JP4717767B2 - Pigment dispersion composition - Google Patents

Description

  The present invention relates to a pigment dispersion composition having excellent suitability for use, particularly non-aggregation property, non-crystallinity, fluidity, and excellent coloring power, and in particular, paint, printing ink, color display plate using them, and liquid crystal The present invention relates to a pigment dispersion composition suitable for producing a color filter used for a color display, a solid-state imaging device or the like.

  In general, a practically useful pigment that exhibits a clear color tone and high coloring power is composed of fine particles. A pigment dispersion composition obtained by dispersing such a pigment is used in various fields because of the excellent color developability and light resistance of the pigment. However, if the pigment particles are made finer to obtain high coloring power, the viscosity of the pigment dispersion tends to increase due to various factors, making it difficult to remove the dispersion from the disperser and to transport it by pipeline. In addition, there is a concern that gelation occurs during storage and it becomes difficult to use.

  In addition, some photosensitive compositions that are cured by light contain a pigment as a colorant, and are known to be useful as an image forming material. A pigment as a coloring material is required to have a clear color tone and a high coloring power. However, when used as a photosensitive composition, the following problems occur and it is difficult to make the pigment fine.

In order to form a colored image using the colored photosensitive composition, a layer of the photosensitive composition is formed on a substrate, exposed and developed. At this time, as the developer, an alkaline aqueous solution is preferably used rather than an organic solvent because of environmental problems, and therefore the colored layer is required to be soluble in the alkaline aqueous solution. Further, as a dispersion medium for the coating liquid of the colored photosensitive composition, an organic solvent is preferably used from the viewpoint of drying after coating, and the binder (binder) used in the colored photosensitive composition is an acidic group. Need to be dissolved in a suitable organic solvent. The organic pigment is dispersed in such an acidic binder.
However, it is difficult to disperse an organic pigment in an acidic binder soluble in an organic solvent, and the pigment is sufficiently finely divided, has a high coloring power, and can be developed with an alkaline aqueous solution. It was difficult to get.

  One field of application of pigment dispersion compositions is color filters used in liquid crystal displays and the like. The color filter is formed by arranging a coloring material in each pixel portion so as to selectively transmit the three primary colors of red, green, and blue. Various methods are known for disposing the coloring material in the pixel portion, and a dyeing method, a printing method, an electrodeposition method, a pigment dispersion method and the like have been put into practical use. Among these, the pigment dispersion method is excellent from the quality of the color filter obtained and the stability of the manufacturing process.

  In the pigment dispersion method, a colored photosensitive composition solution containing a pigment dispersion composition is provided on a transparent substrate, and after pattern exposure, development is performed to form a pixel pattern of the first color, and this is repeated a plurality of times. A method of forming a pixel pattern of a plurality of colors on a substrate is known (for example, see Non-Patent Document 1). Since a pigment is used as the coloring material, if the pigment is not sufficiently refined, light is scattered and absorbed by the pigment particles, and the light transmittance is reduced. Furthermore, there is a problem that the polarization axis rotates due to light scattering, birefringence, etc. by the pigment particles, and the contrast of the liquid crystal display device is lowered, and further miniaturization of the pigment particles is required.

  In order to solve the various problems as described above, many proposals have been made so far in order to produce a pigment dispersion having sufficient fluidity and being miniaturized. The contents can be roughly divided into two categories based on technical methods.

  One is a method of coating a pigment surface by mixing a pigment derivative obtained by introducing a substituent such as a sulfone group, a sulfonamide group, an aminomethyl group, and a phthalimidomethyl group into a side chain using an organic pigment as a base skeleton. (For example, see Patent Document 1). Specific examples include phthalocyanine derivatives effective for dispersing phthalocyanine pigments (see, for example, Patent Documents 2 to 5). However, in order to use these pigment derivatives as a dispersant, it is necessary that the pigment to be treated by the pigment derivative has a similar color tone or a similar skeleton, so that applicable pigments are extremely limited.

The other is a method of coating the pigment surface with a substantially colorless compound. Various compounds have been proposed so far, and compounds composed of terminal carboxyl group-containing polyesters or salts thereof obtained by dehydrating hydroxycarboxylic acids have been described as compounds that are versatile as dispersants (for example, And Patent Documents 6 and 7). Further, ring-opening addition of a higher monocarboxylic acid glycidyl ester is performed on a product obtained by esterifying tetrakis (2-hydroxyalkyl) ethylenediamine with a hydroxyl group-containing and non-containing higher monocarboxylic acid, and then an acidic group, a basic group or A polymer dispersant composed of a modified polyester type compound obtained by introducing both is described (for example, see Patent Document 8). However, it has been difficult to achieve both sufficient fluidity that can solve the above problems and dispersion of fine pigment particles even when these polymer dispersants are used.
Japanese Patent Publication No.41-2466 British Patent No. 949739 U.S. Pat. No. 4,313,766 Japanese Patent Publication No.39-2884 JP-A-57-12067 Japanese Patent Publication No.54-34009 British Patent No. 1342746 JP-A-2-245231 1990 7th Color Optics Conference 512 Color Display 10.4 "Size TFT-LCD Color Filter Ueki, Koseki, Fukunaga, Yamanaka

  The object of the present invention is to suppress the aggregation of the pigment particles, particularly in the case of containing finely divided pigment particles, and is excellent in non-crystallinity and fluidity, and can be suitably used in various fields, and is excellent in coloring power. Another object of the present invention is to provide a pigment dispersion composition having high pigment dispersibility and dispersion stability.

As a result of intensive studies, the present inventors have found that the above-described problems can be solved by using two or more polymers having a specific structure as a pigment dispersant, and have completed the present invention.
That is, the present invention has the following configuration.

<1> (a) pigments, represented by (b) solvent, (c) dispersing agent having a polyester chain, and, (d) Ri Oh an acid value 65~250mgKOH / g, and the following general formula (4) Graft copolymer having a structural unit derived from a macromonomer (hereinafter referred to as “a graft copolymer having a specific structure having an acid value of 65 to 250 mgKOH / g”, “a graft copolymer having an acid value of 65 to 250 mgKOH / g”, "dispersant having an acid value 65~250mgKOH / g" or referred to as "(d) dispersants".) pigment dispersion composition characterized der Rukoto.

In General Formula (4), R ⁷ represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, and L represents —COO—, —CON (R ⁸ ) —, or a phenylene group. R ⁸ represents a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, or an aryl group having 6 to 20 carbon atoms. W represents a single bond, a single divalent linking group selected from the following atomic groups, or a divalent linking group formed by arbitrarily combining two or more of these, and A represents the following general formula The substituent which has at least the structural unit represented by (2) is represented.

In the formula, Z ¹ and Z ² each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, a cyano group, or a hydroxyl group, and Z ³ represents a hydrogen atom, 1 to carbon atoms. 18 represents an alkyl group or an aryl group having 6 to 20 carbon atoms.

In General Formula (2), R ⁴ represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, and R ⁵ represents a hydrogen atom, an alkyl group having 1 to 22 carbon atoms, or 6 to 30 carbon atoms. Represents an aryl group.
<2> pigment according to the (d) acid dispersing agent is 65~250mgKOH / g graft copolymer, characterized in that a copolymer of Weight average molecular weight 1,000 to 100,000 <1> Dispersion composition.

<3 > containing (c) two types of dispersant having a polyester chain and (d) one type of dispersant that is a graft copolymer having a specific structure with an acid value of 65 to 250 mgKOH / g < The pigment dispersion composition according to < 1 > or <2> .
< 4 > Contains (c) one type of dispersant having a polyester chain, and (d) two types of dispersant that is a graft copolymer having a specific structure with an acid value of 65 to 250 mgKOH / g < The pigment dispersion composition according to < 1 > or <2> .
< 5 > (c) 2 types of dispersant having a polyester chain and (d) 2 types of dispersant, which is a graft copolymer having a specific structure with an acid value of 65 to 250 mgKOH / g, < The pigment dispersion composition according to < 1 > or <2> .

