JP2003238835A - Pigment dispersant, pigment dispersion composition and colored photosensitive composition comprising the dispersant - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a pigment dispersant simultaneously realizing good dispersibility of a pigment and excellent alkaline developability, and to provide a pigment dispersion composition and colored photosensitive composition comprising the pigment dispersant. <P>SOLUTION: This pigment dispersant comprises a graft copolymer having a repeating unit containing at least a urea skeleton and/or urethane skeleton in the main chain and a repeating unit containing an acidic group in the main chain and/or grafted chain. The graft copolymer preferably comprises a unit derived from one or more kinds of polymerizable oligomers having an ethylenic unsaturated double bond at the terminal and a unit derived from a monomer containing the urea skeleton and/or urethane skeleton as units of the copolymer. <P>COPYRIGHT: (C)2003,JPO

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a pigment dispersant, a pigment dispersion composition containing the pigment dispersant, and a colored photosensitive composition. More specifically, the pigment dispersant is effectively prevented from agglomerating and the pigment is dispersed well. A pigment dispersant that realizes the above, a pigment that contains the pigment dispersant, is excellent in dispersibility and fluidity of the pigment, is excellent in coloring power, and can be suitably used in a wide range of paints, printing inks, color display boards, and the like. Dispersion composition, and a colored photosensitivity containing the pigment dispersion composition, which can be suitably used for forming a multicolor image on a substrate such as a color proof and for manufacturing a color filter used for a liquid crystal color display and the like. It relates to a composition.

[0002]

2. Description of the Related Art Conventionally, pigments have a vivid color tone and high tinting strength and have been widely used in many fields.
By preventing aggregation of the pigment and making it fine, a clear color tone and high tinting strength can be obtained. Therefore, many pigments that are practically important are generally fine particles. However, as the pigment is made finer, the dispersion liquid of the pigment often exhibits high viscosity. Therefore, when this pigment dispersion is prepared on an industrial scale, it becomes difficult to take out the pigment dispersion from the disperser, it cannot be transported by a pipeline, and further, gelation occurs during storage. There are problems such as being unusable.

A colored photosensitive composition containing the pigment is useful as a proof material for print proofing, a material for a color filter used in a liquid crystal display or the like, and a colored filter using the colored photosensitive composition. In the case of producing, the pigment dispersion method, which is excellent in terms of quality and production stability, is widely adopted. In this pigment dispersion method, the coating liquid of the colored photosensitive composition is applied onto a transparent substrate to form a colored photosensitive layer, or the colored photosensitive layer provided on a temporary support is transferred onto a transparent substrate. After pattern exposure,
The development is performed to form a pixel pattern of the first color, and this is repeated a plurality of times to form a pixel pattern of a plurality of colors on the transparent substrate.

However, since a pigment is used as a coloring material here, if the pigment is not sufficiently miniaturized, light is scattered and absorbed by the pigment, and the light transmittance is lowered. Further, there is a problem that the polarization axis is rotated due to light scattering and birefringence due to the pigment, and the contrast of the liquid crystal display device is lowered (1990 7th Color Optical Conference, 512 color display 10.4 Color filter for size TFT-LCD, Ueki, Ozeki, Fukunaga, Yamanaka). Therefore, in the colored photosensitive composition, it is necessary to disperse the pigment in a highly finely divided state. .

Therefore, conventionally, various dispersants have been used in order to obtain a pigment dispersion or a colored photosensitive composition having excellent fluidity and dispersibility. The dispersant can be roughly classified into a polymer dispersant and a low molecular compound dispersant, and as the polymer dispersant, polyacrylate, sodium maleate olefin copolymer, terminal carboxyl group-containing polyester (Japanese Patent Publication No. 54-34009), a polyester having an acidic group and / or a basic group starting from tetrakis (2-hydroxyalkyl) ethylenediamine (JP-A-2-245231), a macromonomer (ethylenically unsaturated at the end). Group-containing oligomer), a hydroxyl group-containing monomer, a carboxy group-containing monomer and a copolymer other than these (4) (JP-A-8-259876), macromonomer (having an ethylenically unsaturated group at the end) (Oligomer), a copolymer consisting of a monomer having a nitrogen atom (JP-A-1) No. 339949) and the like, and as the low molecular compound dispersant, sorbitan fatty acid ester, polyoxyethylene alkylamine, alkyldiamine, alkanolamine derivative (US Pat. No. 3,536,510), etc. are known. ing.

In the colored photosensitive composition as a material for a color filter, a color proof, etc., among these dispersants, JP-A-8-259876 and JP-A-10-3.
Copolymers containing the macromonomer (oligomer having an ethylenically unsaturated group at the terminal) described in JP-A-39949 are useful, and copolymers containing the macromonomer (oligomer having an ethylenically unsaturated group at the terminal) It is disclosed in the publication that a pigment dispersion having a small pigment particle size and excellent dispersion stability can be obtained by using the combination.

However, the copolymer containing the macromonomer described in JP-A-8-259876 does not function as a dispersant by itself because it does not have a functional group that promotes adsorption to a pigment, and thus it does not function as a dispersant alone. There is a problem that they must be used together. Further, when the copolymer containing the macromonomer is used as a dispersant, the thickening effect found in the polymer dispersant is small and good, but the fine particle effect of the pigment is not sufficient and the dispersibility is sufficient. There is a problem that is not. Further, in the copolymer containing the macromonomer described in JP-A-10-339949, an attempt is made to introduce a nitrogen atom as a functional group that promotes adsorption to the pigment, but when the pigment is not an acidic pigment, a strong adsorption force is obtained. It is considered to be difficult to obtain, and there are problems that sufficient dispersion stability cannot be exhibited at high contrast, and dispersible pigments are limited.

On the other hand, a colored photosensitive composition containing a pigment showing a clear color tone and high tinting strength is useful as an image forming material for producing a color proof, a color filter and the like. When a colored image is formed using the colored photosensitive composition, generally, a coating solution of the colored photosensitive composition is applied onto a substrate, or the colored photosensitive layer provided on a temporary support is transferred onto a transparent substrate. Then, after forming a layer of the colored photosensitive composition, exposure and development are carried out. As a developer used in this development, an alkaline aqueous solution which has little influence on the environment is often used. Generally, the layer formed of the colored photosensitive composition contains a binder that is soluble in an alkaline aqueous solution because the copolymer containing the macromonomer alone has poor solubility in the alkaline aqueous solution. However, the above-mentioned Japanese Patent Laid-Open No. 10-33
Since the copolymer containing the macromonomer described in Japanese Patent Publication No. 9949 is insoluble in an alkaline aqueous solution, there is a problem that the layer formed by the colored photosensitive composition has insufficient alkali developability. It is desired to be soluble in an alkaline aqueous solution.

If the copolymer containing the macromonomer has an acidic group and is soluble in an alkaline aqueous solution, it is not always necessary to use the binder. Further, if the organic pigment can be dispersed in a highly finely divided state, the layer formed of the colored photosensitive composition is considered to be extremely thin, and it is possible to realize a high coloring density with a thin thickness. .

However, at present, a pigment dispersion excellent in dispersibility and fluidity of a pigment and soluble in an alkaline aqueous solution, a pigment dispersion composition containing the same, and a colored photosensitive composition have not been provided yet. Is.

[0011]

SUMMARY OF THE INVENTION It is an object of the present invention to solve the above-mentioned problems of the prior art and achieve the following objects. That is, an object of the present invention is to provide a pigment dispersant which does not aggregate the pigment, realizes stable and good dispersibility and fluidity of the pigment, and is also excellent in light transmittance. In addition, the present invention contains the pigment dispersant, dispersibility of the pigment,
It is an object of the present invention to provide a pigment dispersion composition which is excellent in fluidity and the like, has high coloring power, is excellent in alkali developability, and can be suitably used in a wide range of paints, printing inks, color display boards and the like. Furthermore, the present invention contains the pigment dispersion composition, has a high coloring power, is excellent in alkali developability, and is used for forming a multicolor image on a substrate such as a color proof and a color filter used for a liquid crystal color display and the like. It is an object of the present invention to provide a colored photosensitive composition that can be suitably used for the production of

[0012]

Means for Solving the Problems As a result of intensive studies by the present inventors in order to solve the above problems, the following findings were obtained. That is, when an organic pigment is dispersed in a binder having an acidic group that is soluble in an organic solvent, intermolecular force acts between the acidic group and the organic pigment to increase the viscosity. Although this thickening improves the dispersion stability, it causes a decrease in handleability, workability, etc., and tends to make the organic pigment difficult to be fine. Therefore, a dispersant capable of accelerating the dispersion without increasing the viscosity is desired, and as such a dispersant, a low molecular compound dispersant, in particular, an amine compound is known. However, in the case of this amine compound or the like, a salt is formed with an acidic group, so that the photosensitive resin layer is easily dissolved in the developing solution.
It may adversely affect the subsequent development. Further, an alkaline dispersant and a water-soluble dispersant have the same tendency as that of the amine compound and the like. On the other hand, in the case of the above-mentioned copolymer containing a macromonomer, although the problem of thickening can be suppressed to some extent by the steric effect of the polymer chain, it is a finding that the suitability for alkali development is not sufficient. Based on such knowledge, the present inventor has conducted diligent research and, as a result, has a repeating unit having a urea group and / or a urethane group in the trunk chain,
The present invention has been completed by finding that the above object can be achieved by using a pigment dispersant containing a graft copolymer having a repeating unit having an acidic group in the graft chain.

That is, the present invention provides <1> a graft copolymer having a repeating unit having a urea group and / or a urethane group in the main chain and having a repeating unit having an acidic group in the main chain and / or the graft chain. The present invention provides a pigment dispersant characterized by containing.

The present invention also provides the following. <2> The pigment dispersant according to <1>, wherein the acidic group is a carboxyl group. <3> The graft copolymer contains, as a copolymer unit, a unit derived from a polymerizable oligomer having an ethylenically unsaturated double bond at a terminal and a unit derived from a monomer having a urea group and / or a urethane group. The pigment dispersant according to <1> or <2>. <4> The pigment dispersant according to <3>, wherein the graft copolymer contains a unit derived from a monomer having an acidic group as a copolymer unit. <5> The pigment dispersant according to <3> or <4>, wherein the polymerizable oligomer has a repeating unit having an acidic group. <6> The polymerizable oligomer has a number average molecular weight of 1000 to 2
The pigment dispersant according to any one of <3> to <5>, which has a (meth) acryloyl group at the terminal. <7> The graft copolymer contains 15 to 98% by weight of a unit derived from a polymerizable oligomer as a copolymer unit, and 1 to 40% by weight of a unit derived from a monomer having a urea group and / or a urethane group. <3> to <6> that include
The pigment dispersant according to any one of 1. <8> The acid value of the graft copolymer is 5 to 150 mg-K
The pigment dispersant according to any one of <1> to <7>, which is OH / g. <9> A monomer containing a urea group and / or a urethane group is represented by the following general formula (1)

[0015]

[Chemical 2]

[In the above general formula (1), R ¹¹ represents a hydrogen atom or a methyl group. R ¹² is a single bond or 1 carbon atom
To 10 divalent hydrocarbon groups (the hydrocarbon groups may have a substituent, may form a branch or a ring structure, and may have an ether or ester bond in the middle thereof). R ¹³ represents a hydrocarbon group having 1 to 18 carbon atoms and optionally having a substituent, but does not include a partial skeleton of the organic dye. In addition, X ¹¹ , X ¹² and X ¹³ each independently represent —O—, —N (R ¹⁴ ) — (R ¹⁴ represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms or a phenyl group). However, X ¹² and X ¹³ do not become -O- at the same time. m and n
Indicates 1 or 0. ] The pigment dispersant according to any one of claims <3> to <8>, which is one kind or two or more kinds selected from the compounds represented by: <10> A pigment dispersion composition comprising the pigment dispersant according to any one of <1> to <9> and a pigment dispersed in an organic solvent. <11> A colored photosensitive composition comprising the pigment dispersion composition according to <10>, a polyfunctional monomer having two or more ethylenically unsaturated double bonds, and a photopolymerization initiator. <12> A colored photosensitive composition comprising the colored photosensitive composition according to <11> and a binder polymer having an acidic group.

[0017]

BEST MODE FOR CARRYING OUT THE INVENTION << Pigment Dispersant >> The pigment dispersant of the present invention has a repeating unit having a urea group and / or a urethane group in the backbone chain and an acidic group in the backbone chain and / or the graft chain. It is characterized by containing a graft copolymer having a repeating unit. Since the pigment dispersant of the present invention contains a graft copolymer having a trunk chain having a repeating unit structure having a urea group and / or a urethane group, the interaction between the pigment and the adsorbing part is high, and the pigment dispersant to the dispersion solvent is high. It has good solubility and excellent dispersion stability. Moreover, since the graft polymer has an acidic group, it exhibits excellent alkali developability. Furthermore, the pigment dispersant of the present invention may be used in combination with other components appropriately selected as necessary.

(Graft Copolymer) In the present invention, the above graft copolymer has a repeating unit having a urea group and / or a urethane group in the trunk chain and a repeating unit having an acidic group in the trunk chain and / or the graft chain. It has units,
Units derived from other monomers or polymerizable oligomers may be included as copolymerized units.

The weight average molecular weight (Mw) of the graft copolymer is preferably 3,000 to 100,000, more preferably 5,000 to 50,000. If the weight average molecular weight (Mw) is less than 3,000, it may be difficult to prevent the pigment from aggregating, and the viscosity may increase. The weight average molecular weight (Mw) is 100.
If it exceeds 000, the solubility in an organic solvent may be insufficient and the viscosity may increase. The weight average molecular weight (Mw) is a polystyrene equivalent weight average molecular weight measured by gel permeation chromatography (carrier: tetrahydrofuran).

