment dispersant of 10 to 60, and the organic solvent is used so that the total solid content of the modified pigment (D) and the pigment dispersant is 10 to 25%, preferably 10 to 20%.

(Color filter)
The pigment dispersion composition for a color filter of the present invention can be used for producing a color filter having red, green and blue color pixel portions and a black matrix.
In producing the color filter, any known and commonly used production methods such as a photolithography method, an ink jet method, and a printing method can be employed. Hereinafter, an example of a photolithography method will be described.
The photolithographic method uses a photocurable composition in which a photocurable monomer or oligomer, a photopolymerization initiator, or the like is appropriately mixed with the pigment dispersion composition for a color filter of the present invention, and a black matrix of a transparent substrate for a color filter. After applying and heating and drying (pre-baking) the surface on the provided side, pattern exposure is performed by irradiating ultraviolet rays or visible light in the wavelength range of 200 to 500 nm through a photomask, and the portions corresponding to the pixel portions are exposed. In this method, the photocurable compound is cured, and then the unexposed portion is developed with a developer, the non-pixel portion is removed, and the pixel portion is fixed to the transparent substrate. In this method, a pixel portion made of a cured colored film of a photocurable composition is formed on a transparent substrate. A photocurable composition is prepared for each of the black, red, green, and blue modified pigments (D), and the above-described operation is repeated to form a black matrix. Further, red, green, and blue are formed at predetermined positions. A color filter having each color pixel portion can be manufactured.
In addition, yellow modified pigment (D) or purple modified pigment (D) can be used in combination for the formation of red, green and blue pixel portions. If necessary, the entire color filter after photocuring can be heat-treated (post-baked).

Examples of the method for applying the photocurable composition onto a transparent substrate such as glass include a spin coating method, a roll coating method, and an inkjet method. Moreover, although the heat-drying conditions of the photocurable composition after application | coating differ also with the kind of each component, a mixture ratio, etc., it is 50-150 degreeC and is normally about 1 to 15 minutes.
Examples of the developing method after pattern exposure include a liquid piling method, a dipping method, and a spray method. After exposure and development of the photocurable composition, the transparent substrate on which the necessary color pixel portions are formed is washed with water and dried.
The color filter thus obtained is subjected to heat treatment (post-baking) at 100 to 280 ° C. for a predetermined time by a heating device such as a hot plate or an oven to remove volatile components in the coating film and at the same time photocuring. The unreacted photocurable compound remaining in the cured colored film of the curable composition is thermally cured to complete the color filter.

  The method for producing a color filter by a photolithography method among the pigment dispersion methods has been described in detail, but the color filter using the pigment dispersion composition for a color filter of the present invention is not limited to the method, for example, an electrodeposition method, You may manufacture by methods, such as a transfer method, a micelle electrolysis method, and PVED (Photovoltaic Electrodeposition) method.

  Hereinafter, the present invention will be described with reference to examples. Unless otherwise specified, “parts” and “%” are based on mass.

<Synthesis Example 1 Synthesis of Vinyl Polymer (X1)>
100 parts of xylene and 10 parts of thioglycolic acid were kept at 80 ° C. in a nitrogen stream, and while stirring, 54 parts of methyl methacrylate, 36 parts of butyl acrylate, and a polymerization initiator (“Perbutyl (registered trademark) O” [active ingredient A mixture consisting of 2 parts of peroxy 2-ethylhexanoate t-butyl, manufactured by Nippon Oil & Fats Co., Ltd.] was added dropwise over 4 hours. After completion of the dropwise addition, 0.5 part of “Perbutyl (registered trademark) O” was added every 4 hours and stirred at 80 ° C. for 12 hours. After completion of the reaction, xylene was added to adjust the nonvolatile content to obtain a xylene solution (X1) of a vinyl copolymer having a nonvolatile content of 50% and having a carboxyl group at one end. The resin had a mass average molecular weight of 5000 and an acid value of 60.5 mgKOH / g.

<Synthesis Example 2 Synthesis of Vinyl Polymer (X2)>
While maintaining 100 parts of xylene at 80 ° C. in a nitrogen stream, 68 parts of ethyl methacrylate, 29 parts of 2-ethylhexyl methacrylate, 3 parts of thioglycolic acid, and a polymerization initiator (“Perbutyl (registered trademark) O” [ The active ingredient peroxy 2-ethylhexanoate t-butyl, manufactured by Nippon Oil & Fats Co., Ltd.]) was added dropwise over 4 hours. After completion of the dropwise addition, 0.5 part of “Perbutyl (registered trademark) O” was added every 4 hours and stirred at 80 ° C. for 12 hours. After completion of the reaction, xylene was added to adjust the non-volatile content to obtain a xylene solution of a vinyl copolymer (X2) having a non-volatile content of 50% and having a carboxyl group at one end. The weight average molecular weight of the resin was 7000, the acid value was 18.0 mgKOH / g, and the glass transition temperature Tg was 38 ° C.

