JP2010053182A - Polymer compound, pigment dispersion composition, photocurable composition, color filter and method for manufacturing the color filter - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a polymer compound which excels in the dispersibility and the dispersion stability of a pigment and is useful as a pigment dispersing agent, a process for producing the same, a pigment dispersion composition, a photopolymerizable composition, a color filter, and a method for manufacturing the color filter. <P>SOLUTION: The polymeric compound is represented by any one of formulae (1) to (3) [wherein R<SP>1</SP>is an (m<SB>1</SB>+n<SB>1</SB>) valent organic connecting group; R<SP>4</SP>is an (m<SB>2</SB>+n<SB>2</SB>) valent organic connecting group; R<SP>7</SP>is an (m<SB>3</SB>+n<SB>3</SB>) valent organic connecting group; R<SP>2</SP>, R<SP>3</SP>, R<SP>5</SP>, R<SP>6</SP>, R<SP>8</SP>, and R<SP>9</SP>are each a single bond or a divalent organic connecting group; A<SP>1</SP>, A<SP>2</SP>, and A<SP>3</SP>are each a monovalent organic group containing an organic pigment structure; m<SB>1</SB>to m<SB>3</SB>are each 1-8; n<SB>1</SB>to n<SB>3</SB>are each 2-9; (m<SB>1</SB>+n<SB>1</SB>), (m<SB>2</SB>+n<SB>2</SB>), and (m<SB>3</SB>+n<SB>3</SB>) each meets 3-10; M<SP>1</SP>, M<SP>2</SP>, and M<SP>3</SP>are each a monovalent organic group; p, q, and r are each 2-8; and b, c, and d are each 1-100]. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a novel polymer compound, a pigment dispersion composition using the polymer compound, a photocurable composition, a color filter, and a method for producing the same.

  A color filter is a colored photosensitive composition containing a polyfunctional monomer, a photopolymerization initiator, an alkali-soluble resin, and other components in a pigment dispersion composition in which organic pigments and inorganic pigments are dispersed. Manufactured by law.

  In recent years, the use of color filters in liquid crystal display (LCD) applications has tended to expand not only to monitors but also to televisions (TVs). With this trend of expanding applications, advanced color characteristics such as chromaticity and contrast. Has come to be required. In addition, in the image sensor (solid-state imaging device) application, a device having high color characteristics is also demanded.

  In response to the above requirements, it is required to disperse the pigment in a finer state (good dispersibility) and to disperse in a stable state (good dispersion stability). If the dispersibility is insufficient, fringes (jagged edges) and surface irregularities occur in the formed colored resist film, the chromaticity and dimensional accuracy of the produced color filter are reduced, and the contrast is remarkably high. There is a problem of deterioration. In addition, when the dispersion stability is insufficient, in the color filter manufacturing process, the uniformity of the film thickness particularly in the coating process of the colored photosensitive composition is reduced, or the photosensitive sensitivity in the exposure process is reduced. Or the alkali solubility in the development process is likely to be reduced. Furthermore, when the dispersion stability of the pigment is poor, there is also a problem that the constituent components of the colored photosensitive composition are aggregated with the passage of time, the viscosity is increased, and the pot life is extremely shortened.

  However, since the surface area of the pigment particles is increased when the particle diameter of the pigment is reduced, the cohesive force between the pigment particles is increased, and it is difficult to achieve both dispersibility and dispersion stability at a high level. Many.

In order to solve such problems, various pigment dispersants have been developed.
For example, a polymer pigment dispersant in which an organic dye and a polymer are bonded has been proposed (for example, see Patent Document 1). It is considered that this is because the interaction between the organic dye introduced into the dispersant and the pigment particles becomes strong, so that the adsorption of the polymer pigment dispersant to the pigment particles is promoted and the dispersibility is improved.

  In addition, polymer pigment dispersants in which an organic dye or a heterocyclic ring is introduced only at one end or both ends of a polymer portion have been proposed (see, for example, Patent Documents 2 to 3). Patent document 2 tried to ensure an adsorption layer sufficient for dispersion stabilization by adsorbing organic dyes and heterocycles efficiently on the pigment surface and having sufficient affinity between the polymer portion and the dispersion medium. In Patent Document 3, the synthesis method is improved with respect to Patent Document 2 by using a chain transfer agent having an organic dye or a heterocyclic ring.

  Furthermore, there is one in which dispersibility is improved using an acrylic resin having a carboxylic acid group by adding a basic pigment derivative having a dialkylamino group introduced (see, for example, Patent Document 4). In addition, there is disclosed a polymer pigment dispersant in which a sulfonic acid group or a monosulfate group is introduced only at one end of a polymer portion (see, for example, Patent Document 5), which is a pigment surface (especially a basic pigment). In order to adsorb the sulfonic acid efficiently, the polymer portion and the dispersion medium have sufficient affinity to secure a sufficient adsorption layer for stabilizing the dispersion.

  However, in the polymer pigment dispersant described in Patent Document 1, since an organic dye is randomly introduced into the polymer, the affinity between the polymer portion and the dispersion medium is weakened, and the adsorption layer is sufficient for stabilizing the dispersion. It may be difficult to secure a sufficient adsorption layer for dispersion stabilization because the solubility in the dispersion medium decreases as the amount of organic dye or heterocyclic ring introduced into the polymer increases. There's a problem.

In addition, in the polymer pigment dispersant described in Patent Document 2, a plurality of organic dyes and heterocyclic rings are not introduced at the ends of the polymer, and the introduction is difficult, and the adsorption to the pigment surface is sufficiently strong. It's hard to say. Therefore, there may be a case where a sufficient adsorption layer for dispersion stabilization cannot be secured. Furthermore, it is difficult to say that this polymer pigment dispersant is an easy method from the viewpoint of a synthesis method in which an organic dye or a heterocyclic ring is bonded to a polymer terminal by a polymer reaction.
Similarly, the polymer pigment dispersant described in Patent Document 3 is not obtained by introducing a plurality of organic dyes or heterocycles at the ends of the polymer, and is difficult to introduce, so that the adsorption to the pigment surface is sufficiently strong. Is hard to say. Therefore, there may be a case where a sufficient adsorption layer for dispersion stabilization cannot be secured.

  Further, in Patent Document 4, since the basic pigment derivative is colored by itself, in order to adjust the pigment dispersion composition to a desired color, available pigments are limited or carboxylic acid groups are added. Since the acrylic resin is randomly present in the polymer main chain, there is a problem that a plurality of pigments are cross-linked to deteriorate dispersibility.

In addition, the polymer pigment dispersant of Patent Document 5 is difficult to say that it is a synthetic technique that can advantageously produce a pigment dispersant in terms of introducing a terminal group by a polymer reaction. May not be enough.
JP-A-4-139262 JP-A-9-77987 JP-A-9-77994 JP-A-11-189732 JP 2002-273191 A

  The present invention has been made in view of the above, and is excellent in dispersibility and dispersion stability of a pigment, a polymer compound useful as a pigment dispersant, adjusted with the polymer compound, and having good color characteristics. Provided are a pigment dispersion composition capable of obtaining excellent alkali developability and high contrast when constituting a color filter, a photocurable composition, a color filter having good color characteristics and high contrast, and a method for producing the same. It is an object to achieve this purpose.

  In the present invention, introduction of a plurality of structures or functional groups capable of adsorbing to a pigment at the polymer terminal is effective in improving dispersibility when used as a pigment dispersant and dispersion stability after dispersion. It was achieved based on the findings of Specific means for achieving the above object are as follows.

<1> A polymer compound represented by any one of the following general formulas (1) to (3).

In the formula, R ¹ represents an (m ₁ + n ₁ ) -valent organic linking group, R ⁴ represents an (m ₂ + n ₂ ) -valent organic linking group, and R ⁷ represents an (m ₃ + n ₃ ) -valent organic linking group. Represents a linking group. R ² , R ³ , R ⁵ , R ⁶ , R ⁸ and R ⁹ each independently represents a single bond or a divalent organic linking group. A ¹ , A ² and A ³ are each independently an organic dye structure, a heterocyclic structure, an acidic group, a group having a basic nitrogen atom, a urea group, a urethane group, a group having a coordinating oxygen atom, or a carbon number of 4 It represents a monovalent organic group containing at least one selected from the above hydrocarbon groups, alkoxysilyl groups, epoxy groups, isocyanate groups, and hydroxyl groups. m ₁ , m ₂ and m ₃ each independently represents an integer of 1 to 8. n _{1, n 2} and _{n 3} each independently represent a 2-9 integer. Here, m ₁ + n ₁ , m ₂ + n ₂ , and m ₃ + n ₃ each independently satisfy 3 to 10. M ¹ and M ³ each independently represents a monovalent organic group. M ² each independently represents a hydrogen atom or a monovalent organic group. p, q and r each independently represents an integer of 2 to 8. b, c and d each independently represents an integer of 1 to 100.

<2> A group in which A ¹ , A ² , and A ^{3 in} General Formula (1) to General Formula (3) each independently have an organic dye structure, a heterocyclic structure, an acidic group, or a basic nitrogen atom, The polymer compound according to <1>, which is a monovalent organic group containing at least one selected from a urea group and a hydrocarbon group having 4 or more carbon atoms.

<3> A polymer compound represented by the following general formula (1 ′), (2 ′), (3 ′), (2 ″) or (3 ″).

In the formula, R ¹ represents an (m ₁ + n ₁ ) -valent organic linking group, R ⁴ represents an (m ₂ + n ₂ ) -valent organic linking group, and R ⁷ represents an (m ₃ + n ₃ ) -valent organic linking group. Represents a linking group. The ^{R 2, R 3, R 5} , R 6, R 8 and ^{R 9} each independently represent a single bond or a divalent organic linking group. A ¹ , A ² and A ³ are each independently an organic dye structure, a heterocyclic structure, an acidic group, a group having a basic nitrogen atom, a urea group, a urethane group, a group having a coordinating oxygen atom, or a carbon number of 4 It represents a monovalent organic group containing at least one selected from the above hydrocarbon groups, alkoxysilyl groups, epoxy groups, isocyanate groups, and hydroxyl groups. m ₁ , m ₂ and m ₃ each independently represents an integer of 1 to 8. n _{1, n 2} and _{n 3} each independently represent a 2-9 integer. Here, m ₁ + n ₁ , m ₂ + n ₂ , and m ₃ + n ₃ each independently satisfy 3 to 10. M ¹ and M ³ each independently represents a monovalent organic group. M ² each independently represent a hydrogen atom or a monovalent organic group. p, q and r each independently represents an integer of 2 to 8. b, c and d each independently represents an integer of 1 to 100.

<4> The polymer compound according to any one of <1> to <3>, wherein the weight average molecular weight is 3,000 to 100,000.
<5> The polymer compound according to any one of <1> to <4>, which is a pigment dispersant.

<6> A pigment dispersion composition containing a pigment and the polymer compound according to <5> in an organic solvent.
<7> A photocurable composition comprising the pigment dispersion composition according to <6>, a polymerizable compound, and a photopolymerization initiator.

<8> A color filter comprising a colored pattern formed on the substrate using the photocurable composition according to <7>.
<9> Forming a photosensitive film by applying the photocurable composition according to the above <7> directly or via another layer to form a photosensitive film, and performing pattern exposure and development on the formed photosensitive film The manufacturing method of the color filter which forms a coloring pattern by this.

  According to the present invention, a polymer compound that is excellent in pigment dispersibility and dispersion stability, is useful as a pigment dispersant, is adjusted using the polymer compound, has good color characteristics, and constitutes a color filter. It is possible to provide a pigment dispersion composition capable of obtaining excellent alkali developability and high contrast, a photocurable composition, a color filter having good color characteristics and high contrast, and a method for producing the same.

Hereinafter, the present invention will be described in detail.
<Polymer compound>
The polymer compound of the present invention is a polymer compound represented by any one of the following general formulas (1) to (3) (hereinafter referred to as a specific polymer compound as appropriate). The specific polymer compound represented by any one of the following general formulas (1) to (3) has an organic dye structure, a heterocyclic structure, an acidic group, a group having a basic nitrogen atom, a urea group, A plurality of monovalent organic groups including at least one portion selected from a urethane group, a group having a coordinating oxygen atom, a hydrocarbon group having 4 or more carbon atoms, an alkoxysilyl group, an epoxy group, an isocyanate group, and a hydroxyl group Therefore, it has various characteristics such as excellent adsorptivity to a solid surface, excellent micelle formation ability, and surface activity ability. Therefore, for example, the polymer compound of the present invention can be suitably used as a pigment dispersant. It is also useful as a surface treatment agent for improving the dispersibility by increasing the polarity of the surface by the surface treatment of the pigment.

In the formula, R ¹ represents an (m ₁ + n ₁ ) -valent organic linking group, R ⁴ represents an (m ₂ + n ₂ ) -valent organic linking group, and R ⁷ represents an (m ₃ + n ₃ ) -valent organic linking group. Represents a linking group. The ^{R 2, R 3, R 5} , R 6, R 8 and ^{R 9} each independently represent a single bond or a divalent organic linking group. A ^1, A ² and A ³ are each independently an organic dye structure, a heterocyclic structure, an acidic group, a group having a basic nitrogen atom, a urea group, a urethane group, a group having a coordinating oxygen atom, 4 carbon atoms It represents a monovalent organic group containing at least one selected from the above hydrocarbon groups, alkoxysilyl groups, epoxy groups, isocyanate groups, and hydroxyl groups. m ₁ , m ₂ and m ₃ each independently represents an integer of 1 to 8. n _{1, n 2} and _{n 3} each independently represent a 2-9 integer. Here, m ₁ + n ₁ , m ₂ + n ₂ , and m ₃ + n ₃ each independently satisfy 3 to 10. M ¹ and M ³ each independently represents a monovalent organic group. M ² each independently represents a hydrogen atom or a monovalent organic group. p, q and r each independently represents an integer of 2 to 8. b, c and d each independently represents an integer of 1 to 100.

In the general formula (1), A ¹ represents an organic dye structure, a heterocyclic structure, an acidic group, a group having a basic nitrogen atom, a urea group, a urethane group, a group having a coordinating oxygen atom, or 4 or more carbon atoms. Represents a monovalent organic group containing at least one selected from a hydrocarbon group, an alkoxysilyl group, an epoxy group, an isocyanate group, and a hydroxyl group. n ₁ A ¹ may be the same or different.

That is, the A ¹ has a structure capable of adsorbing to a pigment such as an organic dye structure or a heterocyclic structure, an acid group, a group having a basic nitrogen atom, a urea group, a urethane group, or a coordinating oxygen atom. And a monovalent organic group containing at least one functional group capable of adsorbing to a pigment, such as a group, a hydrocarbon group having 4 or more carbon atoms, an alkoxysilyl group, an epoxy group, an isocyanate group, and a hydroxyl group.
Hereinafter, the site having the ability to adsorb to the pigment (the above structure and functional group) will be collectively referred to as “adsorption site” as appropriate.

The adsorption sites are in one A ^1, it may be contained at least one, may contain two or more kinds.
Further, in the present invention, the “monovalent organic group containing at least one kind of adsorption site” means the above-mentioned adsorption site, 1 to 200 carbon atoms, 0 to 20 nitrogen atoms, 0 to A monovalent organic group formed by bonding an organic linking group composed of up to 100 oxygen atoms, 1 to 400 hydrogen atoms, and 0 to 40 sulfur atoms. . In the case where adsorption sites themselves may constitute a monovalent organic group, adsorption sites itself may be a monovalent organic group represented by A ^1.
First, the adsorption site constituting A ¹ will be described below.

  Examples of the “organic dye structure” include phthalocyanine, insoluble azo, azo lake, anthraquinone, quinacridone, dioxazine, diketopyrrolopyrrole, anthrapyridine, ansanthrone, indanthrone, flavan. Examples of preferable dye structures of throne, perinone, perylene, and thioindigo are phthalocyanine, azo lake, anthraquinone, dioxazine, and diketopyrrolopyrrole, and phthalocyanine and anthraquinone. A diketopyrrolopyrrole dye structure is particularly preferred.

  Examples of the “heterocyclic structure” include thiophene, furan, xanthene, pyrrole, pyrroline, pyrrolidine, dioxolane, pyrazole, pyrazoline, pyrazolidine, imidazole, oxazole, thiazole, oxadiazole, triazole, thiadiazole, pyran, pyridine. , Piperidine, dioxane, morpholine, pyridazine, pyrimidine, piperazine, triazine, trithiane, isoindoline, isoindolinone, benzimidazolone, benzothiazole, succinimide, phthalimide, naphthalimide, hydantoin, indole, quinoline, carbazole, acridine, acridone, Anthraquinone is mentioned as a preferred example, pyrroline, pyrrolidine, pyrazole, pyrazoline, pyrazolidine, imidazole, Riazor, pyridine, piperidine, morpholine, pyridazine, pyrimidine, piperazine, triazine, isoindoline, isoindolinone, benzimidazolone, benzothiazole, succinimide, phthalimide, naphthalimide, hydantoin, carbazole, acridine, acridone, anthraquinone are more preferable.

  The “organic dye structure” or “heterocyclic structure” may further have a substituent. Examples of the substituent include alkyl groups having 1 to 20 carbon atoms such as a methyl group and an ethyl group. An acyloxy group having 1 to 6 carbon atoms, such as an aryl group having 6 to 16 carbon atoms such as a hydroxyl group, a phenyl group or a naphthyl group, a hydroxyl group, an amino group, a carboxyl group, a sulfonamide group, an N-sulfonylamide group or an acetoxy group. Alkoxy groups having 1 to 20 carbon atoms such as methoxy group and ethoxy group, halogen atoms such as chlorine and bromine, alkoxycarbonyl groups having 2 to 7 carbon atoms such as methoxycarbonyl group, ethoxycarbonyl group and cyclohexyloxycarbonyl group , A cyano group, a carbonate group such as t-butyl carbonate, and the like. Here, these substituents may be bonded to the organic dye structure or the heterocyclic ring through the following structural unit or a linking group formed by combining the structural units.

  Preferred examples of the “acidic group” include a carboxylic acid group, a sulfonic acid group, a monosulfate group, a phosphoric acid group, a monophosphate group, and a boric acid group. Sulfuric acid ester groups, phosphoric acid groups, and monophosphoric acid ester groups are more preferable, and carboxylic acid groups, sulfonic acid groups, and phosphoric acid groups are particularly preferable.

Examples of the “group having a basic nitrogen atom” include an amino group (—NH ₂ ), a substituted imino group (—NHR ⁸ , —NR ⁹ R ¹⁰ , wherein R ⁸ , R ⁹ , and R ¹⁰ Each independently represents an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 or more carbon atoms, or an aralkyl group having 7 or more carbon atoms), a guanidyl group represented by the following formula (a1), Preferred examples include the amidinyl group represented by a2).