The above graft copolymer has three modes, each of which will be described with reference to FIGS.
In the first mode, the graft copolymer has a repeating unit containing an acidic group only in the backbone chain. In FIG.
The above graft copolymer is a repeating unit containing an acidic group in the main chain (1) having at least a repeating unit containing a urea group and / or a urethane group (3) and a repeating unit containing an acidic group (5). The graft chain (2) formed by a polymerizable oligomer having no group is bonded by graft copolymerization, and the bonding portion (4) between the trunk chain and the graft chain is formed by the terminal ethylenically unsaturated bond in the polymerizable oligomer. It is the result of the polymerization reaction. The trunk chain (1) may optionally contain units derived from other monomers as copolymerized units.

The second mode is a graft copolymer having a repeating unit containing an acidic group only in the graft chain. In FIG. 2, the above-mentioned graft copolymer is a polymerizable compound having a repeating unit containing an acidic group (5) in the main chain (1) having at least a repeating unit containing a urea group and / or a urethane group (3). The oligomeric graft chain (2) is bonded by graft copolymerization,
The connecting portion (4) between the trunk chain and the graft chain is a result of the polymerization reaction due to the terminal ethylenically unsaturated bond in the polymerizable oligomer. The trunk chain (1) and / or the graft chain (2) may optionally contain a unit derived from another monomer and / or a polymerizable oligomer as a copolymerized unit.

The third aspect is a graft copolymer having a repeating unit containing an acidic group in both the trunk chain and the graft chain. In FIG. 3, the above graft copolymer is
Polymerization having a repeating unit containing an acidic group (5) in the backbone (1) having at least a repeating unit containing a urea group and / or a urethane group (3) and a repeating unit containing an acidic group (5) The graft chain (2) of the oligomer is bonded by graft copolymerization, and the bonding part (4) of the trunk chain and the graft chain is at the end of the polymerizable oligomer having a repeating unit containing the above acidic group (5). It is a result of a polymerization reaction due to an ethylenically unsaturated bond. The trunk chain (1) and / or the graft chain (2) may optionally contain a unit derived from another monomer and / or a polymerizable oligomer as a copolymerized unit.

The above graft copolymer has an ethylenically unsaturated double bond in a monomer having a repeating unit containing at least a urea group and / or a urethane group and an ethylenically unsaturated double bond in a monomer having an acidic group and And / or formed by a polymerization reaction with an ethylenically unsaturated double bond at a terminal of one or more polymerizable oligomers (having a repeating unit having an acidic group).

The above graft copolymer can also be synthesized by a polymer reaction. For example, first
A graft copolymer having a repeating unit containing an isocyanate group in the main chain and a repeating unit containing an acidic group in the main chain and / or the graft chain is synthesized, and then,
Reacting this copolymer with various monoamine compounds or monoalcohol compounds, or having a repeating unit containing a urea group and / or a urethane group in the main chain, and containing a hydroxyl group in the main chain and / or graft chain It can also be synthesized by synthesizing a graft copolymer having a repeating unit and then reacting the copolymer with an acid anhydride. However, a side reaction such as gelation may occur when synthesizing a graft copolymer containing a highly reactive functional group such as an isocyanate group in the main chain, or the reaction rate may be high when performing a polymer reaction. It is low, and it may not be possible to appropriately introduce a urea group and / or urethane group or an acidic group into the graft copolymer. From the viewpoint of synthesis suitability, it is preferable to form the graft copolymer by a polymerization reaction. .

The content of these copolymer units in the graft copolymer is 1 for the repeating unit containing a urea skeleton and / or a urethane skeleton derived from a monomer.
To 40% by weight, preferably 3 to 30% by weight, and the unit derived from the polymerizable oligomer is 15 to 98% by weight, preferably 30 to 95% by weight.

When the content of the unit derived from the polymerizable oligomer is less than 15% by weight, the steric repulsion effect as the pigment dispersant cannot be obtained, and the aggregation of the pigment may not be prevented. In addition, the appropriateness of development in the production of color filters and the like may not be sufficient. Furthermore, the solubility in the dispersion solvent decreases, and it becomes difficult to sufficiently secure the adsorption layer necessary for stabilizing the dispersion. If this amount exceeds 98% by weight, the proportion of the units derived from the above-mentioned monomer having a urea group and / or a urethane group decreases, the adsorption capacity for the pigment decreases, and the dispersibility may not be sufficiently exhibited. If the content of the unit derived from the monomer having a urea group and / or a urethane group is less than 1% by weight, the ability to adsorb the pigment may be lowered, and the dispersibility may not be sufficiently exhibited. And, since the ratio of the polymerizable oligomer is reduced, the steric repulsion effect as a pigment dispersant may not be obtained, the aggregation of the pigment may not be sufficiently prevented, and the solubility in a dispersion solvent is decreased, It may be difficult to sufficiently secure the adsorption layer necessary for dispersion stabilization. When another monomer copolymerizable with these is used, the content of the other monomer is 4 to
It is preferably within the range of 70% by weight.

--Monomer Containing Acidic Group-- Examples of the monomer containing an acid group include (meth)
Acrylic acid, crotonic acid, itaconic acid, maleic acid, fumaric acid, cinnamic acid, acrylic acid dimer, vinylbenzoic acid, styrenesulfonic acid, 2-acrylamido-2-methylpropanesulfonic acid, phosphoric acid mono (meth) acryloylethyl ester Or a monomer obtained by reacting an alcoholic hydroxyl group-containing monomer such as 2-hydroxyethyl methacrylate with a cyclic acid anhydride such as maleic anhydride or phthalic anhydride. Among these, as a preferable example of a monomer,
Examples thereof include monomers obtained by reacting an alcoholic hydroxyl group-containing monomer such as (meth) acrylic acid and 2-hydroxyethyl methacrylate with a cyclic acid anhydride such as maleic anhydride and phthalic anhydride. Examples of the cyclic acid anhydride used here include itaconic anhydride,
Examples thereof include maleic anhydride, phthalic anhydride, succinic anhydride, glutaric anhydride, trimetic anhydride, and the like, with phthalic anhydride and succinic anhydride being particularly preferred.

—Polymerizable Oligomer— The polymerizable oligomer (hereinafter sometimes referred to as “macromonomer”) is an oligomer having a group having an ethylenically unsaturated double bond at the end. In the present invention, among the above-mentioned polymerizable oligomers, it is preferable to have a group having the above-mentioned ethylenically unsaturated double bond only at one of both ends of the oligomer.

The molecular weight of the above polymerizable oligomer is
Number average molecular weight (Mn) in terms of polystyrene is 1000-
It is preferably 20000, 2000-15000
Is more preferable. The number average molecular weight is 100
If it is less than 0, the steric repulsion effect as a pigment dispersant may not be sufficient, and if it exceeds 20,000, it may take time for adsorption to the pigment due to the steric effect.

As the above-mentioned oligomer, generally, for example, a homopolymer or a copolymer formed from at least one monomer selected from alkyl (meth) acrylate, styrene, acrylonitrile, vinyl acetate and butadiene, etc. Among these, homopolymers or copolymers of alkyl (meth) acrylate, polystyrene and the like are preferable. In the present invention, these oligomers may be substituted with a substituent,
The substituent is not particularly limited, but examples thereof include a hydroxyl group and a halogen atom.

The group having an ethylenically unsaturated double bond is preferably, for example, a (meth) acryloyl group or a vinyl group, and of these, a (meth) acryloyl group is particularly preferable.

In the present invention, among the above-mentioned polymerizable oligomers, the oligomer represented by the following general formula (2) is preferable.

[0033]

[Chemical 3]

In the above general formula (2), R ²¹ , R ²³ and R ²⁴ represent a hydrogen atom or a methyl group. R ²² represents an alkylene group having 1 to 8 carbon atoms which may be substituted with an OH group, and an alkylene group having 2 to 4 carbon atoms is preferable. Y ²¹ , Y
²² is, independently of each other, a phenyl group, a phenyl group having an alkyl group having 1 to 4 carbon atoms, or -COOR ²⁵ (R
²⁵ represents an alcoholic hydroxyl group, an alkyl group having 1 to 6 carbon atoms which may be substituted with halogen, a phenyl group, or an arylalkyl group having 7 to 10 carbon atoms, a phenyl group or -COOR ²⁶ (R ²⁶ represents an alkyl group having 1 to 4 carbon atoms which may be substituted with an alcoholic hydroxyl group). p and q indicate the number of repetitions (integer), p +
20-200 are preferable for q.

Specific examples of the above polymerizable oligomer include:
Poly-2hydroxyethyl (meth) acrylate, polystyrene polymer, polymethyl (meth) acrylate,
Preferable examples include poly-n-butyl (meth) acrylate, poly-i-butyl (meth) acrylate, and copolymers thereof, in which a (meth) acryloyl group is bonded to one of the molecular terminals.

The above-mentioned polymerizable oligomer may be a commercially available product or may be an appropriately synthesized product. Examples of the commercially available product include, for example, one-end methacryloylated polystyrene oligomer (Mn = 6000, trade name: AS-6, manufactured by Toagosei Kagaku Kogyo Co., Ltd., one end methacryloylated polymethylmethacrylate oligomer (Mn = 6000,
Trade name: AA-6, manufactured by Toagosei Chemical Industry Co., Ltd., one-terminal methacryloylated poly-n-butyl acrylate oligomer (Mn = 6000, trade name: AB-6, manufactured by Toagosei Chemical Industry Co., Ltd.), One end methacryloylated polymethylmethacrylate / 2-hydroxyethylmethacrylate oligomer (Mn = 7000, trade name: AA-714
SK, Toagosei Chemical Industry Co., Ltd., one end methacryloylated polybutyl methacrylate / 2-hydroxyethyl methacrylate oligomer (Mn = 7000, trade name: AX-707S, Toagosei Chemical Industry Co., Ltd.), one end Methacryloylated poly 2-ethylhexyl methacrylate / 2-hydroxyethyl methacrylate oligomer (Mn = 7000, trade name: AY-707S, AY-
714S, manufactured by Toagosei Kagaku Kogyo Co., Ltd., and the like.

Preferred specific examples of the above-mentioned polymerizable oligomer in the present invention include at least one oligomer selected from a polymer of alkyl (meth) acrylate and a copolymer of alkyl (meth) acrylate and polystyrene. And the number average molecular weight is 1000 to 20
And those having a (meth) acryloyl group at the terminal.

—Polymerizable Oligomer Having Repeating Unit Having Acidic Group— The number average molecular weight (Mn) in terms of polystyrene is preferably 1,000 to 20,000, and more preferably 2,000 to 15,000 as the molecular weight of this oligomer. Is more preferable. If the number average molecular weight is less than 1000, the steric repulsion effect as a pigment dispersant may not be sufficient, and if it exceeds 20,000, it may take time to adsorb to the pigment due to the steric effect, or a color filter or the like. In some cases, the developability during the production of is not sufficient. The content of the repeating unit containing the acidic group in the polymerizable oligomer having the repeating unit containing the acidic group is 2
-100% by weight is preferable, and 5-90% by weight is more preferable. If the content is less than 2% by weight, developability may not be obtained during production of color filters and the like.

The oligomer having a repeating unit having an acidic group generally includes a homopolymer formed from a monomer having the acidic group or a copolymer containing a polymerizable monomer.

The oligomer having a repeating unit having an acidic group may be obtained by deprotecting a polymer (oligomer) having the functional group protected to obtain an acidic group, and vice versa. It may be obtained by a method of converting into an acidic group by a polymer reaction of (oligomer). An example of the polymer reaction may be obtained by reacting an alcoholic hydroxyl group in a polymer obtained from a monomer having an alcoholic hydroxyl group with a cyclic acid anhydride or the like. The method for synthesizing the polymerizable oligomer having a repeating unit containing such an acidic group is not particularly limited, and is, for example, JP-A-1
No. 1-181021. However, there is no description that this is used as a dispersant, and there is no description that it can be used for compatibility of dispersibility and alkali developability.

Examples of the oligomer having a repeating unit having an acidic group include a copolymer of (meth) acrylic acid and a polymerizable monomer copolymerizable with it, an alcoholic hydroxyl group-containing monomer such as 2-hydroxyethyl methacrylate, and anhydrous A copolymer of a monomer obtained by reacting a cyclic acid anhydride such as an acid with a copolymerizable polymerizable monomer, and a copolymer of a monomer having an alcoholic hydroxyl group with a polymerizable monomer A copolymer obtained by reacting a cyclic acid anhydride such as succinic anhydride is preferable. Such cyclic acid anhydrides include, for example, itaconic anhydride, maleic anhydride, phthalic anhydride, succinic anhydride, glutaric anhydride, trimetic anhydride, and the like, but especially phthalic anhydride, succinic anhydride and the like. preferable.

In the present invention, these oligomers may be substituted with a substituent, and the substituent is not particularly limited, but for example, a halogen atom, an alkoxy group,
Examples thereof include hydroxyl group and polyether. Further, as the group having an ethylenically unsaturated double bond necessary for these oligomers, for example, (meth) acryloyl group, vinyl group and the like are preferably mentioned, and among these, (meth) acryloyl group is particularly preferable.

In the present invention, among the polymerizable oligomers having the repeating unit having an acidic group, the oligomer represented by the following general formula (3) is preferable.

[0044]

[Chemical 4]

In the general formula (3), R ³¹ , R ³³ and R ³⁴ represent a hydrogen atom or a methyl group. R ³² represents an alkylene group having 1 to 8 carbon atoms which may be substituted with an OH group, and an alkylene group having 2 to 4 carbon atoms is preferable. Y ³¹ is
Phenyl group, phenyl group having alkyl group having 1 to 4 carbon atoms, or -COOR ³⁵ (R ³⁵ is an alkyl group which may be substituted with halogen, phenyl group, or C 7 to 1
0 represents an arylalkyl group), and a phenyl group or —COOR ³⁵ (R ³⁵ represents an alkyl group which may be substituted with halogen) is preferable. Y ³² is a carboxyl group, —COOR ³⁶ (R ³⁶ is —COO—, —OCO—,
Represents a carboxyl group or a phosphonic acid group having an alkylene group having 1 to 6 carbon atoms, which may contain ether, arylene, or a combination thereof), -CONHR ³⁷
(R ³⁷ represents a sulfonic acid group having an optionally branched alkylene group having 1 to 7 carbon atoms), a carboxyl group, —COOR ³⁶ (R ³⁶ represents —COO—, —OCO)
-, An ether, an arylene, or a carboxylic group having a C1-6 alkylene group which may contain a combination thereof, or a phosphonic acid group) is preferable.
p and q represent the number of repetitions, p represents an integer of 0 to 100, and q represents an integer of 1 to 100.