<Synthesis Example 3 Synthesis of Vinyl Polymer (X3)>
While maintaining 100 parts of xylene at 80 ° C. in a nitrogen stream, stirring, 66 parts of ethyl methacrylate, 28 parts of 2-ethylhexyl methacrylate, 6 parts of thioglycolic acid, and a polymerization initiator (“Perbutyl (registered trademark) O” [ The active ingredient peroxy 2-ethylhexanoate t-butyl, manufactured by NOF Corporation] was added dropwise over 4 hours. After completion of the dropwise addition, 0.5 part of “Perbutyl (registered trademark) O” was added every 4 hours and stirred at 80 ° C. for 12 hours. After completion of the reaction, an appropriate amount of xylene was added to adjust the non-volatile content to obtain a xylene solution of a vinyl copolymer (X3) having a non-volatile content of 50% and having a carboxyl group at one end. The weight average molecular weight of the resin was 4000, the acid value was 36.0 mgKOH / g, and the glass transition temperature Tg was 38 ° C.

<Synthesis Example 4 Synthesis of Vinyl Polymer (X4)>
While maintaining 100 parts of xylene at 80 ° C. in a nitrogen stream, stirring, 66 parts of lauryl methacrylate, 28 parts of 2-ethylhexyl methacrylate, 6 parts of thioglycolic acid, and a polymerization initiator (“Perbutyl (registered trademark) O” [effective Component peroxy 2-ethylhexanoate t-butyl, manufactured by Nippon Oil & Fats Co., Ltd.]) was added dropwise over 4 hours. After completion of the dropwise addition, 0.5 part of “Perbutyl (registered trademark) O” was added every 4 hours and stirred at 80 ° C. for 12 hours. After completion of the reaction, an appropriate amount of xylene was added to adjust the nonvolatile content to obtain a xylene solution of a vinyl copolymer (X4) having a nonvolatile content of 50% and having a carboxyl group at one end. The weight average molecular weight of the resin was 4500, the acid value was 36.0 mgKOH / g, and the glass transition temperature Tg was −51 ° C.

<Synthesis Example 5 Synthesis of Vinyl Polymer (X5)>
While maintaining 100 parts of xylene at 80 ° C. in a nitrogen stream and stirring, 94 parts of lauryl methacrylate, 6 parts of thioglycolic acid, and a polymerization initiator (“Perbutyl® O” [active ingredient peroxy 2-ethylhexanoic acid t -Butyl, manufactured by Nippon Oil & Fats Co., Ltd.]) was added dropwise over 4 hours. After completion of the dropwise addition, 0.5 part of “Perbutyl (registered trademark) O” was added every 4 hours and stirred at 80 ° C. for 12 hours. After completion of the reaction, an appropriate amount of xylene was added to adjust the non-volatile content to obtain a xylene solution of a vinyl copolymer (X5) having a non-volatile content of 50% and having a carboxyl group at one end. The weight average molecular weight of the resin was 5,500, the acid value was 36.0 mgKOH / g, and the glass transition temperature Tg was −65 ° C.

<Synthesis Example 6 Synthesis of Vinyl Polymer (X6)>
While maintaining 100 parts of xylene at 80 ° C. in a nitrogen stream, 94 parts of cetyl methacrylate, 6 parts of thioglycolic acid, and a polymerization initiator (“Perbutyl® O” [active ingredient peroxy 2-ethylhexanoic acid t -Butyl, manufactured by Nippon Oil & Fats Co., Ltd.]) was added dropwise over 4 hours. After completion of the dropwise addition, 0.5 part of “Perbutyl (registered trademark) O” was added every 4 hours and stirred at 80 ° C. for 12 hours. After completion of the reaction, an appropriate amount of xylene was added to adjust the non-volatile content to obtain a xylene solution of a vinyl copolymer (X6) having a non-volatile content of 50% and having a carboxyl group at one end. The resin had a weight average molecular weight of 5000 and an acid value of 36.0 mgKOH /.

<Synthesis Example 7 Synthesis of Vinyl Polymer (X7)>
In a flask equipped with a stirrer, reflux condenser, nitrogen blowing tube and thermometer, 30 parts of ion-exchanged water and 30 parts of isopropyl alcohol are kept at 80 ° C. in a nitrogen stream, and 40 parts of N-vinylformamide are added while stirring. A mixture consisting of 8 parts of mercaptoethanol and 0.8 part of a polymerization initiator (“Perbutyl (registered trademark) O” [active ingredient t-butyl peroxy-2-ethylhexanoate, manufactured by NOF Corporation)] takes 4 hours. And dripped. After completion of the reaction, an appropriate amount of ion-exchanged water was added to adjust the nonvolatile content to obtain a vinyl polymer (X7) having a nonvolatile content of 40%.