According to the present invention, even when the particular a finely divided pigment particles, is suppressed aggregation of pigment particles, amorphous, excellent fluidity, Ru bovine suitably used in the various fields, the coloring power An excellent pigment dispersion composition having high pigment dispersibility and dispersion stability can be provided.

Hereinafter, the present invention will be described in detail.
The pigment dispersion composition of the present invention comprises (b) a dispersant having a polyester chain in a dispersion medium containing a solvent, preferably an organic solvent, and (d) a graft copolymer having an acid value of 65 to 250 mgKOH / g. It is characterized by containing (a) a pigment dispersed by using two kinds of dispersants called a polymer dispersant.
That is, the pigment dispersion composition of the present invention is characterized by using a combination of a dispersant having a polyester chain and a graft copolymer having a specific acid value.
Hereinafter, the constituent components of the pigment dispersion composition of the present invention will be sequentially described.

<(C) Dispersant having a polyester chain>
First, a dispersant having a polyester chain, which is an important component of the present invention (hereinafter referred to as (c) a dispersant as appropriate) will be described.
Specific examples of the dispersant having a polyester chain include compounds obtained by reacting a polyalkyleneimine and a polyester compound described in JP-A No. 54-37082 and JP-A No. 61-174939. A compound in which the side chain amino group of polyallylamine described in Japanese Patent No. 169821 is modified with polyester, a graft polymer containing a polyester type macromonomer described in Japanese Patent Application Laid-Open No. 9-171253 as a copolymerization component, and further Preferred examples include polyester polyol-added polyurethane described in JP-A-60-166318.

These polymers contain a soft polyester chain, so that the adsorptivity to the pigment increases, and it is used in combination with a dispersant which is a graft copolymer having an acid value of 65 to 250 mgKOH / g, which will be described in detail below. Can improve dispersibility.
The physical property of the dispersant having a polyester chain is preferably a base number of 10 to 100 mgKOH / g, more preferably a base number of 10 to 70 mgKOH / g.
(C) Although the kind of basic group which a dispersing agent has is not specifically limited, Amino group, imino group, etc. are preferable. When the basic group acts as an adsorbing group for the pigment, if the base number is within this range, the pigment can be dispersed well without cross-linking the pigments.
Further, this dispersant may have an acid value in addition to the base value.

  (C) The dispersant having a polyester chain preferably has a polystyrene-equivalent weight average molecular weight (hereinafter referred to as “Mw”) of 1,000 to 100,000, particularly preferably 3,000 to 30,000. A polymer having Mw in this range can form steric hindrance sufficient to improve the dispersibility around the adsorbing pigment, so that the aggregation of the pigment hardly occurs and the dispersibility is sufficient in the pigment dispersion. Can be demonstrated. If the molecular weight is too small, it is difficult to form this steric hindrance, and the effect of suppressing the aggregation of the pigment cannot be sufficiently obtained.If the molecular weight is too large, the dispersant itself causes high viscosity, and a plurality of pigments In some cases, the molecular weight range is suitable from this viewpoint.

  As the dispersant having (c) polyester chain in the present invention, a commercially available dispersant may be used. Examples of commercially available (c) dispersants that can be suitably used in the present invention include Solsperse 24000GR, 28000, 32000, 38500 (trade name: manufactured by Nihon Lubrizol), Ajisper PB711, PN411, PA111, PB821, PB822 ( Trade names: Ajinomoto Fine Techno), EFKA 4047, 4050 (trade names: manufactured by Fuka Additives Japan), Disperbyk-161, 162, 167, 168 (trade names: manufactured by Big Chemie Japan).

(C) The dispersant having a polyester chain is preferably added in an amount of 5 to 50 parts by weight with respect to 100 parts by weight of the pigment. Within this range, suitable dispersibility and dispersion stability are achieved, and the viscosity increase and pigment sedimentation over time of the dispersion can be effectively suppressed. However, since the optimum addition amount of the dispersant is appropriately adjusted depending on the combination of the type of pigment to be used, the type of solvent, etc., it is not limited to this addition amount, and exhibits a suitable dispersibility even outside this range. There is also.
Moreover, it is preferable that it is the range of 2-30 mass% with respect to the total solid of a pigment dispersion composition, More preferably, it is the range of 5-25 mass%.
In addition to the above-mentioned dispersants, conventional low-molecular weight surfactants, high-molecular weight surfactants, and conventional dispersants such as pigment derivatives are included as long as the object of the present invention is not impaired. It is also possible to make it. These conventional dispersants are described in detail below.

<(D) Dispersant which is a graft copolymer having a specific structure with an acid value of 65 to 250 mgKOH / g>
Next, a dispersant (hereinafter referred to as (d) a dispersant as appropriate) which is a graft copolymer having a specific structure with an acid value of 65 to 250 mgKOH / g will be described.
Dispersing agent is a graft copolymer of a specific structure of a second dispersing agent used in (d) according to the invention an acid value 65~250mgKOH / g is Ru polymer der.
When the acid value is lower than 65 mgKOH / g, since there are few acidic groups in the dispersant, the adsorption to the pigment and the dispersant having the polyester chain (c) described above is weak, and, for example, in an alkali-soluble photosensitive dispersion In this case, developability is lowered. When it exceeds 250 mgKOH / g, the amount of acidic groups in the dispersant is large, and the possibility of crosslinking between a plurality of pigments increases.

(D) The dispersant which is a graft copolymer having an acid value of 65 to 250 mgKOH / g is preferably a polymer compound having a weight average molecular weight in the range of 1000 to 100,000. By using the dispersant (d) in the weight average molecular weight range, a high dispersion stabilizing effect can be obtained. Even if it shows an acid value in the above range, the number of acidic groups contained in the polymer increases as the molecular weight increases, and the dispersant itself also tends to increase in viscosity and crosslinks between a plurality of pigments. This raises concerns about behavior.

(D) Examples of the dispersant having an acid value of 65 to 250 mgKOH / g include polymers containing a carboxyl group, a phosphoric acid group, a sulfonic acid group, or a phenolic hydroxyl group as an acidic group. In the present invention, a compound containing a carboxy group It is preferable that
There is no particular limitation on the position of acid group introduction, a polymer in which acid groups are randomly introduced in a linear polymer, a polymer having a carboxyl group at one end, a graft polymer having an acid group only at the trunk, and an acid only at the branch Examples thereof include a graft polymer having a group, a block polymer comprising a block having an acid group and a block having no acid group.

The polymer used as the dispersant (d) of the present invention is preferably a graft copolymer containing one or more structural units represented by the general formula (1).

In general formula (1), R ¹ represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms.
As the alkyl group represented by R ¹ , an alkyl group having 1 to 6 carbon atoms is preferable, and a methyl group is particularly preferable. This alkyl group may further have a substituent, and examples of the substituent that can be introduced include a halogen atom, a carboxyl group, an alkoxycarbonyl group, and an alkoxy group.
Specific examples of when R ¹ is an alkyl group include a methyl group, an ethyl group, a hexyl group, an octyl group, a trifluoromethyl group, a carboxymethyl group, and a methoxycarbonylmethyl group. Among such R ¹ , a hydrogen atom or a methyl group is preferable.

Any known method may be used for the synthesis of the copolymer containing at least the structural unit represented by the general formula (1). Specifically, for example, an ethylenically unsaturated monomer containing a carboxyl group included in the structural unit represented by the general formula (1) and another copolymerizable ethylenically unsaturated monomer are used in a conventional manner. And the like.
Here, a preferable copolymerization ratio includes an aspect in which the structural unit represented by the general formula (1) is included in the copolymer in a molar ratio (in terms of charged amount) in an amount of 5 to 50 mol.

  Examples of the ethylenically unsaturated monomer containing a carboxyl group included in the structural unit represented by the general formula (1) include unsaturated carboxylic acids such as acrylic acid, methacrylic acid, and itaconic acid. These ethylenically unsaturated monomers containing a carboxyl group can be used alone or in admixture of two or more.