Specific examples of the polymerizable oligomer having a repeating unit having an acidic group include poly-alkyl (meth) acrylate / (meth) acrylic acid, poly-styrene / (meth) acrylic acid and poly-alkyl (meth). )
A polymer such as a reaction product of an acrylate / hydroxyalkyl (meth) acrylic acid and a cyclic acid anhydride, in which one (meth) acryloyl group is bonded to the molecular end is preferably used.

Specific examples of the polymerizable oligomer having a repeating unit having an acidic group in the present invention include poly-methyl (meth) acrylate / (meth) acrylic acid, poly-styrene / (meth) acrylic acid, At least one oligomer selected from a reaction product of poly-methyl (meth) acrylate / 2-hydroxyethyl (meth) acrylate and a cyclic acid anhydride, having a number average molecular weight of 1,000 to 20,000 and a terminal. And those having a (meth) acryloyl group.
Examples of the cyclic acid anhydride used here include itaconic anhydride, maleic anhydride, phthalic anhydride, succinic anhydride, glutaric anhydride, trimetic anhydride, and the like. Among these, phthalic anhydride, and anhydrous Succinic acid is preferred.

Some examples of the synthesis of the polymerizable oligomer having the repeating unit having an acidic group are shown below.

[Production Example of Macromonomer 1: MM-1] 2
A mixed solution of 58.5 parts by weight of hydroxyethyl methacrylate, 54.0 parts by weight of methyl methacrylate, and 4.77 parts by weight of thioglycolic acid was heated to a temperature of 80 ° C. while stirring under a nitrogen stream. 0.147 parts by weight of 2,2′-azobisisobutyronitrile (abbreviation AIBN) was added and reacted for 2 hours, and further 30 parts by weight of THF was added and reacted for 3 hours. After cooling, this reaction solution was diluted with 200 parts by weight of ethyl acetate and reprecipitated with 3000 parts by weight of hexane to obtain 105.5 parts by weight of a white powder. Next, to 90 parts by weight of this white powder, 200 parts by weight of xylene, 13.5 parts by weight of glycidyl methacrylate and 0.1 parts of N, N-dimethyldodecylamine were added.
42 parts by weight and 0.1 part by weight of hydroquinone were added to 1
The mixture was stirred at 50 ° C for 3 hours. After cooling, the reaction solution was reprecipitated with 3000 parts by weight of hexane to obtain 88 parts by weight of white powder. Furthermore, while stirring a mixed solution of 80 parts by weight of the obtained white powder, 31.0 parts by weight of succinic anhydride, and 160 parts by weight of 1-methoxy-2-propylacetate,
The reaction was carried out at 0 ° C for 6 hours. The reaction solution is ethyl acetate 2
The mixture was diluted with 00 parts by weight and reprecipitated with 3000 parts by weight of hexane to obtain 70 parts by weight of white powder (a macromonomer having a repeating unit having a carboxyl group: MM-1).
The number average molecular weight of the obtained macromonomer was 4000. The number average molecular weight was measured by gel permeation chromatography (C-R4A, manufactured by Shimadzu Corporation).

[Production Example 2 of Macromonomer: MM-2] 2
-A mixed solution of 32.5 parts by weight of hydroxyethyl methacrylate, 75.1 parts by weight of methyl methacrylate, and 2.65 parts by weight of thioglycolic acid was heated to a temperature of 80 ° C while stirring under a nitrogen stream. 0.02 parts by weight of 2,2′-azobisisobutyronitrile (abbreviation AIBN) was added and reacted for 2 hours, and further 30 parts by weight of THF was added and reacted for 3 hours. After cooling, this reaction solution was diluted with 200 parts by weight of ethyl acetate and reprecipitated with 3000 parts by weight of hexane to obtain 99.2 parts by weight of a white powder. Next, to 90 parts by weight of this white powder, 200 parts by weight of xylene, 13.5 parts by weight of glycidyl methacrylate, and 0.14 of N, N-dimethyldodecylamine were added.
Add 2 parts by weight and 0.1 parts by weight of hydroquinone to give 15
The mixture was stirred at 0 ° C for 3 hours. After cooling, the reaction solution was
Re-precipitation with 3000 parts by weight of hexane gave 87.5 parts by weight of white powder. Furthermore, while stirring a mixed solution of 80 parts by weight of the obtained white powder, 17.8 parts by weight of succinic anhydride, and 160 parts by weight of 1-methoxy-2-propylacetate,
The reaction was carried out at 0 ° C for 6 hours. The reaction solution is ethyl acetate 2
The mixture was diluted with 00 parts by weight and reprecipitated with 3000 parts by weight of hexane to obtain 73.6 parts by weight of white powder (a macromonomer having a repeating unit having a carboxyl group: MM-2). The number average molecular weight of the obtained macromonomer is 550.
It was 0.

[Production Example 3 of Macromonomer: MM-3] methoxymethylmethacrylate (Bull. Chem. Soc. Jpn.,
41, 1968, 2521-2523) 11.7 parts by weight, 81 parts by weight of methyl methacrylate, 1.38 parts by weight of thioglycolic acid were added to a mixed solution at a temperature of 80 ° C. with stirring under a nitrogen stream. Warmed. Add 0.049 parts by weight of 2,2'-azobisisobutyronitrile (abbreviation AIBN) and react for 3 hours. Further, 0.024 parts by weight of AIBN, TH
F30 parts by weight was added and the reaction was carried out for 2 hours. After cooling, the reaction solution was reprecipitated in 2000 parts by weight of hexane to obtain 90 parts by weight of white powder. Next, to 90 parts by weight of this white powder,
200 parts by weight of 1-methoxy-2-propyl acetate,
13.5 parts by weight of glycidyl methacrylate, 0.142 parts by weight of N, N-dimethyldodecylamine and 0.1 part by weight of hydroquinone were added, and the mixture was stirred at 150 ° C. for 3 hours.
After cooling, the reaction solution was reprecipitated in 2000 parts by weight of hexane to obtain 80 parts by weight of white powder. Further, 80 parts by weight of this white powder was dissolved in 160 parts by weight of THF, about 3 parts by weight of 12N hydrochloric acid was added, and the mixture was reacted (deprotected) at 70 ° C. for 2 hours. The reaction solution was reprecipitated with 2000 parts by weight of H2O to obtain 70 parts by weight of white powder (a macromonomer having a repeating unit having a carboxyl group: MM-3).
The number average molecular weight of the obtained macromonomer was 7,000.

[Production Example 4 of Macromonomer: MM-4] Methacryloylated poly-methyl methacrylate / 2 at one end
-Hydroxyethyl methacrylate oligomer (Mw =
7,000, trade name: AA-714SK, manufactured by Toagosei Kagaku Kogyo Co., Ltd.) 100 parts by weight of a solution (solid content concentration: 45 wt%), 4.84 parts by weight of succinic anhydride were mixed with 90 parts.
The reaction was carried out at 0 ° C for 6 hours. The reaction solution is ethyl acetate 20
Dilute with 0 parts by weight, reprecipitate with 3000 parts by weight of hexane,
48 parts by weight of white powder (a macromonomer having a repeating unit having a carboxyl group: MM-4) was obtained. The number average molecular weight of the obtained macromonomer was 7,900. --Urea group and / or urethane group-containing monomer--
-As the monomer having a urea group and / or a urethane group used in the present invention, for example, those represented by the following general formula (1) are preferable.

[0053]

[Chemical 5]

In the general formula (1), R¹¹Is a hydrogen atom or methyl
Represents a radical. R¹²Is a single bond or 1 to 10 carbon atoms
Is a divalent hydrocarbon group. The hydrocarbon group has a substituent
May have, or may form a branched or ring structure
Well, also in the middle bond through ether, ester bond
It may have been done. Specifically, a single bond, (CH₂)_lNa
Which alkylene (l is an integer from 1 to 10), isopropyl
Branched alkylene such as lidene, cyclohexylene
Cyclic alkylene, phenylene, toluylene, xylile
Groups having an aromatic ring such as benzene and naphthylene, (C ₂H
_FourO)_m, (C₃H₆O)_nVia ether bonds such as
(M is an integer from 1 to 5, n is an integer from 1 to 3), (C
H₂)_p1-OCO- (CH₂)_p2And (CH₂)_p1-COO
-(CH₂)_p2Via an ester bond such as (p1 +
p2 is an integer of 1 to 9), further carbon-carbon double bond, triple bond
And the combination of these.
And (CH₂)_lSuch as alkylene (l is from 1 to 10
An integer), a group having an aromatic ring such as phenylene, (C₂
H_FourO)_m, (C₃H₆O)_nVia ether bonds such as
Things (m is an integer from 1 to 5 and n is an integer from 1 to 3)
Good

R ¹³ represents a hydrocarbon group having 1 to 18 carbon atoms which may have a substituent. However, the partial skeleton of the organic dye is not included. Preferred specific examples include alkyl (eg, methyl, ethyl, n-propyl, i-propyl, n
-Butyl, sec-butyl, t-butyl, hexyl, 2
-Ethylhexyl, decyl, dodecyl, octadecyl, etc.) group, cyclic alkyl (eg, cyclobutyl, cyclopentyl, methylcyclopentyl, cyclohexyl, ethylcyclohexyl, cyclooctyl, adamantyl, etc.) group, alkyl having a cyclic structure (eg, cyclobutylmethyl, cyclopentyl) Methyl, methylcyclopentylmethyl, cyclopentylbutyl, cyclohexylmethyl, cyclohexylethyl, 1-adamantanemethyl), aralkyl (eg, benzyl, phenethyl, phenylpropyl, etc.) groups, aryl (eg, phenyl, toluyl, xylyl, naphthyl, etc.) groups, and further Contains substituents (trifluoroethyl, hexafluoroisopropyl, chloropropyl, bromohexyl, tetrahydrofurfuryl, methoxypropyl, Kishifeniru, butoxy phenyl, methoxynaphthyl, benzyloxyphenyl,
Methoxybenzyl, hydroxyphenyl, hydroxyphenethyl, hydroxypropyl, hydroxyhexyl,
Carboxypropyl, carboxypentyl, acetamidoethyl, etc.) groups, and the like.

X ¹¹ , X ¹² , and X ¹³ are each independently-
O-, -N (R ¹⁴ )-(R ¹⁴ is a hydrogen atom or a carbon number 1
??? 6 represents an alkyl group or a phenyl group). It is preferably —O— or —NH—, and X ¹² and X ¹³ do not become —O— at the same time.

The above-mentioned monomer containing a urea group and / or a urethane group can be appropriately synthesized by utilizing an addition reaction of an isocyanate group and a hydroxyl group or an isocyanate group and an amino group. Specifically, it can be appropriately synthesized by an addition reaction of an isocyanate group-containing monomer and a monoamine, a hydroxyl group-containing monomer and a monoisocyanate, an isocyanate group-containing monomer and a monohydroxyl group compound, and the like.

This addition reaction is carried out, for example, in an aprotic solvent (eg acetonitrile, tetrahydrofuran, ethyl acetate, chloroform etc.) at room temperature or under heating or in the presence of a catalyst (tin compound, tertiary amines etc.). At room temperature or by heating as necessary. Specific examples of the isocyanate group-containing monomer include the following compounds (R represents a hydrogen atom or a methyl group).

[0059]

[Chemical 6]

Specific examples of the hydroxyl group-containing monomer include the following compounds (R represents a hydrogen atom or a methyl group, and n represents an integer of 1 or more).

[0061]

[Chemical 7]

Specific examples of the monoisocyanate include cyclohexyl isocyanate, n-butyl isocyanate, toluyl isocyanate, phenyl isocyanate and the like.

Specific examples of monoamines include alkylamines (methylamine, ethylamine, n-propylamine, i-propylamine, n-butylamine, sec-
Butylamine, t-butylamine, hexylamine, 2
-Ethylhexylamine, decylamine, dodecylamine, octadecylamine), cyclic alkylamines (cyclopentylamine, cyclohexylamine, etc.), aralkylamines (benzylamine, phenethylamine, etc.),
Examples thereof include arylamines (aniline, toluylamine, xylylamine, naphthylamine, etc.) and amines having a substituent (trifluoroethylamine, hexafluoroisopropylamine, methoxyaniline, methoxypropylamine, etc.).

Examples of the monohydroxyl group-containing compound include alcohols (methanol, ethanol, n-propanol, i
-Propanol, n-butanol, sec-butanol, t-butanol, n-hexanol, 2-ethylhexanol, n-decanol, n-dodecanol, n-
Octadecanol), cyclopentanol, cyclohexanol, benzyl alcohol, phenylethyl alcohol, etc.), phenols (phenol, cresol, naphthyl alcohol, etc.), and those containing a substituent,
Fluoroethanol, trifluoroethanol, methoxyethanol, phenoxyethanol, chlorophenol,
Dichlorophenol, methoxyphenol, acetoxyphenol and the like are also included.

Specific examples of the monomer having a urea skeleton and / or a urethane skeleton (exemplified compounds M-1 to M) are shown below.
-25), but the present invention is not limited thereto, and includes, for example, those in which the combination of the isocyanate group and the hydroxyl group or the combination of the isocyanate group and the amino group of the above compound is changed.