<Synthesis Example 8 Synthesis of Polyvinylamine Copolymer (PA-1)>
A flask equipped with a stirrer, a reflux condenser, a nitrogen blowing tube, and a thermometer, 125 parts of the vinyl polymer (X7) having a nonvolatile content of 40% obtained in Synthesis Example 7 and 141 parts of a 20% sodium hydroxide solution In addition, the mixture was reacted at 80 ° C. for 16 hours with stirring. After completion of the reaction, acetone was added to precipitate the resin component, followed by separation and drying to obtain a solid content of the polyvinylamine copolymer (PA-1). The amine value of the polyvinylamine copolymer (PA-1) was 1174 mg KOH / g, and the hydrolysis rate of N-vinylformamide calculated from the amine value was 90%.

<Synthesis Example 9 Synthesis of Polyvinylamine Copolymer (PA-2)>
A flask equipped with a stirrer, reflux condenser, nitrogen blowing tube and thermometer was 125 parts of the vinyl polymer (X7) having a non-volatile content of 40% obtained in Synthesis Example 7 and 42 parts of a 20% sodium hydroxide solution. In addition, the mixture was reacted at 80 ° C. for 2 hours with stirring. After completion of the reaction, acetone was added to precipitate the resin component, followed by separation and drying to obtain a solid content of the polyvinylamine copolymer (PA-2). The amine value of the polyvinylamine copolymer (PA-2) was 305 mg KOH / g, and the hydrolysis rate of N-vinylformamide calculated from the amine value was 23%.

<Synthesis Example 10 Synthesis of Modified Polyamine (BJ-1)>
In a flask equipped with a stirrer, reflux condenser, nitrogen blowing tube and thermometer, 100 parts of xylene and 20% aqueous solution of polyallylamine (“PAA-05” manufactured by Nittobo Co., Ltd., number average molecular weight of about 5,000) A mixture consisting of 37.5 parts was charged, stirred at 140 ° C. with stirring under a nitrogen stream, water was distilled off using a separator, and xylene was returned to the reaction solution while being mixed with Synthesis Example 1 The vinyl copolymer (X1) obtained in (1) (used as the vinyl copolymer (B-1) in the present application) 168.8 parts of which was heated to 140 ° C was added, and the reaction was carried out at 140 ° C for 8 hours. After completion of the reaction, an appropriate amount of xylene was added to adjust the nonvolatile content to obtain a modified polyamine (BJ-1) having a nonvolatile content of 40%. The resin had a mass average molecular weight of 7,500 and an amine value of 32.5 mg KOH / g.

<Synthesis Example 11 Synthesis of Modified Polyamine (BJ-2)>
In a flask equipped with a stirrer, a reflux condenser, a nitrogen blowing tube and a thermometer, 54.5 parts of xylene, the vinyl copolymer (X2) obtained in Synthesis Example 2 (the vinyl copolymer (B-1 in this application)) )) 19.0 parts, vinyl copolymer (X3) obtained in Synthesis Example 3 (used as vinyl copolymer (B-2-1) in this application) 38.0 parts, and polyallylamine 20% aqueous solution (Nittobo Co., Ltd. “PAA-05”, number average molecular weight of about 5,000) was charged with a mixture of 7.5 parts, stirred at 140 ° C. while stirring under a nitrogen stream, and water was removed using a separator. The reaction was carried out at 140 ° C. for 8 hours while returning xylene to the reaction solution.
After completion of the reaction, an appropriate amount of xylene was added to adjust the nonvolatile content to obtain a modified polyamine (BJ-2) having a nonvolatile content of 40%. The resin had a weight average molecular weight of 10,000 and an amine value of 22.0 mg KOH / g.

<Synthesis Example 12 Synthesis of Modified Polyamine (BJ-3)>
In a flask equipped with a stirrer, reflux condenser, nitrogen blowing tube, and thermometer, 10.5 parts of 20% aqueous solution of polyallylamine “PAA-03” and polyethylene glycol-polypropylene glycol monomethacrylate (manufactured by NOF Corporation) "Blemmer 70PEP-350B", average ethylene glycol chain number 5, average propylene glycol chain number 2) (used as (meth) acrylate (B-3) in the present application) 1.5 parts, and stirring at 50 ° C under a nitrogen stream And stirred for 3 hours. Next, 35.2 parts of xylene and 52.8 parts of the vinyl copolymer (X3) obtained in Synthesis Example 3 (used as the vinyl copolymer (B-1) in the present application) were charged, and the mixture was stirred at 140 ° C. under a nitrogen stream. The reaction was carried out at 140 ° C. for 8 hours while returning water to the reaction solution while distilling off water using a separator. After completion of the reaction, an appropriate amount of xylene was added to adjust the nonvolatile content to obtain a modified polyamine (BJ-3) having a nonvolatile content of 40%. The weight average molecular weight of the resin was 8,000, and the amine value was 31.0 mg KOH / g.