  Other copolymerizable ethylenically unsaturated monomers used as the copolymer component of the structural unit represented by the general formula (1) are not particularly limited, and examples thereof include (meth) acrylic acid esters and crotonic acid. Esters, vinyl esters, maleic diesters, fumaric diesters, itaconic diesters, (meth) acrylamides, vinyl ethers, vinyl alcohol esters, styrenes, (meth) acrylonitrile and the like are preferred. Specific examples of the monomer (structural unit) that can be used as such a copolymerization component include the following compounds.

  Examples of (meth) acrylic acid esters include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, and n-butyl (meth) acrylate. , Isobutyl (meth) acrylate, t-butyl (meth) acrylate, n-hexyl (meth) acrylate, cyclohexyl (meth) acrylate, t-butylcyclohexyl (meth) acrylate, (meth) acrylic acid 2- Ethylhexyl, t-octyl (meth) acrylate, dodecyl (meth) acrylate, octadecyl (meth) acrylate, acetoxyethyl (meth) acrylate, phenyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-Methoxyethyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate 2- (2-methoxyethoxy) ethyl (meth) acrylate, 3-phenoxy-2-hydroxypropyl (meth) acrylate, benzyl (meth) acrylate, glycidyl (meth) acrylate, diethylene glycol monomethyl (meth) acrylate Ether, (meth) acrylic acid diethylene glycol monoethyl ether,

(Meth) acrylic acid triethylene glycol monomethyl ether, (meth) acrylic acid triethylene glycol monoethyl ether, (meth) acrylic acid polyethylene glycol monomethyl ether, (meth) acrylic acid polyethylene glycol monoethyl ether, (meth) acrylic acid β -Phenoxyethoxyethyl, nonylphenoxy polyethylene glycol (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, trifluoroethyl (meth) acrylate, octa (meth) acrylate Fluoropentyl, perfluorooctylethyl (meth) acrylate, dicyclopentanyl (meth) acrylate, tribromophenyl (meth) acrylate, tribromophenyl (meth) acrylate Kishiechiru, polystyrene terminated with (meth) acryloyl group; polymethyl (meth) acrylate, polybutyl (meth) arylate, such as macro-monomers containing such poly silicone.
In addition, in this specification, when showing either or both of "acryl and methacryl", it may describe as "(meth) acryl".

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

  Examples of vinyl esters include vinyl acetate, vinyl propionate, vinyl butyrate, vinyl methoxyacetate, vinyl benzoate, and the like.

Examples of maleic acid diesters include dimethyl maleate, diethyl maleate, and dibutyl maleate.
Examples of the fumaric acid diesters include dimethyl fumarate, diethyl fumarate, and dibutyl fumarate.
Examples of itaconic acid diesters include dimethyl itaconate, diethyl itaconate, and dibutyl itaconate.

  (Meth) acrylamides include (meth) acrylamide, N-methyl (meth) acrylamide, N-ethyl (meth) acrylamide, N-propyl (meth) acrylamide, N-isopropyl (meth) acrylamide, and Nn-butyl. Acrylic (meth) amide, Nt-butyl (meth) acrylamide, N-cyclohexyl (meth) acrylamide, N- (2-methoxyethyl) (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N, N -Diethyl (meth) acrylamide, N-phenyl (meth) acrylamide, N-benzyl (meth) acrylamide, (meth) acryloylmorpholine, diacetone acrylamide, etc. are mentioned.

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

  Examples of vinyl ethers include methyl vinyl ether, butyl vinyl ether, hexyl vinyl ether, and methoxyethyl vinyl ether.

  Specific examples of the copolymer containing at least the structural unit represented by the general formula (1) include a carboxyl group-containing unsaturated monomer containing acrylic acid and / or methacrylic acid, styrene, α-methylstyrene, vinyltoluene. Aromatic vinyl compounds such as: ethyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, ethylenically unsaturated carboxylic acid ester such as benzyl (meth) acrylate; acetic acid Carboxylic acid vinyl esters such as vinyl and vinyl propionate; Vinyl cyanide such as (meth) acrylonitrile and α-chloroacrylonitrile; Aliphatic conjugates such as 1,3-butadiene, 2-methyl-1,3-butadiene and isoprene Diene, aminoethyl acrylate Unsaturated fatty acid glycidyl ester such as glycidyl (meth) acrylate; polystyrene having a (meth) acryloyl group at its terminal; polymethyl (meth) acrylate, polybutyl (meth) arylate, polysilicone And a copolymer with a macromonomer containing such as.

Among these (d) dispersants having an acid value of 65 to 250 mgKOH / g, in the present invention, a dispersant made of a graft copolymer is used. The graft copolymer is detailed in, for example, Macromonomer Chemistry and Industry (IPC Publishing, 1989). Examples of the branch part of the graft copolymer that can be used as the dispersant (d) of the present invention include polystyrene, polyethylene oxide, poly (meth) acrylic acid ester, etc., and the structural unit represented by the following general formula (2) a graft copolymer having at least a branch portion.

In General Formula (2), R ⁴ represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, and R ⁵ represents a hydrogen atom, an alkyl group having 1 to 22 carbon atoms, or an aryl group having 6 to 30 carbon atoms. Represents.

The alkyl group represented by R ⁴ has the same meaning as R ¹ in the general formula (1), and preferred examples thereof are also the same.
As the alkyl group represented by R ⁵ , an alkyl group having 1 to 12 carbon atoms is preferable, and an alkyl group having 1 to 8 carbon atoms is particularly preferable. The alkyl group may have a substituent, and examples of the substituent that can be introduced include a halogen atom, an alkenyl group, an aryl group, a hydroxyl group, an alkoxy group, an alkoxycarbonyl group, an amino group, an acylamino group, and a carbamoyl group. .
Specific examples of the alkyl group represented by R ⁵ include methyl, ethyl, propyl, butyl, heptyl, hexyl, octyl, decyl, dodecyl, tridecyl, tetradecyl, hexadecyl, Octadecyl group, 2-chloroethyl group, 2-bromoethyl group, 2-methoxycarbonylethyl group, 2-methoxyethyl group, 2-bromopropyl group, 2-butenyl group, 2-pentenyl group, 3-methyl-2-pentenyl group 2-hexenyl group, 4-methyl-2-hexenyl group, benzyl group, phenethyl group, 3-phenylpropyl group, naphthylmethyl group, 2-naphthylethyl group, chlorobenzyl group, bromobenzyl group, methylbenzyl group, ethyl Benzyl, methoxybenzyl, dimethylbenzyl, dimethoxybenzyl, cyclohexyl Sil group, 2-cyclohexylethyl group, 2-cyclopentylethyl group, bicyclo [3,2,1] oct-2-yl group, 1-adamantyl group, dimethylaminopropyl group, acetylaminoethyl group, N, N-dibutyl An aminocarbamoylmethyl group etc. are mentioned.
Of these alkyl groups, an unsubstituted alkyl group, a halogen atom, an aryl group, or an alkyl group substituted with a hydroxyl group is preferred, and more specifically, a methyl group, an ethyl group, a propyl group, a butyl group, a heptyl group. Hexyl group, benzyl group, methylbenzyl group, ethylbenzyl group, methoxybenzyl group, 2-cyclohexylethyl group, 2-cyclopentylethyl group and the like are preferable.

As the aryl group represented by R ⁵ , an aryl group having 6 to 20 carbon atoms is preferable, and an aryl group having 6 to 12 carbon atoms is particularly preferable. The aryl group may have a substituent, and examples of the substituent that can be introduced include a halogen atom, an alkyl group, an alkenyl group, an alkoxy group, an alkoxycarbonyl group, and an acylamino group. Specific examples of such aryl groups include phenyl, naphthyl, tolyl, xylyl, propylphenyl, butylphenyl, octylphenyl, dodecylphenyl, methoxyphenyl, ethoxyphenyl, butoxy. Phenyl group, decyloxyphenyl group, chlorophenyl group, dichlorophenyl group, bromophenyl group, methoxycarbonylphenyl group, ethoxycarbonylphenyl group, butoxycarbonylphenyl group, acetamidophenyl group, propioamidophenyl group, dodeciloylamidophenyl group, Etc.
Among such aryl groups, an aryl group substituted with an unsubstituted aryl group, a halogen atom, an alkyl group, or an alkoxy group is preferable, and more specifically, a phenyl group, a naphthyl group, a tolyl group, a xylyl group, a propyl group. A phenyl group, a butylphenyl group and the like are preferable.