[0066]

[Chemical 8]

[0067]

[Chemical 9]

—Other Monomer— The above graft copolymer may further contain the above other monomer as a copolymer unit, and the other monomer is not particularly limited and may be selected depending on the purpose. Can be appropriately selected by, for example, aromatic vinyl compounds (eg, styrene, α-methylstyrene and vinyltoluene),
(Meth) acrylic acid alkyl ester (eg, methyl (meth) acrylate, ethyl (meth) acrylate, n-
Butyl (meth) acrylate and i-butyl (meth)
Acrylate), (meth) acrylic acid alkylaryl ester (eg, benzyl (meth) acrylate), glycidyl (meth) acrylate, carboxylic acid vinyl ester (eg, vinyl acetate and vinyl propionate), vinyl cyanide (eg, (meth ) Acrylonitrile and α-
Chloroacrylonitrile), and aliphatic conjugated dienes (eg, 1,3-butadiene and isoprene), and the like. Among these, (meth) acrylic acid ester and (meth) acrylic acid alkylaryl ester are preferable. In addition to the above, a monomer containing an ether group may be contained as a copolymerized unit. Examples of the monomer containing an ether group include polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, polyethylene glycol polypropylene glycol mono (meth) acrylate, polytetramethylene glycol mono (meth) acrylate and the like. These may be commercially available products or may be appropriately synthesized. As the commercial product, methoxy polyethylene glycol methacrylate (trade name: NK ester M-40G, M-90G, M-
230G (above, manufactured by Toagosei Chemical Industry Co., Ltd.); Trade name: Bremmer-PME-100, PME-200, PM
E-400, PME-1000, PME-2000, P
ME-4000 (above, NOF Corporation), polyethylene glycol monomethacrylate (trade name: Blemmer PE-90, PE-200, PE-350 (NOF Corporation)), polypropylene glycol monomethacrylate (commodity) Name: Bremmer PP-500, PP-80
0, PP-1000 (manufactured by NOF CORPORATION), polyethylene glycol polypropylene glycol monomethacrylate (trade name: Bremmer 70PEP-370B (manufactured by NOF CORPORATION)), polyethylene glycol polytetramethylene glycol monomethacrylate (trade name) : Bremmer 55PET-800 (manufactured by NOF CORPORATION),
Polypropylene glycol polytetramethylene glycol monomethacrylate (trade name: Blemmer NHK-5
050 (manufactured by Nippon Oil & Fats Co., Ltd.) and the like.

The content of the other monomer in the graft copolymer is preferably 4 to 70% by weight. If the content is less than 4% by weight, the physical properties of the coating film may not be controlled, and if it exceeds 70% by weight, the ability as a pigment dispersant may not be sufficiently exhibited.

Preferred Specific Examples of Graft Copolymers Specific preferred examples of graft copolymers include the following. (1) Monomers shown in the above specific examples (exemplary compound M-1
~ M-25) / (meth) acrylic acid / methacryloyl-terminated polymethylmethacrylate oligomer copolymer,
(2) Monomers shown in the above specific examples (exemplary compound M-1
.About.M-25) / (meth) acrylic acid / methacryloyl-terminated polystyrene oligomer copolymer, (3) the monomers (exemplary compounds M-1 to M-25) shown in the above specific examples /
(Meth) acrylic acid / methacryloyl-terminated poly-n-
Butyl acrylate oligomer copolymer, (4) Monomers shown in the above specific examples (exemplary compounds M-1 to M-25)
/ (Meth) acrylic acid / methacryloyl-terminated poly (methyl methacrylate / 2-hydroxyethyl methacrylate) oligomer copolymer, (5) Monomers (exemplary compounds M-1 to M-25) / (meth) shown in the above specific examples. ) Acrylic acid / methyl (meth) acrylate / methacryloyl-terminated polymethylmethacrylate oligomer copolymer, (6) Monomers shown in the above specific examples (exemplary compound M
-1 to M-25) / (meth) acrylic acid / methyl (meth) acrylate / methacryloyl-terminated polystyrene oligomer copolymer, (7) monomers shown in the above specific examples (exemplified compounds M-1 to M-25) / (Meth) acrylic acid / methyl (meth) acrylate / methacryloyl-terminated poly-n-butyl acrylate oligomer copolymer,
(8) Monomers shown in the above specific examples (exemplary compound M-1
To M-25) / (meth) acrylic acid / methyl (meth) acrylate / methacryloyl-terminated poly (methyl methacrylate / 2-hydroxyethyl methacrylate) oligomer copolymer, (9) the monomer (exemplified compound) shown in the above specific example. M-1 to M-25) / (meth) acrylic acid / benzyl (meth) acrylate / terminal methacryloylated polymethylmethacrylate oligomer copolymer, (1
0) Monomers shown in the above specific examples (exemplary compounds M-1 to M-1)
M-25) / (meth) acrylic acid / benzyl (meth) acrylate / methacryloyl-terminated polystyrene oligomer copolymer (11) Monomers (exemplified compounds M-1 to M-25) / (meth) shown in the above specific examples. ) Acrylic acid / benzyl (meth) acrylate / methacryloyl-terminated poly-n-butyl acrylate oligomer copolymer,
(12) Monomers shown in the above specific examples (exemplary compound M-
1-M-25) / (meth) acrylic acid / benzyl (meth) acrylate / terminal methacryloylated poly (methyl methacrylate / 2-hydroxyethyl methacrylate) oligomer copolymer, (13) the monomers shown in the above specific examples (exemplification) Compounds M-1 to M-25) / methacryloyl-terminated polymethylmethacrylate oligomer / polymerizable oligomer (MM-1 to MM-) shown in the above production example.
4) Copolymer, (14) Monomer (Exemplified Compounds M-1 to M-25) shown in the above specific examples / methacryloyl-terminated polystyrene oligomer / Polymerizable oligomer shown in the above Production Examples (MM-1 to MM- 4) Copolymer, (15)
Monomers shown in the above specific examples (exemplified compounds M-1 to M-
25) / methacryloyl-terminated poly-n-butyl acrylate oligomer / polymerizable oligomer (MM-1 to MM-4) copolymer shown in the above production example, (16) monomer shown in the above specific example (exemplary compound M) -1 to M-25) /
Terminal methacryloylated poly (methyl methacrylate / 2
-Hydroxyethyl methacrylate) oligomer / polymerizable oligomer (MM-1 to MM-
4) Copolymer, (17) Monomer (Exemplified Compounds M-1 to M-25) / Methyl (meth) acrylate / Terminal methacryloylated polymethylmethacrylate oligomer / Polymerizability shown in the above Production Example Oligomer (MM-1 to MM-4) Copolymer, (18) Monomer (Exemplified Compounds M-1 to M-25) / Methyl (meth) acrylate / Methacryloyl-Terminated Polystyrene Oligomer / Production Above Polymerizable oligomers (MM-1 to MM-4) copolymers shown in the examples, (19) Monomers (exemplary compounds M-1 to M-25) shown in the above specific examples
/ Methyl (meth) acrylate / methacryloyl-terminated poly-n-butyl acrylate oligomer / polymerizable oligomer (MM-1 to MM-4) copolymer shown in the above production example,

(20) Monomers (Exemplified Compounds M-1 to M-25) shown in the above specific examples / methyl (meth) acrylate / methacryloyl-terminated poly (methyl methacrylate / 2-hydroxyethyl methacrylate) oligomers / Production examples above Polymerizable oligomer shown in (MM-1 to M
M-4) copolymer, (21) monomer (exemplary compounds M-1 to M-25) / benzyl (meth) shown in the above specific examples
Acrylate / methacryloyl-terminated polymethylmethacrylate oligomer / polymerizable oligomer (MM-1 to MM-4) copolymer shown in the above production example, (22) Monomer shown in the above specific examples (exemplified compounds M-1 to M) -25)
/ Benzyl (meth) acrylate / methacryloyl-terminated polystyrene oligomer / polymerizable oligomer (MM-1 to MM-4) copolymer shown in the above production example, (23)
Monomers shown in the above specific examples (exemplified compounds M-1 to M-
25) / benzyl (meth) acrylate / methacryloyl-terminated poly-n-butyl acrylate oligomer / polymerizable oligomer (MM-1 to MM- shown in the above production example.
4) Copolymer, (24) Monomer (Exemplified Compounds M-1 to M-25) / Benzyl (meth) acrylate / Terminal methacryloylated poly (methyl methacrylate / 2-hydroxyethyl methacrylate) oligomer / (24) The polymerizable oligomer (MM-
1 to MM-4) Copolymer, (25) Monomers (Exemplified Compounds M-1 to M-25) shown in the above specific examples / Polymerizable oligomers (MM-1 to MM-4) shown in the above Production Examples Copolymer, (26) Monomer (Exemplified Compounds M-1 to M-25) / Methyl (meth) acrylate /
The polymerizable oligomer (MM-1 to MM
-4) Copolymer, (27) Monomer (Exemplified Compounds M-1 to M-25) / Benzyl (meth) acrylate / Polymerizable Oligomer (M)
M-1 to MM-4) copolymer,

(28) Monomer (Exemplified Compounds M-1 to M-25) / (meth) acrylic acid / polymerizable oligomer (MM-1 to MM-) shown in the above Production Examples.
4) Copolymer, (29) Monomer (M-1 to M-8) / (meth) acrylic acid / methyl (meth) acrylate shown in the above synthesis example / Polymerizable oligomer (MM- shown in the above production example 1 to MM-4) copolymer, (30) monomers shown in the above specific examples (exemplified compounds M-1 to M-25) /
(Meth) acrylic acid / benzyl (meth) acrylate /
The polymerizable oligomer (MM-1 to MM
-4) copolymer,

(31) Monomers (Exemplified Compounds M-1 to M-25) / (meth) acrylic acid / methacryloyl-terminated polymethylmethacrylate oligomers / polymerizable oligomers (MM) shown in the above-mentioned production examples -1-
MM-4) Copolymer, (32) Monomer (Exemplified Compounds M-1 to M-25) / (meth) acrylic acid / methacryloyl-terminated polystyrene oligomer copolymer / shown in the above Production Examples Polymerizable oligomer (MM-
1 to MM-4), (33) Monomers (exemplary compounds M-1 to M-25) / (meth) acrylic acid / methacryloyl-terminated poly-n-butyl acrylate oligomer / in the above production examples shown in the above specific examples. Shown polymerizable oligomer (M
M-1 to MM-4) copolymer, (34) Monomers (exemplary compounds M-1 to M-25) / (meth) acrylic acid / methacryloyl-terminated poly (methyl methacrylate / 2-) shown in the above specific examples. Hydroxyethyl methacrylate)
Oligomer / polymerizable oligomer (M
M-1 to MM-4) copolymer, (35) Monomer (exemplified compound M-1 to M-25) / (meth) acrylic acid / methyl (meth) acrylate / methacryloyl-terminated poly (meth) acrylate shown in the above specific examples. Methyl methacrylate oligomer /
The polymerizable oligomer (MM-1 to MM
-4) Copolymer, (36) Monomer (Exemplified Compounds M-1 to M-25) / (meth) acrylic acid / methyl (meth) acrylate / methacryloyl-terminated polystyrene oligomer / manufacturing example described in the above specific examples Polymerizable oligomer (MM-1 to MM-4) copolymer shown in (37) Monomer (exemplified compounds M-1 to M-2) shown in the above specific examples.
5) / (meth) acrylic acid / methyl (meth) acrylate / methacryloyl-terminated poly-n-butyl acrylate oligomer / polymerizable oligomer (MM-1 to MM-4) copolymer shown in the above Production Example, (38 ) Monomers (Exemplified Compounds M-1 to M-25) shown in the above specific examples /
(Meth) acrylic acid / methyl (meth) acrylate / methacryloyl-terminated poly (methyl methacrylate / 2-
(Hydroxyethyl methacrylate) oligomer / polymerizable oligomer (MM-1 to MM-4) shown in the above production example
Copolymer, (39) Monomers (Exemplified Compounds M-1 to M-25) / (meth) acrylic acid / benzyl (meth) acrylate / methacryloylated terminal polymethylmethacrylate oligomer / in the above production examples The polymerizable oligomers (MM-1 to MM-4) copolymers shown,
(40) Monomers shown in the above specific examples (exemplary compound M-
1-M-25) / (meth) acrylic acid / benzyl (meth) acrylate / methacryloyl-terminated polystyrene oligomer / polymerizable oligomer (M
M-1 to MM-4) Copolymer, (41) Monomer (Exemplified Compounds M-1 to M-25) / (meth) acrylic acid / benzyl (meth) acrylate / methacryloylated poly (terminal) shown in the above specific examples. -N-butyl acrylate oligomer / polymerizable oligomer shown in the above production example (MM-1
~ MM-4) copolymer,

(42) Monomers (Exemplified Compounds M-1 to M-25) / (meth) acrylic acid / benzyl (meth) acrylate / methacryloylated poly (methyl methacrylate / 2-hydroxyethyl methacrylate) shown in the above specific examples ) Oligomer / polymerizable oligomer (MM-1 to MM-4) copolymer shown in the above production example, (43) Monomer shown in the above specific example (exemplified compounds M-1 to M2)
5) / (meth) acrylic acid / polyethylene glycol mono (meth) acrylate / terminal methacryloylated polymethylmethacrylate oligomer copolymer, (44) the monomers shown in the above specific examples (exemplary compounds M-1 to M-2)
5) / (meth) acrylic acid / methyl (meth) acrylate / polyethylene glycol mono (meth) acrylate / terminal methacryloylated polystyrene oligomer copolymer, (45) the monomers shown in the above specific examples (exemplary compounds M-1 to M) -25) / (meth) acrylic acid / benzyl (meth) acrylate / polypropylene glycol mono (meth) acrylate / methacryloyl-terminated poly (methyl methacrylate / 2-hydroxyethyl methacrylate) oligomer copolymer, (46) in the above specific examples Shown monomer (exemplary compounds M-1 to M-25) / (meth)
Acrylic acid / polyethylene glycol mono (meth) acrylate / polymerizable oligomer (MM
-1 to MM4) copolymer, (47) Monomer (exemplary compound M-1 to M-25) / (meth) acrylic acid / methyl (meth) acrylate / polyethylene glycol mono (meth) acrylate shown in the above specific examples. / Polymerizable oligomers (MM-1 to MM-4) copolymers shown in the above production examples, (48) Monomers (exemplary compounds M-1 to M-25) shown in the above specific examples / (meth) acrylic acid / Benzyl (meth) acrylate / polypropylene glycol mono (meth) acrylate / polymerizable oligomer (MM-1 to MM-4) copolymer shown in the above production example.