In formula (a1), R ¹¹ and R ¹² each independently represents an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 or more carbon atoms, or an aralkyl group having 7 or more carbon atoms.
In formula (a2), R ¹³ and R ¹⁴ each independently represents an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 or more carbon atoms, or an aralkyl group having 7 or more carbon atoms.

Among these, amino _(-NH 2), substituted imino group ^{(-NHR 8,} -NR ^{9 R 10, wherein,} R 8, ^{R 9,} and ^{R 10} are each independently from 1 to 10 carbon atoms alkyl group, a phenyl group, a benzyl group.), in a guanidyl group represented by the formula (a1) [formula ^{(a1), R 11} and ^{R 12} each independently represent an alkyl group having from 1 to 10 carbon atoms Represents a phenyl group or a benzyl group. ] An amidinyl group represented by the formula (a2) [in the formula (a2), R ¹³ and R ¹⁴ each independently represents an alkyl group having 1 to 10 carbon atoms, a phenyl group, or a benzyl group. ] Is more preferable.
In particular, an amino group (—NH ₂ ), a substituted imino group (—NHR ⁸ , —NR ⁹ R ¹⁰ , wherein R ⁸ , R ⁹ , and R ¹⁰ are each independently an alkyl group having 1 to 5 carbon atoms. , A phenyl group and a benzyl group.), A guanidyl group represented by the formula (a1) [in the formula (a1), R ¹¹ and R ¹² are each independently an alkyl group having 1 to 5 carbon atoms, phenyl Represents a benzyl group. ] An amidinyl group represented by the formula (a2) [in the formula (a2), R ¹³ and R ¹⁴ each independently represents an alkyl group having 1 to 5 carbon atoms, a phenyl group, or a benzyl group. Etc. are preferably used.

Examples of the “urea group” include —NR ¹⁵ CONR ¹⁶ R ¹⁷ (wherein R ¹⁵ , R ¹⁶ , and R ¹⁷ are each independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, a carbon number, Preferred examples include aryl groups having 6 or more and aralkyl groups having 7 or more carbon atoms, and —NR ¹⁵ CONHR ¹⁷ (wherein R ¹⁵ and R ¹⁷ are each independently a hydrogen atom or 1 carbon atom). More preferably an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 or more carbon atoms, or an aralkyl group having 7 or more carbon atoms.) —NHCONHR ¹⁷ (wherein R ¹⁷ represents a hydrogen atom or 1 to 10 carbon atoms) An alkyl group, an aryl group having 6 or more carbon atoms, and an aralkyl group having 7 or more carbon atoms are particularly preferable.

Examples of the “urethane group” include —NHCOOR ¹⁸ , —NR ¹⁹ COOR ²⁰ , —OCONHR ²¹ , —OCONR ²² R ²³ (where R ¹⁸ , R ¹⁹ , R ²⁰ , R ²¹ , R ²² and R ²³ are Each independently represents an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 or more carbon atoms, or an aralkyl group having 7 or more carbon atoms), and the like. -NHCOOR ¹⁸ , -OCONHR ²¹ (here And R ¹⁸ and R ²¹ each independently represents an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 or more carbon atoms, or an aralkyl group having 7 or more carbon atoms), and the like, more preferably —NHCOOR ¹⁸ , -OCONHR ^{21 (wherein,} R ^{18, R 21} each independently represents an alkyl group having from 1 to 10 carbon atoms, having 6 or more ant carbon Group, represents a number of 7 or more aralkyl group having a carbon.), Etc. are particularly preferred.

  Examples of the “group having a coordinating oxygen atom” include an acetylacetonato group and a crown ether.

  Preferred examples of the “hydrocarbon group having 4 or more carbon atoms” include an alkyl group having 4 or more carbon atoms, an aryl group having 6 or more carbon atoms, an aralkyl group having 7 or more carbon atoms, and the like. More preferred are an alkyl group, an aryl group having 6 to 20 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, an alkyl group having 4 to 15 carbon atoms (for example, an octyl group, a dodecyl group, etc.), and an aryl having 6 to 15 carbon atoms. A group (for example, phenyl group, naphthyl group, etc.), an aralkyl group having 7 to 15 carbon atoms (for example, benzyl group, etc.) and the like are particularly preferable.

  Examples of the “alkoxysilyl group” include a trimethoxysilyl group and a triethoxysilyl group.

The organic linking group bonded to the adsorption site may be a single bond or 1 to 100 carbon atoms, 0 to 10 nitrogen atoms, 0 to 50 oxygen atoms, 1 to 200. An organic linking group consisting of up to 20 hydrogen atoms and 0 to 20 sulfur atoms is preferred, and this organic linking group may be unsubstituted or may further have a substituent.
Specific examples of the organic linking group include the following structural units or groups formed by combining the structural units.

  When the organic linking group has a substituent, examples of the substituent include an alkyl group having 1 to 20 carbon atoms such as a methyl group and an ethyl group, and a carbon group having 6 to 16 carbon atoms such as a phenyl group and a naphthyl group. C1-C6 alkoxy such as aryl group, hydroxyl group, amino group, carboxyl group, sulfonamide group, N-sulfonylamide group, acetoxy group, etc., C1-C6 acyloxy group, methoxy group, ethoxy group, etc. Group, halogen atoms such as chlorine and bromine, alkoxycarbonyl groups having 2 to 7 carbon atoms such as methoxycarbonyl group, ethoxycarbonyl group and cyclohexyloxycarbonyl group, carbonate groups such as cyano group and t-butyl carbonate, etc. Can be mentioned.

Among the above, as the A ^1, an organic dye structure, a heterocyclic structure, an acidic group, a group having a basic nitrogen atom, a urea group, and at least one site selected from the hydrocarbon group having 4 or more carbon atoms It is preferably a monovalent organic group containing, more preferably a monovalent organic group containing at least one portion selected from an organic dye structure, a heterocyclic structure, an acidic group and a group having a basic nitrogen atom. .

The A ¹ is more preferably a monovalent organic group represented by the following general formula (4).

In the general formula (4), B ¹ is the adsorption sites (i.e., an organic dye structure, a heterocyclic structure, an acidic group, a group having a basic nitrogen atom, a urea group, a urethane group, a group having a coordinating oxygen atom , hydrocarbon group having 4 or more carbon atoms, an alkoxysilyl group, an epoxy group, an isocyanate group, and the site) selected from a hydroxyl group, R ²⁴ represents a single bond or a (a + 1) -valent organic linking group. a represents an integer of 1 to 10. When a is 2 to 10, a number of B ¹ may be the same or different.

Examples of the adsorption site represented by B ¹ include the same adsorption sites that constitute A ¹ in the general formula (1), and preferred examples are also the same.
Among these, a site selected from an organic dye structure, a heterocyclic structure, an acidic group, a group having a basic nitrogen atom, a urea group, and a hydrocarbon group having 4 or more carbon atoms is preferable.

R ²⁴ represents a single bond, or (a + 1) -valent organic linking group, a is an integer of 1 to 10. Preferably, a is 1-7, more preferably, a is 1-5, and particularly preferably, a is 1-3.
(A + 1) valent organic linking group includes 1 to 100 carbon atoms, 0 to 10 nitrogen atoms, 0 to 50 oxygen atoms, 1 to 200 hydrogen atoms, And a group composed of 0 to 20 sulfur atoms, which may be unsubstituted or may further have a substituent.

  Specific examples of the (a + 1) -valent organic linking group include the following structural units or groups formed by combining the structural units (which may form a ring structure).

R ²⁴ may be a single bond or 1 to 50 carbon atoms, 0 to 8 nitrogen atoms, 0 to 25 oxygen atoms, 1 to 100 hydrogen atoms, and An (a + 1) valent organic linking group consisting of 0 to 10 sulfur atoms is preferred, a single bond or 1 to 30 carbon atoms, 0 to 6 nitrogen atoms, 0 to 15 More preferred are (a + 1) valent organic linking groups consisting of up to 1 oxygen atom, 1 to 50 hydrogen atoms, and 0 to 7 sulfur atoms, a single bond, or 1 to 10 (A + 1) valence consisting of 0 to 5 nitrogen atoms, 0 to 10 oxygen atoms, 1 to 30 hydrogen atoms, and 0 to 5 sulfur atoms The organic linking group is particularly preferred.

  Among the above, when the (a + 1) -valent organic linking group has a substituent, examples of the substituent include an alkyl group having 1 to 20 carbon atoms such as a methyl group and an ethyl group, a phenyl group, a naphthyl group, and the like. Such as an aryloxy group having 6 to 16 carbon atoms, a hydroxyl group, an amino group, a carboxyl group, a sulfonamide group, an N-sulfonylamide group, an acetoxy group and the like, an acyloxy group having 1 to 6 carbon atoms, a methoxy group, an ethoxy group, etc. Alkoxy groups having 1 to 6 carbon atoms, halogen atoms such as chlorine and bromine, alkoxycarbonyl groups having 2 to 7 carbon atoms such as methoxycarbonyl groups, ethoxycarbonyl groups, and cyclohexyloxycarbonyl groups, cyano groups, and t-butyl carbonate And the like, and the like.

A ² in the general formula (2) and A ³ in the general formula (3) have the same meaning as A ¹ in the general formula (1), and the preferred ranges are also the same.

In the general formula (1), R ² and R ³ each independently represents a single bond or a divalent organic linking group. A plurality of R ² and R ³ may be the same or different.
The divalent organic linking group includes 1 to 100 carbon atoms, 0 to 10 nitrogen atoms, 0 to 50 oxygen atoms, 1 to 200 hydrogen atoms, and 0 Groups comprising from 20 to 20 sulfur atoms are included and may be unsubstituted or further substituted.

  Specific examples of the divalent organic linking group include the following structural units or groups formed by combining the structural units.

R ² and R ³ may be a single bond or 1 to 50 carbon atoms, 0 to 8 nitrogen atoms, 0 to 25 oxygen atoms, 1 to 100 hydrogen atoms. Preferred are divalent organic linking groups consisting of atoms and 0 to 10 sulfur atoms, single bonds, 1 to 30 carbon atoms, 0 to 6 nitrogen atoms, 0 to More preferred is a divalent organic linking group consisting of up to 15 oxygen atoms, 1 to 50 hydrogen atoms, and 0 to 7 sulfur atoms, a single bond or 1 to 10 A divalent organic linkage consisting of carbon atoms, 0 to 5 nitrogen atoms, 0 to 10 oxygen atoms, 1 to 30 hydrogen atoms, and 0 to 5 sulfur atoms. The group is particularly preferred.

  Among the above, when the divalent organic linking group has a substituent, examples of the substituent include carbon having 1 to 20 carbon atoms such as a methyl group and an ethyl group, a carbon such as a phenyl group and a naphthyl group. Carbon number such as acyloxy group having 1 to 6 carbon atoms such as aryl group, hydroxyl group, amino group, carboxyl group, sulfonamido group, N-sulfonylamido group, acetoxy group, etc., methoxy group, ethoxy group, etc. Alkoxy groups having 1 to 6 carbon atoms, halogen atoms such as chlorine and bromine, alkoxycarbonyl groups having 2 to 7 carbon atoms such as methoxycarbonyl group, ethoxycarbonyl group, cyclohexyloxycarbonyl group, cyano group, t-butyl carbonate, etc. And carbonate ester groups.

R ⁵ and R ⁶ in the general formula (2), and R ⁸ and R ⁹ in the general formula (3) are synonymous with R ² and R ³ in the general formula (1), and preferable ranges thereof are also the same. is there.

In the general formula (1), ^{R 1} _represents a _(m 1 + _{n 1)} -valent organic linking group. m ₁ + _{n 1} satisfies 3-10.
Examples of the (m ₁ + n ₁ ) -valent organic linking group represented by R ¹ include 1 to 100 carbon atoms, 0 to 10 nitrogen atoms, 0 to 50 oxygen atoms, Groups consisting of 1 to 200 hydrogen atoms and 0 to 20 sulfur atoms are included, which may be unsubstituted or further substituted.

Specific examples of the (m ₁ + n ₁ ) -valent organic linking group include the following structural units or a group composed of a combination of the structural units (which may form a ring structure). Can do.

The _(m 1 + _{n 1)} -valent organic linking group, of 1 to 60 carbon atoms, nitrogen atoms from 0 to 10 oxygen atoms from 0 to 40, from 1 to 120 Preferred are groups consisting of hydrogen atoms and 0 to 10 sulfur atoms, preferably 1 to 50 carbon atoms, 0 to 10 nitrogen atoms, 0 to 30 oxygen atoms, 1 More preferred are groups consisting of from 1 to 100 hydrogen atoms and 0 to 7 sulfur atoms, 1 to 40 carbon atoms, 0 to 8 nitrogen atoms, 0 to 20 atoms. Particularly preferred are groups consisting of oxygen atoms, 1 to 80 hydrogen atoms, and 0 to 5 sulfur atoms.

Among the above, when the (m ₁ + n ₁ ) -valent organic linking group has a substituent, examples of the substituent include an alkyl group having 1 to 20 carbon atoms such as a methyl group and an ethyl group, a phenyl group, C1-C6 acyloxy groups such as naphthyl groups such as aryl groups having 6 to 16 carbon atoms, hydroxyl groups, amino groups, carboxyl groups, sulfonamido groups, N-sulfonylamide groups, acetoxy groups, methoxy groups, ethoxy groups An alkoxy group having 1 to 6 carbon atoms such as a group, a halogen atom such as chlorine or bromine, an alkoxycarbonyl group having 2 to 7 carbon atoms such as a methoxycarbonyl group, an ethoxycarbonyl group or a cyclohexyloxycarbonyl group, a cyano group, t -Carbonic acid ester groups, such as butyl carbonate, etc. are mentioned.

The illustrated specific examples represented by _(m 1 + _{n 1)} -valent organic linking group ^{R 1} [specific examples (1) to (17)] are shown below. However, the present invention is not limited to these.

Among the above specific examples, the most preferred (m ₁ + n ₁ ) -valent organic linking group is the following group from the viewpoint of availability of raw materials, ease of synthesis, and solubility in various solvents.

R ⁴ in the general formula (2) and R ⁷ in the general formula (3) have the same meanings as R ¹ in the general formula (1), and preferred ranges thereof are also the same.

In the general formula (1), m ₁ represents an integer of ₁ to 8. The m _1, preferably 1 to 5, more preferably 1 to 4, 1 to 3 is particularly preferable.
Further, in the general formula (1), _{n 1} represents an integer of 2-9. The n _1, preferably from 2 to 8, more preferably 2 to 7, 3 to 6 is particularly preferred.

Formula (2) _{m 2} and the general formula in (3) _{m 3} in the general formula (1) is _{m 1} and synonymous, and preferred ranges are also the same.
N ₂ in the general formula (2) and n ₃ in the general formula (3) are synonymous with n ₁ in the general formula (1), and the preferred ranges are also the same.

  In the general formulas (1), (2) and (3), p, q and r each independently represent an integer of 2 to 8. In view of dispersion stability and developability, 4 to 6 is preferable, and 5 is most preferable.

  In the general formulas (1), (2) and (3), b, c and d each independently represent an integer of 1 to 100. b, c and d are preferably 5 to 60, more preferably 5 to 40, and still more preferably 5 to 20 from the viewpoints of dispersion stability and developability.

M ¹ in the general formula (1) represents a monovalent organic group.
As the monovalent organic group, a substituted or unsubstituted alkyl group or a substituted or unsubstituted aryl group is preferable.

  Examples of preferable alkyl groups include linear, branched, and cyclic alkyl groups having 1 to 20 carbon atoms. Specific examples thereof include a methyl group, an ethyl group, a propyl group, Butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, hexadecyl, octadecyl, eicosyl, isopropyl, isobutyl, s-butyl, Examples thereof include t-butyl group, isopentyl group, neopentyl group, 1-methylbutyl group, isohexyl group, 2-ethylhexyl group, 2-methylhexyl group, cyclohexyl group, cyclopentyl group and 2-norbornyl group.

  Examples of the substituent of the substituted alkyl group include a monovalent nonmetallic atomic group excluding hydrogen, and preferable examples include a halogen atom (—F, —Br, —Cl, —I), a hydroxyl group, an alkoxy group, Aryloxy group, mercapto group, alkylthio group, arylthio group, alkyldithio group, aryldithio group, amino group, N-alkylamino group, N, N-dialkylamino group, N-arylamino group, N, N-diarylamino group N-alkyl-N-arylamino group, acyloxy group, carbamoyloxy group, N-alkylcarbamoyloxy group, N-arylcarbamoyloxy group, N, N-dialkylcarbamoyloxy group, N, N-diarylcarbamoyloxy group, N-alkyl-N-arylcarbamoyloxy group, alkylsulfoxy group, Reelsulfoxy group, acyloxy group, acylthio group, acylamino group, N-alkylacylamino group, N-arylacylamino group, ureido group, N′-alkylureido group, N ′, N′-dialkylureido group, N ′ An arylureido group, an N ′, N′-diarylureido group, an N′-alkyl-N′-arylureido group, an N-alkylureido group, an N-arylureido group, an N′-alkyl-N-alkylureido group, N′-alkyl-N-arylureido group, N ′, N′-dialkyl-N-alkylureido group, N ′, N′-dialkyl-N-arylureido group,

N′-aryl-N-alkylureido group, N′-aryl-N-arylureido group, N ′, N′-diaryl-N-alkylureido group, N ′, N′-diaryl-N-arylureido group, N′-alkyl-N′-aryl-N-alkylureido group, N′-alkyl-N′-aryl-N-arylureido group, alkoxycarbonylamino group, aryloxycarbonylamino group, N-alkyl-N-alkoxy Carbonylamino group, N-alkyl-N-aryloxycarbonylamino group, N-aryl-N-alkoxycarbonylamino group, N-aryl-N-aryloxycarbonylamino group, formyl group, acyl group, carboxyl group, alkoxycarbonyl Group, aryloxycarbonyl group, carbamoyl group, N-alkylcarbamoyl group, N , N-dialkylcarbamoyl group, N-arylcarbamoyl group, N, N-diarylcarbamoyl group, N-alkyl-N-arylcarbamoyl group, alkylsulfinyl group, arylsulfinyl group, alkylsulfonyl group, arylsulfonyl group, sulfo group ( -SO 3 _H) and its conjugated base group (hereinafter referred to as sulfonato group), alkoxy sulfonyl group, aryloxy sulfonyl group, sulfinamoyl group, N- alkylsulfinamoyl group, N, N- dialkyl sulfinamoyl group, N -Arylsulfinamoyl group, N, N-diarylsulfinamoyl group, N-alkyl-N-arylsulfinamoyl group, sulfamoyl group, N-alkylsulfamoyl group, N, N-dialkylsulfamoyl group, N-arylsulfamoy Group, N, N- diaryl sulfamoyl group, N- alkyl -N- arylsulfamoyl group,

Phosphono group (—PO ₃ H ₂ ) and its conjugate base group (hereinafter referred to as phosphonato group), dialkylphosphono group (—PO ₃ (alkyl) ₂ ), diarylphosphono group (—PO ₃ (aryl) ₂ ) , alkyl aryl phosphono group _(-PO 3 (alkyl) (aryl)), monoalkyl phosphono group _(-PO 3 H (alkyl)) and its conjugated base group (hereinafter referred to as alkylphosphonato group), monoaryl Phosphono group (—PO ₃ H (aryl)) and its conjugate base group (hereinafter referred to as arylphosphonate group), phosphonooxy group (—OPO ₃ H ₂ ) and its conjugate base group (hereinafter referred to as “phosphonatoxy group”) , dialkylphosphono group _{(-OPO 3 (alkyl) 2)} , diaryl phosphono group _(-OPO 3 _{(aryl) 2} , Alkylaryl phosphono group _(-OPO 3 (alkyl) (aryl)), monoalkyl phosphono group _(-OPO 3 H (alkyl)) and its conjugated base group (hereinafter referred to as alkylphosphonato group) , monoarylphosphono group _(-OPO 3 H (aryl)) and its conjugated base group (hereinafter referred to as aryl phosphite Hona preparative group), a cyano group, a nitro group, an aryl group, a heteroaryl group, an alkenyl group, an alkynyl Group and silyl group.