  The branch part of the graft copolymer having at least the structural unit represented by the general formula (2) in the branch part includes not only the structural unit represented by a single general formula (2) but also two or more general formulas. It may consist of the structural unit represented by (2), and may contain the structural unit represented by the following general formula (3) in addition to the structural unit represented by the general formula (2). .

In General Formula (3), R ⁶ represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, and Q represents a cyano group or an aryl group having 6 to 30 carbon atoms.

R ⁶ has the same meaning as R ¹ in the general formula (1), and preferred examples thereof are also the same.
When Q represents an aryl group, the aryl group is preferably an aryl group having 6 to 20 carbon atoms, and particularly preferably an aryl group having 6 to 12 carbon atoms. The aryl group may have a substituent, and examples of the substituent that can be introduced include a halogen atom, an alkyl group, an alkoxy group, and an alkoxycarbonyl group.
Specific examples of such aryl groups include phenyl, naphthyl, tolyl, xylyl, propylphenyl, butylphenyl, octylphenyl, dodecylphenyl, methoxyphenyl, ethoxyphenyl, butoxy. Examples thereof include a phenyl group, a decyloxyphenyl group, a chlorophenyl group, a dichlorophenyl group, a bromophenyl group, a methoxycarbonylphenyl group, an ethoxycarbonylphenyl group, and a butoxycarbonylphenyl group.
Of the aryl groups represented by Q, an aryl group substituted with an unsubstituted aryl group, a halogen atom, an alkyl group, or an alkoxy group is preferred, and an unsubstituted aryl group and an aryl group substituted with an alkyl group are particularly preferred.

  As a specific example of the branch part of the graft polymer having such a structural unit represented by the general formula (2) and, if desired, a structural unit represented by the general formula (3) in the branch part, polymethyl ( Meth) acrylate, poly-n-butyl (meth) acrylate, poly-i-butyl (meth) acrylate, poly (methyl (meth) acrylate-co-benzyl (meth) acrylate), poly (methyl (meth) acrylate-co -Styrene), poly (methyl (meth) acrylate-co- (meth) acrylic acid), poly (methyl (meth) acrylate-co-acrylonitrile) and the like.

  Any known method may be used for the synthesis of the graft polymer having at least the structural unit represented by the general formula (2) in the side chain. Specifically, a method of copolymerizing a macromonomer having at least the structural unit represented by the general formula (2) and a copolymerizable ethylenically unsaturated monomer can be mentioned.

The at least has macromonomer structural unit represented by the general formula (2), is represented by the following general formula (4).

In General Formula (4), R ⁷ represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, and L represents —COO—, —CON (R ⁸ ) —, or a phenylene group. Here, R ⁸ represents a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, or an aryl group having 6 to 20 carbon atoms. W represents a single bond, a single divalent linking group selected from the following atomic groups, or a linking group formed by arbitrarily combining two or more of these, and A represents the general formula (2 ) Represents a substituent having at least a structural unit represented by:

In the formula, Z ¹ and Z ² each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, a cyano group, or a hydroxyl group, and Z ³ represents a hydrogen atom or 1 to carbon atoms. 18 represents an alkyl group or an aryl group having 6 to 20 carbon atoms.

  Specific examples of the macromonomer represented by the general formula (4) include the following.

  (D) The macromonomer as described above that can be used for the synthesis of the dispersant is also available as a commercial product, and as such a macromonomer, one-end methacryloylated polymethyl methacrylate oligomer (Mn = 6000, trade name: AA-6, manufactured by Toa Gosei Chemical Co., Ltd.) and one-terminal methacryloylated poly-n-butyl acrylate oligomer (Mn = 6000, trade name: AB-6, manufactured by Toa Gosei Chemical Co., Ltd.). it can.

Examples of the ethylenically unsaturated monomer copolymerizable with the above-described macromonomer that constitutes the graft polymer of the present invention include, for example, acrylic acid, methacrylic acid, itaconic acid, etc. Of unsaturated monocarboxylic acids. These ethylenically unsaturated monomers containing a carboxyl group can be used alone or in admixture of two or more.
Examples of the other copolymerizable ethylenically unsaturated monomers include the ethylenically unsaturated monomers mentioned in the description of the copolymer containing at least the structural unit represented by the general formula (1).

  Specific examples of the graft polymer that can be suitably used as the dispersant (d) include a macromonomer containing a polymethyl (meth) acrylate having a (meth) acryloyl group at the terminal, a polybutyl (meth) arylate, etc. Carboxyl group-containing unsaturated monomers containing acid and / or methacrylic acid; aromatic vinyl compounds such as styrene, α-methylstyrene, vinyltoluene; methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, Ethylenically unsaturated carboxylic acid esters such as 2-hydroxyethyl (meth) acrylate and benzyl (meth) acrylate; carboxylic acid vinyl esters such as vinyl acetate and vinyl propionate; methacrylic acid such as (meth) acrylonitrile and α-chloroacrylonitrile Vinyl anion; aliphatic conjugated dienes such as 1,3-butadiene, 2-methyl-1,3-butadiene and isoprene; ethylenically unsaturated carboxylic acid aminoalkyl esters such as aminoethyl acrylate; glycidyl (meth) acrylate Examples thereof include copolymers with one or more ethylenically unsaturated monomers selected from such unsaturated fatty acid glycidyl esters.

  Such a graft polymer has a main chain composed of at least an acid monomer such as (meth) acrylic acid, a side chain composed of at least an acid monomer such as (meth) acrylic acid, a main chain and a side chain. In which the main chain is composed of at least an acid monomer such as (meth) acrylic acid is preferred.

(D) It is preferable to add so that the dispersing agent which is a graft copolymer with an acid value of 65-250 mgKOH / g may be 5-50 weight part with respect to 100 weight part of pigments. Within this range of addition amount, excellent dispersion stability is achieved, and the increase in viscosity and pigment sedimentation over time are effectively suppressed. However, the optimal amount of dispersant added is appropriately adjusted depending on the combination of the type of pigment used, the type of solvent, and other additives, and is not necessarily limited to the above-mentioned amount of addition, and even outside this range. It may show suitable dispersibility.
(D) It is preferable that it is the range of 2-30 mass% with respect to the total solid of the pigment dispersion composition of a dispersing agent, More preferably, it is the range of 5-25 mass%.

In the pigment dispersion composition of the present invention, it is necessary for the pigment dispersion to contain two specific types of dispersants, the (c) dispersant and the (d) dispersant. Among these, the (c) polyester 3 or more types of dispersants including one or two types of dispersants having a chain and (d) one or two types of dispersants which are graft copolymers having an acid value of 65 to 250 mgKOH / g. It is preferable from the viewpoint of high pigment dispersibility and dispersion stability. That is, as the dispersant, at least one type of (c) dispersant and (d) at least one type of dispersant are respectively contained, and in addition, at least selected from (c) dispersant and (d) dispersant The aspect which uses 3 types or more in total of a dispersing agent containing (c) dispersing agent and (d) dispersing agent by containing 1 type is preferable.
Among these combinations, a combination of two types (c) and one type (d), a combination of one type (c) and two types (d) is preferable, and in particular one type (c) and A combination with two types of (d) is preferred.
The ratio of (c) and (d) is not particularly limited, but a 10/90 to 90/10 mass ratio is preferable, and a 20/80 to 80/20 mass ratio is particularly preferable.

<(A) Pigment>
In the pigment dispersion composition of the present invention, conventionally known various inorganic pigments or organic pigments can be appropriately selected and used.
Considering that it is preferable that the pigment has a high transmittance, whether it is an inorganic pigment or an organic pigment, it is preferable to use a pigment having a particle size as small as possible. In consideration of handling properties, the average particle size of the pigment is 0. 0.01 to 0.1 μm is preferable, and 0.01 to 0.05 μm is more preferable.