Among these, the following are particularly preferable. Monomers shown in the above specific examples (exemplified compounds M-1 to M-
6, M-14, M-20) / (meth) acrylic acid / methacryloyl-terminated polymethylmethacrylate oligomer copolymer, the monomers shown in the above specific examples (exemplary compound M
-1 to M-6, M-14, M-20) / (meth) acrylic acid / methacryloyl-terminated polystyrene oligomer copolymer, monomers shown in the above synthesis examples Monomers shown in the above specific examples (exemplified compound M- 1-M-6, M-14, M
-20) / (meth) acrylic acid / methyl (meth) acrylate / terminal methacryloylated polymethylmethacrylate oligomer copolymer, the monomers shown in the above specific examples (exemplified compounds M-1 to M-6, M-14 and M). -20) /
(Meth) acrylic acid / methyl (meth) acrylate / methacryloyl-terminated polystyrene oligomer copolymer,
Monomers shown in the above specific examples (exemplified compounds M-1 to M-
6, M-14, M-20) / (meth) acrylic acid / benzyl (meth) acrylate / methacryloyl-terminated polymethylmethacrylate oligomer copolymer, the monomers shown in the above specific examples (exemplified compounds M-1 to M- 6, M-1
4, M-20) / (meth) acrylic acid / benzyl (meth) acrylate / terminal methacryloylated polystyrene oligomer copolymer,

Monomers shown in the above specific examples (exemplified compounds M-1 to M-6, M-14, M-20) / methacryloyl-terminated polymethylmethacrylate oligomer / polymerizable oligomer shown in the above production example (MM- 1-MM-4)
Copolymer, monomer shown in the above specific example (exemplified compound M
-1 to M-6, M-14, M-20) / methacryloyl-terminated polystyrene oligomer / polymerizable oligomer (MM-1 to MM-4) copolymer shown in the above production examples, shown in the above specific examples. Monomer (exemplified compounds M-1 to M-6,
M-14, M-20) / methyl (meth) acrylate /
Methacryloyl-terminated polymethylmethacrylate oligomer / polymerizable oligomer shown in the above production example (MM-1
To MM-4) copolymer, the monomers shown in the above specific examples (exemplified compounds M-1 to M-6, M-14, M-20) /
Methyl (meth) acrylate / methacryloyl-terminated polystyrene oligomer / polymerizable oligomer (MM-1 to MM-4) copolymer shown in the above production examples, monomers shown in the above specific examples (exemplified compounds M-1 to M- 6, M-1
4, M-20) / benzyl (meth) acrylate / methacryloyl-terminated polymethylmethacrylate oligomer / polymerizable oligomer (MM-1 to M) shown in the above production example.
M-4) Copolymer, monomer (exemplary compounds M-1 to M-6, M-14, M-20) / benzyl (meth) acrylate / methacryloyl-terminated polystyrene oligomer / manufacturing example described in the above specific examples Polymerizable oligomer (MM-1 to MM-4) copolymer shown in the above, and the monomers (exemplified compounds M-1 to M-6, M-14, M) shown in the above specific examples.
-20) / Polymerizable oligomer (MM
-1 to MM-4) copolymer, the monomers shown in the above specific examples (exemplified compounds M-1 to M-6, M-14, M-20)
/ Methyl (meth) acrylate / polymerizable oligomer (MM-1 to MM-4) copolymer shown in the above Production Example, monomers shown in the above specific examples (Exemplified compounds M-1 to M-6,
M-14, M-20) / benzyl (meth) acrylate / polymerizable oligomer (MM-1 to M) shown in the above production example.
M-4) copolymer,

Monomers shown in the above specific examples (exemplified compounds M-1 to M-6, M-14, M-20) / (meth) acrylic acid / polymerizable oligomer shown in the above production examples (MM-
1 to MM-4) copolymer, the monomers shown in the above specific examples (exemplified compounds M-1 to M-6, M-14, M-20) /
(Meth) acrylic acid / methyl (meth) acrylate / polymerizable oligomer (MM-1 to MM-
4) Copolymer, monomer shown in the above specific examples (exemplified compounds M-1 to M-6, M-14, M-20) / (meth) acrylic acid / benzyl (meth) acrylate / shown in the above production example Polymerizable oligomer (MM-1 to MM-4) copolymer,

Monomers shown in the above specific examples (exemplified compounds M-1 to M-6, M-14 and M-20) / (meth) acrylic acid / methacryloyl-terminated polymethylmethacrylate oligomer / shown in the above production examples. Polymerizable oligomer (MM-1 to MM-4) copolymer, monomers shown in the above specific examples (exemplified compounds M-1 to M-6, M-14, M-)
20) / (meth) acrylic acid / methacryloyl-terminated polystyrene oligomer copolymer / polymerizable oligomers (MM-1 to MM-4) shown in the above production examples, monomers shown in the above specific examples (exemplary compound M-1) ~ M-6, M-1
4, M-20) / (meth) acrylic acid / methyl (meth)
Acrylate / methacryloyl-terminated polymethylmethacrylate oligomer / polymerizable oligomer (MM-1 to MM-4) copolymer shown in the above production examples, monomers shown in the above specific examples (exemplified compounds M-1 to M-6, M-14,
M-20) / (meth) acrylic acid / methyl (meth) acrylate / methacryloyl-terminated polystyrene oligomer / polymerizable oligomer (MM-1 to 1)
MM-4) copolymer, the monomers (exemplified compounds M-1 to M-6, M-14, M-20) shown in the above specific examples / (meth) acrylic acid / benzyl (meth) acrylate / terminal methacryloylation Polymethylmethacrylate oligomer / polymerizable oligomer shown in the above production example (MM-1 to M
M-4) Copolymer, monomer (exemplified compounds M-1 to M-6, M-14, M-20) / (meth) acrylic acid / benzyl (meth) acrylate / terminal methacryloylation shown in the above specific examples. Polystyrene oligomer / polymerizable oligomer (MM-1 to MM-4) copolymer shown in the above production example, monomer shown in the above specific example (exemplified compound M-1)
~ M-6, M-14, M-20) / (meth) acrylic acid / polyethylene glycol mono (meth) acrylate /
Terminal-methacryloylated polymethylmethacrylate oligomer copolymer, monomers (exemplified compounds M-1 to M-6, M-14, M-20) shown in the above specific examples (meth) acrylic acid / methyl (meth) acrylate / polyethylene Glycol mono (meth) acrylate / methacryloyl-terminated poly (ethylene) oligomer copolymer, monomers shown in the above specific examples (exemplified compounds M-1 to M-6, M-1)
4, M-20) / (meth) acrylic acid / benzyl (meth) acrylate / polypropylene glycol mono (meth) acrylate / terminal methacryloylated poly (methyl methacrylate / 2-hydroxyethyl methacrylate) oligomer copolymer, in the above specific examples Shown monomers (exemplified compounds M-1 to M-6, M-14, M-20) /
(Meth) acrylic acid / polyethylene glycol mono (meth) acrylate / polymerizable oligomer (MM-1 to MM-4) copolymer shown in the above production examples, monomers shown in the above specific examples (exemplified compounds M-1 to M-1) M-6, M-14, M
-20) / (meth) acrylic acid / methyl (meth) acrylate / polyethylene glycol mono (meth) acrylate / polymerizable oligomer (MM-1) shown in the above production example.
To MM-4) copolymer, the monomers shown in the above specific examples (exemplified compounds M-1 to M-6, M-14, M-20) /
(Meth) acrylic acid / benzyl (meth) acrylate /
Polypropylene glycol mono (meth) acrylate /
The polymerizable oligomers (MM-1 to M shown in the above product examples
M4) Copolymer.

The graft copolymer can be obtained by, for example, radically polymerizing the components to be the respective copolymer units in a suitable solvent. In the radical polymerization, a radical polymerization initiator can be used, and further, a chain transfer agent (eg, 2-mercaptoethanol and dodecyl mercaptan) can be used.

Examples of suitable solvents are, depending on the monomers used and the solubility of the resulting graft copolymer,
Although it can be arbitrarily selected, for example, methanol, ethanol, propanol, isopropanol, 1-methoxy-
2-propanol, acetone, methyl ethyl ketone, methyl isobutyl ketone, 1-methoxy-2-propyl acetate, ethyl lactate, ethyl acetate, acetonitrile,
Tetrahydrofuran, dioxane, dimethylformamide, dimethylacetamide, dimethylsulfoxide, chloroform, toluene, xylene and the like and mixtures thereof can be used. Further, as the radical polymerization initiator,
2,2'-Azobis (isobutyronitrile) (AIB
N) An azo type such as 2,2′-azobis (2,4-dimethylvaleronitrile) and a peroxide type such as benzoyl peroxide can be used.

Hereinafter, some examples of the synthesis of the monomer having a urea skeleton and / or the urethane skeleton and the graft copolymer will be illustrated, but the present invention is not limited thereto.

Contains urea skeleton and / or urethane skeleton
Example of Synthetic Monomer [Synthesis Example 1] 2-Isocyanatoethylmethacrylate 1
While stirring a mixed solution of 6.9 parts by weight and 40.0 parts by weight of ethyl acetate, 8.05 parts by weight of n-butylamine was added dropwise at room temperature. After completion of dropping, the mixture was further stirred for 1 hour, and the reaction solution was put into 1000 parts by weight of hexane. The precipitated solid was filtered and then air-dried to obtain 22.0 parts by weight of the monomer (A: Exemplified compound M-1).

[Synthesis Example 2] Monomer (B : 25.1 parts by weight of Exemplified Compound M-2) was obtained.

[Synthesis Example 3] Monomer (C: exemplified compound M-3) 24.2 parts by weight were obtained.

[Synthesis Example 4] A monomer (D: Exemplified compound M-
4) 23.9 parts by weight were obtained.

[Synthesis Example 5] While stirring a mixed solution of 16.9 parts by weight of 2-isocyanatoethyl methacrylate and 40.0 parts by weight of ethyl acetate, 8.91 parts by weight of 3-methoxypropylamine was added dropwise at room temperature. . After completion of the dropwise addition, the reaction solution was stirred for 1 hour, and the reaction solution was concentrated to obtain 25.1 parts by weight of the monomer (E: Exemplified compound M-5).

[Synthesis Example 6] Monomer was prepared in the same manner as in Synthesis Example 5 except that 8.91 parts by weight of 3-methoxypropylamine was changed to 12.9 parts by weight of 2-ethylhexylamine in Synthesis Example 5. (F: Exemplified compound M-6) 29.0
Parts by weight were obtained.

Synthesis Example 7 While stirring a mixed solution of 9.91 parts by weight of normal butyl isocyanate and 40.0 parts by weight of ethyl acetate, 13.0 parts by weight of 2-hydroxyethyl methacrylate was added dropwise at room temperature. After completion of dropping, the mixture was further stirred for 1 hour, and the reaction solution was put into 1000 parts by weight of hexane. The precipitated solid was filtered and then air-dried to obtain 21.3 parts by weight of a monomer (G: exemplified compound M-14).

[Synthesis Example 8] A mixed solution of 16.9 parts by weight of 2-isocyanatoethyl methacrylate, 40.0 parts by weight of ethyl acetate and 0.96 parts by weight of dibutyltin diacetate was stirred at 50 ° C. and n- Butanol 7.41
Part by weight was dropped. After completion of the dropwise addition, the reaction solution is stirred for a further 5 hours to concentrate the monomer (H: exemplified compound M-
20) 23.6 parts by weight were obtained.

(Synthesis Example of Graft Copolymer) [Synthesis Example 9] 40.0 parts by weight of dimethyl sulfoxide, the macromonomer (MM-2) 3 synthesized in Production Example 2 above.
2.0 parts by weight was introduced into a three-necked flask in which the atmosphere was replaced with nitrogen, stirred with a three-one motor, heated while flowing nitrogen into the flask, and the internal temperature was raised to 78 ° C. The following separately prepared monomer solution and initiator solution were simultaneously added dropwise over 2 hours. (Monomer solution) Monomer (A) synthesized in Synthesis Example 1 above 4.00 parts by weight Methyl methacrylate ...................................................... 4.00 parts by weight 1 -Methoxy-2-propanol: 43.3 parts by weight (initiator solution) 2,2-azobis (2,4-dimethylvaleronitrile): 0.079 parts by weight (trade name: V-65, manufactured by Wako Pure Chemical Industries, Ltd. 1-methoxy-2-propylacetate ..... 10.0 parts by weight and then stirred for 1 hour and stirred for 2,2-azobis (2,4-dimethyl). 0.158 parts by weight of valeronitrile) (trade name: V-65) was added, and the internal temperature was kept at 78 ° C. for 2 hours, and then heated and kept at 90 ° C. for 30 minutes. Then, the reaction solution was cooled to room temperature to obtain a 1-methoxy-2-propanol solution (solid content: 30% by weight) of the graft copolymer. The weight average molecular weight of the obtained graft copolymer (pigment dispersant 1) was 24,000. The weight average molecular weight is determined by gel permeation chromatography (C-
R4A, manufactured by Shimadzu Corporation). [Synthesis Example 10] 1-methoxy-2-propanol 40.
0 parts by weight, methacryloylated polymethyl methacrylate at one end (number average molecular weight: 6000, trade name: AA-6,
30.0 parts by weight of Toagosei Kagaku Kogyo Co., Ltd.) was introduced into a nitrogen-substituted three-necked flask, stirred with a three-one motor, and heated while flowing nitrogen into the flask to adjust the internal temperature to 78.
The temperature was raised to ° C. The following separately prepared monomer solution and initiator solution were simultaneously added dropwise over 2 hours. (Monomer solution) Monomer (A) synthesized in Synthesis Example 1 ... 6.00 parts by weight Methacrylic acid ……………………………………………… 4. 00 parts by weight 1-methoxy-2-propanol ……………………………… 43.3 parts by weight (initiator solution) 2,2-azobis (2,4-dimethylvaleronitrile)… 0.097 parts by weight (Brand name: V-65, manufactured by Wako Pure Chemical Industries, Ltd.) 1-methoxy-2-propylacetate ………………………… 10.0 parts by weight of the solution and stirred for 1 hour, then 2,2-azobis (2 0.194 parts by weight of (4-dimethylvaleronitrile) (trade name: V-65) was added, and the internal temperature was kept at 78 ° C for 2 hours, and then heated and kept at 90 ° C for 30 minutes. Then, the reaction solution was cooled to room temperature to obtain a 1-methoxy-2-propanol solution (solid content: 30% by weight) of the graft copolymer. The weight average molecular weight of the obtained graft copolymer (pigment dispersant 2) was 26000.