Specific examples of the alkyl group in these substituents include the alkyl groups described above, and these may further have a substituent.
Furthermore, as a substituent in the case of having a substituent, an alkoxy group, an aryloxy group, an alkylthio group, an arylthio group, an N, N-dialkylamino group, an N, N-diarylamino group, an N-alkyl-N-arylamino group, An acyloxy group, an aryl group, a heteroaryl group, an alkenyl group, an alkynyl group, and a silyl group are preferable from the viewpoint of dispersion stability.

  Specific examples of the aryl group include phenyl, biphenyl, naphthyl, tolyl, xylyl, mesityl, cumenyl, chlorophenyl, bromophenyl, chloromethylphenyl, hydroxyphenyl, methoxyphenyl, ethoxy Phenyl group, phenoxyphenyl group, acetoxyphenyl group, benzoyloxyphenyl group, methylthiophenyl group, phenylthiophenyl group, methylaminophenyl group, dimethylaminophenyl group, acetylaminophenyl group, carboxyphenyl group, methoxycarbonylphenyl group, Ethoxyphenylcarbonyl group, phenoxycarbonylphenyl group, N-phenylcarbamoylphenyl group, phenyl group, cyanophenyl group, sulfophenyl group, sulfonatophenyl group, phosphonophenyl group It can be exemplified phosphonophenyl phenyl group.

  Examples of the substituent for the substituted aryl group include the same groups as those described above for the substituted alkyl group.

The M ^1, dispersion stability, in terms of developing property, linear from 1 carbon atom to 20, alkyl of annular-shaped branch from carbon atoms 3 to 20, or from 5 carbon atoms to 20 Group is preferable, linear alkyl group having 4 to 15 carbon atoms, branched alkyl group having 4 to 15 carbon atoms, or cyclic alkyl group having 6 to 10 carbon atoms, more preferably 6 to 10 carbon atoms. More preferred are straight-chain or branched alkyl groups having 6 to 12 carbon atoms.

M ² in the general formula (2) represents a hydrogen atom or a monovalent organic group. The monovalent organic group represented by M ² has the same meaning as M ¹ in the general formula (1), and the preferred range is also the same.
M ³ in the general formula (3) has the same meaning as M ¹ in the general formula (1), and the preferred range is also the same.

  The acid value of the polymer compound of the present invention is not particularly limited, but when the polymer compound of the present invention is used as a pigment dispersant, the acid value is preferably 200 (mgKOH / g) or less, and 160 (mgKOH / g ) Or less is more preferable, and 120 (mgKOH / g) or less is particularly preferable. By setting it as the said range, the dispersibility of a pigment and dispersion stability become favorable.

  Moreover, when using the specific polymer compound of this invention for the photocurable composition which needs an alkali image development process with a pigment, it is preferable that the acid value is 30-200 (mgKOH / g), 40-160 ( mgKOH / g) is more preferable, and 50 to 120 (mgKOH / g) is particularly preferable. By setting it as the said range, the alkali developability of a photocurable composition, the dispersibility of a pigment, and dispersion stability become favorable.

  The molecular weight of the specific polymer compound of the present invention is preferably 3000 to 100,000, more preferably 5000 to 80000, and particularly preferably 7000 to 60000 in terms of weight average molecular weight. When the weight average molecular weight is within the above range, the effects of the plurality of adsorption sites introduced at the ends of the polymer are sufficiently exerted, and the performance with excellent adsorptivity to the solid surface, micelle formation ability, and surface activity is achieved. Demonstrate. In particular, when the specific polymer compound according to the present invention is used as a pigment dispersant, good dispersibility and dispersion stability can be achieved.

(Synthesis method)
The specific polymer compound represented by the general formulas (1) to (3) is not particularly limited, but can be synthesized by the following method.
1. A polymer composed of a polycaprolactone compound in which a functional group selected from a carboxyl group, a hydroxyl group, an amino group, or the like is introduced at the end, and an acid halide having a plurality of the adsorption sites or an alkyl halide having a plurality of the adsorption sites. How to react.
2. A method of Michael addition reaction of a polycaprolactone compound having a carbon-carbon double bond introduced at a terminal thereof and a mercaptan having a plurality of the adsorption sites.
3. A method of reacting a polycaprolactone compound having a carbon-carbon double bond introduced at a terminal thereof with a mercaptan having the adsorption site in the presence of a radical generator.
4). A method of reacting a polycaprolactone compound having a plurality of mercaptans introduced at its ends with a compound having a carbon-carbon double bond and the adsorption site in the presence of a radical generator.
5). A method in which a polycaprolactone compound having a carboxylic acid introduced at its terminal is added to an epoxy having a plurality of the adsorption sites.
6). A method in which a polycaprolactone compound having a functional group selected from a hydroxyl group, an amino group and the like introduced at the end thereof and an isocyanate having a plurality of the adsorption sites are subjected to an addition reaction.
7). A method of synthesizing ε-caprolactone by ring-opening polymerization using the mercaptan having the adsorption site as a terminal initiator monomer.

  Among the above, the specific polymer compound of the present invention is preferably a synthesis method of 2, 3, 5, 6 and more preferably a synthesis method of 2, 3, 5 because of ease of synthesis.

<Synthesis Method 2>
In the case of synthesizing by the above method 2, specifically, a compound represented by the following general formula (4) is preferable as the polycaprolactone compound having a carbon-carbon double bond introduced at the terminal.

In the general formula (4), _{X 1} and _{X 2} are a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, -COOH, -COOR (R is an alkyl group having 1 to 10 carbon _atoms), - CH 2 _COOH, - CH ₂ COOR (R is an alkyl group having 1 to 10 carbon _{atoms), - CH 2 CONH 2,} ( the R alkyl group having 1 to 10 carbon _{atoms) -CH 2 CONHR, - CH 2} -OH, -CH 2 -O -CO-R (R is an alkyl group having 1 to 10 carbon atoms), - COPh (Ph is _phenyl), - CONH 2, represents a -CONHR (R is an alkyl group or phenyl group having 1 to 10 carbon atoms). R ³³ has the same meaning as R ² in the general formula (1). P ₁ represents any one selected from the following general formulas (1-1) to (3-1).

Formula (1-1) ^{M 1,} M ² in the ~ (3-1), M 3, p, q, r, b, c and d are, ^M 1 in the general formula (1) to (3), respectively, ^{M 2, M 3, p,} q, r, b, have the same meanings as c and d, a preferred range is also the same.

Specific examples of the compound represented by the general formula (4) include the following compounds.
However, Ma in the following formula represents any of a linear or branched alkyl group having 1 to 20 carbon atoms, a cyclohexyl group, a benzyl group, and a phenylethyl group. Note that b represents an integer of 5 to 80, c represents an integer of 5 to 80, and d represents an integer of 5 to 80.

  When synthesizing by the method 2, the mercaptan having a plurality of the adsorption sites is specifically preferably a compound represented by the following general formula (S-1).

In the general formula (S-1), R ⁴¹ , R ⁴² , A ⁴ , m ₄ , and n ₄ are R ² , R ³ , A ¹ , m ₁ , and n ₁ in the general formula (1), respectively. The preferable aspect is also the same.

A mercaptan having a plurality of the adsorption sites is an addition reaction between a compound having 3 to 10 mercapto groups in one molecule and a compound having the adsorption sites and a functional group capable of reacting with a mercapto group. Can be synthesized.
Preferred examples of the “functional group capable of reacting with a mercapto group” include acid halides, alkyl halides, isocyanates, and carbon-carbon double bonds.
It is particularly preferable that the “functional group capable of reacting with a mercapto group” is a carbon-carbon double bond, and the addition reaction is a radical addition reaction or a Michael addition reaction.

  Specific examples of the compound having 3 to 10 mercapto groups in one molecule [specific examples (18) to (34)] include the following compounds.

  Among the above, the following compounds are particularly preferable from the viewpoints of availability of raw materials, ease of synthesis, and solubility in various solvents.

  A compound having the adsorption site and having a carbon-carbon double bond (specifically, an organic dye structure, a heterocyclic structure, an acidic group, a group having a basic nitrogen atom, a urea group, a urethane group, a coordination group) A group having a coordinated oxygen atom, a hydrocarbon group having 4 or more carbon atoms, an alkoxysilyl group, an epoxy group, an isocyanate group, and a hydroxyl group; and a carbon-carbon double bond Although it does not restrict | limit especially as a compound which has, The following are mentioned.

<Synthesis Method 3>
In the case of synthesizing by the above method 3, specifically, a compound represented by the following general formula (5) or (6) is preferable as the polycaprolactone compound having a carbon-carbon double bond introduced at the terminal.

In General Formula (5), X ₃ and X ₄ are a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, —COOH, —COOR (R is an alkyl group having 1 to 10 carbon atoms), —CH ₂ COOH, — CH ₂ COOR (R is an alkyl group having 1 to 10 carbon _{atoms), - CH 2 CONH 2,} -CH 2 CONHR (R is an alkyl group having 1 to 10 carbon atoms), - COPh (Ph is phenyl), - CONH _2, -CONHR (R is an alkyl group or phenyl group having 1 to 10 carbon atoms). R ³⁴ has the same meaning as ^{R 2} in the general formula (1). P ₂ has the same meaning as P ₁ in the general formula (4).

In General Formula (6), X ₅ and X ₆ are a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, —CH ₂ —OH, —CH ₂ —O—CO—R (R is a carbon atom having 1 to 10 carbon atoms). Alkyl group). R ³⁵ represents the same meaning as ^{R 2} in the general formula (1). R ₃₆ represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms. P ₃ has the same meaning as P ₁ in the general formula (4).

Specific examples of the compound represented by the general formula (5) include the specific examples (4-1) to (4-2) and (4-5) to (4-14).
Specific examples of the compound represented by the general formula (6) include the following compounds. However, Ma represents either a C1-C20 linear or branched alkyl group, a cyclohexyl group, a benzyl group, and a phenylethyl group. Note that b represents an integer of 5 to 80, c represents an integer of 5 to 80, and d represents an integer of 5 to 80.

  In the case of synthesizing by the method 3, the compound represented by the general formula (S-1) is specifically preferred as the mercaptan having a plurality of the adsorption sites.

<Synthesis Method 5>
When synthesizing by the above method 5, specifically, a compound represented by the following general formula (3-2) is preferred as the polycaprolactone compound having a carboxylic acid introduced at the terminal. ^M 3, d and r in the general formula (3-2) has the same meaning as ^M 3, d and r, respectively, in the general formula (3-1), and preferred ranges are also the same.

  When synthesizing by the above method 5, specifically, a compound represented by the following general formula (S-2) is preferable as the epoxy having a plurality of the adsorption sites.

In Formula ^{(S-2), R 43} , R 44, A 5, m 5 and _{n 5} are, ^{R 2,} R ³ in each of the general formula _{^{(1), A 1, m}} 1 and _{n 1} synonymous The preferred embodiment is also the same. L is at least one linking group selected from the following general formulas (L-1) and (L-2).

The epoxy having a plurality of adsorption sites is an addition reaction between a compound having 3 to 10 epoxy groups in one molecule and a compound having the adsorption sites and having a functional group capable of reacting with an epoxy group. Can be synthesized.
Preferred examples of the “functional group capable of reacting with an epoxy group” include carboxylic acid and acid halide, and carboxylic acid is preferable from the viewpoint of ease of synthesis.

  Specific examples of the epoxy compound represented by the general formula (S-2) include the following compounds.

  As the specific polymer compound obtained by the synthesis methods 2 and 3 described above, a polymer compound represented by the following general formula (1 '), (2') or (3 ') is preferable.

  As the specific polymer compound obtained by the synthesis method described above, a polymer compound represented by the following general formula (3 ″) is preferable. As the specific polymer compound obtained by the synthesis method 1 described above, a polymer compound represented by the following general formula (2 ″) is preferable.

In the general formulas (1 ′), (2 ′), (3 ′), (2 ″) and (3 ″), R ¹ represents an (m ₁ + n ₁ ) -valent organic linking group, and R ⁴ the _{(m 2} + _n 2) -valent organic linking group, ^{R 7} represents a _{(m 3} + _n 3) valent organic linking group. ^{R 2, R 3, R 5} , R 6, R 8 and ^{R 9} each independently represent a single bond or a divalent organic linking group. A ¹ , A ² and A ³ are each independently an organic dye structure, a heterocyclic structure, an acidic group, a group having a basic nitrogen atom, a urea group, a urethane group, a group having a coordinating oxygen atom, or a carbon number of 4 It represents a monovalent organic group containing at least one selected from the above hydrocarbon groups, alkoxysilyl groups, epoxy groups, isocyanate groups, and hydroxyl groups.
m _{1, m 2} and _{m 3} each independently represents an integer of 1 to 8. n _{1, n 2} and _{n 3} each independently represent a 2-9 integer. Here, m ₁ + n ₁ , m ₂ + n ₂ , and m ₃ + n ₃ each independently satisfy 3 to 10. M ¹ and M ³ each independently represents a monovalent organic group. M ² each independently represents a hydrogen atom or a monovalent organic group. p, q and r each independently represents an integer of 2 to 8. b, c and d each independently represents an integer of 1 to 100.

  In the pigment dispersion composition of the present invention, the content of the specific polymer compound is preferably a pigment: specific polymer compound = 1: 0.1 to 1: 2, more preferably 1: 0. It is 2 to 1: 1, and more preferably 1: 0.2 to 1: 0.8.

  The specific polymer compound according to the present invention described above can be suitably used as a pigment dispersant for dispersing a pigment, and the pigment dispersion composition containing the specific polymer compound together with the pigment is capable of dispersing and dispersing the pigment. Stability is improved.

<Pigment dispersion composition>
The pigment dispersion composition of the present invention contains the above-described specific polymer compound according to the present invention and at least one pigment in an organic solvent.
Moreover, it can comprise using other components, such as a resin component, as needed. This pigment dispersion composition contains at least one kind of the polymer compound of the present invention described above, and since the polymer compound functions as a pigment dispersant, the dispersion state of the pigment in the organic solvent is good, and the pigment dispersion composition is good. For example, when a color filter is formed using color characteristics, a high contrast can be obtained. In particular, the specific polymer compound of the present invention exhibits an excellent dispersion effect for organic pigments.

Moreover, in the range which does not impair the effect of this invention, you may use together other high molecular compounds from which a structure differs in addition to this specific high molecular compound mentioned above as needed.
As other polymer compounds, natural resins, modified natural resins, synthetic resins, synthetic resins modified with natural resins, and the like are used.

The natural resin is typically rosin, and the modified natural resin includes rosin derivatives, fiber derivatives, rubber derivatives, protein derivatives and oligomers thereof. Examples of the synthetic resin include an epoxy resin, an acrylic resin, a maleic acid resin, a butyral resin, a polyester resin, a melamine resin, a phenol resin, and a polyurethane resin. Examples of synthetic resins modified with natural resins include rosin-modified maleic acid resins and rosin-modified phenolic resins.
Synthetic resins include polyamidoamine and its salt, polycarboxylic acid and its salt, high molecular weight unsaturated acid ester, polyurethane, polyester, poly (meth) acrylate, (meth) acrylic copolymer, naphthalenesulfonic acid formalin condensate Is mentioned.

Known dispersants (pigment dispersants) include polymer dispersants such as polyamidoamines and salts thereof, polycarboxylic acids and salts thereof, high molecular weight unsaturated acid esters, modified polyurethanes, modified polyesters, and modified poly (meth). Acrylate, (meth) acrylic copolymer, naphthalenesulfonic acid formalin condensate], polyoxyethylene alkyl phosphate ester, polyoxyethylene alkylamine, alkanolamine, pigment derivative, and the like.
The polymer dispersant can be further classified into a linear polymer, a terminal-modified polymer, a graft polymer, and a block polymer according to the structure.

  The polymer dispersant is adsorbed on the surface of the pigment and acts to prevent reaggregation. Therefore, a terminal-modified polymer, a graft polymer and a block polymer having an anchor site to the pigment surface can be mentioned as preferred structures. On the other hand, the pigment derivative has an effect of promoting the adsorption of the polymer dispersant by modifying the pigment surface.

  Specific examples of known dispersants (pigment dispersants) that can be used in the present invention include “Disperbyk-101 (polyamidoamine phosphate), 107 (carboxylic acid ester), 110 (copolymer containing acid groups) manufactured by BYK Chemie. ), 130 (polyamide), 161, 162, 163, 164, 165, 166, 170 (polymer copolymer) ”,“ BYK-P104, P105 (high molecular weight unsaturated polycarboxylic acid) ”,“ manufactured by EFKA ” EFKA 4047, 4050, 4010, 4165 (polyurethane), EFKA 4330, 4340 (block copolymer), 4400, 4402 (modified polyacrylate), 5010 (polyester amide), 5765 (high molecular weight polycarboxylate), 6220 (fatty acid) Polyester), 6745 (phthalocyanine derivative) 6750 (azo pigment derivative) ”,“ Ajisper PB821, PB822 ”manufactured by Ajinomoto Fan Techno Co.,“ Floren TG-710 (urethane oligomer) ”manufactured by Kyoeisha Chemical Co., Ltd.,“ Polyflow No. 50E, No. 300 (acrylic copolymer) "" Disparon KS-860, 873SN, 874, # 2150 (aliphatic polyvalent carboxylic acid), # 7004 (polyetherester), DA-703-50, DA-705, DA-725 "manufactured by Enomoto Kasei Co., Ltd. “Demol RN, N (Naphthalenesulfonic acid formalin polycondensate), MS, C, SN-B (aromatic sulfonic acid formalin polycondensate)”, “Homogenol L-18 (polymer polycarboxylic acid)” "," Emulgen 920, 930, 935, 985 (polyoxyethylene nonylphenyl ether) " "Acetamine 86 (stearylamine acetate)", Lubrizol "Solsperse 5000 (phthalocyanine derivative), 22000 (azo pigment derivative), 13240 (polyesteramine), 3000, 17000, 27000 (having a functional part at the terminal part) Polymer), 24000, 28000, 32000, 38500 (graft type polymer) "," Nikkor T106 (polyoxyethylene sorbitan monooleate), MYS-IEX (polyoxyethylene monostearate) "manufactured by Nikko Chemical Co., Ltd. It is done.