  Examples of inorganic pigments include metal compounds represented by metal oxides, metal complex salts, and the like. Specifically, iron, cobalt, aluminum, cadmium, lead, copper, titanium, magnesium, chromium, zinc, antimony And metal oxides such as the above, and complex oxides of the above metals.

Examples of the organic pigment include:
C. I. Pigment Yellow 11, 24, 31, 53, 83, 93, 99, 108, 109, 110, 138, 139, 147, 150, 151, 154, 155, 167, 180, 185, 199;
C. I. Pigment orange 36, 38, 43, 71;
C. I. Pigment Red 81, 105, 122, 149, 150, 155, 171, 175, 176, 177, 179, 209, 220, 224, 242, 254, 255, 264, 270;
C. I. Pigment violet 19, 23, 32, 37, 39;
C. I. Pigment Blue 1, 2, 15, 15: 1, 15: 3, 15: 6, 16, 22, 60, 66;
C. I. Pigment green 7, 36, 37;
C. I. Pigment brown 25, 28;
C. I. Pigment black 1,7;
Etc.

Although it does not specifically limit in this invention, The following pigment is more preferable.
C. I. Pigment Yellow 11, 24, 108, 109, 110, 138, 139, 150, 151, 154, 167, 180, 185
C. I. Pigment Orange 36, 71,
C. I. Pigment Red 122,150,171,175,177,179,209,224,242,254,255,264
C. I. Pigment violet 19, 23, 37,
C. I. Pigment Blue 15: 1, 15: 3, 15: 6, 16, 22, 60, 66,
C. I. Pigment Green 7,36,
C. I. Pigment Black 7

These organic pigments can be used alone or in various combinations to increase color purity. Specific examples of combinations are shown below.
For example, as a red pigment, an anthraquinone pigment, a perylene pigment, a diketopyrrolopyrrole pigment alone or at least one of them, a bisazo yellow pigment, an isoindoline yellow pigment, a quinophthalone yellow pigment or a perylene red pigment, A mixture with an anthraquinone pigment can be used. For example, as an anthraquinone pigment, C.I. I. Pigment red 177, and perylene pigments include C.I. I. Pigment red 155, C.I. I. Pigment Red 224, and diketopyrrolopyrrole pigments include C.I. I. Pigment red 254, and C.I. I. Pigment yellow 139, or C.I. I. Mixture with CI Pigment Yellow 150 is preferable. The mass ratio of the red pigment to the yellow pigment is preferably 100: 0 to 100: 100. When the ratio exceeds 100: 100, the dominant wavelength becomes shorter than the short wavelength, and the deviation from the NTSC target hue may increase. In particular, the mass ratio is optimally in the range of 100: 0 to 100: 50. In the case of a combination of red pigments, it can be arbitrarily adjusted in accordance with chromaticity. Examples of combinations include C.I. I. Pigment red 254 and C.I. I. Pigment red 177, C.I. I. Pigment red 254 and C.I. I. Pigment red 224, C.I. I. Pigment red 224 and C.I. I. Pigment red 177.

  As the green pigment, a halogenated phthalocyanine pigment can be used alone, or a mixture thereof with a bisazo yellow pigment, a quinophthalone yellow pigment, an azomethine yellow pigment or an isoindoline yellow pigment can be used. For example, C.I. I. Pigment Green 7, 36, 37 and C.I. I. Pigment yellow 83, C.I. I. Pigment yellow 138, C.I. I. Pigment yellow 139, C.I. I. Pigment yellow 150, C.I. I. Pigment yellow 180 or C.I. I. Mixing with Pigment Yellow 185 is preferred. The mass ratio of the green pigment to the yellow pigment is preferably 100: 5 to 100: 150. If the mass ratio is less than 100: 5, it is difficult to suppress the light transmittance of 400 nm to 450 nm, and the color purity may not be increased. On the other hand, if the ratio exceeds 100: 150, the dominant wavelength becomes longer and the deviation from the NTSC target hue may become large. A mass ratio of 100: 20 to 100: 120 is particularly preferable.

  As the blue pigment, a phthalocyanine pigment can be used alone, or a mixture thereof with a dioxazine purple pigment can be used. For example, C.I. I. Pigment blue 15: 6 and C.I. I. Mixing with pigment violet 23 is preferred. The mass ratio of the blue pigment to the violet pigment is preferably 100: 0 to 100: 50, more preferably 100: 0 to 100: 30.

  Further, examples of the black pigment include carbon, titanium black, iron oxide, titanium oxide alone or a mixture thereof, and a combination of carbon and titanium black is preferable. Further, the mass ratio of carbon to titanium black is preferably in the range of 100: 0 to 100: 60, and good dispersion stability can be obtained in this mass ratio range. Further, the black pigments mentioned here can be suitably used, for example, when the pigment dispersion composition of the present invention is used for a curable composition for a black matrix.

  As content of (a) pigment in the pigment dispersion composition of this invention, 40-90 mass% is preferable with respect to the total solid (mass) of this composition, and 50-80 mass% is more preferable. When the pigment content is within the above range, the color density is sufficient and it is effective to ensure excellent color characteristics.

  Moreover, as content in the pigment dispersion composition of the polymer which concerns on this invention, and the dispersing agent which has a polyester chain, 0.5-100 mass% is preferable with respect to the mass of the said pigment, and 3-80 mass% Is more preferable. When the amount of the pigment dispersant is within the above range, a sufficient pigment dispersion effect can be obtained. Even if the pigment dispersant is added in an amount of more than 100 parts by mass, a further improvement effect of the pigment dispersion effect may not be expected.

<(B) Solvent>
Examples of the solvent used as a dispersion medium for the preparation of the pigment dispersion composition of the present invention include 1-methoxy-2-propyl acetate, 1-methoxy-2-propanol, ethylene glycol monomethyl ether, diethylene glycol monomethyl ether, ethyl acetate, and butyl acetate. , Ethyl lactate, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, n-propanol, 2-propanol, n-butanol, cyclohexanol, cyclohexanol acetate, ethylene glycol, diethylene glycol, toluene, xylene and the like.
Further, (b) the amount of the solvent added is appropriately selected according to the use of the pigment dispersion composition, but when used for the preparation of a photocurable composition described later, from the viewpoint of handleability, the pigment and the pigment It can add so that solid content concentration containing a dispersing agent may be 5-50 mass%.

(Other dispersants)
The pigment dispersion composition of the present invention may contain a known dispersant as other components as necessary as long as the effects of the present invention are not impaired.
Specific examples of known dispersants that can be used in combination include amides such as nonanamide, decanamide, dodecanamide, N-dodecylhexadecanamide, N-octadecylpropioamide, N, N-dimethyldodecanamide and N, N-dihexylacetamide. Compounds, amine compounds such as diethylamine, diheptylamine, dibutylhexadecylamine, N, N, N ′, N′-tetramethylmethanamine, triethylamine, tributylamine and trioctylamine, monoethanolamine, diethanolamine, triethanolamine N, N, N ′, N ′-(tetrahydroxyethyl) -1,2-diaminoethane, N, N, N′-tri (hydroxyethyl) -1,2-diaminoethane, N, N, N ′ , N'-Tetra (hydroxyethylpolyoxyethylene) -1,2-diaminoethane, 1,4-bis (2-hydroxyethyl) piperazine, amines having a hydroxy group such as 1- (2-hydroxyethyl) piperazine, and the like, and other examples include nipecotamide, isonipecotamide, Mention may be made of compounds such as nicotinamide.
As commercially available products, Shigenox-105 (trade name, manufactured by Hakkor Chemical Co.), “Disperbyk-101 (polyamideamine phosphate), 110 (copolymer containing an acid group), 130 (polyamide)” manufactured by BYK Chemie. "EFKA 4047, 4050, 4010, 4165 (polyurethane type), EFKA 4330, 4340 (block copolymer), 4400, 4402 (modified polyacrylate), 6745 (phthalocyanine derivative), 6750 (azo pigment derivative)" manufactured by EFKA, Examples include “Floren TG-710 (urethane oligomer)” manufactured by Kyoeisha Chemical Co., “Solsperse 5000 (phthalocyanine derivative), 22000 (azo pigment derivative)” manufactured by Lubrizol.
The content of these known dispersants is preferably 30 parts by mass or less with respect to the total amount of (c) dispersant and (d) dispersant, which are essential constituents of the present invention described above. The total solid content of the dispersion composition is preferably in the range of 0 to 15% by mass, and more preferably in the range of 0 to 10% by mass.