[Synthesis Example 11] In Synthesis Example 9, the monomer (A) synthesized in Synthesis Example 1 was used as the monomer (B) synthesized in Synthesis Example 2, methyl methacrylate was used as benzyl methacrylate, and the production example was used. 32.0 parts by weight of the macromonomer (MM-2) synthesized in 2 above and 16.0 parts by weight of the macromonomer (MM-1) synthesized in Preparation Example 1 and a polymethacrylate methacrylate having one terminal methacryloyl group (number average molecular weight: 6000). , Trade name: AA-6, manufactured by Toagosei Kagaku Kogyo Co., Ltd.)
In the same manner as in Synthesis Example 9, 1 of the graft copolymer
A methoxy-2-propanol solution (solid content: 30% by weight) was obtained. The weight average molecular weight of the obtained graft copolymer (pigment dispersant 3) was 21,000.

[Synthesis Example 12] In Synthesis Example 10,
Monomer (A) synthesized in Synthesis Example 1 is used in Synthesis Example 2
Methacrylic acid 4.00 parts by weight to 2.00 parts by weight of the monomer (B) synthesized in 1., and methacryloylated polymethyl methacrylate at one end (number average molecular weight: 6000, trade name: AA-6, Toagosei Chemical Industry ( Co., Ltd.) 1-methoxy-2 of the graft copolymer in the same manner as in Synthesis Example 10 except that 30.0 parts by weight was replaced with 32.0 parts by weight.
-Propanol solution (solid content: 30% by weight) was obtained. The weight average molecular weight of the obtained graft copolymer (pigment dispersant 4) was 29000.

[Synthesis Example 13] In Synthesis Example 10,
6.00 parts by weight of the monomer (A) synthesized in Synthesis Example 1 was added to 1.20 parts by weight of the monomer (C) synthesized in Synthesis Example 3, and 4.00 parts by weight of methacrylic acid was added to 6.0 parts of methacrylic acid.
To 80 parts by weight of benzyl methacrylate and 2.80 parts by weight of benzyl methacrylate, 28 parts of 30.0 parts by weight of methacryloylated polymethylmethacrylate at one end (number average molecular weight: 6000, trade name: AA-6, manufactured by Toagosei Chemical Industry Co., Ltd.) A 1-methoxy-2-propanol solution (solid content: 30% by weight) of the graft copolymer was obtained in the same manner as in Synthesis Example 10 except that the amount was changed to 0.0 part by weight. The weight average molecular weight of the obtained graft copolymer (pigment dispersant 5) was 32,000.
Met.

[Synthesis Example 14] In Synthesis Example 10,
The monomer (A) synthesized in Synthesis Example 1 is used in Synthesis Example 4
Methacrylic acid (4.00 parts by weight) was added to the monomer (D) synthesized in (1), and methacryloylated polymethyl methacrylate at one end (number average molecular weight: 6000, trade name: AA-6, Toagosei Chemical Industry ( Co., Ltd.) 1-methoxy-2 of the graft copolymer in the same manner as in Synthesis Example 10 except that 30.0 parts by weight was replaced with 32.0 parts by weight.
-Propanol solution (solid content: 30% by weight) was obtained. The weight average molecular weight of the obtained graft copolymer (pigment dispersant 6) was 30,000.

[Synthesis Example 15] In Synthesis Example 9, 4.00 parts by weight of the monomer (A) synthesized in Synthesis Example 1 was added to 6.00 parts by weight of the monomer (E) synthesized in Synthesis Example 5, and methyl was added. To 4.0 parts by weight of methacrylate to 0 parts by weight, the macromonomer (MM-
2) In the same manner as in Synthesis Example 9 except that 32.0 parts by weight was replaced with 34.0 parts by weight, 1-of the graft copolymer was used.
A methoxy-2-propanol solution (solid content: 30% by weight) was obtained. The weight average molecular weight of the obtained graft copolymer (pigment dispersant 7) was 27,000.

[Synthesis Example 16] In the above Synthesis Example 10,
6.00 parts by weight of the monomer (A) synthesized in Synthesis Example 1 was added to 4.00 parts by weight of the monomer (F) synthesized in Synthesis Example 6, and 4.00 parts by weight of methacrylic acid was added to 8.0 parts of methacrylic acid.
00 parts by weight and 6.00 parts by weight of methyl methacrylate,
Methacryloylated polymethylmethacrylate at one end (number average molecular weight: 6000, trade name: AA-6, manufactured by Toagosei Kagaku Kogyo Co., Ltd.) except that 32.0 parts by weight was replaced with 22.0 parts by weight. In the same manner as in 10, a 1-methoxy-2-propanol solution (solid content: 30% by weight) of the graft copolymer was obtained. The weight average molecular weight of the obtained graft copolymer (pigment dispersant 8) was 25,000.

Synthesis Example 17 In Synthesis Example 9, 4.00 parts by weight of the monomer (A) synthesized in Synthesis Example 1 was added to 8.00 parts by weight of the monomer (G) synthesized in Synthesis Example 7, and methyl 4.00 parts by weight of methacrylate was added to 2.00 parts by weight of methylmethacrylate and 2.00 parts by weight of methacrylic acid, and the macromonomer (MM-
2) 30.0 parts by weight of 20.0 parts by weight of the macromonomer (MM-3) synthesized in Production Example 3 and methacryloylated polymethylmethacrylate at one end (number average molecular weight: 60)
00, trade name: AA-6, manufactured by Toagosei Chemical Industry Co., Ltd.)
A 1-methoxy-2-propanol solution (solid content: 30% by weight) of the graft copolymer was obtained in the same manner as in Synthesis Example 9 except that the amount was changed to 8.00 parts by weight. The weight average molecular weight of the obtained graft copolymer (pigment dispersant 7) was
It was 24,000.

[Synthesis Example 18] In Synthesis Example 9, 4.00 parts by weight of the monomer (A) synthesized in Synthesis Example 1 was added to 6.00 parts by weight of the monomer (H) synthesized in Synthesis Example 8 and methyl was added. Except that 4.00 parts by weight of methacrylate was replaced with 2.00 parts by weight of methacrylic acid and the macromonomer (MM-2) synthesized in Production Example 2 was replaced with the macromonomer (MM-4) synthesized in Production Example 4. A 1-methoxy-2-propanol solution (solid content: 30% by weight) of the graft copolymer was obtained in the same manner as in Synthesis Example 9. The weight average molecular weight of the obtained graft copolymer (pigment dispersant 7) was 26000.

The pigment dispersant of the present invention may contain only the above-mentioned graft copolymer, or may further contain other components appropriately selected according to need. Examples of the other components include known dispersants, and specifically, nonanoamide, decanamide, dodecaneamide, N
-Amide compounds such as dodecylhexadecaneamide, N-octadecylpropioamide, N, N-dimethyldodecaneamide and N, N-dihexylacetamide, diethylamine, diheptylamine, dibutylhexadecylamine, N, N, N ', N Amine compounds such as'-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 (hydroxyethyl polyoxyethylene)-
Amine having a hydroxy group such as 1,2-diaminoethane, 1,4-bis (2-hydroxyethyl) piperazine and 1- (2-hydroxyethyl) piperazine, and other compounds such as pecotamide, isonipecotamide and nicotinic acid amide, And so on. These may be commercially available products or those synthesized as appropriate, and examples of the commercially available products include Shigenox-105 (trade name,
Hakkol Chemical Co., Ltd.) and the like.

The content of the other components in the pigment dispersant is preferably 1 to 90% by weight, and 1 to 7% by weight.
0% by weight is more preferred. If the content exceeds 90% by weight, the performance as a pigment dispersant may not be sufficiently exhibited.

The pigment dispersant of the present invention may further contain an amine compound represented by the following general formula (4) or (5). General formula (4)

[0102]

[Chemical 10]

In the above general formula (4), R ⁴¹ and R
⁴² represents a hydrogen atom, or an optionally substituted alkyl group or aralkyl group, which may be bonded to each other to form a 5-membered to 6-membered saturated ring containing a nitrogen atom. The saturated ring may further contain 1 to 3 atoms selected from oxygen atom, sulfur atom and nitrogen atom. R ⁴³ represents an alkylene group or an alkylene group containing an ether bond. X ⁴ is -CON (Y ⁴¹ ) (Y
^{42), - OCON (Y 41} ) (Y 42), - N (Y 4 3) CO
(Y ^{44), or, -N (Y 43) CON (} Y 41)
(Y ⁴² ) is shown. Y ⁴¹ , Y ⁴² , Y ⁴³ and Y ^{44 each} represent a hydrogen atom or an optionally substituted alkyl group, aralkyl group or aryl group.

[0104]

[Chemical 11]

In the above general formula (5), R ⁵¹ , R ⁵² ,
R ⁵⁶ and R ⁵⁷ represent a hydrogen atom or an optionally substituted alkyl group or aralkyl group, which are bonded to each other to form a 5-membered to 6-membered saturated ring containing a nitrogen atom. May be. The saturated ring may further contain 1 to 3 atoms selected from oxygen atom, sulfur atom and nitrogen atom. R ⁵⁴ and R ⁵⁵ represent an alkylene group or an alkylene group having an ether bond. Z
^{5, -CON (Y 51) -,} - OCON (Y 51) - or ^{N (Y 52) CON (Y} 53) -, shows the. Y ⁵¹ , Y ⁵² and Y ⁵³ have the same meanings as Y ⁴¹ , Y ⁴² and Y ⁴³ in the above general formula (4) in this order.

Specific examples of the amine compound represented by the above general formula (4) or (5) include bis (2- (1-morpholino) ethyl) terephthalamide and the like.

The pigment dispersant of the present invention may contain various surfactants, and the presence of the surfactant is effective for improving dispersion stability. Examples of the surfactant include an alkylnaphthalene sulfonate, an anionic surfactant represented by a phosphoric acid ester salt, a cationic surfactant represented by an amine salt, an aminocarboxylic acid, and a betaine type. Examples include amphoteric surfactants.

-Dispersion-Next, dispersion of the pigment by the pigment dispersant of the present invention will be described with reference to the drawings. FIG. 4 is a schematic explanatory view showing a state in which the pigment dispersant containing the above graft copolymer is adsorbed on the surface of pigment particles.

As shown in FIG. 4, when the pigment dispersant of the present invention is used, the pigment dispersant is adsorbed on the surface of the pigment particles 6. At this time, the repeating unit 3 having a urea group and / or a urethane group present in the backbone 1 of the graft copolymer in the pigment dispersant is adsorbed on the surface of the pigment particle 6. The pigment particles 6 are in a state of being covered with the trunk chain 1 in the above graft copolymer. A graft chain 2 is branched from the trunk chain 1, and the graft chain 2 extends outward from the surface of the pigment particle 6 and exists as if a cloud covers the periphery of the pigment particle 6. is doing. Since the graft copolymer is adsorbed on the surface of each pigment particle 6, the pigment particles 6 are not adsorbed to each other and aggregated, and the pigment particles 6 are uniformly dispersed by the graft copolymer in a fine state. It is dispersed and becomes in a state of easy flow.

When an ordinary pigment dispersant is used in the colored photosensitive composition, the acidic group in the binder polymer having an acidic group and the nitrogen atom in the pigment dispersant contained in the colored photosensitive composition are contained. Etc. form a salt,
In many cases, they are bonded by a strong intermolecular force, but in the case of the pigment dispersant of the present invention, such behavior is suppressed by the presence of the graft chain 2 in the above graft copolymer, while The stability can be improved and the effect of improving the dispersibility can be increased. Further, according to the above graft copolymer, when the organic pigment is dispersed, the organic pigment is not thickened and the dispersibility of the organic pigment is good.

Dispersion with the pigment dispersant of the present invention means that the pigment particles that are generally present in the state of secondary particles are loosened to the state of primary particles to prevent reaggregation. The pigment dispersant of the present invention is a graft type dispersant having an adsorption site on the pigment and a steric repulsion site that prevents re-aggregation after the pigment is dispersed in the form of primary particles, and is used alone. However, it exhibits a sufficiently excellent dispersion effect. Dispersion of the pigment by the pigment dispersant of the present invention is effectively achieved by directly mixing the pigment dispersant and the pigment, and it is preferable to carry out in the state where there are as few particles as the dispersible other than the pigment as much as possible. When the pigment is dispersed in such a state, the pigment dispersant of the present invention is instantly adsorbed around the pigment particles, the pigment particles are well dispersed and flow well, and the pigment particles are aggregated. Is effectively suppressed. On the other hand, when the pigment is dispersed in the presence of particles that can be dispersed in addition to the pigment particles,
The pigment dispersant of the present invention may not be adsorbed on the surface of the intended pigment particle but adsorbed on the surface of another particle, and the pigment dispersing effect of the pigment dispersant may be impaired. Therefore, for example, in the case of producing a light-sensitive material or the like, in order to allow the pigment to be dispersed in the light-sensitive material or the like in a well-dispersed state, the pigment and the pigment dispersant of the present invention are mixed at an early stage. It is preferable that the pigment dispersant of the present invention be added and mixed at a late time such as when the coating solution for the photosensitive layer is prepared.