  The content of the specific polymer compound in the pigment dispersion composition of the present invention is preferably a mass ratio with respect to the pigment, and is preferably pigment: specific polymer compound = 10: 1 to 1: 1, more preferably 5: 1 to 1. It is 1.25: 1, more preferably 4: 1 to 1.5: 1.

As the pigment dispersant in the pigment dispersion composition of the present invention, the specific polymer compound of the present invention may be used alone or in combination of two or more.
Moreover, you may use combining the specific polymer compound of this invention, and 1 or more types of the said well-known dispersing agent.
In addition, when using the said well-known dispersing agent together, it is preferable to use 70 mass% or more of the specific polymer compound of this invention in the pigment dispersant whole quantity.

(Pigment)
As the pigment that can be used in the pigment dispersion composition of the present invention, conventionally known various inorganic pigments or organic pigments can be appropriately selected and used.
As the pigment, considering that the pigment dispersion composition of the present invention is used in the colored region of the color filter and preferably having a high transmittance, an organic pigment is preferable, and the particle size is as small as possible. It is preferable to use one.
Considering the handling properties of the pigment dispersion composition and the colored photosensitive composition containing the same, the average primary particle size of the pigment is preferably 100 nm or less, more preferably 30 nm or less, and most preferably 5 nm to 25 nm. When the particle diameter is within the above range, the transmittance is high, the color characteristics are good, and it is effective for forming a color filter with high contrast.
The average primary particle diameter is obtained by observing with an SEM or TEM, measuring 100 particle sizes in a portion where the particles are not aggregated, and calculating an average value.

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

Examples of the organic pigment include:
C. I. Pigment Red 1, 2, 3, 4, 5, 6, 7, 9, 10, 14, 17, 22, 23, 31, 38, 41, 48: 1, 48: 2, 48: 3, 48: 4 49, 49: 1, 49: 2, 52: 1, 52: 2, 53: 1, 57: 1, 60: 1, 63: 1, 66, 67, 81: 1, 81: 2, 81: 3 83, 88, 90, 105, 112, 119, 122, 123, 144, 146, 149, 150, 155, 166, 168, 169, 170, 171, 172, 175, 176, 177, 178, 179, 184 185, 187, 188, 190, 200, 202, 206, 207, 208, 209, 210, 216, 220, 224, 226, 242, 246, 254, 255, 264, 270, 272, 279,
C. I. Pigment Yellow 1, 2, 3, 4, 5, 6, 10, 11, 12, 13, 14, 15, 16, 17, 18, 20, 24, 31, 32, 34, 35, 35: 1, 36, 36: 1, 37, 37: 1, 40, 42, 43, 53, 55, 60, 61, 62, 63, 65, 73, 74, 77, 81, 83, 86, 93, 94, 95, 97, 98, 100, 101, 104, 106, 108, 109, 110, 113, 114, 115, 116, 117, 118, 119, 120, 123, 125, 126, 127, 128, 129, 137, 138, 139, 147, 148, 150, 151, 152, 153, 154, 155, 156, 161, 162, 164, 166, 167, 168, 169, 170, 171, 172, 173, 17 , 175,176,177,179,180,181,182,185,187,188,193,194,199,213,214,
C. I. Pigment Orange 2, 5, 13, 16, 17: 1, 31, 34, 36, 38, 43, 46, 48, 49, 51, 52, 55, 59, 60, 61, 62, 64, 71, 73,
C. I. Pigment Green 7, 10, 36, 37,
C. I. Pigment Blue 1, 2, 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, 16, 22, 60, 64, 66, 79, 79 were changed to OH. Things, 80,
C. I. Pigment Violet 1, 19, 23, 27, 32, 37, 42,
C. I. Pigment Brown 25, 28,
C. I. Pigment Black 1, 7 and the like.
However, the present invention is not limited to these.

Among these, the pigments that can be preferably used include the following.
C. I. Pigment Yellow 11, 24, 108, 109, 110, 138, 139, 150, 151, 154, 167, 180, 185,
C. I. Pigment Orange 36, 71,
C. I. Pigment Red 122, 150, 171, 175, 177, 209, 224, 242, 254, 255, 264,
C. I. Pigment Violet 19, 23, 32,
C. I. Pigment Blue 15: 1, 15: 3, 15: 6, 16, 22, 60, 66,
C. I. Pigment Green 7, 36, 37,
C. I. Pigment Black 1, 7

These organic pigments can be used alone or in various combinations to increase color purity. Specific examples of combinations of organic pigments are shown below.
For example, as a red pigment, an anthraquinone pigment, perylene pigment, diketopyrrolopyrrole pigment alone or at least one of them, a disazo yellow pigment, an isoindoline yellow pigment, a quinophthalone yellow pigment Alternatively, a perylene red pigment, an anthraquinone red pigment, and a diketopyrrolopyrrole red pigment can be mixed and used.
For example, as an anthraquinone pigment, C.I. I. Pigment Red 177, and perylene pigments include C.I. I. Pigment red 155, C.I. I. Pigment Red 224, and diketopyrrolopyrrole pigments include C.I. I. Pigment Red 254, and C.I. I. Pigment yellow 83, C.I. I. Pigment yellow 139 or C.I. I. Mixing with Pigment Red 177 is preferred. The mass ratio of the red pigment to the other pigment is preferably 100: 5 to 100: 80 from the viewpoint of light transmittance and color purity from 400 nm to 500 nm. Particularly, the mass ratio is optimally in the range of 100: 10 to 100: 65. In addition, in the case of the combination of red pigments, it can adjust according to chromaticity.

As the green pigment, a halogenated phthalocyanine pigment is used alone or in combination with a disazo yellow pigment, a quinophthalone yellow pigment, an azomethine yellow pigment, or an isoindoline yellow pigment. be able to.
For example, C.I. I. Pigment Green 7, 36, 37 and C.I. I. Pigment yellow 83, C.I. I. Pigment yellow 138, C.I. I. Pigment yellow 139, C.I. I. Pigment yellow 150, C.I. I. Pigment yellow 180 or C.I. I. Mixing with Pigment Yellow 185 is preferred. The mass ratio of the green pigment to the yellow pigment is preferably 100: 5 to 100: 200 from the viewpoint of light transmittance of 400 nm to 450 nm and color purity. The mass ratio is particularly preferably in the range of 100: 20 to 100: 150.

As a blue pigment, a phthalocyanine pigment can be used alone or in combination with a dioxazine purple pigment.
As a particularly preferred example, C.I. I. Pigment blue 15: 6 and C.I. I. A mixture with pigment violet 23 can be mentioned.
The mass ratio of the blue pigment to the violet pigment is preferably 100: 0 to 100: 100, more preferably 100: 70 or less.

Moreover, as a pigment suitable for black matrix use, carbon black, graphite, titanium black, iron oxide, titanium oxide alone or a mixture thereof can be used, and a combination of carbon black and titanium black is preferable.
The mass ratio of carbon black to titanium black is preferably in the range of 100: 0 to 100: 60. If it is 100: 61 or more, the dispersion stability may decrease.

(Miniaturization of pigment)
In the present invention, if necessary, a pigment obtained by finely pulverizing the pigment as described above may be used.
In order to make the pigment finer, it is preferable to use a method including a step of preparing a liquid composition having a high viscosity together with a water-soluble organic solvent and a water-soluble inorganic salt and grinding the pigment.
In the present invention, it is more preferable to use the following method for refining the pigment.
That is, first, for a mixture (liquid composition) of an organic pigment, a water-soluble organic solvent, and a water-soluble inorganic salt, a two-roll, a three-roll, a ball mill, a tron mill, a disper, a kneader, a kneader, a homogenizer, a blender, a single By applying a strong shearing force by using a kneader such as a screw or twin screw extruder, the pigment in the mixture is ground, and then the mixture is put into water and made into a slurry with a stirrer or the like. Next, this slurry is filtered, washed with water, the water-soluble organic solvent and the water-soluble inorganic salt are removed, and then dried to obtain a finer pigment.

Examples of the water-soluble organic solvent used for the above-mentioned miniaturization include methanol, ethanol, isopropanol, n-propanol, isobutanol, n-butanol, ethylene glycol, diethylene glycol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether. , Propylene glycol, propylene glycolic monomethyl ether acetate and the like.
Also, if it is adsorbed to the pigment by using a small amount and does not run away in the wastewater, benzene, toluene, xylene, ethylbenzene, chlorobenzene, nitrobenzene, aniline, pyridine, quinoline, tetrahydrofuran, dioxane, ethyl acetate, isopropyl acetate, butyl acetate , Hexane, heptane, octane, nonane, decane, undecane, dodecane, cyclohexane, methylcyclohesasan, halogenated hydrocarbon, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, dimethylformamide, dimethyl sulfoxide, N-methylpyrrolidone, etc. May be. Moreover, you may mix and use 2 or more types of solvents as needed.
The amount of these water-soluble organic solvents used is preferably in the range of 50% by mass to 300% by mass and more preferably in the range of 100% by mass to 200% by mass with respect to the pigment.

In the present invention, sodium chloride, potassium chloride, calcium chloride, barium chloride, sodium sulfate and the like are used as the water-soluble inorganic salt.
The amount of the water-soluble inorganic salt used is preferably 1 to 50 times the mass of the organic pigment, and a larger amount has a grinding effect, but from the viewpoint of productivity, a more preferred amount is 1 to 10 times the mass. is there.
In order to prevent dissolution of the water-soluble inorganic salt, the water content in the liquid composition to be ground is preferably 1% by mass or less.

In the present invention, when a liquid composition containing a pigment, a water-soluble organic solvent, and a water-soluble inorganic salt is ground, a wet pulverizing apparatus such as the kneader described above may be used. There are no particular restrictions on the operating conditions of this wet pulverizer, but the operating conditions when the apparatus is a kneader are used to rotate the blades in the apparatus in order to effectively proceed grinding with pulverizing media (water-soluble inorganic salt). The number is preferably 10 rpm to 200 rpm, and a relatively large biaxial rotation ratio is preferable because the grinding effect is large. The operation time is preferably 1 to 8 hours in combination with the dry pulverization time, and the internal temperature of the apparatus is preferably 50 ° C to 150 ° C. Further, the water-soluble inorganic salt that is a pulverizing medium preferably has a pulverized particle size of 5 μm to 50 μm, a sharp particle size distribution, and a spherical shape.
The mixture after milling as described above is mixed with warm water at 80 ° C. to dissolve the water-soluble organic solvent and the water-soluble inorganic salts, and then filtered, washed with water, dried in an oven, A pigment can be obtained.

In addition, when the above-described organic pigment is refined, by using a resin that is at least partially soluble in a water-soluble organic solvent in the liquid composition, the surface is coated with the resin. A processed pigment with little aggregation of the pigment can be obtained.
Here, as the resin that is used in obtaining the processed pigment and is at least partially soluble in the water-soluble organic solvent, a known resin used as a pigment dispersant can be used, and the above-described resin of the present invention can be used. Specific polymer compounds can also be used.

  5 mass%-50 mass% are preferable, as for content of the pigment in the pigment dispersion composition of this invention, 10 mass%-30 mass% are more preferable, and 10 mass%-20 mass% are still more preferable.

(Organic solvent)
The pigment dispersion composition of the present invention contains at least one organic solvent.
Examples of the organic solvent used in the pigment dispersion composition of the present invention include 1-methoxy-2-propyl acetate, 1-methoxy-2-propanol, ethylene glycol monomethyl ether, diethylene glycol monomethyl ether, ethyl acetate, butyl acetate, ethyl lactate, Examples include acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, n-propanol, 2-propanol, n-butanol, cyclohexanol, ethylene glycol, diethylene glycol, toluene, xylene, ethyl benzoate, and the like.
Further, the amount of the organic solvent added is appropriately selected according to the use of the pigment dispersion composition, etc., but when used for the preparation of the photocurable composition described later, from the viewpoint of handleability, the pigment is included. It can add so that solid content concentration may be 5 mass%-50 mass%.

(Other ingredients)
A pigment derivative is suitably used for the pigment dispersion composition of the present invention.
In the present invention, a part having affinity with the dispersant or a pigment derivative having a polar group introduced is adsorbed on the surface of the treated pigment, and this is used as an adsorption point of the dispersant, whereby the pigment is made into fine particles. It can be dispersed in the dispersion composition and re-aggregation can be prevented. That is, the pigment derivative has the effect of promoting the adsorption of the pigment dispersant by modifying the pigment surface.

Specifically, the pigment derivative is a compound in which an organic pigment is used as a base skeleton, and an acidic group, a basic group, or an aromatic group is introduced into a side chain as a substituent. Specific examples of organic pigments serving as a base skeleton include quinacridone pigments, phthalocyanine pigments, azo pigments, quinophthalone pigments, isoindoline pigments, isoindolinone pigments, quinoline pigments, diketopyrrolopyrrole pigments, benzoic acids. Examples include imidazolone pigments.
In addition, the host skeleton also includes light yellow aromatic polycyclic compounds such as naphthalene-based, anthraquinone-based, triazine-based, and quinoline-based compounds that are not generally called pigments.

  Examples of the pigment derivative in the present invention include JP-A-11-49974, JP-A-11-189732, JP-A-10-245501, JP-A-2006-265528, JP-A-8-295810, and JP-A-Hei. Those described in JP-A-11-199796, JP-A-2005-234478, JP-A-2003-240938, JP-A-2001-356210, and the like can be used.

When a pigment derivative is used in the pigment dispersion composition of the present invention, the amount used is preferably in the range of 1% by mass to 80% by mass with respect to the pigment, and 3% by mass to 65% by mass. More preferably, it is in the range of 5% by mass to 50% by mass. When the content is within this range, the pigment can be favorably dispersed while keeping the viscosity low, and the dispersion stability after dispersion can be improved.
By applying this pigment dispersion composition to the production of a color filter, a color filter having high transmittance, excellent color characteristics, and high contrast can be obtained.

  In the pigment dispersion composition of the present invention, a dispersant such as a surfactant can also be used.

(Preparation of pigment dispersion composition)
The pigment dispersion composition of the present invention can be prepared by passing through a mixing and dispersing step of mixing and dispersing using various mixers and dispersers.
The mixing and dispersing step preferably comprises kneading and dispersing followed by fine dispersion treatment, but kneading and dispersing can be omitted.

Specifically, the pigment dispersion composition of the present invention specifically includes, for example, a specific polymer compound, a pigment, and an organic solvent according to the present invention, a vertical or horizontal sand grinder, a pin mill, a slit mill, an ultrasonic disperser, etc. Can be obtained by performing fine dispersion treatment with beads made of glass, zirconia or the like having a particle diameter of 0.01 mm to 1 mm.
Before carrying out fine dispersion with beads, use a two-roll, three-roll, ball mill, tron mill, disper, kneader, conifer, homogenizer, blender, single- or twin-screw extruder, etc. It is also possible to carry out the kneading and dispersing process while giving.

  For details on kneading and dispersing, see T.W. C. “Paint Flow and Pigment Dispersion” by Patton (published by John Wiley and Sons, 1964) and the like, and the method described herein can also be applied to the present invention.

  Since the pigment dispersion composition of the present invention comprises the specific polymer compound of the present invention, it is excellent in pigment dispersibility and dispersion stability and can be used for various applications.

<Photocurable composition>
The photocurable composition of the present invention comprises the above-described pigment dispersion composition of the present invention, a polymerizable compound, and a photopolymerization initiator, and preferably further contains an alkali-soluble resin. Depending on the situation, other components may be included.
Hereinafter, each component contained in the photocurable composition of the present invention will be described in detail.

(Pigment dispersion composition)
The pigment dispersion composition contained in the photocurable composition of the present invention is the above-described pigment dispersion composition of the present invention.

  As content of the pigment dispersion composition in the photocurable composition of this invention, content of a pigment is 5 mass%-70 mass% with respect to the total solid (mass) of a photocurable composition. The quantity which becomes is preferable, and the quantity used as the range of 15 mass%-60 mass% is more preferable. When the content of the pigment dispersion composition is within this range, the color density is sufficient and effective in securing excellent color characteristics.

(Polymerizable compound)
The photocurable composition of the present invention contains at least one polymerizable compound.
The polymerizable compound that can be used in the present invention is an addition polymerizable compound having at least one ethylenically unsaturated double bond, and is a compound having at least one terminal ethylenically unsaturated bond, preferably two or more. To be elected. Such a compound group is widely known in the industrial field, and can be used without any particular limitation in the present invention. The polymerizable compound has a chemical form such as a monomer, a prepolymer, that is, a dimer, a trimer and an oligomer, or a mixture thereof and a copolymer thereof.

  Examples of monomers and copolymers thereof include unsaturated carboxylic acids (for example, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.), and esters and amides thereof. In this case, an ester of an unsaturated carboxylic acid and an aliphatic polyhydric alcohol compound, or an amide of an unsaturated carboxylic acid and an aliphatic polyvalent amine compound is used. In addition, an addition reaction product of an unsaturated carboxylic acid ester or amide having a nucleophilic substituent such as a hydroxyl group, amino group or mercapto group with a monofunctional or polyfunctional isocyanate or epoxy, and monofunctional or polyfunctional A dehydration condensation reaction product with a functional carboxylic acid is also preferably used. Further, an addition reaction product of an unsaturated carboxylic acid ester or amide having an electrophilic substituent such as an epoxy group or an epoxy group with a monofunctional or polyfunctional alcohol, amine or thiol, a halogen group or In addition, a substitution reaction product of an unsaturated carboxylic acid ester or amide having a leaving substituent such as a tosyloxy group and a monofunctional or polyfunctional alcohol, amine or thiol is also suitable. As another example, it is also possible to use a group of compounds substituted with unsaturated phosphonic acid, styrene, vinyl ether or the like instead of the unsaturated carboxylic acid.