(Surfactant)
Moreover, various surfactants are mentioned as another component contained in the pigment dispersion composition of this invention. The use of a surfactant is effective from the viewpoint of improving dispersion stability. Examples of the surfactant include anionic surfactants typified by alkyl naphthalene sulfonates and phosphate ester salts, cationic surfactants typified by amine salts, aminocarboxylic acids, and betaine types. Nonionic surfactants such as amphoteric surfactants, polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene nonylphenyl ether, and the like are preferable.

<Preparation of pigment dispersion composition>
The method for preparing the pigment dispersion composition of the present invention is not particularly limited. For example, a pigment or a pigment dispersant and a solvent are used, and a vertical or horizontal sand grinder, a pin mill, a slit mill, an ultrasonic disperser, or the like is used. It can be obtained by performing fine dispersion treatment with beads made of glass, zirconia or the like having a particle diameter of 0.01 to 1 mm.
Also, before carrying out bead dispersion, while applying a strong shearing force using a two-roll, three-roll, ball mill, tron mill, disper, kneader, kneader, homogenizer, blender, single or twin screw extruder, etc. It is also possible to perform a kneading and dispersing process.

  For details on kneading and dispersing, see T.W. C. “Paint Flow and Pigment Dispersion” by Patton (published by John Wiley and Sons, 1964) and the like.

  The pigment dispersion composition of the present invention thus obtained contains two specific types of dispersants, and even when a finer pigment capable of high color development is used, Excellent dispersibility and dispersion stability, no increase in viscosity due to crystallization of the dispersion, excellent fluidity, and excellent coloring power. For this reason, it is suitable for various uses, and forms multicolored colored images on substrates such as paints, printing inks, color display boards using them, or color proofs, especially liquid crystal color displays, solid-state imaging It is suitably used for the production of color filters used for devices and the like, and its application range is wide.

EXAMPLES Hereinafter, although an Example demonstrates this invention further more concretely, it is not limited to a following example. Unless otherwise specified, “%” and “part” are based on mass.
( Reference Example 1)
<Preparation of pigment dispersion composition>
The components of the following composition (1) are mixed, and using a homogenizer, the rotational speed is 3,000 r. p. m. And mixed for 3 hours to prepare a mixed solution containing the pigment.
[Composition (1)]
・ C. I. Pigment Red 254 [(a) Pigment] 90 parts C.I. I. Pigment Red 177 [(a) pigment] 10 parts cyclohexyl methacrylate / benzyl methacrylate / methacrylic acid copolymer (= 45/40/15 [weight ratio], weight average molecular weight 20000,
Acid value 100) (Polymer 1: a dispersant) of 1-methoxy-2-propyl acetate 30% solution 30 parts Solsperse 24000GR solvent (manufactured by Nippon Lubrizol Co .;
Polyester-based dispersant) [(c) Dispersant] 40 parts, 1-methoxy-2-propyl acetate [(b) solvent] 820 parts

Subsequently, the mixed solution obtained above was further subjected to dispersion treatment for 6 hours with a bead disperser disperse mat (made by GETZMANN) using 0.1 mmφ zirconia beads, and then further a high-pressure disperser NANO with a decompression mechanism. The dispersion treatment was performed at a flow rate of 500 g / min under a pressure of 2000 kg / cm ³ using −3000-10 (manufactured by Nippon BEE Co., Ltd.). This dispersion treatment was repeated 10 times to obtain a red pigment dispersion composition.

<Evaluation of pigment dispersion composition>
The following evaluation was performed about the obtained pigment dispersion composition.
(1) Measurement and Evaluation of Viscosity For the obtained pigment dispersion composition, using an E-type viscometer, viscosity η ¹ of the pigment dispersion composition immediately after dispersion and after 1 week after dispersion (at room temperature) The viscosity η ² of the pigment dispersion composition was measured and the degree of thickening was evaluated. The evaluation results are shown in Table 1 below. Here, a low viscosity indicates that the dispersibility and dispersion stability are good.

(2) Measurement and Evaluation of Contrast The obtained pigment dispersion composition was applied on a glass substrate, and a sample was prepared so that the thickness of the coating film after drying was 1 μm. This sample was placed between two polarizing plates, the amount of transmitted light was measured when the polarization axis was parallel and when the polarization axis was parallel, and the ratio was taken as contrast. 512 color display 10.4 “size TFT-LCD color filter, planting, Koseki, Fukunaga, Yamanaka”). The results of measurement evaluation are shown in Table 1 below. Here, a high contrast indicates that the pigment is highly miniaturized and has high transmittance, that is, coloring power.

( Reference Example 2)
Reference Example 1 is a dispersant (polymer 1) of 1-methoxy-2 30% solution 30 parts of propyl acetate solvent, cyclohexyl methacrylate / butyl acrylate / methacrylic acid copolymer (= 45/44 / 11 [weight ratio], weight average molecular weight 20000, acid value 71): except that instead of the 30% solution, 30 parts of 1-methoxy-2-propyl acetate solvent [polymer 2 a dispersant] same manner as in reference example 1 A red pigment dispersion composition was prepared and evaluated in the same manner as in Reference Example 1. The results are shown in Table 1 below.

( Reference Example 3)
Reference Example 1: 30% solution, 30 parts of 1-methoxy-2-propyl acetate solvent (polymer 1 minute powders), cyclohexyl methacrylate / methyl methacrylate / methacrylic acid copolymer (= 37/40 / 23 [weight ratio], weight average molecular weight 20000, acid value 150) (polymer 3: except that instead of the 30% solution, 30 parts of a dispersant) of 1-methoxy-2-propyl acetate solvent, the same manner as in reference example 1 A red pigment dispersion composition was prepared and evaluated in the same manner as in Reference Example 1. The results are shown in Table 1 below.

Example 4
Reference Example 1, (Polymer 1: a dispersant) of 1-methoxy-2-propyl acetate 30% solution 30 parts of solvent, benzyl methacrylate / methacrylic acid / terminal methacryloylated polymethyl methacrylate (AA-6, Toa Gosei Chemical Co., Ltd.) copolymer (= 10/15/75 [weight ratio], weight average molecular weight 20000, acid value 98) (polymer 4: (d) dispersant) 1-methoxy-2 A red pigment dispersion composition was prepared in the same manner as in Reference Example 1 except that 30 parts of a 30% solution of propyl acetate solvent was used, and the same evaluation as in Reference Example 1 was performed. The results are shown in Table 1 below.

(Example 5)
In Example 4, 30 parts of a 30% solution of 1-methoxy-2-propyl acetate solvent in (Polymer 4: (d) Dispersant) was added to benzyl methacrylate / methacrylic acid / terminal methacryloylated polybutyl acrylate (AB). -6, manufactured by Toa Gosei Chemical Co., Ltd.) copolymer (= 14/11/75 [weight ratio], weight average molecular weight 20000, acid value 71) (polymer 5: (d) dispersant) A red pigment dispersion composition was prepared in the same manner as in Reference Example 1 except that 30 parts of a 30% solution of methoxy-2-propyl acetate solvent was used, and the same evaluation as in Example 4 was performed. The results are shown in Table 1 below.

(Example 6)
In Example 4, 30 parts of a 30% solution of 1-methoxy-2-propyl acetate solvent of (Polymer 4: (d) Dispersant) was added to butyl acrylate / methacrylic acid / terminal methacryloylated polymethyl acrylate (AA-). 6. Toa Gosei Chemical Co., Ltd.) copolymer (= 7/23/70 [weight ratio], weight average molecular weight 25000, acid value 150) (polymer 6: (d) dispersant) 1-methoxy A red pigment dispersion composition was prepared in the same manner as in Example 4 except that 30 parts of a 30% solution of 2-propyl acetate solvent was used, and the same evaluation as in Reference Example 1 was performed. The results are shown in Table 1 below.