The pigment dispersant of the present invention can be preferably used for dispersing known pigments, and can be particularly preferably used for the pigment dispersion composition and the colored photosensitive composition of the present invention described later.

<< Pigment Dispersion Composition >> The pigment dispersion of the present invention comprises the pigment dispersant of the present invention and a pigment dispersed in an organic solvent.

—Pigment— Examples of the pigment include organic pigments. Examples of the organic pigments include yellow pigments, orange pigments, red pigments, violet pigments, blue pigments, green pigments, brown pigments, black pigments, and the like.

Examples of the yellow pigment include C.I. I.
Pigment Yellow 20, C.I. I. Pigment Yellow 24, C.I. I. Pigment Yellow 12, C.I. I pigment yellow 17, C.I. I. Pigment Yellow 83,
C. I. Pigment Yellow 86, C.I. I. Pigment Yellow 93, C.I. I. Pigment Yellow 109,
C. I. Pigment Yellow 110, C.I. I. Pigment Yellow 117, C.I. I. Pigment Yellow 12
5, C.I. I. Pigment Yellow 137, C.I. I. Pigment Yellow 138, C.I. I. Pigment Yellow 1
39, C.I. I. Pigment Yellow 185, C.I. I. Pigment Yellow 147, C.I. I. Pigment Yellow 148, C.I. I pigment yellow 153, C.I. I. Pigment Yellow, C.I. I. Pigment Yellow 15
4, C.I. I. Pigment Yellow 166, C.I. I. Pigment Yellow 168, C.I. I. Pigment Yellow 1
85, and the like.

Examples of the orange pigment include C.I.
I. Pigment Orange 36, C.I. I. Pigment Orange 43, C.I. I. Pigment Orange 51, C.I. I.
Pigment Orange 55, C.I. I. Pigment Orange 59, C.I. I. Pigment Orange 61, C.I. I. Pigment Orange 71, and the like.

Examples of the red pigment include C.I. I.
Pigment Red 9, C.I. I. Pigment Red 97,
C. I. Pigment Red 122, C.I. I. Pigment Red 123, C.I. I. Pigment Red 149, C.I.
I. Pigment Red 168, C.I. I. Pigment Red 177, C.I. I. Pigment Red 180, C.I. I.
Pigment Red 192, C.I. I. Pigment Red 2
15, C.I. I. Pigment Red 216, C.I. I. Pigment Red 217, C.I. I. Pigment Red 22
0, C.I. I. Pigment Red 223, C.I. I. Pigment Red 224, C.I. I. Pigment Red 226,
C. I. Pigment Red 227, C.I. I. Pigment Red 228, C.I. I. Pigment Red 240, C.I.
I. Pigment Red 48: 1, C.I. I. Pigment Red 209, C.I. I. Pigment Red 146, C.I.
I. Pigment Red 11, C.I. I. Pigment Red 81, C.I. I. Pigment Red 123, C.I. I. Pigment Red 213, C.I. I. Pigment Red 27
2, C.I. I. Pigment Red 270, C.I. I. Pigment Red 255, C.I. I. Pigment Red 264,
C. I. Pigment Red 254, and the like.

Examples of the violet pigment include, for example,
C. I. Pigment violet 19, C.I. I. Pigment Violet 23, C.I. I. Pigment Violet 29, C.I. I. Pigment Violet 30, C.I.
I. Pigment Violet 37, C.I. I. PIMEND violet 40, C.I. I. Pigment Violet 5
0, etc.

Examples of the blue pigment include C.I. I.
Pigment Blue 15, C.I. I. Pigment Blue 1
5: 6, C.I. I. Pigment Blue 22, C, I.I. Pigment Blue 60, C.I. I. Pigment Blue 64, and the like.

Examples of the green pigment include C.I. I.
Pigment Green 7, C.I. I. Pigment Green 3
6, and the like. Examples of the brown pigment include C.I. I. Pigment Brown 23, C.I. I. Pigment Brown 25, C.I. I. Pigment Brown 2
6, and the like. Examples of the black pigment include C.I. I. Pigment Black 7 and the like.

These pigments may be used alone or in combination of two or more.

—Organic Solvent— The organic solvent is not particularly limited and may be appropriately selected from known ones. Examples thereof include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol monomethyl ether and propylene glycol. (Poly) alkylene glycol monoalkyl ethers such as monoethyl ether, diethylene glycol monomethyl ether, ethylene glycol monoethyl ether and acetic acid esters thereof; ethyl acetate, n-propyl acetate, i-propyl acetate, n-butyl acetate, i acetate -Acetic acid esters such as butyl; aromatic hydrocarbons such as benzene, toluene, xylene; ketones such as methyl ethyl ketone, acetone, methyl isobutyl ketone, cyclohexanone; Examples thereof include alcohols such as knoll, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, diethylene glycol and glycerin. These may be used alone or in combination of two or more. Among these, alkylene glycol monoalkyl ethers, and their acetic acid esters, acetic acid esters, and methyl ethyl ketone are preferable.

The content of the above pigment in the above pigment dispersion composition is usually 5 to 80% by weight, and 10 to 70% by weight.
Weight percent is preferred. If the content is less than 5% by weight, the coloring power may not be sufficient, and if it exceeds 80% by weight, the viscosity of the pigment dispersion composition may increase.

The content of the pigment dispersant in the pigment dispersion composition is usually 0.1 to 200 parts by weight, preferably 1 to 50 parts by weight, per 100 parts by weight of the pigment. If the content is less than 0.1 parts by weight, the viscosity of the pigment dispersion composition may increase, and if it exceeds 200 parts by weight, chromaticity may be obtained during production of a color filter or the like. It may be difficult to adjust the thickness of the coating film.

The content of the organic solvent in the pigment dispersion composition is usually 10 to 1000 parts by weight, preferably 20 to 500 parts by weight, based on 100 parts by weight of the pigment. When the content is less than 10 parts by weight,
The viscosity of the pigment dispersion composition may increase to 1000
If it exceeds the weight part, it may be difficult to secure a space during storage.

The pigment dispersion composition of the present invention can be prepared, for example, by the following method. 1) A method in which a composition obtained by previously mixing the pigment and the pigment dispersant is added to and dispersed in the organic solvent (or vehicle) 2) The organic solvent (or vehicle) is mixed with the pigment and the above Method in which pigment dispersant is added separately to disperse 3) Method in which the above pigment and the above pigment dispersant are separately dispersed in the above organic solvent (or vehicle) in advance, and the resulting dispersion is mixed (in this case, The pigment dispersant may be dispersed only in the organic solvent) 4) A method of dispersing the pigment in the organic solvent (or vehicle) and then adding the pigment dispersant to the obtained dispersion.

The vehicle means a portion of a medium in which the pigment is dispersed when the coating material is in a liquid state, and is a component (binder) which is in a liquid state and binds with the pigment to harden the coating film. And a component for dissolving and diluting (the above organic solvent).

The disperser used to disperse the pigment is not particularly limited, and examples thereof include known dispersers such as a kneader, roll mill, attritor, super mill, dissolver, homomixer and sand mill.

To form a colored image using the pigment dispersion composition, for example, a coating liquid containing the pigment dispersion composition is applied onto a support and dried to form a layer of the pigment dispersion composition.
Alternatively, a layer of this pigment dispersion composition formed on a temporary support is transferred onto a support, and a layer of a known positive or negative photosensitive resin composition is formed thereon, exposed and developed. ,
Then, a method of removing the unexposed layer of the photosensitive resin composition and the layer of the pigment dispersion composition in the same region can be performed.

<< Colored Photosensitive Composition >> The colored photosensitive composition contains at least the pigment dispersion composition and the photosensitive composition.

—Photosensitive Composition— As the photosensitive composition, for example, JP-A-3-282 can be used.
Examples thereof include a photosensitive composition described in Japanese Patent No. 404, and specifically, a photosensitive composition containing a negative diazo resin and a binder, a photopolymerizable composition, and a photosensitive composition containing an azide compound and a binder. And a cinnamic acid type photosensitive composition. As the photosensitive composition, those developable with an alkaline aqueous solution and those developable with an organic solvent are known, but those developable with an alkaline aqueous solution in terms of pollution prevention, labor safety, etc. preferable.

—Photopolymerizable Composition— In the invention, the photopolymerizable composition is particularly preferable among the photosensitive compositions. The photopolymerizable composition is a polyfunctional monomer having two or more ethylenically unsaturated double bonds,
It is preferable to contain a binder polymer containing at least a photopolymerization initiator and further having an acidic group.

—Polyfunctional Monomer Having Two or More Ethylenically Unsaturated Double Bonds— Examples of the polyfunctional monomer having two or more ethylenically unsaturated double bonds include those described in JP-A-60-258539.
Known (meth) acrylic acid ester, urethane (meth) acrylate, (meth)
Acrylic amides, allyl compounds, vinyl esters and the like can be mentioned. These may be used alone or in combination of two or more. Among these, (meth) acrylic acid ester is preferable.

The content of the polyfunctional monomer having an ethylenically unsaturated double bond in the colored photosensitive composition is preferably 10 to 60% by weight based on the total solid content. If the content is less than 10% by weight, the curing power at the time of exposure may be insufficient, and if it exceeds 60% by weight, the ability of other materials may be difficult to be exhibited.

—Photopolymerization Initiator— As the above-mentioned photopolymerization initiator, the wavelength is about 300 to 500 n.
It is preferable to use at least one compound having a molecular extinction coefficient of at least about 50 in m, and examples of such a compound include, for example, JP-A-2-48664, JP-A-1-152449, and JP-A-1-152449. 2-153
Aromatic ketones, lophine dimers, benzoin, benzoin ethers, polyhalogens, and the like, as described in Japanese Patent No. 353,353 are cited. These are 1
They may be used alone or in combination of two or more. Among these, 4,4'-bis (diethylamino) benzophenone and 2- (o-chlorophenyl)-
A combination of 4,5-diphenylimidazole dimers,
And 4- [p-N, N-di (ethoxycarbonylmethyl) -2,6-di (trichloromethyl) -s-triazine] are preferred.

The content of the photopolymerization initiator in the colored photosensitive composition is preferably 0.2 to 10% by weight based on the solid content of the colored photosensitive composition. The above content is
If it is less than 0.2% by weight, the exposure sensitivity may be low, and if it exceeds 10% by weight, the exposure sensitivity may be too high (control may be difficult).

—Binder Polymer Having Acidic Group—
The binder polymer having an acidic group is capable of imparting both the dispersion stability of the pigment and the alkali developability, and for example, a copolymer of (meth) acrylic acid and (meth) acrylic ester Examples thereof include polymers, styrene / maleic anhydride copolymers, and reaction products of styrene / maleic anhydride copolymers with alcohols. These may be used alone or in combination of two or more. Among these, those having excellent pigment dispersibility, excellent compatibility with polyfunctional monomers and photopolymerization initiators, solubility in an alkali developing solution, solubility in an organic solvent, strength, softening temperature and the like are preferable. In particular, a copolymer of (meth) acrylic acid and (meth) acrylic acid ester is preferable.

The weight average molecular weight of the binder polymer having an acidic group is preferably 5,000 to 200,000. If the weight average molecular weight is less than 5,000, there may be a problem in forming a coating film.
If it exceeds 0, the viscosity of the colored photosensitive composition may increase.

The content of the binder polymer having an acidic group in the colored photosensitive composition is about 20 to 80% by weight based on the total solid content. If the content is less than 20% by weight, problems may occur in forming the coating film, and if it exceeds 80% by weight, the ability of other materials may be difficult to be exhibited.

The colored photosensitive composition can be prepared, for example, by mixing the pigment dispersion composition and the photosensitive composition according to appropriately selected conditions and techniques.

The formation of a colored image using the above colored photosensitive composition can be basically performed by the following steps (1) to (3). (1) After preparing the pigment dispersion composition, the step of preparing the colored photosensitive composition using the same (2) The obtained colored photosensitive composition is applied onto a substrate and dried, or A step of transferring a layer formed by coating on another temporary support and drying it to a substrate to form a layer of the colored photosensitive composition (3) Layer of the colored photosensitive composition formed on the substrate Of exposing and developing a pattern to form a pattern

A color filter used for a liquid crystal display or the like can be manufactured by repeating the steps (2) and (3) and combining the patterns of the second and subsequent colors. A method of manufacturing a color filter by a transfer method is described in, for example, Japanese Patent Application Laid-Open No. 4-208940, Japanese Patent Application Laid-Open No. 5-72724, Japanese Patent Application Laid-Open No. 5-80503, and Japanese Patent Application Laid-Open No. 5-173320.

A transparent material such as a glass plate or a transparent plastic plate is generally used as the substrate. In order to improve the adhesion between the substrate and the colored photosensitive composition, various commercially available silane coupling agents or the like are added to the colored photosensitive composition, or the substrate is subjected to a coupling treatment in advance. You may stay.

The coating liquid of the colored photosensitive composition can be applied to the substrate by using a known coating means such as a spin coater, a roll coater, a bar coater or a curtain coater.

As a method of transferring the layer of the colored photosensitive composition formed on the temporary support to the substrate, a method of using a heat roll laminator under normal pressure or reduced pressure can be preferably mentioned.

Examples of the developer used in the above development include alkali metal or alkaline earth metal hydroxides or carbonates, hydrogen carbonates, asimonia water, quaternary ammonium salt aqueous solutions, and the like. To be These may be used alone or in combination of two or more. Among these, sodium carbonate aqueous solution is particularly preferable.