<Synthesis Example 13 Synthesis of Modified Polyamine (BJ-4)>
To a flask equipped with a stirrer, a reflux condenser, a nitrogen blowing tube, and a thermometer, 100 parts of the modified polyamine (BJ-3) having a nonvolatile content of 40% obtained in Synthesis Example 12 and 1.6 parts of glycidyl methacrylate were added. , And reacted at 80 ° C. for 8 hours. After completion of the reaction, an appropriate amount of xylene was added to adjust the nonvolatile content to obtain a modified polyamine (BJ-4) having a nonvolatile content of 40%.

<Synthesis Example 14 Synthesis of Modified Polyamine (BJ-5)>
In a flask equipped with a stirrer, reflux condenser, nitrogen blowing tube and thermometer, 11 parts of xylene and 7.5 parts of polyethyleneimine (Epomin SP-006, manufactured by Nippon Shokubai Chemical Industry Co., Ltd., average molecular weight of about 600) In addition, the mixture was stirred at 140 ° C. while stirring under a nitrogen stream, and water was distilled off using a separator, while the xylene was returned to the reaction solution, and the vinyl copolymer obtained in Synthesis Example 1 ( X1) (Used as vinyl copolymer (B-1) in the present application) 168.8 parts heated to 140 ° C were added and reacted at 140 ° C for 8 hours. After completion of the reaction, an appropriate amount of xylene was added to adjust the nonvolatile content to obtain a modified polyamine (BJ-5) having a nonvolatile content of 40%.

<Synthesis Example 15 Synthesis of Modified Polyamine (BJ-6)>
To a flask equipped with a stirrer, reflux condenser, nitrogen blowing tube and thermometer, 11 parts of xylene and 7.5 parts of the polyvinylamine copolymer (PA-1) obtained in Synthesis Example 8 were added, While stirring, the mixture is stirred at 140 ° C., and water is distilled off using a separation device. While returning xylene to the reaction solution, the vinyl copolymer (X1) obtained in Synthesis Example 1 (in this application) (Used as vinyl copolymer (B-1)) 152 parts heated to 140 ° C were added and reacted at 140 ° C for 8 hours. After completion of the reaction, an appropriate amount of xylene was added to adjust the water content in the reaction solution to obtain a nonvolatile content, to obtain a modified polyamine (BJ-6) having a nonvolatile content of 40%.

<Synthesis Example 16 Synthesis of Modified Polyamine (BJ-7)>
To a flask equipped with a stirrer, reflux condenser, nitrogen blowing tube and thermometer, 11 parts of xylene and 7.5 parts of the polyvinylamine copolymer (PA-2) obtained in Synthesis Example 9 were added, While stirring, the mixture is stirred at 140 ° C., and water is distilled off using a separation device. While returning xylene to the reaction solution, the vinyl copolymer (X1) obtained in Synthesis Example 1 (in this application) (Used as vinyl copolymer (B-1)) 42.2 parts heated to 140 ° C were added and reacted at 140 ° C for 8 hours. After completion of the reaction, an appropriate amount of xylene was added to adjust the water content in the reaction solution to obtain a non-volatile content, thereby obtaining a modified polyamine (BJ-7) having a non-volatile content of 40%.

<Synthesis Example 17 Synthesis of Modified Polyamine (BJ-8)>
In a flask equipped with a stirrer, reflux condenser, nitrogen blowing tube and thermometer, 100 parts of xylene and 20% aqueous solution of polyallylamine (“PAA-05” manufactured by Nittobo Co., Ltd., number average molecular weight of about 5,000) A mixture consisting of 37.5 parts was charged, stirred at 140 ° C. with stirring under a nitrogen stream, water was distilled off using a separator, and xylene was returned to the reaction solution while being mixed with Synthesis Example 4 172.5 parts (used as vinyl copolymer (B-1) in the present application) of vinyl copolymer (X4) obtained in 1 above was added to 140 ° C., and the reaction was carried out at 140 ° C. for 8 hours. After completion of the reaction, an appropriate amount of xylene was added to adjust the nonvolatile content to obtain a modified polyamine (BJ-8) having a nonvolatile content of 40%. The mass average molecular weight of the resin was 6,200, and the amine value was 46.0 mg KOH / g.