(Example 7)
Reference Example 1: 30% solution, 30 parts of 1-methoxy-2-propyl acetate solvent (polymer 1 minute powder) (Polymer 1: a dispersant) of 1-methoxy-2-propyl acetate solvent In the same manner as in Reference Example 1, except that 15 parts of 30% solution and 15 parts of 30% solution of 1-methoxy-2-propylacetate solvent in (Polymer 4: (d) Dispersant) were used. A pigment dispersion composition was prepared and evaluated in the same manner as in Reference Example 1. The results are shown in Table 1 below.

(Example 8)
Reference Example 1: 30% solution, 30 parts of 1-methoxy-2-propyl acetate solvent (polymer 1 minute powder) (Polymer 4: (d) dispersant) of 1-methoxy-2-propyl a 30% solution of 15 parts of acetate solvent, butyl acrylate / methacrylic acid copolymer (= 70/30 [weight ratio], weight average molecular weight 20000, acid value 195) (polymer 7: a dispersant) 1-methoxy A red pigment dispersion composition was prepared in the same manner as in Reference Example 1 except that it was replaced with 15 parts of a 30% solution of 2-propyl acetate solvent, and the same evaluation as in Reference Example 1 was performed. The results are shown in Table 1 below.

Example 9
Reference Example 1: 30% solution, 30 parts of 1-methoxy-2-propyl acetate solvent (polymer 1 minute powder) (Polymer 4: (d) dispersant) of 1-methoxy-2-propyl Instead of 30 parts of 30% acetate solvent solution, 40 parts of Solsperse 24000GR [(c) Dispersant], 20 parts Solsperse 24000GR [(c) Dispersant] and Solsperse 32000 ([(c) Dispersant]) (Japan) A red pigment dispersion composition was prepared in the same manner as in Reference Example 1 except that 20 parts by Lubrizol Corporation (polyester dispersant) was used, and the same evaluation as in Reference Example 1 was performed. The results are shown in Table 1 below.

( Reference Example 10)
In Example 9, 30 parts of a 30% solution of 1-methoxy-2-propyl acetate solvent in (polymer 4: (d) dispersant) was added to 1-methoxy-2-propyl in (polymer 1: dispersant). A red pigment dispersion composition was prepared in the same manner as in Example 9, except that 30 parts of a 30% solution of acetate solvent was used, and the same evaluation as in Reference Example 1 was performed. The results are shown in Table 1 below.

(Example 11)
In Example 9, 30 parts of a 30% solution of (polymer 4: (d) dispersant) in 1-methoxy-2-propyl acetate solvent was added to 1-methoxy- of (polymer 4: (d) dispersant). a 30% solution 15 parts of 2-propyl acetate solvent,: except that instead of the 30% solution of 15 parts of 1-methoxy-2-propyl acetate solvent (polymer 7 a dispersant) in the same manner as in example 9 A red pigment dispersion composition was prepared and evaluated in the same manner as in Reference Example 1. The results are shown in Table 1 below.

(Comparative Example 1)
Reference Example 1: (polymer 1 minute powders), except that instead of a comparative dispersing agent EFKA4047 (EFKA Co.) (hereinafter referred to as D-1), in the same manner as in Reference Example 1, the red A pigment dispersion composition was prepared and evaluated in the same manner as in Reference Example 1. The results are shown in Table 1 below.

(Comparative Example 2)
Reference Example 1, (Polymer 1: a dispersant) and a comparative dispersing agent N- vinylimidazole and terminal methacryloylated polymethyl methacrylate copolymer D-2 (= 15/85 [ weight ratio], weight average molecular weight except that instead of 30000), in the same manner as in reference example 1, a red pigment dispersion composition was prepared and evaluated in the same manner as in reference example 1. The results are shown in Table 1 below.

(Comparative Example 3)
Reference Example 1, (Polymer 1: a dispersant) and cyclohexyl methacrylate / benzyl methacrylate / methacrylic acid copolymer D-3 is a comparative dispersing agent (= 42/50/8 [weight ratio], weight average A red pigment dispersion composition was prepared in the same manner as in Reference Example 1 except that the molecular weight was changed to 20000 and the acid value was 52), and the same evaluation as in Reference Example 1 was performed. The results are shown in Table 1 below.

(Comparative Example 4)
Reference Example 1, (Polymer 1: a dispersant) and benzyl methacrylate / methacrylic acid / terminal methacryloylated polymethyl methacrylate D-4 is a comparative dispersing agent (AA-6, Toagosei Chemical Industry Co., Ltd. ) copolymer (= 17/8/75 [weight ratio], except that instead of the weight-average molecular weight 20000, acid value 52), in the same manner as in reference example 1, to prepare a red pigment dispersion composition, reference Evaluation similar to Example 1 was performed. The results are shown in Table 1 below.

( Reference Example 12)
Reference Example 1, except that instead of the red pigment dispersion composition in the pigment dispersion composition obtained by using a mixed solution containing a green pigment of the following composition (2), in the same manner as in Reference Example 1, the green A pigment dispersion composition was prepared and evaluated in the same manner as in Reference Example 1. The results are shown in Table 2 below.
[Composition (2)]
・ C. I. Pigment Green 36 [(a) Pigment] 60 parts C.I. I. Pigment Yellow 150 [(a) Pigment] 40 parts Polymer 1 [a dispersant] 1-methoxy-2-propyl 30% acetate solvent solution 70 parts · EFKA6750 (EFKA Co., azo pigment derivative)
[Other dispersants] 10 parts BYK161 (byk Chemie; polyester chain-containing polyurethane dispersant) [(c) dispersant] 30 parts 1-methoxy-2-propyl acetate [(b) solvent] 790 parts

( Reference Examples 13-14 , Examples 15-17 )
Reference Example pigment dispersing agent used in the 12: (polymer 1 minute powders), wherein (the polymer 4 to 6 (d) dispersant) polymer 2 polymer 6 except that instead of each of Reference Example 12 In the same manner as above, a green pigment dispersion composition was prepared and evaluated in the same manner as in Reference Example 12. The results are shown in Table 2 below.

(Example 18)
Reference Example 12: 30% solution of 70 parts of 1-methoxy-2-propyl acetate solvent (polymer 1 minute powder) (Polymer 1: a dispersant) of 1-methoxy-2-propyl acetate solvent Similar to Reference Example 12, except that 35 parts of 30% solution and 35 parts of 30% solution of 1-methoxy-2-propyl acetate solvent of (Polymer 4: (d) Dispersant) A pigment dispersion composition was prepared and evaluated in the same manner as in Reference Example 12. The results are shown in Table 2 below.

(Example 19)
Reference Example 12: 30% solution of 70 parts of 1-methoxy-2-propyl acetate solvent (polymer 1 minute powder) (Polymer 4: (d) dispersant) of 1-methoxy-2-propyl a 30% solution 35 parts of acetate solvents: except that instead of the 30% solution 35 parts of 1-methoxy-2-propyl acetate solvent (polymer 7 a dispersant) in the same manner as in reference example 1, the green A pigment dispersion composition was prepared and evaluated in the same manner as in Reference Example 12. The results are shown in Table 2 below.

(Example 20)
Reference Example 12: 30% solution of 70 parts of 1-methoxy-2-propyl acetate solvent (polymer 1 minute powder) (Polymer 4: (d) dispersant) of 1-methoxy-2-propyl Instead of 70 parts of a 30% solution of acetate solvent, 30 parts of BYK161 were replaced with 15 parts of BYK161 ((c) dispersant) and Solsperse 32000 (manufactured by Nippon Lubrizol Corporation: (c) dispersant). except that, in the same manner as in reference example 12, a green pigment dispersion composition was prepared and evaluated in the same manner as in reference example 12. The results are shown in Table 2 below.

( Reference Example 21)
In Example 20, (Polymer 4: (d) dispersing agent) 30% solution 70 parts of 1-methoxy-2-propyl acetate solvent, (Polymer 1: a dispersant) of 1-methoxy-2-propyl A green pigment dispersion composition was prepared in the same manner as in Example 20 except that 70 parts of a 30% solution of acetate solvent was used, and the same evaluation as in Example 20 was performed. The results are shown in Table 2 below.