  Specific examples of the monomer of an ester of an aliphatic polyhydric alcohol compound and an unsaturated carboxylic acid include acrylic acid esters such as ethylene glycol diacrylate, triethylene glycol diacrylate, 1,3-butanediol diacrylate, and tetramethylene glycol. Diacrylate, propylene glycol diacrylate, neopentyl glycol diacrylate, trimethylolpropane triacrylate, trimethylolpropane tri (acryloyloxypropyl) ether, trimethylolethane triacrylate, hexanediol diacrylate, 1,4-cyclohexanediol diacrylate , Tetraethylene glycol diacrylate, pentaerythritol diacrylate, pentaerythritol triacrylate , Pentaerythritol tetraacrylate, dipentaerythritol diacrylate, dipentaerythritol hexaacrylate, sorbitol triacrylate, sorbitol tetraacrylate, sorbitol pentaacrylate, sorbitol hexaacrylate, tri (acryloyloxyethyl) isocyanurate, polyester acrylate oligomer, isocyanuric acid Examples include EO-modified triacrylate, bisphenol EO-modified diacrylate, biphenol EO-modified diacrylate, hydrogenated bisphenol EO-modified diacrylate, and diphenyl sulfide EO-modified diacrylate.

  Methacrylic acid esters include tetramethylene glycol dimethacrylate, triethylene glycol dimethacrylate, neopentyl glycol dimethacrylate, trimethylolpropane trimethacrylate, trimethylolethane trimethacrylate, ethylene glycol dimethacrylate, 1,3-butanediol dimethacrylate, Hexanediol dimethacrylate, pentaerythritol dimethacrylate, pentaerythritol trimethacrylate, pentaerythritol tetramethacrylate, dipentaerythritol dimethacrylate, dipentaerythritol hexamethacrylate, sorbitol trimethacrylate, sorbitol tetramethacrylate, bis [p- (3-methacryloxy- 2-hydroxypro ) Phenyl] dimethyl methane, bis - [p- (methacryloxyethoxy) phenyl] dimethyl methane.

Itaconic acid esters include ethylene glycol diitaconate, propylene glycol diitaconate, 1,3-butanediol diitaconate, 1,4-butanediol diitaconate, tetramethylene glycol diitaconate, pentaerythritol diitaconate And sorbitol tetritaconate.
Examples of crotonic acid esters include ethylene glycol dicrotonate, tetramethylene glycol dicrotonate, pentaerythritol dicrotonate, and sorbitol tetradicrotonate. Examples of isocrotonic acid esters include ethylene glycol diisocrotonate, pentaerythritol diisocrotonate, and sorbitol tetraisocrotonate. Examples of maleic acid esters include ethylene glycol dimaleate, triethylene glycol dimaleate, pentaerythritol dimaleate, and sorbitol tetramaleate.

  Examples of other esters include aliphatic alcohol esters described in JP-B-51-47334 and JP-A-57-196231, JP-A-59-5240, JP-A-59-5241, and JP-A-2-226149. Those having the aromatic skeleton described above and those having an amino group described in JP-A-1-165613 are also preferably used. Furthermore, the ester monomers described above can also be used as a mixture.

  Specific examples of amide monomers of aliphatic polyvalent amine compounds and unsaturated carboxylic acids include methylene bis-acrylamide, methylene bis-methacrylamide, 1,6-hexamethylene bis-acrylamide, 1,6-hexamethylene bis. -Methacrylamide, diethylenetriamine trisacrylamide, xylylene bisacrylamide, xylylene bismethacrylamide and the like. Examples of other preferable amide monomers include those having a cyclohexylene structure described in JP-B-54-21726.

  In addition, urethane-based addition polymerizable compounds produced by using an addition reaction of isocyanate and hydroxyl group are also suitable, and specific examples thereof include, for example, one molecule described in JP-B-48-41708. A vinyl urethane containing two or more polymerizable vinyl groups in one molecule obtained by adding a vinyl monomer containing a hydroxyl group represented by the following general formula (a) to a polyisocyanate compound having two or more isocyanate groups. Compounds and the like.

Formula (a)
_{CH 2 = C (R) COOCH} 2 CH (R ') OH
(However, R and R ′ each represent H or CH _3. )

  Also, urethane acrylates such as those described in JP-A-51-37193, JP-B-2-32293, and JP-B-2-16765, JP-B-58-49860, JP-B-56-17654, Urethane compounds having an ethylene oxide skeleton described in JP-B-62-39417 and JP-B-62-39418 are also suitable. Further, by using addition polymerizable compounds having an amino structure or a sulfide structure in the molecule described in JP-A-63-277653, JP-A-63-260909, and JP-A-1-105238, It is possible to obtain a photopolymerizable composition excellent in the photosensitive speed.

  Other examples include polyester acrylates, epoxy resins and (meth) acrylic acid as described in JP-A-48-64183, JP-B-49-43191, JP-B-52-30490, and JP-A-52-30490. Mention may be made of polyfunctional acrylates and methacrylates such as reacted epoxy acrylates. Further, specific unsaturated compounds described in JP-B-46-43946, JP-B-1-40337 and JP-B-1-40336, vinylphosphonic acid compounds described in JP-A-2-25493, and the like can also be mentioned. . In some cases, a structure containing a perfluoroalkyl group described in JP-A-61-22048 is preferably used. Furthermore, Journal of Japan Adhesion Association vol. 20, no. 7, pages 300 to 308 (1984), which are introduced as photocurable monomers and oligomers, can also be used.

About these polymeric compounds, the details of usage methods, such as the structure, single use, combined use, and addition amount, can be arbitrarily set according to the performance design of the final colored photosensitive composition.
For example, it is selected from the following viewpoints. From the viewpoint of sensitivity, a structure having a large unsaturated group content per molecule is preferable, and in many cases, a bifunctional or higher functionality is preferable. Further, in order to increase the strength of the cured film, those having three or more functionalities are preferable, and furthermore, different functional numbers and different polymerizable groups (for example, acrylic acid ester, methacrylic acid ester, styrene compound, vinyl ether compound). It is also effective to adjust both sensitivity and intensity by using both of these.

In addition, the selection of the polymerized compound is also possible with respect to the compatibility and dispersibility with other components in the photocurable composition (for example, binder polymers such as alkali-soluble resins, photopolymerization initiators, and colorants (pigments)). The method of use is an important factor. For example, the compatibility may be improved by the use of a low-purity compound or a combination of two or more.
In addition, a specific structure may be selected for the purpose of improving the adhesion with a substrate or the like. The polymerizable compound is preferably used in the range of 5% by mass to 70% by mass, and more preferably 10% by mass to 60% by mass with respect to the non-volatile component in the photocurable composition. These may be used alone or in combination of two or more. In addition, as for the method of using the polymerizable compound, an appropriate structure, blending, and addition amount can be arbitrarily selected from the viewpoint of polymerization inhibition with respect to oxygen, resolution, fogging property, refractive index change, surface tackiness, and the like.

(Photopolymerization initiator)
Examples of the photopolymerization initiator constituting the photocurable composition of the present invention include halomethyloxadiazole described in JP-A-57-6096, JP-B-59-1281, JP-A-53-133428. Active halogen compounds such as halomethyl-s-triazine described in US Pat. Nos. 4,697, and the like, aromatic carbonyls such as ketals, acetals, or benzoin alkyl ethers described in US Pat. Compounds, aromatic ketone compounds such as benzophenones described in U.S. Pat. No. 4,199,420, (thio) xanthones or acridine compounds described in French Patent No. 2456741, JP-A-10-62986 Compounds such as coumarins or lophine dimers described in JP-A-8-01552 No. sulfonium organic boron complexes such as publications, and the like.

  As the photopolymerization initiator in the present invention, acetophenone, ketal, benzophenone, benzoin, benzoyl, xanthone, active halogen compounds (triazine, oxadiazole, coumarin), acridine, biimidazole An oxime ester type is preferable.

  Examples of the acetophenone photopolymerization initiator include 2,2-diethoxyacetophenone, p-dimethylaminoacetophenone, 2-hydroxy-2-methyl-1-phenyl-propan-1-one, p-dimethylaminoacetophenone, 4′-isopropyl-2-hydroxy-2-methyl-propiophenone, 1-hydroxy-cyclohexyl-phenyl-ketone, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1, Suitable examples include 2-tolyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropanone-1. be able to.

  Preferable examples of the ketal photopolymerization initiator include benzyl dimethyl ketal and benzyl-β-methoxyethyl acetal.

  Preferred examples of the benzophenone photopolymerization initiator include benzophenone, 4,4 ′-(bisdimethylamino) benzophenone, 4,4 ′-(bisdiethylamino) benzophenone, and 4,4′-dichlorobenzophenone. it can.

  Preferred examples of the benzoin-based or benzoyl-based photopolymerization initiator include benzoin isopropyl ether, zenzoin isobutyl ether, benzoin methyl ether, methyl o-benzoyl bezoate, and the like.

  Preferable examples of the xanthone photopolymerization initiator include diethylthioxanthone, diisopropylthioxanthone, monoisopropylthioxanthone, chlorothioxanthone, and the like.

  Examples of the active halogen compound (triazine-based, oxadiazole-based, coumarin-based) include 2,4-bis (trichloromethyl) -6-p-methoxyphenyl-s-triazine, 2,4-bis (trichloromethyl). ) -6-p-methoxystyryl-s-triazine, 2,4-bis (trichloromethyl) -6- (1-p-dimethylaminophenyl) -1,3-butadienyl-s-triazine, 2,4-bis (Trichloromethyl) -6-biphenyl-s-triazine, 2,4-bis (trichloromethyl) -6- (p-methylbiphenyl) -s-triazine, p-hydroxyethoxystyryl-2,6-di (trichloromethyl) ) -S-triazine, methoxystyryl-2,6-di (trichloromethyl-s-triazine, 3,4-dimethoxystyryl -2,6-di (trichloromethyl) -s-triazine, 4-benzoxolane-2,6-di (trichloromethyl) -s-triazine, 4- (o-bromo-pN, N- (di) Ethoxycarbonylamino) -phenyl) -2,6-di (chloromethyl) -s-triazine, 4- (pN, N- (diethoxycarbonylamino) -phenyl) -2,6-di (chloromethyl) -S-triazine, 2-trichloromethyl-5-styryl-1,3,4-oxodiazole, 2-trichloromethyl-5- (cyanostyryl) -1,3,4-oxodiazole, 2-trichloromethyl -5- (naphth-1-yl) -1,3,4-oxodiazole, 2-trichloromethyl-5- (4-styryl) styryl-1,3,4-oxodiazole, 3-methyl-5 -A No-((s-triazin-2-yl) amino) -3-phenylcoumarin, 3-chloro-5-diethylamino-((s-triazin-2-yl) amino) -3-phenylcoumarin, 3-butyl- Preferable examples include 5-dimethylamino-((s-triazin-2-yl) amino) -3-phenylcoumarin.

  Preferable examples of the acridine photopolymerization initiator include 9-phenylacridine, 1,7-bis (9-acridinyl) heptane, and the like.

  Examples of the biimidazole photopolymerization initiator include 2- (o-chlorophenyl) -4,5-diphenylimidazolyl dimer, 2- (o-methoxyphenyl) -4,5-diphenylimidazolyl dimer, Preferred examples include 2- (2,4-dimethoxyphenyl) -4,5-diphenylimidazolyl dimer.

  Examples of the oxime ester polymerization initiator include J.M. C. S. Perkin II (1979) 1653-1660), J. MoI. C. S. Perkin II (1979) 156-162, Journal of Photopolymer Science and Technology (1995) 202-232, JP-A 2000-66385, compounds described in JP-A 2000-80068, JP-T 2004-534797 Compounds and the like.

  In addition to the above, 1-phenyl-1,2-propanedione-2- (o-ethoxycarbonyl) oxime, O-benzoyl-4 ′-(benzmercapto) benzoyl-hexyl-ketoxime, 2,4,6-trimethylphenyl Examples thereof include carbonyl-diphenyl phosphonyl oxide and hexafluorophospho-trialkylphenyl phosphonium salt.

In this invention, it is not limited to the above photoinitiator, Other well-known things can also be used. For example, a vicinal polykettle aldonyl compound described in US Pat. No. 2,367,660 and an α-carbonyl compound described in US Pat. Nos. 2,367,661 and 2,367,670. An acyloin ether described in US Pat. No. 2,448,828, an α-hydrocarbon-substituted aromatic acyloin compound described in US Pat. No. 2,722,512, US Pat. , 046,127 and 2,951,758, a triarylimidazole dimer / p-aminophenyl ketone combination described in US Pat. No. 3,549,367, Benzothiazole compounds / trihalomethyl-s-triazine compounds described in JP-A-51-48516; C. S. Perkin II (1979) 1653-1660, J. MoI. C. S. Examples include Perkin II (1979) 156-162, Journal of Photopolymer Science and Technology (1995) 202-232, and oxime ester compounds described in JP-A No. 2000-66385.
Moreover, these photoinitiators can also be used together.

  As content in the photocurable composition of a photoinitiator, 0.1 mass%-10.0 mass% are preferable with respect to the total solid of this composition, More preferably, 0.5 mass% It is -5.0 mass%. When the content of the photopolymerization initiator is within this range, the polymerization reaction can proceed well to form a film with good strength.

(Alkali-soluble resin)
The photocurable composition of the present invention preferably contains an alkali-soluble resin. By containing the alkali-soluble resin in the photocurable composition, the pattern formability can be further improved when the photocurable composition is applied to pattern formation by a photolithography method.

  The alkali-soluble resin is a linear organic polymer, and promotes at least one alkali-solubility in a molecule (preferably a molecule having an acrylic copolymer or a styrene copolymer as a main chain). It can be appropriately selected from alkali-soluble resins having a group (for example, carboxyl group, phosphoric acid group, sulfonic acid group, etc.). Of these, more preferred are those which are soluble in an organic solvent and can be developed with a weak alkaline aqueous solution.

  For production of the alkali-soluble resin, for example, a known radical polymerization method can be applied. Polymerization conditions such as temperature, pressure, type and amount of radical initiator, type of solvent, etc. when producing an alkali-soluble resin by radical polymerization can be easily set by those skilled in the art, and the conditions are determined experimentally. It can also be done.

  As the linear organic polymer, a polymer having a carboxylic acid in the side chain is preferable. For example, JP-A-59-44615, JP-B-54-34327, JP-B-58-12777, JP-B-54-25957, JP-A-59-53836, JP-A-59-71048 As described, methacrylic acid copolymer, acrylic acid copolymer, itaconic acid copolymer, crotonic acid copolymer, maleic acid copolymer, partially esterified maleic acid copolymer, etc., and side chain Preferred examples also include acidic cellulose derivatives having a carboxylic acid, and polymers having a hydroxyl group and an acid anhydride added to the polymer, and a polymer having a (meth) acryloyl group in the side chain.

Among these, benzyl (meth) acrylate / (meth) acrylic acid copolymers and multi-component copolymers composed of benzyl (meth) acrylate / (meth) acrylic acid / other monomers are particularly suitable.
In addition, those obtained by copolymerizing 2-hydroxyethyl methacrylate are also useful.

  In addition to the above, 2-hydroxypropyl (meth) acrylate / polystyrene macromonomer / benzyl methacrylate / methacrylic acid copolymer, 2-hydroxy-3-phenoxypropyl acrylate / polymethyl methacrylate described in JP-A-7-140654 Macromonomer / benzyl methacrylate / methacrylic acid copolymer, 2-hydroxyethyl methacrylate / polystyrene macromonomer / methyl methacrylate / methacrylic acid copolymer, 2-hydroxyethyl methacrylate / polystyrene macromonomer / benzyl methacrylate / methacrylic acid copolymer Etc.

  As a suitable thing of alkali-soluble resin in this invention, the copolymer of (meth) acrylic acid and the other monomer copolymerizable with this is mentioned especially. Here, (meth) acrylic acid is a general term that combines acrylic acid and methacrylic acid, and (meth) acrylate is also a general term for acrylate and methacrylate.

Examples of other monomers copolymerizable with (meth) acrylic acid include alkyl (meth) acrylates, aryl (meth) acrylates, and vinyl compounds. Here, the hydrogen atom of the alkyl group and the aryl group may be substituted with a substituent.
Specific examples of the alkyl (meth) acrylate and aryl (meth) acrylate include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, pentyl ( Examples include meth) acrylate, hexyl (meth) acrylate, octyl (meth) acrylate, phenyl (meth) acrylate, benzyl (meth) acrylate, tolyl (meth) acrylate, naphthyl (meth) acrylate, cyclohexyl (meth) acrylate, and the like. it can.

Examples of the vinyl compound include styrene, α-methylstyrene, vinyl toluene, glycidyl methacrylate, acrylonitrile, vinyl acetate, N-vinyl pyrrolidone, tetrahydrofurfuryl methacrylate, phenylmaleimide, benzylmaleimide, polystyrene macromonomer, and polymethyl. Methacrylate macromonomer, CH ₂ = CR ¹ R ² , CH ₂ = C (R ¹ ) (COOR ³ ) [wherein R ¹ represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and R ² represents the number of carbon atoms. 6-10 of an aromatic hydrocarbon ring, ^{R 3} represents an alkyl group or an aralkyl group having 6 to 12 carbon atoms having 1 to 8 carbon atoms. And the like.

These other copolymerizable monomers can be used singly or in combination of two or more.
Preferred other copolymerizable monomers are selected from CH ₂ ═CR ¹ R ² , CH ₂ ═C (R ¹ ) (COOR ³ ), phenyl (meth) acrylate, benzyl (meth) acrylate, and styrene. At least one selected from the group consisting of CH ₂ ═CR ¹ R ² and / or CH ₂ ═C (R ¹ ) (COOR ³ ).

  The content of the alkali-soluble resin in the photocurable composition is preferably 1% by mass to 30% by mass, and more preferably 1% by mass to 25% by mass with respect to the total solid content of the composition. Especially preferably, it is 2 mass%-20 mass%.

(solvent)
In general, the photocurable composition of the present invention can be suitably prepared by using a solvent together with the aforementioned components.
Examples of the solvent used include esters such as ethyl acetate, n-butyl acetate, isobutyl acetate, amyl formate, isoamyl acetate, isobutyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, alkyl esters, and lactic acid. Methyl, ethyl lactate, methyl oxyacetate, ethyl oxyacetate, butyl oxyacetate, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate; methyl 3-oxypropionate, ethyl 3-oxypropionate Alkyl 3-esters such as methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl 2-oxypropionate, 2-oxy Ethyl propionate, propyl 2-oxypropionate, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, 2-oxy- Methyl 2-methylpropionate, ethyl 2-oxy-2-methylpropionate, methyl 2-methoxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate, methyl pyruvate, ethyl pyruvate, pyruvate Propyl, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutanoate, ethyl 2-oxobutanoate, etc .; ethers such as diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol No ethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate, propylene glycol propyl ether acetate, etc .; ketones such as methyl ethyl ketone , Cyclohexanone, 2-heptanone, 3-heptanone and the like; aromatic hydrocarbons such as toluene and xylene.