<Synthesis Example 18 Synthesis of Modified Polyamine (BJ-9)>
In a flask equipped with a stirrer, reflux condenser, nitrogen blowing tube and thermometer, 100 parts of xylene and 20% aqueous solution of polyallylamine (“PAA-05” manufactured by Nittobo Co., Ltd., number average molecular weight of about 5,000) A mixture consisting of 32.8 parts was charged, stirred at 140 ° C. while stirring under a nitrogen stream, water was distilled off using a separator, and xylene was returned to the reaction solution while being mixed with Synthesis Example 2. The vinyl copolymer (X2) 75 parts obtained in the above (used as the vinyl copolymer (B-1) in the present application) and the vinyl copolymer (X5) 99.4 parts obtained in Synthesis Example 5 are 140 ° C. The mixture was heated to 140 ° C. for 8 hours. After completion of the reaction, an appropriate amount of xylene was added to adjust the nonvolatile content to obtain a modified polyamine (BJ-9) having a nonvolatile content of 40%. The resin had a mass average molecular weight of 7,000 and an amine value of 35.7 mg KOH / g.

<Synthesis Example 19 Synthesis of Modified Polyamine (BJ-10)>
In a flask equipped with a stirrer, reflux condenser, nitrogen blowing tube and thermometer, 100 parts of xylene and 20% aqueous solution of polyallylamine (“PAA-05” manufactured by Nittobo Co., Ltd., number average molecular weight of about 5,000) A mixture consisting of 32.8 parts was charged, stirred at 140 ° C. while stirring under a nitrogen stream, water was distilled off using a separation device, and xylene was returned to the reaction solution while being mixed with Synthesis Example 6 174.4 parts (used as vinyl copolymer (B-1) in the present application) of the vinyl copolymer (X6) obtained in 1 above were added up to 140 ° C. and reacted at 140 ° C. for 8 hours. After completion of the reaction, an appropriate amount of xylene was added to adjust the nonvolatile content to obtain a modified polyamine (BJ-10) having a nonvolatile content of 40%. The resin had a weight average molecular weight of 8,000 and an amine value of 31.7 mg KOH / g.

<Comparative Synthesis Example 1 Synthesis of Polymer (BH-1)>
A four-necked flask equipped with a thermometer, a stirrer, a reflux condenser and a nitrogen gas inlet tube was charged with 800 parts of heptane and 170 parts of butyl acetate, and the temperature was raised to 90 ° C. A mixture comprising 950 parts of 2-ethylhexyl acid, 50 parts of dimethylaminoethyl methacrylate, and 7 parts of 2,2′-azobis (2-methylbutyronitrile) was added dropwise over 5 hours, and the same temperature was maintained after completion of the addition. For 10 hours to continue the reaction. Thereafter, a solution in which 0.2 part of t-butylpyrocatechol was dissolved in 15 parts of butyl acetate was added, and further 15 parts of glycidyl methacrylate and 30 parts of dimethylaminoethanol were added, and the temperature was raised to 80 ° C. By performing the reaction at the same temperature for 10 hours, a polymer (BH-1) solution containing a polymerizable unsaturated group soluble in a non-aqueous solvent was obtained.

<Modification Example 1 Synthesis of Modified Pigment (1)>
C. I. 200 parts of Pigment Green 58 wet cake (pigment content 50%), 10 parts of the modified polyamine (BJ-1) obtained in Synthesis Example 10 as solids, 400 parts of 1.25 mm zirconia beads, 200 parts of heptane The portion was placed in a polyethylene jar and mixed for 90 minutes with a paint shaker (Toyo Seiki Co., Ltd.). After dilution with 100 parts of heptane, the zirconia beads were removed to prepare a pigment mixture.
400 parts of the obtained pigment mixed solution was charged into a separable flask equipped with a thermometer, a stirrer, a reflux condenser and a nitrogen gas introduction tube, and then 2 parts of t-butylacrylamidesulfonic acid was added to 20 parts of ion-exchanged water. 2 parts of 2,2′-azobis (2-methylbutyronitrile) were dissolved in 3 parts of methyl methacrylate and 5 parts of ethylene glycol dimethacrylate in a polymerizable monomer composition. I added what I did. After stirring for 30 minutes at room temperature, the temperature was raised to 80 ° C., and the reaction was continued for 15 hours at the same temperature. After cooling, the polymer-treated pigment and the polymerization solvent were separated by filtration. The obtained polymer pigment was dried at 100 ° C. for 5 hours with a hot air dryer and then pulverized with a pulverizer to obtain a modified pigment (1).

<Modification Examples 2 to 21 Synthesis of Modified Pigments (2) to (21)>
A pigment mixture was prepared in the same manner as in Example 1 except that the pigment (A) and the modified polyamine (BJ-1) used were changed to the pigments shown in Tables 1 to 5 and the modified polyamine (B). .
The same procedure as in Example 1 was conducted except that 400 parts of the obtained pigment mixed solution was used and the polymerizable monomer (C) was changed to the polymerizable monomer (C) shown in Tables 1 to 5. Modified pigments (2) to (21) were obtained.