(Example 22)
In Example 20, 70 parts of a 30% solution of (polymer 4: (d) dispersant) in 1-methoxy-2-propyl acetate solvent was added to 1-methoxy- of (polymer 4: (d) dispersant). a 30% solution 35 parts of 2-propyl acetate solvent,: except that instead of the 30% solution 35 parts of 1-methoxy-2-propyl acetate solvent (polymer 7 a dispersant) in the same manner as in example 20 A green pigment dispersion composition was prepared and evaluated in the same manner as in Example 20. The results are shown in Table 2 below.

( Reference Example 23)
In Reference Example 1, the same procedure as in Reference Example 1 was conducted except that the red pigment dispersion composition was replaced with a blue pigment dispersion composition obtained using a mixed solution containing a blue pigment having the following composition (3). A blue pigment dispersion composition was prepared and evaluated in the same manner as in Reference Example 1. The results are shown in Table 3 below.
[Composition (3)]
・ C. I. Pigment Blue 15; 6 [(a) pigment] 80 parts C.I. I. Pigment Violet 23 [(a) Pigment] 20 parts Polymer 1 [a dispersant] 1-methoxy-2-propyl 30% acetate solvent solution 70 parts Solsperse 5000 (Lubrizol Corporation; a phthalocyanine derivative)
[Other dispersants] 10 parts Ajisper PB821 (manufactured by Ajinomoto Fine Chemical;
Polyester-based dispersant) [(c) Dispersant] 10 parts, 1-methoxy-2-propyl acetate [(b) solvent] 810 parts

( Reference Examples 24 to 25, Examples 26 to 28)
Reference Example 23, the polymer 1 wherein the (a dispersant) polymer 2 polymer 6 (polymer 4-6 (d) In the dispersant) except that instead of each, in the same manner as in Reference Example 23, A blue pigment dispersion composition was prepared and evaluated in the same manner as in Reference Example 23. The results are shown in Table 3 below.

(Example 29)
Reference Example 23: 30% solution of 70 parts of 1-methoxy-2-propyl acetate solvent (polymer 1 minute powder) (Polymer 1: a dispersant) of 1-methoxy-2-propyl acetate solvent In the same manner as in Reference Example 23, except that 35 parts of 30% solution and 35 parts of 30% solution of 1-methoxy-2-propyl acetate solvent of (Polymer 4: (d) Dispersant) A pigment dispersion composition was prepared and evaluated in the same manner as in Reference Example 23. The results are shown in Table 3 below.

(Example 30)
Reference Example 23: 30% solution of 70 parts of 1-methoxy-2-propyl acetate solvent (polymer 1 minute powder) (Polymer 4: (d) dispersant) of 1-methoxy-2-propyl a 30% solution 35 parts of acetate solvents: except that instead of the 30% solution 35 parts of 1-methoxy-2-propyl acetate solvent (polymer 7 a dispersant) in the same manner as in reference example 23, the blue A pigment dispersion composition was prepared and evaluated in the same manner as in Reference Example 23. The results are shown in Table 3 below.

(Example 31)
Reference Example 23: 30% solution of 70 parts of 1-methoxy-2-propyl acetate solvent (polymer 1 minute powder) (Polymer 4: (d) dispersant) of 1-methoxy-2-propyl Instead of 70 parts of a 30% solution of acetate solvent, 10 parts of Ajisper PB821 ((c) dispersant), 5 parts of Azisper PB821 ((c) dispersant) and Solsperse 32000 (manufactured by Nippon Lubrizol Corporation; polyester dispersant) : (C) Dispersant) A blue pigment dispersion composition was prepared in the same manner as in Reference Example 23 except that 5 parts was used, and the same evaluation as in Reference Example 23 was performed. The results are shown in Table 3 below.

( Reference Example 32)
In Example 31, (Polymer 4: (d) dispersing agent) 30% solution 70 parts of 1-methoxy-2-propyl acetate solvent, (Polymer 1: a dispersant) of 1-methoxy-2-propyl A blue pigment dispersion composition was prepared in the same manner as in Example 31 except that 70 parts of a 30% solution of acetate solvent was used, and the same evaluation as in Example 31 was performed. The results are shown in Table 3 below.

(Example 33)
In Example 31, 70 parts of a 30% solution of (polymer 4: (d) dispersant) in 1-methoxy-2-propyl acetate solvent was added to 1-methoxy- of (polymer 4: (d) dispersant). a 30% solution 35 parts of 2-propyl acetate solvent,: except that instead of the 30% solution 35 parts of 1-methoxy-2-propyl acetate solvent (polymer 7 a dispersant) in the same manner as in example 31 A blue pigment dispersion composition was prepared and evaluated in the same manner as in Example 31. The results are shown in Table 3 below.

(Comparative Examples 5 to 8)
Reference Example 12, the polymer 1 (a dispersant), except that instead of each one of said D-1 to D-4 (Comparison dispersant), in the same manner as in Reference Example 12, a green pigment A dispersion composition was prepared and evaluated in the same manner as in Example 7. The results are shown in Table 2 below.

(Comparative Examples 9-12)
Reference Example 23, the polymer 1 (a dispersant), to any of the preceding D-1 to D-4 (Comparative Dispersant), except that instead of each in the same manner as in Reference Example 23, the blue A pigment dispersion composition was prepared and evaluated in the same manner as in Reference Example 23. The results are shown in Table 3 below.

As is apparent from Tables 1 to 3, all of the pigment dispersion compositions of Examples using the specific pigment dispersant according to the present invention have low composition viscosity and excellent pigment dispersibility and dispersion stability. It can be seen that the film obtained by this pigment dispersion composition can provide high contrast. The reason why the coating with the pigment dispersion composition of the present invention achieves high contrast is presumed to be because the pigment particles are uniformly dispersed in a finely divided state.
On the other hand, the pigment dispersion composition of the comparative example using a known pigment dispersant outside the scope of the present invention has a relatively high viscosity, the dispersibility of the pigment is lower than that of the present invention, and the dispersion stability. The film obtained using the pigment dispersion composition did not have sufficient contrast.

Claims (5)

(A) a pigment, (b) a solvent, a dispersing agent (c) having a polyester chain, and, (d) Ri Oh an acid value 65~250mgKOH / g, and a macromonomer represented by the following general formula (4) pigment dispersion composition characterized graft copolymer der Rukoto having structural units derived from.

In General Formula (4), R ⁷ represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, and L represents —COO—, —CON (R ⁸ ) —, or a phenylene group. R ⁸ represents a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, or an aryl group having 6 to 20 carbon atoms. W represents a single bond, a single divalent linking group selected from the following atomic groups, or a divalent linking group formed by arbitrarily combining two or more of these, and A represents the following general formula The substituent which has at least the structural unit represented by (2) is represented.

In the above formula, Z ¹ and Z ² each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, a cyano group, or a hydroxyl group, and Z ³ represents a hydrogen atom, 1 to carbon atoms. 18 represents an alkyl group or an aryl group having 6 to 20 carbon atoms.

In General Formula (2), R ⁴ represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, and R ⁵ represents a hydrogen atom, an alkyl group having 1 to 22 carbon atoms, or 6 to 30 carbon atoms. Represents an aryl group. Wherein (d) grayed RAFT copolymer is a dispersant, a pigment dispersion composition according to claim 1, characterized in that a copolymer of Weight average molecular weight 1,000 to 100,000. Wherein (c) and 2 kinds of dispersants having a polyester chain, wherein (d) grayed RAFT copolymer one and the dispersing agent is, containing claim 1 or the pigment dispersion composition according to claim 2 . Wherein (c) and one or a dispersing agent having a polyester chain, wherein (d) a dispersing agent is grayed raft copolymer containing the two, the claim 1 or the pigment dispersion composition according to claim 2 . Wherein (c) and 2 kinds of dispersants having a polyester chain, wherein (d) a dispersing agent is grayed raft copolymer containing the two, the claim 1 or the pigment dispersion composition according to claim 2 .