Among these, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl cellosolve acetate, ethyl lactate, diethylene glycol dimethyl ether, butyl acetate, methyl 3-methoxypropionate, 2-heptanone, cyclohexanone, propylene glycol methyl ether acetate, etc. Is preferred.
You may use a solvent in combination of 2 or more types besides using independently.

(Other ingredients)
In the photocurable composition of the present invention, if necessary, other than a sensitizing dye, an epoxy resin, a fluorinated organic compound, a thermal polymerization initiator, a thermal polymerization component, a thermal polymerization inhibitor, a filler, and the above alkali-soluble resin. Various additives such as a polymer compound, a surfactant, an adhesion promoter, an antioxidant, an ultraviolet absorber, and an aggregation inhibitor.

[Sensitizing dye]
A sensitizing dye may be added to the photocurable composition of the present invention as necessary. The sensitizing dye can accelerate the radical generating reaction of the photopolymerization initiator and the polymerization reaction of the polymerizable compound by the exposure at a wavelength that can be absorbed by the sensitizing dye.
Examples of such a sensitizing dye include a known spectral sensitizing dye or dye, or a dye or pigment that absorbs light and interacts with a photopolymerization initiator.

(Spectral sensitizing dye or dye)
Spectral sensitizing dyes or dyes preferred as the sensitizing dye used in the present invention are polynuclear aromatics (eg, pyrene, perylene, triphenylene), xanthenes (eg, fluorescein, eosin, erythrosine, rhodamine B, rose bengal). ), Cyanines (eg, thiacarbocyanine, oxacarbocyanine), merocyanines (eg, merocyanine, carbomerocyanine), thiazines (eg, thionine, methylene blue, toluidine blue), acridines (eg, acridine orange, chloroflavin) , Acriflavine), phthalocyanines (eg, phthalocyanine, metal phthalocyanine), porphyrins (eg, tetraphenylporphyrin, central metal-substituted porphyrin), chlorophylls (eg, chlorophyll) Chlorophyllin, center metal-substituted chlorophyll), metal complexes (for example, the following compound), anthraquinones (e.g., anthraquinone), squaryliums (e.g., squarylium), and the like.

The example of a more preferable spectral sensitizing dye or dye is illustrated below.
A styryl dye described in JP-B-37-13034; a cationic dye described in JP-A-62-143044; a quinoxalinium salt described in JP-B-59-24147; described in JP-A-64-33104 A new methylene blue compound; anthraquinones described in JP-A 64-56767; benzoxanthene dyes described in JP-A-2-17714; acridines described in JP-A-2-226148 and JP-A-2-226149 Pyryllium salts described in JP-B-40-28499; Cyanines described in JP-B-46-42363; Benzofuran dyes described in JP-A-2-63053; JP-A-2-85858, JP-A-2-216154 Conjugated ketone dyes; dyes described in JP-A-57-1605; Azocinnamylidene derivatives described in Japanese Patent No. 0321; cyanine dyes described in Japanese Patent Laid-Open No. 1-287105; Japanese Patent Laid-Open Nos. 62-31844, 62-31848, 62-1443043 Xanthene dyes described above; aminostyryl ketone described in JP-B-59-28325; dye described in JP-A-2-17943; merocyanine dye described in JP-A-2-244050; described in JP-B-59-28326 Merocyanine dyes described in JP-A-59-89303; merocyanine dyes described in JP-A-8-129257; benzopyran dyes described in JP-A-8-334897.

(Dye having maximum absorption wavelength at 350 nm to 450 nm)
Other preferred embodiments of the sensitizing dye include dyes belonging to the following compound group and having a maximum absorption wavelength at 350 nm to 450 nm.
For example, polynuclear aromatics (eg, pyrene, perylene, triphenylene), xanthenes (eg, fluorescein, eosin, erythrosine, rhodamine B, rose bengal), cyanines (eg, thiacarbocyanine, oxacarbocyanine), merocyanine (Eg, merocyanine, carbomerocyanine), thiazines (eg, thionine, methylene blue, toluidine blue), acridines (eg, acridine orange, chloroflavin, acriflavine), anthraquinones (eg, anthraquinone), squalium (eg, , Squalium).

  More preferable examples of the sensitizing dye include compounds represented by the following general formulas (i) to (v).

(In Formula (i), A ¹ represents a sulfur atom or NR ⁵⁰ , R ⁵⁰ represents an alkyl group or an aryl group, and L ² represents the basic nucleus of the dye in combination with the adjacent A ¹ and the adjacent carbon atom. Represents a non-metallic atomic group to be formed, R ⁵¹ and R ⁵² each independently represent a hydrogen atom or a monovalent non-metallic atomic group, and R ⁵¹ and R ⁵² are bonded to each other to form an acidic nucleus of the dye. W represents an oxygen atom or a sulfur atom.)

(In Formula (ii), Ar ¹ and Ar ² each independently represent an aryl group, and are linked via a bond with —L ³ —, where L ³ represents —O— or —S—. W is synonymous with that shown in the general formula (i).)

(In the formula (iii), A ² represents a sulfur atom or NR ⁵⁹ , L ⁴ represents a nonmetallic atomic group that forms a basic nucleus of a dye in combination with an adjacent A ² and a carbon atom, R ⁵³ , R ⁵⁴ , R ⁵⁵ , R ⁵⁶ , R ⁵⁷ and R ⁵⁸ each independently represent a monovalent non-metallic atomic group, and R ⁵⁹ represents an alkyl group or an aryl group.)

(In the formula (iv), A ³ and A ⁴ each independently represent —S— or —NR ⁶² — or —NR ⁶³ —, and R ⁶² and R ⁶³ each independently represent a substituted or unsubstituted alkyl group, substituted Or an unsubstituted aryl group, and L ⁵ and L ⁶ each independently represent a nonmetallic atomic group that forms a basic nucleus of a dye together with adjacent A ³ , A ⁴ and an adjacent carbon atom; ⁶⁰ and R ⁶¹ are each independently a monovalent non-metallic atomic group or can be bonded to each other to form an aliphatic or aromatic ring.)

(In the formula (v), R ⁶⁶ represents an aromatic ring or a hetero ring which may have a substituent, and A ⁵ represents an oxygen atom, a sulfur atom or —NR ⁶⁷ —. R ⁶⁴ , R ⁶⁵ and R ⁶⁷ each independently represents a hydrogen atom or a monovalent nonmetallic atomic group, and R ⁶⁷ and R ⁶⁴ , and R ⁶⁵ and R ⁶⁷ may be bonded together to form an aliphatic or aromatic ring, respectively. it can.)

  Preferable specific examples of the compounds represented by the general formulas (i) to (v) include those shown below.

  With respect to the above-mentioned sensitizing dye, various chemical modifications as described below can be performed for the purpose of improving the characteristics of the photocurable composition of the present invention. For example, by combining a sensitizing dye and an addition polymerizable compound structure (for example, an acryloyl group or a methacryloyl group) by a method such as a covalent bond, an ionic bond, or a hydrogen bond, An improvement in the effect of suppressing the unnecessary precipitation of the dye from the crosslinked cured film can be obtained.

The content of the sensitizing dye is preferably 0.01% by mass to 20% by mass, more preferably 0.01% by mass to 10% by mass, and still more preferably with respect to the total solid content of the photocurable composition. Is 0.1% by mass to 5% by mass.
When the content of the sensitizing dye is within this range, it is highly sensitive to the exposure wavelength of the ultra-high pressure mercury lamp, and it is preferable in terms of development margin and pattern formability as well as deep film curability.

(Epoxy resin)
The photocurable composition of the present invention can use an epoxy resin as a thermal polymerization component in order to increase the strength of the formed coating film.
The epoxy resin is a compound having two or more epoxy rings in the molecule such as bisphenol A type, cresol novolac type, biphenyl type, and alicyclic epoxy compound.
For example, as bisphenol A type, Epototo YD-115, YD-118T, YD-127, YD-128, YD-134, YD-8125, YD-7011R, ZX-1059, YDF-8170, YDF-170 and the like ( In addition to Toto Kasei Co., Ltd., Denacol EX-1101, EX-1102, EX-1103 and the like (Nagase Chemical Co., Ltd.), Plaxel GL-61, GL-62, G101, G102 (Made by Daicel Chemical) Similar bisphenol F type and bisphenol S type can also be mentioned. Epoxy acrylates such as Ebecryl 3700, 3701, and 600 (manufactured by Daicel UC) can also be used.

Examples of the cresol novolak type include Epototo YDPN-638, YDPN-701, YDPN-702, YDPN-703, YDPN-704, etc. (manufactured by Tohto Kasei), Denacol EM-125, etc. (manufactured by Nagase Kasei), and biphenyl type As alicyclic epoxy compounds such as 3,5,3 ′, 5′-tetramethyl-4,4′-diglycidylbiphenyl, Celoxide 2021, 2081, 2083, 2085, Epolide GT-301, GT-302, GT-401, GT-403, EHPE-3150 (manufactured by Daicel Chemical), Santo Tote ST-3000, ST-4000, ST-5080, ST-5100 and the like (manufactured by Toto Kasei), Epilon 430, 673, 695, 850S, 4032 (Dainippon Ink) It can be mentioned.
1,1,2,2-tetrakis (p-glycidyloxyphenyl) ethane, tris (p-glycidyloxyphenyl) methane, triglycidyltris (hydroxyethyl) isocyanurate, o-phthalic acid diglycidyl ester, terephthalic acid Diglycidyl ester, amine type epoxy resins such as Epototo YH-434 and YH-434L, and glycidyl ester obtained by modifying dimer acid in the skeleton of bisphenol A type epoxy resin can also be used.

Among these, “molecular weight / number of epoxy rings” is preferably 100 or more, and more preferably 130 to 500. If the “molecular weight / number of epoxy rings” is small, the curability is high, the shrinkage during curing is large, and if it is too large, the curability is insufficient, the reliability is poor, and the flatness is poor.
Specific preferred compounds include Epototo YD-115, 118T, 127, YDF-170, YDPN-638, YDPN-701, Plaxel GL-61, GL-62, 3,5,3 ', 5'-tetramethyl. -4,4 'diglycidyl biphenyl, ceroxide 2021, 2081, epolide GT-302, GT-403, EHPE-3150, etc. are mentioned.

(Fluorine organic compounds)
The photocurable composition of the present invention contains a fluorine-based organic compound, thereby improving liquid properties (particularly fluidity) when used as a coating solution, and improving coating thickness uniformity and liquid-saving properties. be able to.
That is, the photocurable composition containing a fluorine-based organic compound reduces the interfacial tension between the coated surface and the coating liquid, improves the wettability to the coated surface, and improves the coating property to the coated surface. Therefore, even when a thin film of about several μm is formed with a small amount of liquid, it is effective in that a film having a uniform thickness with small thickness unevenness can be formed.

  The fluorine content in the fluorine-based organic compound is preferably 3% by mass to 40% by mass, more preferably 5% by mass to 30% by mass, and particularly preferably 7% by mass to 25% by mass. When the fluorine content is within this range, it is effective in terms of coating thickness uniformity and liquid-saving properties, and the solubility in the composition is also good.

  Examples of the fluorinated organic compound include MegaFuck F171, F172, F173, F177, F141, F142, F143, F144, R30, and F437 (above, Dainippon Ink and Chemicals, Inc.) Manufactured), FLORARD FC430, FC431, FC171 (above, manufactured by Sumitomo 3M), Surflon S-382, SC-101, SC-103, SC-104, SC-105, SC1068, SC-381, SC-383, S393, and KH-40 (manufactured by Asahi Glass Co., Ltd.).

In particular, the fluorine-based organic compound is effective in preventing coating unevenness and thickness unevenness when forming the thin coating film using the colored photosensitive composition of the present invention. Furthermore, it is also effective when the colored photosensitive composition of the present invention is applied to slit coating that easily causes liquid breakage.
The addition amount of the fluorine-based organic compound is preferably 0.001% by mass to 2.0% by mass, and more preferably 0.005% by mass to 1.0% by mass with respect to the total mass of the colored photosensitive composition. is there.

(Thermal polymerization initiator)
It is also effective to include a thermal polymerization initiator in the photocurable composition of the present invention.
Examples of the thermal polymerization initiator include various azo compounds and peroxide compounds.
Examples of the azo compounds include azobis compounds, and examples of the peroxide compounds include ketone peroxide, peroxyketal, hydroperoxide, dialkyl peroxide, diacyl peroxide, peroxyester, and peroxide. Examples thereof include oxydicarbonate.

(Surfactant)
Various surfactants may be added to the photocurable composition of the present invention from the viewpoint of improving coatability. As the surfactant, various nonionic, cationic, and anionic surfactants can be used in addition to the above-mentioned fluorine-based surfactant.
Among these, the above-described nonionic surfactants are preferably fluorine-based surfactants having a perfluoroalkyl group and nonionic surfactants.
Specific examples of the fluorosurfactant include the MegaFac (registered trademark) series manufactured by Dainippon Ink and Chemicals, Inc., and the Fluorad (registered trademark) series manufactured by 3M.

Specific examples of cationic surfactants include phthalocyanine derivatives (commercially available product EFKA-745 (manufactured by Morishita Sangyo)), organosiloxane polymer KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), (meth) acrylic acid (co) Polymer Polyflow No. 75, no. 90, no. 95 (manufactured by Kyoeisha Yushi Chemical Co., Ltd.), W001 (manufactured by Yusho Co., Ltd.) and the like.
Specific examples of nonionic surfactants include polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octyl phenyl ether, polyoxyethylene nonyl phenyl ether, polyethylene glycol dilaurate, polyethylene glycol dilaurate. Stearate, sorbitan fatty acid ester (pluronic L10, L31, L61, L62, 10R5, 17R2, 25R2, manufactured by BASF, Tetronic 304, 701, 704, 901, 904, 150R1, etc. are mentioned.
Specific examples of the anionic surfactant include W004, W005, W017 (manufactured by Yusho Co., Ltd.) and the like.

(Other additives)
In addition to the above, various additives can be added to the photocurable composition of the present invention.
Specific examples of additives include fillers such as glass and alumina; itaconic acid copolymer, crotonic acid copolymer, maleic acid copolymer, partially esterified maleic acid copolymer, acidic cellulose derivative, and hydroxyl group Alkali-soluble resins such as those obtained by adding acid anhydride to polymers, alcohol-soluble nylon, phenoxy resin formed from bisphenol A and epichlorohydrin; EFKA-46, EFKA-47, EFKA-47EA, EFKA polymer 100, Polymer dispersing agents such as EFKA polymer 400, EFKA polymer 401, EFKA polymer 450 (manufactured by Morishita Industrial Co., Ltd.), disperse aid 6, disperse aid 8, disperse aid 15, disperse aid 9100 (manufactured by Sannopco); Solsparse 3000, 5000, 000, 12000, 13240, 13940, 17000, 24000, 26000, 28000 and other Solsperse dispersants (manufactured by Geneca); Adeka Pluronic L31, F38, L42, L44, L61, L64, F68, L72, P95, F77, P84 , F87, P94, L101, P103, F108, L121, P-123 (Asahi Denka) and Isonet S-20 (Sanyo Kasei); 2- (3-t-butyl-5-methyl-2-hydroxy UV absorbers such as phenyl) -5-chlorobenzotriazole and alkoxybenzophenone; and anti-aggregation agents such as sodium polyacrylate.

In the case where the alkali solubility of the uncured part is promoted and the developability of the photocurable composition is further improved, the photocurable composition of the present invention contains an organic carboxylic acid, preferably a molecular weight of 1000 or less. It is preferable to add a low molecular weight organic carboxylic acid.
Specifically, for example, aliphatic monocarboxylic acids such as formic acid, acetic acid, propionic acid, butyric acid, valeric acid, pivalic acid, caproic acid, diethyl acetic acid, enanthic acid, caprylic acid; oxalic acid, malonic acid, succinic acid, Aliphatic dicarboxylic acids such as glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, brassic acid, methylmalonic acid, ethylmalonic acid, dimethylmalonic acid, methylsuccinic acid, tetramethylsuccinic acid, citraconic acid; Aliphatic tricarboxylic acids such as tricarballylic acid, aconitic acid, camphoric acid; aromatic monocarboxylic acids such as benzoic acid, toluic acid, cumic acid, hemelitic acid, mesitylene acid; phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid, Aromatic polycarboxylic acids such as trimesic acid, melophanoic acid, pyromellitic acid; phenylacetic acid Hydratropic acid, hydrocinnamic acid, mandelic acid, phenyl succinic acid, atropic acid, cinnamic acid, methyl cinnamate, benzyl cinnamate, cinnamylidene acetic acid, coumaric acid, other carboxylic acids such as umbellic acid.

Furthermore, you may add a thermal polymerization inhibitor to the photocurable composition of this invention.
Examples of the thermal polymerization inhibitor include hydroquinone, p-methoxyphenol, di-t-butyl-p-cresol, pyrogallol, t-butylcatechol, benzoquinone, 4,4′-thiobis (3-methyl-6-t- Butylphenol), 2,2′-methylenebis (4-methyl-6-tert-butylphenol), 2-mercaptobenzimidazole, and the like are useful.

  The photocurable composition of the present invention is a polymerizable compound, a photopolymerization initiator, and, if necessary, an alkali-soluble resin, a solvent, and a surfactant with respect to the above-described pigment dispersion composition of the present invention. It can prepare by adding additives, such as.

Since the photocurable composition of the present invention includes the pigment dispersion composition of the present invention containing the specific polymer compound of the present invention, it is excellent in pigment dispersibility, and the color characteristics of the cured film formed thereby. Also excellent.
Therefore, it can be suitably used to form a colored region of a color filter that requires good color characteristics.

<Color filter>
The color filter of the present invention has a colored region formed of the above-described photocurable composition of the present invention on a substrate.
Here, the coloring region includes both a three-color or four-color coloring pattern (pixel portion) and a black matrix.
Hereinafter, the color filter of the present invention will be described in detail through its manufacturing method.

A method for producing the color filter of the present invention will be described.
First, the photocurable composition of the present invention is applied on a substrate directly or via another layer by a coating method such as spin coating, slit coating, cast coating, roll coating, bar coating, etc., and photocuring. A coating film made of the composition is formed (coating step). Thereafter, the coating film is exposed through a predetermined mask pattern (exposure process). After exposure, the uncured portion of the coating film is developed and removed with a developer (development process). By passing through these steps, a colored pattern composed of pixels of each color (3 colors or 4 colors) is formed, and a color filter can be obtained.
By such a method, a color filter used for a liquid crystal display element or a solid-state imaging element can be manufactured with low process difficulty, high quality, and low cost.
Hereinafter, each step will be described in detail.