(C.I.Pigment Green 58)：Ｃ．Ｉ．ピグメントグリーン５８のウェットケーキ（顔料分５０％）
(C.I.Pigment Red 254)：Ｃ．Ｉ．ピグメントレッド２５４の粉末
(C.I.Pigment Blue 15:6)：Ｃ．Ｉ．ピグメントブルー１５：６の粉末
(C.I.Pigment yellow 150)：Ｃ．Ｉ．ピグメントイエロー１５０の粉末

(CIPigment Green 58): C.I. I. Pigment Green 58 wet cake (50% pigment content)
(CIPigment Red 254): C.I. I. Pigment Red 254 powder
(CIPigment Blue 15: 6): C.I. I. Pigment Blue 15: 6 powder
(CIPigment yellow 150): C.I. I. Pigment Yellow 150 powder

(C.I.Pigment Green 58)：Ｃ．Ｉ．ピグメントグリーン５８のウェットケーキ（顔料分５０％）

(CIPigment Green 58): C.I. I. Pigment Green 58 wet cake (50% pigment content)

(C.I.Pigment Green 58)：Ｃ．Ｉ．ピグメントグリーン５８のウェットケーキ（顔料分５０％）

(CIPigment Green 58): C.I. I. Pigment Green 58 wet cake (50% pigment content)

(C.I.Pigment Green 58)：Ｃ．Ｉ．ピグメントグリーン５８のウェットケーキ（顔料分５０％）

(CIPigment Green 58): C.I. I. Pigment Green 58 wet cake (50% pigment content)

ＰＧ５８：Ｃ．Ｉ．ピグメントグリーン５８のウェットケーキ（顔料分５０％）

PG58: C.I. I. Pigment Green 58 wet cake (50% pigment content)

<Comparative Modification Example 1>
C. I. 192 parts of Pigment Green 58 wet cake (pigment content 52%), 5 parts of solid polymer (BH-1) obtained in Comparative Synthesis Example 1, 400 parts of 1.25 mm zirconia beads, 200 parts of heptane The portion was placed in a polyethylene jar and mixed for 90 minutes with a paint shaker (Toyo Seiki Co., Ltd.). After dilution with 100 parts of heptane, the zirconia beads were removed. 400 parts of the obtained pigment mixed solution was charged into a separable flask equipped with a thermometer, a stirrer, a reflux condenser and a nitrogen gas introduction tube, and then 2 parts of t-butylacrylamide sulfonic acid was 20 parts while stirring. Of 2,2′-azobis (2-methylbutyronitrile) was added to a polymerizable monomer composition of 5 parts of ethylene glycol dimethacrylate and 3 parts of butyl methacrylate. What dissolved 2 parts was added. After stirring for 30 minutes at room temperature, the temperature was raised to 80 ° C., and the reaction was continued for 15 hours at the same temperature. After cooling, the polymer-treated pigment and the polymerization solvent were separated by filtration. The obtained polymer pigment was dried with a hot air dryer at 100 ° C. for 5 hours and then pulverized with a pulverizer to obtain a comparatively modified pigment (1).

<Preparation of Example 1 Pigment Dispersion Liquid (1) and Color Filter>
5 parts of the modified pigment (1) obtained in Modification Example 1 and 1.5 parts of Ajisper PB-821 (pigment dispersant manufactured by Ajinomoto Fine Techno Co., Ltd.) are mixed with 26.8 parts of propylene glycol monomethyl ether acetate (hereinafter PGMAc). 65 parts of 0.5 mm zirconia beads dissolved in 1 ml are placed in a polyethylene jar and dispersed in a paint shaker (Toyo Seiki Co., Ltd.) for 2 hours, after which the zirconia beads are removed and a pigment dispersion (1) Got. 75.00 parts of pigment dispersion and 5.50 parts of polyester acrylate resin (Aronix M7100, manufactured by Toa Gosei Chemical Co., Ltd.), 5.00 parts of dipentaerythrate hexaacrylate (KAYARDADDHA, manufactured by Nippon Kayaku Co., Ltd.), 1.00 parts of benzophenone (KAYACURE BP-100, manufactured by Nippon Kayaku Co., Ltd.) and 13.5 parts of Euker Ester EFP are stirred with a dispersion stirrer and filtered with a filter having a pore size of 1.0 μm to obtain a pigment dispersion resist (color resist). Obtained. The pigment dispersion resist is a 1 mm thick glass using a spectrophotometer MCPD-3000 manufactured by Otsuka Electronics Co., Ltd., and the chromaticity coordinate y value is calculated by C2 light source colorimetry, so that y = 0.48. And then pre-dried at 60 ° C. for 5 minutes to form a coating film. Next, after performing pattern exposure with ultraviolet rays through a photomask, the unexposed portion was washed in a 0.5% sodium carbonate aqueous solution, then further washed with pure water, and the resulting coating film was then washed at 230 ° C. The coating film was cured by heat treatment for 15 minutes to obtain a color filter. The viscosity of the pigment dispersion (1) thus obtained and the brightness and contrast of the color filter pixel portion were evaluated by the following methods and are shown in Table 6.