[0147]

EXAMPLES Examples of the present invention will be described below, but the present invention is not limited to these examples.

Example 1 A red pigment dispersion composition having the following composition was prepared. C. I. Pigment Red 254 ······································································· but .28 parts by weight. 1-Methoxy-2-propylacetate ... 63.44 parts by weight

The red pigment composition having the above composition was dispersed in a motor mill M50 (manufactured by Eiger) using zirconia beads having a diameter of 0.65 mm at a peripheral speed of 9 m / s for 9 hours to obtain a red pigment dispersion composition. The thing was prepared. The following evaluation was performed on the obtained pigment dispersion composition. (1) Viscosity measurement: For the obtained pigment dispersion composition, E
The viscosity was measured using a type viscometer to evaluate the degree of thickening. The results are shown in Table 1. Here, the low viscosity means that the dispersion stability and the fluidity are stable and good. (2) Contrast measurement: The obtained pigment dispersion composition was applied on a glass substrate to a thickness of 6 μm to prepare a sample. This sample was placed between two polarizing plates, the amount of transmitted light when the polarization axes were parallel and when it was vertical was measured, and the ratio was used as the contrast (see “1990
Convergence optical conference, 512 color display 10.4 "size TFT-LCD color filter, plant, Ozeki,
Fukunaga, Yamanaka "was referred to). The results are shown in Table 1. Here, high contrast means that the film is highly miniaturized and the transmittance, that is, the coloring power is high.

(Examples 2 to 10) A pigment dispersion composition was prepared in the same manner as in Example 1 except that the pigment dispersant 1 was changed to the pigment dispersants 2 to 10, respectively. Did. The results are shown in Table 1.

(Example 11) A green pigment dispersion composition was prepared in the same manner as in Example 1 except that the red pigment dispersion composition in Example 1 was replaced with the green pigment dispersion composition having the following composition. Then, the same evaluation as in Example 1 was performed. The results are shown in Table 1.
Shown in. C. I. Pigment Green 36 …………………… 9.20 parts by weight C.I. I. Pigment Yellow 138 ... 4.96 parts by weight Pigment Dispersant 1 of Synthesis Example 9 (1-methoxy-2-propylacetate solution, solid content: 30% by weight) 14.16 parts by weight Parts 1-methoxy-2-propylacetate 51.68 parts by weight

Example 12 A blue pigment dispersion composition was prepared in the same manner as in Example 1 except that the red pigment dispersion composition in Example 1 was replaced with the blue pigment dispersion composition having the following composition. Then, the same evaluation as in Example 1 was performed. The results are shown in Table 1.
Shown in. C. I. Pigment Blue 15; 6 ...... 14.20 parts by weight Pigment Dispersant 1 of Synthesis Example 9 (1-methoxy-2-propylacetate solution, solid content: 30% by weight) ...... 14. 20 parts by weight 1-methoxy-2-propylacetate ... 51.70 parts by weight

(Comparative Example 1) In Example 1, instead of the pigment dispersant 1 of Synthesis Example 9, a copolymer of monomer A / methacrylic acid / methyl methacrylate of Synthesis Example 1 (weight ratio: 15/10). / 75, 1-methoxy-2-propanol solution, solid content: 30% by weight, weight average molecular weight:
25000) was used, and a red pigment dispersion composition was prepared in the same manner as in Example 1, and the same evaluation as in Example 1 was performed.

(Comparative Example 2) In Example 1, instead of the pigment dispersant 1 of Synthesis Example 9, the monomer A of Synthesis Example 1 and one end methacryloylated polymethylmethacrylate (number average molecular weight: 6000, trade name) : AA-6, a copolymer of Toagosei Chemical Industry Co., Ltd. (weight ratio: 15/8)
5, 1-methoxy-2-propanol solution, solid content: 3
A red pigment dispersion composition was prepared in the same manner as in Example 1 except that a 0% by weight, weight average molecular weight: 27,000) solution was used, and the same evaluation as in Example 1 was performed.

(Comparative Example 3) In Example 1, instead of the pigment dispersant 1 of Synthesis Example 9, methacrylic acid / benzyl methacrylate / methacryloylated polymethyl methacrylate having one end (number average molecular weight: 6000, trade name: A
A-6, Toagosei Chemical Industry Co., Ltd. copolymer (weight ratio: 15/20/65, 1-methoxy-2-propanol solution, solid content: 30% by weight, weight average molecular weight: 220)
No. 00) was used, a red pigment dispersion composition was prepared in the same manner as in Example 1, and the same evaluation as in Example 1 was performed.

Comparative Example 4 In Example 1, instead of the pigment dispersant 1 of Synthesis Example 9, benzyl methacrylate / macromonomer synthesized in Production Example 1 (MM-) was used.
1) / One-end methacryloylated polymethylmethacrylate (number average molecular weight: 6000, trade name: AA-6, manufactured by Toagosei Chemical Industry Co., Ltd.) copolymer (weight ratio: 15/40)
/ 55, 1-methoxy-2-propanol solution, solid content: 30% by weight, weight average molecular weight: 22000) except that a red pigment dispersion composition was prepared in the same manner as in Example 1. The same evaluation as in 1 was performed.

Example 13 The following compositions were mixed to prepare a colored photosensitive composition for producing a color filter. Red pigment dispersion composition of Example 1 32.4 parts by weight Methacrylic acid / benzyl methacrylate polymer 9.0 parts by weight (molar ratio: 28/72, weight average) Molecular weight: 30000, 30 wt% 1-methoxy-2-propylacetate solution) 4- [p-N, N'-di (ethoxycarbonylmethyl) -2,6-di (trichloromethyl) -S-triazine ... 0.2 parts by weight Hydroquinone monomethyl ether …………………… 0.01 parts by weight 1-methoxy-2-propylacetate ………… 62 parts by weight The above mixture is in a motor mill M50 (manufactured by Eiger). ,
Using zirconia beads with a diameter of 0.65 mm, a peripheral speed of 9
It was carried out at m / s for 9 hours. With respect to the obtained colored photosensitive composition for producing a color filter, the viscosity was measured in the same manner as in Example 1, the color filter was produced in the following manner, and the contrast was measured in the same manner as in Example 1. That is, the colored photosensitive composition for producing the color filter is applied onto a glass substrate by using a spin coater, and 10
It was dried at 0 ° C. for 2 minutes to form a film having a thickness of about 2 μm. Then, after exposing with a super high pressure mercury lamp under a nitrogen stream,
It was developed with a 1% aqueous sodium carbonate solution. The contrast of the obtained color filter was measured in the same manner as in Example 1. In addition, the development time required until the film disappeared was measured. Here, a short development time (40 seconds or less) indicates that it has excellent suitability for alkali development. Table 1 shows the evaluation of the suitability for alkali development according to the following criteria. Criteria ◯: Time required for development is 40 seconds or less ×: Time required for development is 50 seconds or more

(Example 14) Colored photosensitive material was prepared in the same manner as in Example 13 except that the red pigment dispersion composition of Example 1 was replaced with the red pigment dispersion composition of Example 2. A sex composition was prepared and evaluated in the same manner as in Example 13. The results are shown in Table 1.

(Examples 15 to 22) Except that the red pigment dispersion composition of Example 1 was replaced with the red pigment dispersion composition of Examples 3 to 10, respectively. A colored photosensitive composition was prepared in the same manner and evaluated in the same manner as in Example 13. The results are shown in Table 1.

(Examples 23 and 24) In Example 13, except that the red pigment dispersion composition of Example 1 was replaced with the green and blue pigment dispersion compositions of Examples 11 and 12, respectively. A colored photosensitive composition was prepared in the same manner as in Example 13, and evaluated in the same manner as in Example 13. The results are shown in Table 1.

(Comparative Example 5) Colored photosensitive material was prepared in the same manner as in Example 13 except that the red pigment dispersion composition of Example 1 was replaced with the red pigment dispersion composition of Comparative Example 2. A sex composition was prepared and evaluated in the same manner as in Example 13. The results are shown in Table 1.

(Comparative Example 6) Colored photosensitive material was prepared in the same manner as in Example 13 except that the red pigment dispersion composition of Example 1 was replaced with the red pigment dispersion composition of Comparative Example 3. A sex composition was prepared and evaluated in the same manner as in Example 13. The results are shown in Table 1.

(Comparative Example 7) Colored photosensitive material was prepared in the same manner as in Example 13 except that the red pigment dispersion composition of Example 1 was replaced with the red pigment dispersion composition of Comparative Example 4. A sex composition was prepared and evaluated in the same manner as in Example 13. The results are shown in Table 1.

[0164]

[Table 1]

From the results shown in Table 1, the pigment dispersion composition containing the pigment dispersant of the present invention and the colored photosensitive composition using the same have low viscosity, high contrast and excellent alkali developability. It was clear that it was possible to achieve both good dispersibility and suitability for alkali development. It is speculated that the high contrast is obtained because the pigment particles are dispersed in a finely divided state. on the other hand,
The pigment dispersion composition of Comparative Example and the colored photosensitive composition using the same exhibit at least one of high viscosity, low contrast, and low alkali developability, and exhibit good dispersibility and alkali developability. It became clear that there is no compatible one.

[0166]

EFFECTS OF THE INVENTION According to the present invention, a pigment dispersion having stable and good dispersibility and fluidity of the pigment without agglomerating the pigment, excellent light transmittance, and versatile for use in various pigments. An agent can be provided. Further, according to the present invention, containing the pigment dispersant, the pigment has excellent dispersibility, fluidity, etc., and has high coloring power, and also has excellent alkali developability,
It is possible to provide a pigment dispersion composition that can be suitably used in a wide range of paints, printing inks, color display boards and the like. Furthermore, according to the present invention, a color filter containing the pigment dispersion composition, having high coloring power, excellent alkali developability, multicolor image formation on a substrate such as a color proof, and a liquid crystal color display is used. It is possible to provide a colored photosensitive composition that can be suitably used for the production of the above.

[Brief description of drawings]

FIG. 1 is a schematic explanatory view showing Embodiment 1 of the pigment dispersant of the present invention.

FIG. 2 is a schematic explanatory view showing Embodiment 2 of the pigment dispersant of the present invention.

FIG. 1 is a schematic explanatory view showing Embodiment 3 of the pigment dispersant of the present invention.

FIG. 4 is a schematic explanatory view showing a state in which the pigment dispersant of the present invention is adsorbed on the surface of pigment particles.

[Explanation of symbols]

1 Stem chain 2 Graft chain 3 Repeating unit having urea group and / or urethane group 4 Bonding part between stem chain and graft chain 5 Repeating unit having acidic group 6 Pigment particles

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁷ Identification code FI theme code (reference) C09B 67/46 C09B 67/46 B (72) Inventor Akihiko Takeda 200, Onakazato, Fujinomiya-shi, Shizuoka Fuji Photo Film In-house F-term (reference) 4D077 AA03 AA08 AB05 AB06 AC05 BA02 BA05 BA07 DC38Z DC39Z DD06 DD18Z DD46X DE07X DE07Z DE10X DE10Z DE15Z DE17Z 4J027 AA02 BA07 BA13 CB09 CD08

Claims (12)

[Claims] 1. A graft copolymer having a repeating unit having a urea group and / or a urethane group in a main chain and a repeating unit having an acidic group in a main chain and / or a graft chain. Pigment dispersant. 2. The pigment dispersant according to claim 1, wherein the acidic group is a carboxyl group. 3. A graft copolymer comprising a unit derived from a polymerizable oligomer having an ethylenically unsaturated double bond at a terminal,
The pigment dispersant according to claim 1 or 2, which comprises a unit derived from a monomer having a urea group and / or a urethane group as a copolymer unit. 4. The pigment dispersant according to claim 3, wherein the graft copolymer contains a unit derived from a monomer having an acidic group as a copolymer unit. 5. The pigment dispersant according to claim 3, wherein the polymerizable oligomer has a repeating unit having an acidic group. 6. The polymerizable oligomer has a number average molecular weight of 100.
The pigment dispersant according to any one of claims 3 to 5, wherein the pigment dispersant is from 0 to 20,000 and has a (meth) acryloyl group at the terminal. 7. The graft copolymer contains 15 to 98% by weight of a unit derived from a polymerizable oligomer as a copolymer unit, and 1 to 40 units derived from a monomer having a urea group and / or a urethane group. The pigment dispersant according to any one of claims 3 to 6, which comprises a weight percentage. 8. The acid value of the graft copolymer is 5 to 150 m.
The pigment dispersant according to any one of claims 1 to 7, which is g-KOH / g. 9. A monomer containing a urea group and / or a urethane group is represented by the following general formula (1): [In the general formula (1), R ¹¹ represents a hydrogen atom or a methyl group. R ¹² is a single bond or 2 having 1 to 10 carbon atoms.
A valent hydrocarbon group (the hydrocarbon group may have a substituent, may form a branch or a ring structure, and may have an ether or ester bond in the middle), R ¹³ represents a hydrocarbon group having 1 to 18 carbon atoms which may have a substituent, but does not include the partial skeleton of the organic dye. X ¹¹ , X ¹² and X ¹³ are each independently --O.
^{-, - N (R 14)} - (R 14 is a hydrogen atom or 1 to carbon atoms
6 represents an alkyl group or a phenyl group of 6), X ¹²
And X ¹³ do not become -O- at the same time. m and n represent 1 or 0. ] The pigment dispersant according to any one of claims 3 to 8, which is one kind or two or more kinds selected from the compounds represented by: 10. A pigment dispersion composition comprising the pigment dispersant according to any one of claims 1 to 9 and a pigment dispersed in an organic solvent. 11. A colored photosensitive composition comprising the pigment dispersion composition according to claim 10, a polyfunctional monomer having two or more ethylenically unsaturated double bonds, and a photopolymerization initiator. object. 12. A colored photosensitive composition comprising the colored photosensitive composition according to claim 11 and a binder polymer having an acidic group.