[Coating process]
First, the substrate used in the coating process will be described.
As a substrate used for the color filter of the present invention, for example, alkali-free glass, soda glass, Pyrex (registered trademark) glass, quartz glass used for liquid crystal display elements and the like, and those obtained by attaching a transparent conductive film to these, And a photoelectric conversion element substrate used for a solid-state imaging device or the like, for example, a silicone substrate or a plastic substrate.
On these substrates, a black matrix for isolating each pixel may be formed, or a transparent resin layer may be provided for promoting adhesion.
The plastic substrate preferably has a gas barrier layer and / or a solvent resistant layer on its surface.

In addition, a driving substrate (hereinafter referred to as “TFT type liquid crystal driving substrate”) on which a thin film transistor (TFT) of a thin film transistor (TFT) type color liquid crystal display device is disposed is used. In addition, a color filter formed using the photocurable composition of the present invention can be formed to produce a color filter.
Examples of the substrate in the TFT type liquid crystal driving substrate include glass, silicone, polycarbonate, polyester, aromatic polyamide, polyamideimide, and polyimide. These substrates may be subjected to appropriate pretreatment such as chemical treatment with a silane coupling agent or the like, plasma treatment, ion plating, sputtering, gas phase reaction method, vacuum deposition, etc., if desired. For example, a substrate in which a passivation film such as a silicon nitride film is formed on the surface of the TFT liquid crystal driving substrate can be used.

In the coating step, the method for applying the photocurable composition of the present invention to the substrate is not particularly limited, but a method using a slit nozzle such as a slit-and-spin method or a spinless coating method (hereinafter, Slit nozzle coating method) is preferable.
In the slit nozzle coating method, the slit-and-spin coating method and the spinless coating method have different conditions depending on the size of the coated substrate. For example, a fifth generation glass substrate (1100 mm × 1250 mm) is coated by the spinless coating method. In this case, the discharge amount of the colored photosensitive composition from the slit nozzle is usually 500 microliter / second to 2000 microliter / second, preferably 800 microliter / second to 1500 microliter / second. The speed is usually 50 mm / second to 300 mm / second, preferably 100 mm / second to 200 mm / second.
Moreover, as solid content of the photocurable composition used at the application | coating process, it is 10%-20% normally, Preferably it is 13%-18%.

When forming the coating film by the photocurable composition of this invention on a board | substrate, as thickness (after a prebaking process) of this coating film, it is generally 0.3 micrometer-5.0 micrometers, Preferably 0.5 micrometer-4 0.0 μm, most desirably 0.5 μm to 3.0 μm.
In the case of a color filter for a solid-state image sensor, the thickness of the coating film (after pre-baking) is preferably in the range of 0.5 μm to 5.0 μm.

In the coating process, usually, a pre-bake treatment is performed after coating. If necessary, vacuum treatment can be performed before pre-baking.
The vacuum drying conditions are such that the degree of vacuum is usually about 0.1 to 1.0 torr, preferably about 0.2 to 0.5 torr.
The pre-bake treatment is performed in a temperature range of 50 ° C. to 140 ° C., preferably about 70 ° C. to 110 ° C. using a hot plate, an oven, etc., and can be performed under conditions of 10 seconds to 300 seconds. Note that high-frequency treatment or the like may be used in combination with the pre-bake treatment. The high frequency treatment can be used alone.

[Exposure process]
In the exposure step, the coating film made of the photocurable composition formed as described above is exposed through a predetermined mask pattern.
The radiation used for exposure is particularly preferably ultraviolet rays such as g-line, h-line, i-line, and j-line.
In manufacturing a color filter for a liquid crystal display device, exposure using mainly h-line and i-line is preferably used by a proximity exposure machine and a mirror projection exposure machine.
Further, when manufacturing a color filter for a solid-state image sensor, it is preferable to mainly use i-line in a stepper exposure machine.
When manufacturing a color filter using a TFT type liquid crystal driving substrate, the photomask used has a through hole or a U-shaped depression in addition to a pattern for forming a pixel (colored pattern). The thing in which the pattern for forming is provided is used.

[Development process]
In the development step, the uncured portion of the coating film after exposure is eluted in the developer, and only the cured portion remains on the substrate.
The development temperature is usually 20 ° C. to 30 ° C., and the development time is 20 seconds to 90 seconds.
Any developer can be used as long as it dissolves the coating film of the photocurable composition in the uncured portion while not dissolving the cured portion.
Specifically, a combination of various organic solvents or an alkaline aqueous solution can be used.

Examples of the organic solvent used for development include the solvents described above that can be used in preparing the photocurable composition of the present invention.
Examples of the alkaline aqueous solution include sodium hydroxide, potassium hydroxide, sodium carbonate, sodium hydrogen carbonate, sodium oxalate, sodium metasuccinate, aqueous ammonia, ethylamine, diethylamine, dimethylethanolamine, tetramethylammonium hydroxide. , Tetraethylammonium hydroxide, choline, pyrrole, piperidine, alkaline compounds such as 1,8-diazabicyclo- [5,4,0] -7-undecene, in a concentration of 0.001% by mass to 10% by mass, preferably 0 An alkaline aqueous solution dissolved so as to be 0.01 mass% to 1 mass% can be mentioned.
An appropriate amount of a water-soluble organic solvent such as methanol or ethanol, a surfactant, or the like can be added to the alkaline aqueous solution.

The development method may be any of a dip method, a shower method, a spray method, and the like, and may be combined with a swing method, a spin method, an ultrasonic method, or the like. Before the developer is touched, the surface to be developed can be previously moistened with water or the like to prevent uneven development. In addition, development can be performed with the substrate inclined.
Further, when manufacturing a color filter for a solid-state image sensor, paddle development is also used.

After the development process, a rinsing process for washing and removing excess developer is performed, followed by drying, followed by heat treatment (post-baking) to complete the curing.
The rinsing process is usually performed with pure water, but in order to save liquid, pure water is used in the final cleaning, and used pure water is used at the initial stage of cleaning. You may use the method of using ultrasonic irradiation together.

After the rinse treatment, draining and drying are performed, and then a heat treatment of about 200 ° C. to 250 ° C. is usually performed.
In this heat treatment (post-bake), the coating film after development is continuously or batch-treated using a heating means such as a hot plate, a convection oven (hot air circulation dryer) or a high-frequency heater so as to satisfy the above conditions. It can be done with a formula.

By sequentially repeating the above steps for each color according to the desired number of hues, it is possible to produce a color filter in which a cured film (colored pattern) colored in a plurality of colors is formed.
Since the color filter of the present invention has high contrast, small color density unevenness, and good color characteristics, it can be suitably used for a solid-state imaging device or a liquid crystal display device.

As for the use of the photocurable composition of the present invention, the description has mainly focused on the application to the color pattern of the color filter. However, the photocurable composition of the present invention is also used to form a black matrix that isolates the color pattern (pixels) constituting the color filter. Can be applied.
The black matrix on the substrate is a colored photosensitive composition containing a black pigment processed pigment such as carbon black or titanium black, and is subjected to coating, exposure, and development steps. It can be formed by baking.

<Liquid crystal display device, solid-state imaging device>
The color filter of the present invention can be suitably used for liquid crystal display elements and solid-state imaging elements. More specifically, for example, an alignment film is formed on the inner surface side of the color filter, is opposed to the electrode substrate, and a gap portion is filled with liquid crystal and sealed to obtain a panel that is a liquid crystal display element. Further, for example, a solid-state imaging device can be obtained by forming a color filter on the light receiving device.

  EXAMPLES Hereinafter, although an Example demonstrates this invention further more concretely, this invention is not limited to a following example. Unless otherwise specified, “%” and “part” are based on mass.

<Synthesis of dispersant according to the present invention>
[Synthesis Example 1]
114.1 g of ε-caprolactone and 18.6 g of dodecanol were reacted at 90 ° C. for 8 hours in the presence of 0.5 g of monobutyltin catalyst. Itaconic anhydride 11.2g was thrown into this reaction material, and also it heated at 90 degreeC for 2 hours, and obtained the polycaprolactone compound (4-11).
This reaction solution, dipentaerythritol hexakis (3-mercaptopropionate) [DPMP; Sakai Chemical Industry Co., Ltd.] 39.1 g, and the following adsorption site, and a carbon-carbon double bond The compound (A-1) 58.4 g having 1-methoxypropanol was adjusted and dissolved so as to have a solid content concentration of 30% by mass, and heated to 70 ° C. in a nitrogen stream. To this, 0.06 g of 2,2′-azobis (2,4-dimethylvaleronitrile) [V-65, manufactured by Wako Pure Chemical Industries, Ltd.] was added and heated for 3 hours. Further, 0.06 g of V-65 was added and reacted at 70 ° C. for 3 hours under a nitrogen stream. By cooling to room temperature, a 30% solution of Dispersant 1 of the present invention shown below was obtained.

[Synthesis Example 2]
A 30% solution of the dispersant 2 of the present invention shown below was synthesized in the same manner as in Synthesis Example 1 except that the compound (A-1) was changed to 26.0 g of itaconic acid.

[Synthesis Example 3]
Dipentaerythritol hexakis (Similar to Synthesis Example 1 except that the amount of 3-mercaptopropionate was changed to 26.1 g and compound (A-1) was changed to 57.6 g of compound (A-2). A 30% solution of the dispersant 3 of the present invention shown below was synthesized.

[Synthesis Example 4]
114.1 g of ε-caprolactone and 7.9 g of octanoic acid were reacted at 150 ° C. for 8 hours in the presence of 0.5 g of titanium tetrabutoxide catalyst. To this reaction product, 12.5 g of allyl glycidyl ether was added and further heated at 90 ° C. for 2 hours to obtain a polycaprolactone compound (6-8).
19.6 g of this reaction solution, dipentaerythritol hexakis (3-mercaptopropionate) [DPMP; manufactured by Sakai Chemical Industry Co., Ltd.], and the following adsorption site, and a carbon-carbon double bond The compound (A-3) 23.2 g having 1-methoxypropanol was adjusted and dissolved so as to have a solid content concentration of 30% by mass, and heated to 70 ° C. under a nitrogen stream. To this, 0.06 g of 2,2′-azobis (2,4-dimethylvaleronitrile) [V-65, manufactured by Wako Pure Chemical Industries, Ltd.] was added and heated for 3 hours. Further, 0.06 g of V-65 was added and reacted at 70 ° C. for 3 hours under a nitrogen stream. By cooling to room temperature, the following 30% solution of the dispersant 4 of the present invention was obtained.

[Synthesis Example 5]
The same as in Synthesis Example 4 except that the amount of dipentaerythritol hexakis (3-mercaptopropionate) was changed to 39.1 g and the compound (A-3) was changed to 43.3 g of phenylmaleimide. A 30% solution of Dispersant 5 of the present invention was obtained.

[Synthesis Example 6]
Ε-caprolactone 10 mol adduct of hydroxymethyl acrylate [Placcel FA-10L, 30% toluene diluted solution; manufactured by Daicel Chemical Industries, Ltd.] 280.0 g and dipentaerythritol hexakis (3-mercaptopropionate) [ DPMP; manufactured by Sakai Chemical Industry Co., Ltd.] 39.2 g, propylene glycol monomethyl ether acetate was adjusted to a total solid content concentration of 30% by mass and heated to 50 ° C. To this, 31.2 g of dimethylaminopropyl acrylate was added dropwise over 30 minutes, and the mixture was heated for 6 hours to perform a Michael addition reaction. After completion of the reaction, the mixture was cooled to room temperature to obtain a 30% solution of the dispersant 6 of the present invention shown below.

[Synthesis Example 7]
114.1 g of ε-caprolactone and 6.5 g of ethylhexanol were reacted at 100 ° C. for 8 hours in the presence of 0.5 g of monobutyltin catalyst. To this reaction product, 7.0 g of Karenz AOI (manufactured by Kyowa Hakko) was added and further heated at 80 ° C. for 2 hours to obtain a polycaprolactone compound (4-5).
19.6 g of this reaction liquid, dipentaerythritol hexakis (3-mercaptopropionate) [DPMP; manufactured by Sakai Chemical Industry Co., Ltd.], and propylene glycol monomethyl ether acetate so that the total solid content concentration is 30% by mass. Preparation and heating to 50 ° C. To this was added dropwise 15.6 g of dimethylaminopropyl acrylate over 30 minutes, and the mixture was heated for 6 hours to cause a Michael addition reaction. After completion of the reaction, the mixture was cooled to room temperature to obtain a 30% solution of the dispersant 7 of the present invention shown below.

[Synthesis Example 8]
114.1 g of ε-caprolactone and 7.9 g of octanoic acid were reacted in the presence of 0.5 g of titanium tetrabutoxide catalyst at 150 ° C. for 8 hours to obtain a polycaprolactone compound (3-2-1).
In this reaction liquid, 14.8 g of isocyanuric acid triglycidyl [manufactured by Tokyo Chemical Industry Co., Ltd.], and 25.2 g of the following compound (A-4) having an adsorption site and having a carboxylic acid that reacts with glycidyl. Was added, and 1-methoxypropanol was adjusted and dissolved so as to have a solid content concentration of 30% by mass. This was heated at 100 ° C. for 6 hours under a nitrogen stream. After completion of the reaction, the mixture was cooled to room temperature to obtain a 30% solution of the dispersant 8 of the present invention shown below.

[Synthesis Example 9]
A 30% solution of the dispersant 9 of the present invention shown below was obtained in the same manner as in Synthesis Example 8 except that the compound (A-4) was changed to 20.5 g of the compound (A-5).

<Synthesis of comparative dispersant>
[Synthesis Example 10]
The following Comparative Dispersant 1 was synthesized according to the synthesis method described in JP-A-2007-277514.

[Synthesis Example 11]
According to a known method, a polyamine polyester was synthesized and used as Comparative Dispersant 2. The structural formula is as follows.

[Synthesis Example 12]
A polyester compound (3-2-1) was synthesized according to the method of Synthesis Example 8 and used as Comparative Dispersant 3.

Example 1
<Preparation of pigment dispersion composition>
The components of the following composition (1) are mixed, and using a homogenizer, the rotational speed is 3,000 r. p. m. And mixed for 3 hours to prepare a mixed solution containing the pigment.

[Composition (1)]
・ C. I. 90 parts of Pigment Red 254 10 parts of a pigment derivative listed in Table 1 below or a specific polymer compound or a comparative polymer compound listed in Table 1 below (30% by mass solution)
150 parts, 1-methoxy-2-propyl acetate 600 parts

Subsequently, the mixed solution obtained above was further subjected to a dispersion treatment for 6 hours with a bead disperser disperse mat (made by GETZMANN) using 0.2 mmφ zirconia beads, and then further a high-pressure disperser NANO with a decompression mechanism. The dispersion treatment was performed at a flow rate of 500 g / min under a pressure of 2000 kg / cm ³ using −3000-10 (manufactured by Nippon BEE Co., Ltd.). This dispersion treatment was repeated 10 times to obtain a pigment dispersion composition.

<Evaluation of pigment dispersion composition>
The following (1) to (2) were evaluated for the obtained pigment dispersion composition. The results are summarized in Table 1.

(1) Measurement and Evaluation of Viscosity For the obtained pigment dispersion composition, using an E-type viscometer, the viscosity η1 (initial viscosity) of the pigment dispersion composition immediately after dispersion and after one week at room temperature after dispersion The viscosity η2 (viscosity with time) of the pigment dispersion composition was measured, and the degree of thickening was evaluated. Here, low initial viscosity and low viscosity with time indicate that the dispersibility of the pigment is good. In addition, a small difference between the initial viscosity and the time-dependent viscosity indicates that the increase in the viscosity due to the dispersant is suppressed and the dispersion stability is good.

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

  From the results shown in Table 1, the pigment dispersion compositions of Examples containing the specific polymer compound of the present invention were excellent in pigment dispersibility and dispersion stability as compared with the pigment dispersion compositions of Comparative Examples. It can be seen that the contrast of the film is high.

(Examples 2-9 and Comparative Examples 1-2)
The pigments of Examples 2 to 9 and Comparative Examples 1 and 2 were the same as Example 1 except that the polymer compound and pigment derivative of composition (1) in Example 1 were changed to the compounds shown in Table 1. A dispersion composition was obtained. The pigment dispersion composition was evaluated for viscosity and contrast in the same manner as in Example 1. The results are shown in Table 1.

The polymer compounds in Table 1 are the polymer compounds (dispersants 1 to 9 and comparative dispersants 1 to 3) in the synthesis examples described above.
The structural formulas of the pigment derivatives in Table 1 are shown below.

(Example 10)
<Preparation of pigment dispersion composition>
The components of the following composition (2) were mixed, and the rotational speed was 3,000 r.m. using a homogenizer. p. m. And mixed for 3 hours to prepare a mixed solution containing the pigment.

[Composition (2)]
・ C. I. Pigment Green 36 100 parts • 10 parts of pigment derivatives listed in Table 2 below • Specific polymer compound or comparative polymer compound listed in Table 2 below (30% by mass solution)
120 parts ・ 750 parts of 1-methoxy-2-propyl acetate

Subsequently, the mixed solution obtained above was further subjected to a dispersion treatment for 6 hours using a bead disperser disperse mat (manufactured by GETZMANN) using 0.3 mmφ zirconia beads, and then further a high pressure disperser NANO with a decompression mechanism. The dispersion treatment was performed at a flow rate of 500 g / min under a pressure of 2000 kg / cm ³ using −3000-10 (manufactured by Nippon BEE Co., Ltd.). This dispersion treatment was repeated 10 times to obtain a pigment dispersion composition.

<Evaluation of pigment dispersion composition>
About the obtained pigment dispersion composition, it carried out similarly to Example 1, and evaluated said (1)-(2). The results are summarized in Table 2.

  From the results in Table 2, it can be seen that the pigment dispersion compositions of Examples containing the specific polymer compound of the present invention are excellent in the dispersibility and dispersion stability of the pigment and have a high contrast of the formed film.

(Examples 11-16 and Comparative Examples 3-4)
The pigment dispersion compositions of Examples 11 to 16 and Comparative Examples 3 to 4 were the same as Example 10 except that the polymer compound having the composition (2) in Example 10 was changed to the compounds shown in Table 1. Got. The pigment dispersion composition was evaluated for viscosity and contrast in the same manner as in Example 10. The results are shown in Table 2.

The polymer compounds in Table 2 are the polymer compounds (dispersants 1 to 9 and comparative dispersants 1 to 3) in the synthesis examples described above.
The structural formulas of the pigment derivatives in Table 1 are the same as those described above.

(Example 17)
<Preparation of pigment dispersion composition>
The components of the following composition (3) were mixed, and the rotational speed was 3,000 r.m. using a homogenizer. p. m. And mixed for 3 hours to prepare a mixed solution containing the pigment.