(viscosity)
The viscosity was measured using a Brookfield product “Digital Viscometer DV-II Pro”. In general, the viscosity of the dispersion is preferably low.

(Luminance)
Luminance (Y value) was measured using a spectrophotometer MCPD-3000 manufactured by Otsuka Electronics Co., Ltd., and the Y value in CIE color development system chromaticity was measured by C2 light source colorimetry. Here, it was evaluated that the visual brightness was higher as the luminance (Y value) was higher.

(contrast)
The color filter pixel portion was installed between two polarizing plates, a light source was installed on one side, and a CCD camera was installed on the opposite side to measure the luminance. It was calculated from the ratio of luminance (transmitted light intensity) between when the polarization axis was parallel and when it was vertical.

<Examples 2, 3, 7 to 21>
Pigment dispersion, painting, and evaluation were performed in the same manner as in Example 1 except that the modified pigment (1) was changed as shown in Tables 6 and 7.

<Example 4 Preparation of pigment dispersion (4) and color filter>
5 parts of the modified pigment (4) obtained in Modification Example 4 and 1.5 parts of Ajisper PB-821 (pigment dispersant manufactured by Ajinomoto Fine Techno Co., Ltd.) were mixed with 26.8 parts of propylene glycol monomethyl ether acetate (hereinafter PGMAc). 65 parts of 0.5 mm zirconia beads dissolved in 1 ml are put into a polyethylene jar and dispersed with a paint shaker (Toyo Seiki Co., Ltd.) for 2 hours. Then, the zirconia beads are removed to obtain a pigment dispersion (4). Got. 75.00 parts of pigment dispersion and 5.50 parts of polyester acrylate resin (Aronix M7100, manufactured by Toa Gosei Chemical Co., Ltd.), 5.00 parts of dipentaerythrate hexaacrylate (KAYARDADDHA, manufactured by Nippon Kayaku Co., Ltd.), 1.00 parts of benzophenone (KAYACURE BP-100, manufactured by Nippon Kayaku Co., Ltd.) and 13.5 parts of Euker Ester EFP are stirred with a dispersion stirrer and filtered with a filter having a pore size of 1.0 μm to obtain a pigment dispersion resist (color resist). Obtained. The pigment dispersion resist is a 1 mm thick glass using a spectrophotometer MCPD-3000 manufactured by Otsuka Electronics Co., Ltd., and the chromaticity coordinate y value is calculated by C2 light source colorimetry, so that y = 0.107. And then pre-dried at 60 ° C. for 5 minutes to form a coating film. Next, after performing pattern exposure with ultraviolet rays through a photomask, the unexposed portion was washed in a 0.5% sodium carbonate aqueous solution, then further washed with pure water, and the resulting coating film was then washed at 230 ° C. The coating film was cured by heat treatment for 15 minutes to obtain a color filter. The viscosity of the pigment dispersion (5) thus obtained, the brightness of the color filter pixel portion, and the contrast were evaluated by the following methods and listed in Table 6.

<Example 5 Preparation of pigment dispersion (5) and color filter>
5 parts of the modified pigment (5) obtained in Modification Example 5 and 1.5 parts of Ajisper PB-821 (pigment dispersant manufactured by Ajinomoto Fine Techno Co., Ltd.) are mixed with 26.8 parts of propylene glycol monomethyl ether acetate (hereinafter PGMAc). 65 parts of a 0.5 mm zirconia bead solution in a polyethylene jar and dispersed in a paint shaker (Toyo Seiki Co., Ltd.) for 2 hours, the zirconia beads were removed and a pigment dispersion (5) Got. 75.00 parts of pigment dispersion and 5.50 parts of polyester acrylate resin (Aronix M7100, manufactured by Toa Gosei Chemical Co., Ltd.), 5.00 parts of dipentaerythrate hexaacrylate (KAYARDADDHA, manufactured by Nippon Kayaku Co., Ltd.), 1.00 parts of benzophenone (KAYACURE BP-100, manufactured by Nippon Kayaku Co., Ltd.) and 13.5 parts of Euker Ester EFP are stirred with a dispersion stirrer and filtered with a filter having a pore size of 1.0 μm to obtain a pigment dispersion resist (color resist). Obtained. The pigment dispersion resist is a 1 mm thick glass using a spectrophotometer MCPD-3000 manufactured by Otsuka Electronics Co., Ltd., and the chromaticity coordinate x value is calculated by C2 light source colorimetry, so that x = 0.64. And then pre-dried at 60 ° C. for 5 minutes to form a coating film. Next, after performing pattern exposure with ultraviolet rays through a photomask, the unexposed portion was washed in a 0.5% sodium carbonate aqueous solution, then further washed with pure water, and the resulting coating film was then washed at 230 ° C. The coating film was cured by heat treatment for 15 minutes to obtain a color filter. The viscosity of the pigment dispersion (5) thus obtained, the brightness of the color filter pixel portion, and the contrast were evaluated by the following methods and listed in Table 6.