[Composition (3)]
・ C. I. Pigment Blue 15: 6 85 parts-Pigment derivative described in Table 3 below 15 parts-Specific polymer compound or comparative polymer compound listed in Table 3 below (30% by mass solution)
150 parts, 1-methoxy-2-propyl acetate 600 parts

Subsequently, the mixed solution obtained above was further subjected to a dispersion treatment for 6 hours with a bead disperser disperse mat (made by GETZMANN) using 0.2 mmφ zirconia beads, and then further a high-pressure disperser NANO with a decompression mechanism. The dispersion treatment was performed at a flow rate of 500 g / min under a pressure of 2000 kg / cm ³ using −3000-10 (manufactured by Nippon BEE Co., Ltd.). This dispersion treatment was repeated 10 times to obtain a pigment dispersion composition.

<Evaluation of pigment dispersion composition>
About the obtained pigment dispersion composition, it carried out similarly to Example 1, and evaluated said (1)-(2). The results are summarized in Table 3.

  From the results in Table 3, it can be seen that the pigment dispersion compositions of Examples containing the specific polymer compound of the present invention are excellent in the dispersibility and dispersion stability of the pigment, and the contrast of the formed film is high.

(Examples 18 to 23 and Comparative Examples 5 to 6)
The pigment dispersion compositions of Examples 18 to 23 and Comparative Examples 5 to 6 were the same as Example 17 except that the polymer compound having the composition (3) in Example 17 was changed to the compounds shown in Table 3. Got. The pigment dispersion composition was evaluated for viscosity and contrast in the same manner as in Example 17. The results are shown in Table 3.

The polymer compounds in Table 3 are the polymer compounds (dispersants 1 to 9 and comparative dispersants 1 to 3) in the synthesis examples described above.
The structural formulas of the pigment derivatives in Table 3 are the same as those described above.

  As is clear from Tables 1 to 3, it can be seen that the pigment dispersion compositions of Examples containing the specific polymer of the present invention are superior in pigment dispersibility and dispersion stability and have high contrast compared to Comparative Examples. .

(Example 24)
<Preparation of pigment dispersion composition>
Components of the following composition (4) are mixed, and the number of revolutions is 3,000 r.m. using a homogenizer. p. m. And mixed for 3 hours to prepare a mixed solution containing the pigment.

[Composition (4)]
・ C. I. Pigment Blue 15: 6 80 parts C.I. I. Pigment Violet 23 (average primary particle size: 26 nm) 20 parts • Pigment derivative described in Table 4 below 15 parts • Specific polymer compound or comparative polymer compound listed in Table 4 below (30% by mass solution)
260 parts 1-methoxy-2-propyl acetate 750 parts

Subsequently, the mixed solution obtained above was further subjected to a dispersion treatment for 6 hours by a bead disperser disperse mat (made by GETZMANN) using 0.3 mmφ zirconia beads, and then further a high-pressure disperser NANO with a decompression mechanism. The dispersion treatment was performed at a flow rate of 500 g / min under a pressure of 2000 kg / cm ³ using −3000-10 (manufactured by Nippon BEE Co., Ltd.). This dispersion treatment was repeated 10 times to obtain a pigment dispersion composition.

<Preparation of colored photosensitive composition>
Using the pigment dispersion composition obtained as described above, the following colored photosensitive composition was prepared.

-Pigment dispersion composition prepared above 2000 parts-KAYARAD DPHA (manufactured by Nippon Kayaku Co., Ltd.) (photopolymerizable compound) 100 parts-4- [o-bromo-pN, N-di (ethoxycarbonyl) amino Phenyl] -2,6-di (trichloromethyl) -S-triazine (photopolymerization initiator) 30 parts benzyl methacrylate / methacrylic acid (= 75/25 [mass ratio]) copolymer (weight average molecular weight: 12) , 000) propylene glycol monomethyl ether acetate solution (solid content 30%) (alkali-soluble resin) 400 parts 1-methoxy-2-propyl acetate (solvent) 390 parts

<Preparation of color filter using colored photosensitive composition>
The obtained colored photosensitive composition (color resist solution) was applied on a 100 mm × 100 mm glass substrate (1737, manufactured by Corning) so that the x value serving as an index of color density was 0.650. It was dried in an oven at 90 ° C. for 60 seconds (pre-baking). Thereafter, the entire surface of the coating film is exposed at 200 mJ / cm ² (illuminance 20 mW / cm ² ), and the exposed coating film is a 1% aqueous solution of an alkali developer CDK-1 (manufactured by Fuji Film Electronics Materials Co., Ltd.). And developed with a shower for 60 seconds. After standing still, pure water was sprayed in a shower to wash away the developer. Then, the coating film that has been exposed and developed as described above is heat-treated in an oven at 220 ° C. for 1 hour (post-baking) to form a colored pattern (colored region) for the color filter on the glass substrate. A filter substrate (color filter) was produced.

<Evaluation of colored photosensitive composition and color filter>
The produced colored photosensitive composition and colored filter substrate (color filter) were evaluated as follows. The results are summarized in Table 4 below.

(1) Contrast A polarizing plate is placed on the colored pattern of the color filter, the colored pattern is sandwiched, and the luminance when the polarizing plate is parallel and the luminance when orthogonal are measured using a BM-5 manufactured by Topcon Corporation. A value obtained by dividing the luminance of the above by the luminance at the time of orthogonality (= the luminance at the time of parallel / the luminance at the time of orthogonality) was used as an index for evaluating contrast. Larger values indicate higher contrast.

(2) Solubility in alkali developer and evaluation of suspension in alkali developer 150 ml beaker with 100 g of 10% aqueous solution of alkali developer (trade name: CDK-1, manufactured by Fuji Film Electronics Materials Co., Ltd.) Measure.
On the other hand, the colored photosensitive composition was applied on a 100 mm × 100 mm glass substrate (trade name: manufactured by 1737 Corning) so as to have a film thickness of 2.5 μm and dried (prebaked) in an oven at 90 ° C. for 60 seconds. The glass was cut so that the sample had a size of 25 mm × 100 mm, and two of them were superposed so that the coated surface was on the outside, thereby preparing a measurement sample.
The measurement sample is dipped in the developer prepared as described above and the up-and-down operation of drawing it out is repeated 20 times, and the solubility of the coating film after pre-baking and the presence or absence of the suspension in the developer are visually observed. It was judged.
The immersion time in the developer was 1 second to 2 seconds per time.

The evaluation index is as follows. Here, the larger the index number, the better the developability of the coating film.
-Evaluation index-
5: The coating film is completely dissolved in the vertical movement 1 to 10 times, and there is no suspension in the alkaline developer 4: The coating film is completely dissolved in the vertical movement 11 to 20 times, and in the alkaline developer No suspension 3: The coating film is completely dissolved in 1 to 10 times in the vertical motion, but there is a suspension in the alkaline developer 2: The coating film is completely dissolved in 11 to 20 times in the vertical motion. There is a suspension in the developer 1: The coating film is insoluble even after 20 vertical movements

  As is clear from Table 4, it can be seen that the color filter produced using the pigment dispersion composition containing the specific polymer compound of the present invention has excellent alkali developability and high contrast.

(Examples 25 to 27 and Comparative Example 7)
The color photosensitivity of Examples 25 to 27 and Comparative Example 7 was the same as Example 24 except that the polymer compound and pigment derivative of composition (4) in Example 24 were changed to the compounds shown in Table 4. A composition was prepared to produce a color filter. The colored photosensitive composition and the color filter were evaluated in the same manner as in Example 24 by (1) contrast, (2) solubility in an alkali developer, and suspension in the alkali developer. The results are shown in Table 4.

The polymer compounds in Table 4 are the polymer compounds (dispersants 1 to 9 and comparative dispersants 1 to 3) in the synthesis examples described above.
The structural formulas of the pigment derivatives in Table 4 are shown below.

(Example 28)
<Preparation of resist solution>
Components of the following composition were mixed and dissolved to prepare a resist solution.

[Composition of resist solution]
Propylene glycol monomethyl ether acetate 19.20 parts Ethyl lactate 36.67 parts Benzyl methacrylate / methacrylic acid / -2-hydroxyethyl methacrylate (molar ratio = 60/22/18) copolymer 40% propylene glycol Monomethyl ether acetate (PGMEA) solution 30.51 parts KAYARAD DPHA (manufactured by Nippon Kayaku Co., Ltd.) 12.20 parts Polymerization inhibitor (p-methoxyphenol) 0.0061 parts Fluorosurfactant (F-475, Dainippon Ink and Chemicals Co., Ltd.) 0.83 parts TAZ-107 (Midori Chemical Co., Ltd.) 0.586 parts

<Preparation of silicon wafer with undercoat layer>
A 6 inch silicon wafer was heat-treated in an oven at 200 ° C. for 30 minutes. Next, the resist solution is applied onto the silicon wafer so that the dry film thickness is 1.5 μm, and further heated and dried in an oven at 220 ° C. for 1 hour to form an undercoat layer. A silicon wafer substrate with an undercoat layer Got.

<Preparation of pigment dispersion composition>
The components of the following composition (5) were mixed, and the rotational speed was 3,000 r.m. using a homogenizer. p. m. And mixed for 3 hours to prepare a mixed solution containing the pigment.

[Composition (5)]
-100 parts of the pigment described in Table 5 below-Specific polymer compound or comparative polymer compound described in Table 5 below (30% by mass solution)
200 parts 1-methoxy-2-propyl acetate 750 parts

Subsequently, the mixed solution obtained above was further subjected to a dispersion treatment for 3 hours by a bead disperser disperse mat (manufactured by GETZMANN) using 0.8 mmφ zirconia beads, and then further a high pressure disperser NANO with a pressure reducing mechanism. Dispersion treatment was performed at a flow rate of 500 g / min under a pressure of 2,000 kg / cm ³ using −3000-10 (manufactured by Nippon BEE Co., Ltd.). This dispersion treatment was repeated 5 times to obtain a pigment dispersion composition.

<Preparation of colored photosensitive composition>
Using the pigment dispersion composition obtained above, stirring and mixing were performed to obtain the following composition to prepare a colored photosensitive composition solution.

・ Pigment dispersion composition 1000 parts ・ CGI-124 (manufactured by Ciba Specialty Chemicals; oxime photopolymerization initiator) 20 parts ・ KAYARAD DPHA (manufactured by Nippon Kayaku Co., Ltd.) (photopolymerizable compound) 20 parts ・ TO- 756 (manufactured by Toagosei Co., Ltd., photopolymerizable compound) 35 parts / propylene glycol monomethyl ether acetate 20 parts

<Production and Evaluation of Color Filter Using Colored Photosensitive Composition>
(Evaluation of sensitivity)
The colored photosensitive composition prepared as described above was applied onto the undercoat layer of the silicon wafer with an undercoat layer obtained by the above-described method, thereby forming a coating film. Then, heat treatment (pre-baking) was performed for 120 seconds using a hot plate at 100 ° C. so that the dry film thickness of the coating film became 0.7 μm.
Next, using an i-line stepper exposure apparatus FPA-3000i5 + (manufactured by Canon Inc.), various exposure doses in the range of 50 to 1200 mJ / cm ² through an Island pattern mask having a pattern of 1.5 μm square at a wavelength of 365 nm. And exposed.
Thereafter, the silicon wafer substrate on which the coating film after exposure is formed is placed on a horizontal rotating table of a spin shower developing machine (DW-30 type, manufactured by Chemitronics), and CD-2000 (Fuji Film Electronics Material). Paddle development was carried out at 23 ° C. for 60 seconds to form a colored pattern (colored region) on the silicon wafer.

  A silicon wafer on which a colored pattern is formed is fixed to the horizontal rotary table by a vacuum chuck method, and the silicon wafer is rotated at a rotational speed of 50 r. p. m. While being rotated, pure water was supplied from the upper part of the center of rotation to the shower nozzle to perform a rinsing treatment, and then spray-dried.

  Here, the minimum exposure amount in which the film thickness after development in the region irradiated with light in the exposure process was 95% or more with respect to the film thickness 100% before exposure was evaluated as the exposure sensitivity. A smaller exposure sensitivity value indicates higher sensitivity. The evaluation results are shown in Table 5.

(Evaluation of uneven color)
The luminance distribution was analyzed by the following method, and color unevenness was evaluated based on the ratio of pixels with a deviation from the average within ± 5% to the total number of pixels. The evaluation criteria are as follows.
First, the colored photosensitive composition prepared as described above was applied onto the undercoat layer of the silicon wafer with an undercoat layer obtained by the above-described method, thereby forming a coating film. Then, heat treatment (pre-baking) was performed for 120 seconds using a hot plate at 100 ° C. so that the dry film thickness of the coating film became 0.7 μm.

The monochromatic colored cured film obtained in this way is placed between the observation lens of the optical microscope and the light source, and irradiates light toward the observation lens. Observation was made with an installed optical microscope. A digital camera installed in an optical microscope is equipped with a CCD with 1.28 million pixels, and the colored cured film surface in a transmitted light state was photographed. The photographed image was stored as digitally converted data (digital image) in an 8-bit bitmap format. The colored cured film surface was photographed for 20 arbitrarily selected regions.
In addition, the digitally converted data was stored by digitizing the captured image as a density distribution of 256 gradations from 0 to 255 for each of the three primary colors of RGB.

Next, the stored digital image was divided into a lattice shape so that one lattice size corresponds to 2 μm square on the actual substrate, and the luminance in one partition was averaged.
In this example, since an image of 1000 times optical was captured with a 1.28 million pixel digital camera, 2 μm on the actual substrate was 2 mm on the captured image, and the image size on the display was 452 mm × 352 mm. The total number of sections in one area was 39976.

  For all the sections in each region, an arbitrary luminance and the average luminance of all adjacent sections adjacent to it were measured. A partition having a difference of 5 or more from the average brightness of adjacent partitions is recognized as a significant difference partition, and the average total number of significant difference partitions in all regions and the average total number of significant difference partitions in all regions are the total number of partitions in each region (39976). The ratio of the total to the total) was calculated.

The evaluation criteria are as follows. The evaluation results are shown in Table 5.
-Evaluation criteria-
○: Deviation from the average is less than 2% △: Deviation from the average is 2% or more and less than 5% ×: Deviation from the average is 5% or more

(Examples 29 to 30 and Comparative Examples 8 to 10)
The pigments and polymer compounds having the composition (5) in Example 28 were the same as in Example 28 except that the pigments and polymer compounds in Table 5 were changed, and the colored photosensitivities of Examples 29 to 30 and Comparative Examples 8 to 10 were used. Sex composition was obtained. Using the colored photosensitive composition, sensitivity and color unevenness were evaluated in the same manner as in Example 28. The results are shown in Table 5.
The polymer compounds in Table 5 are the polymer compounds (dispersants 1 to 9 and comparative dispersants 1 to 3) in the synthesis examples described above.

  As shown in Table 5, the colored photosensitive compositions of the examples had higher sensitivity than the comparative examples, and color unevenness occurred in the colored cured films obtained from the colored photosensitive compositions of the examples. I understand that there is no.

Claims (9)

The high molecular compound represented by either of the following general formula (1)-(3).

[Wherein, R ¹ represents an (m ₁ + n ₁ ) -valent organic linking group, R ⁴ represents an (m ₂ + n ₂ ) -valent organic linking group, and R ⁷ represents an (m ₃ + n ₃ ) -valent organic linking group. Represents an organic linking group. The ^{R 2, R 3, R 5} , R 6, R 8 and ^{R 9} each independently represent a single bond or a divalent organic linking group. A ^1, A ² and A ³ are each independently an organic dye structure, a heterocyclic structure, an acidic group, a group having a basic nitrogen atom, a urea group, a urethane group, a group having a coordinating oxygen atom, 4 carbon atoms It represents a monovalent organic group containing at least one selected from the above hydrocarbon groups, alkoxysilyl groups, epoxy groups, isocyanate groups, and hydroxyl groups. m ₁ , m ₂ and m ₃ each independently represents an integer of 1 to 8. n _{1, n 2} and _{n 3} each independently represent a 2-9 integer. Here, m ₁ + n ₁ , m ₂ + n ₂ , and m ₃ + n ₃ each independently satisfy 3 to 10. M ¹ and M ³ each independently represents a monovalent organic group. M ² each independently represents a hydrogen atom or a monovalent organic group. p, q and r each independently represents an integer of 2 to 8. b, c and d each independently represents an integer of 1 to 100. ] In general formula (1) to general formula (3), A ¹ , A ² , and A ³ are each independently an organic dye structure, a heterocyclic structure, an acidic group, a group having a basic nitrogen atom, a urea group, The polymer compound according to claim 1, which is a monovalent organic group containing at least one selected from hydrocarbon groups having 4 or more carbon atoms. A polymer compound represented by the following general formula (1 ′), (2 ′), (3 ′), (2 ″) or (3 ″).


[Wherein, R ¹ represents an (m ₁ + n ₁ ) -valent organic linking group, R ⁴ represents an (m ₂ + n ₂ ) -valent organic linking group, and R ⁷ represents an (m ₃ + n ₃ ) -valent organic linking group. Represents an organic linking group. The ^{R 2, R 3, R 5} , R 6, R 8 and ^{R 9} each independently represent a single bond or a divalent organic linking group. A ^1, A ² and A ³ are each independently an organic dye structure, a heterocyclic structure, an acidic group, a group having a basic nitrogen atom, a urea group, a urethane group, a group having a coordinating oxygen atom, 4 carbon atoms It represents a monovalent organic group containing at least one selected from the above hydrocarbon groups, alkoxysilyl groups, epoxy groups, isocyanate groups, and hydroxyl groups. m ₁ , m ₂ and m ₃ each independently represents an integer of 1 to 8. n _{1, n 2} and _{n 3} each independently represent a 2-9 integer. Here, m ₁ + n ₁ , m ₂ + n ₂ , and m ₃ + n ₃ each independently satisfy 3 to 10. M ¹ and M ³ each independently represents a monovalent organic group. M ² each independently represents a hydrogen atom or a monovalent organic group. p, q and r each independently represents an integer of 2 to 8. b, c and d each independently represents an integer of 1 to 100. ]   The polymer compound according to any one of claims 1 to 3, which has a weight average molecular weight of 3,000 to 100,000.   It is a pigment dispersant, The high molecular compound of any one of Claims 1-4.   A pigment dispersion composition containing a pigment and the polymer compound according to claim 5 in an organic solvent.   The photocurable composition containing the pigment dispersion composition of Claim 6, a polymeric compound, and a photoinitiator.   A color filter comprising a colored pattern formed using the photocurable composition according to claim 7 on a substrate.   A photosensitive film is formed by applying the photocurable composition according to claim 7 directly or via another layer to form a photosensitive film, and pattern exposure and development are performed on the formed photosensitive film. The manufacturing method of the color filter which forms.