<Example 6 Preparation of pigment dispersion (6) and color filter>
5 parts of the modified pigment (6) obtained in Modification Example 6 and 1.5 parts of Ajisper PB-821 (pigment dispersant manufactured by Ajinomoto Fine Techno Co., Ltd.) are mixed with 26.8 parts of propylene glycol monomethyl ether acetate (hereinafter PGMAc). 65 parts of a 0.5 mm zirconia bead solution in a polyethylene jar and dispersed in a paint shaker (Toyo Seiki Co., Ltd.) for 2 hours, the zirconia beads were removed and a pigment dispersion (6) Got. 75.00 parts of pigment dispersion and 5.50 parts of polyester acrylate resin (Aronix M7100, manufactured by Toa Gosei Chemical Co., Ltd.), 5.00 parts of dipentaerythrate hexaacrylate (KAYARDADDHA, manufactured by Nippon Kayaku Co., Ltd.), 1.00 parts of benzophenone (KAYACURE BP-100, manufactured by Nippon Kayaku Co., Ltd.) and 13.5 parts of Euker Ester EFP are stirred with a dispersion stirrer and filtered with a filter having a pore size of 1.0 μm to obtain a pigment dispersion resist (color resist). Obtained. The pigment dispersion resist is a 1 mm thick glass using a spectrophotometer MCPD-3000 manufactured by Otsuka Electronics Co., Ltd., and the chromaticity coordinate x value is calculated by C2 light source colorimetry, so that x = 0.45. And then pre-dried at 60 ° C. for 5 minutes to form a coating film. Next, after performing pattern exposure with ultraviolet rays through a photomask, the unexposed portion was washed in a 0.5% sodium carbonate aqueous solution, then further washed with pure water, and the resulting coating film was then washed at 230 ° C. The coating film was cured by heat treatment for 15 minutes to obtain a color filter. The viscosity of the pigment dispersion (6) thus obtained, the brightness of the color filter pixel portion, and the contrast were evaluated by the following methods and listed in Table 6.

<Comparative Examples 1 and 5>
Pigment dispersion, painting, and evaluation were performed in the same manner as in Example 1 except that the modified pigment (1) was changed as shown in Table 7.

<Comparative example 2>
Pigment dispersion, coating, and evaluation were performed in the same manner as in Example 4 except that the modified pigment (4) was changed as shown in Table 7.

<Comparative Example 3>
Pigment dispersion, coating, and evaluation were performed in the same manner as in Example 5 except that the modified pigment (5) was changed as shown in Table 7.

<Comparative example 4>
Pigment dispersion, coating, and evaluation were performed in the same manner as in Example 6 except that the modified pigment (6) was changed as shown in Table 7.

(Measurement of retardation value)
The retardation value of the color filter obtained in Examples 19 to 21 was measured. The retardation value is J.P. A. Using a spectroscopic ellipsometer “M-2000X” manufactured by Woollam, the amplitude Ψ and phase difference Δ between wavelengths 245 to 1000 nm at an incident angle of 0 degree and 45 degrees of the color filter pixel portion were measured. Based on this, a retardation value Rth at 550 nm was calculated, and a value converted to a film thickness of 2 μm was described.

As a result, the brightness and contrast of the color filter pixel portion using the modified pigments (1) to (21) were higher than those of Comparative Examples 1 to 4 using the pigment that was not modified. Comparative Example 5 is the same pigment as in Example 1, C.I. I. In this example, Pigment Green 58 is used as a modified pigment using a polymer containing a polymerizable unsaturated group that is soluble in a non-aqueous solvent, but the color filter of Example 1 gives higher contrast.
Moreover, the color filter using the modified pigments (19) to (21) was able to greatly reduce the retardation value as compared with Comparative Example 1 using a pigment that was not modified.

Claims (4)

A pigment dispersion composition for a color filter containing a colorant, a resin, and an organic solvent capable of dissolving the resin,
On the surface of the pigment (A),
A modified polyamine (B) obtained by reacting a vinyl copolymer (B-1) having a functional group that reacts with an amino group to form an amide bond at one end with an amino group of the polyamine;
Polymer (P) obtained by polymerizing at least one polymerizable unsaturated monomer (C) that is soluble in a non-aqueous solvent and becomes insoluble or hardly soluble after polymerization
A pigment dispersion composition for a color filter, characterized by using a modified pigment (D) having: The pigment dispersion composition for a color filter according to claim 1, wherein the polyamine is at least one selected from the group consisting of polyallylamine, polyvinylamine, and polyethyleneimine. The pigment (A) is C.I. I. The pigment dispersion composition for a color filter according to claim 1, which is CI Pigment Green 58. A color filter using the pigment dispersion composition for a color filter according to claim 1.