JP5982177B2 - Acrylic copolymer - Google Patents

Description

  The present invention relates to an acrylic copolymer which is excellent in pigment dispersion stability and exhibits high heat resistance and developability.

  In recent years, a color liquid crystal display (LCD) has been rapidly spread as a flat display for personal computers and mobile phones. This color filter for LCD is a method in which different hues of red, green, and blue are sequentially formed in a color pattern such as stripes or mosaics on the surface of a transparent substrate such as a glass or plastic sheet in which a black matrix is usually formed. The coloring material dispersion technology plays an important role in both the colored layer and the black matrix.

  In addition, due to the rise of various display devices such as organic EL and the diversification of display information, there is an increasing demand for the color characteristics of the above-described color filter for LCD. In particular, there is an increasing demand for a wide color reproducibility range, and a technique for stably dispersing a colorant at a high concentration is important as a color filter coloring material. Generally, a colorant dispersion is composed of a colorant, a solvent, a dispersant, and a binder resin, and a colorant can be stably dispersed by adding a large amount of a dispersant to the composition. In the heating process to produce a yellowing agent, the brightness of the dispersant is lowered, or the concentration of the alkali-soluble photocurable resin is diluted, resulting in a decrease in sensitivity, poor curing, poor coating strength, and poor developability. In some cases, this causes problems such as In particular, poor developability causes serious problems in production, so the colorant dispersion is made with as little dispersant as possible, and the dispersion of the pigment is ensured by imparting a high degree of dispersion stability to the binder resin itself. However, it was a problem to achieve both developability and compatibility. In addition, the demand for color characteristics has been diversifying in recent years, and as a coloring material, not only conventional organic pigments but also coloring materials using dyes and inorganic pigments are being developed. It is difficult to disperse and stabilize the colored material at a high concentration.

  Also in the field of touch panel displays, where technological innovation is remarkable, a black matrix is formed as a light-shielding film in the same way as color filters, and it is generally formed by printing ink on a cover glass or cover film facing the sensor substrate. Has been made. On the other hand, there is an increasing demand for weight reduction of the touch panel, and technological development for simultaneously forming a light-shielding film and a touch sensor on a cover glass is progressing. In such a case, since it is necessary to form an electrode etc. after forming a black matrix on a cover glass, the high heat resistance which can endure the process of forming an electrode under a high temperature vacuum is requested | required.

  As pigments used in the black matrix, carbon black, titanium black such as low-order titanium oxide and titanium oxynitride, metal oxides such as iron oxide, and other organic pigment color mixing systems are used. Titanium is the mainstream. In order to obtain a black matrix having high insulation properties, carbon black surface-treated with titanium black, resin, or the like, or a mixture of organic pigments is used as a light shielding material (see, for example, Patent Document 1). However, in order to obtain a high light-shielding property, it is necessary to stably disperse various pigments at a high pigment concentration, and the conventional technology is insufficient from the viewpoint of long-term storage stability.

  As a technique for stabilizing dispersion with a small amount of a dispersant, a technique using a polymer dispersant having both an acid value and an amine value, and a copolymer having an imide group and a photocurable functional group is disclosed ( For example, refer to Patent Document 2), which is insufficient to stabilize the dispersion of a coloring material such as titanium black or carbon black which is difficult to disperse. Further, as a technique for stably dispersing a pigment even at a high pigment concentration, a technique in which an acid value dispersant having an acid value and an amine value dispersant having an amine value are used in combination (for example, see Patent Document 3) or a base. The technique (for example, refer patent document 4) using the resin type dispersing agent which made the block structure which has both a property block and an acidic block is mentioned. Although it is useful as a coloring liquid for inkjet coating, it has been difficult to apply it to a coloring liquid for photolithography that requires photosensitivity and developability.

  On the other hand, as an acrylic resin for pigment dispersion, an acrylic copolymer having a carboxyl group and an acryloyl group or a methacrylo group in the side chain (for example, see Patent Document 5), an acid value or an amine value at a specific molecular weight or hydroxyl value. Examples thereof include acrylic resins (see, for example, Patent Document 6), but all are insufficient from the viewpoint of achieving all of dispersion stability, photosensitivity, developability and heat resistance.

JP 2010-95716 A Japanese Patent No. 4195323 Japanese Patent No. 4544292 JP 2009-167303 A Japanese Patent No. 3120476 JP 2003-171605 A

  The present invention was devised in view of the drawbacks of the prior art, and the object of the present invention is to achieve both dispersion stability and alkali development solubility in a composition containing a colorant at a high concentration, and also has heat resistance. It is to provide an acrylic copolymer for obtaining a colorant dispersion having excellent properties and a photosensitive colored resin composition having excellent plate making characteristics.

  As a result of intensive studies to solve the problems of the prior art, the present inventors have solved the problems of the present invention by using an acrylic copolymer having a specific structure as follows when dispersing the coloring material. I found it possible to solve it. That is, the acrylic copolymer of the present invention has the following constitution.

（式中Ｒ¹，Ｒ²は互いに独立に水素原子又はメチル基、Ｒ³は炭素数１〜４のアルキレン基、炭素数３〜６の２価の脂環式炭化水素基、炭素数６〜１０の２価の芳香族炭化水素基から選ばれるいずれかを表す。)

（式中Ｒ⁴は水素原子又はメチル基、Ｒ⁵は炭素数１〜４のアルキレン基、炭炭素数３〜６の２価の脂環式炭化水素基、炭素数６〜１０の２価の芳香族炭化水素基から選ばれるいずれか、Ｒ⁶，Ｒ⁷は互いに独立に炭素数１〜４のアルキル基、炭素数１〜４のアルコキシ基、炭素数３〜６の脂環式炭化水素基、炭素数６〜１０の芳香族炭化水素基から選ばれるいずれかを表す。)

（式中Ｒ⁸は水素原子又はメチル基、Ｒ⁹は炭素数１〜４のアルキレン基、炭素数３〜６の２価の脂環式炭化水素基、炭素数６〜１０の２価の芳香族炭化水素基から選ばれるいずれか、Ｒ¹⁰，Ｒ¹¹，Ｒ¹²は互いに独立に炭素数１〜４のアルキル基、炭素数１〜４のアルコキシ基、炭素数３〜６の脂環式炭化水素基、炭素数６〜１０の芳香族炭化水素基から選ばれるいずれか、Ｘは臭素、塩素、ヨウ素、硫酸水素塩および水酸化物のいずれかを表す。) (1) Structure represented by the following formula (A) having an ethylenically unsaturated group in the molecular side chain, and structure and / or side chain represented by the following formula (B) having a tertiary amino group in the side chain And an acrylic copolymer having a structure represented by the following formula (C) having a quaternary ammonium salt, a structure (D) having a carboxyl group, and a structure (E) having an aromatic ring. Acrylic copolymer having a base number of 5 to 70 mmol / 100 g, an acid value of 50 to 120 mg KOH / g, and a polystyrene-reduced weight average molecular weight by gel permeation chromatography of 5,000 to 30,000 Coalescence.

(Wherein R ¹ and R ² are each independently a hydrogen atom or a methyl group, R ³ is an alkylene group having 1 to 4 carbon atoms, a divalent alicyclic hydrocarbon group having 3 to 6 carbon atoms, and 6 to 6 carbon atoms) Represents any one selected from 10 divalent aromatic hydrocarbon groups.)

(Wherein R ⁴ is a hydrogen atom or a methyl group, R ⁵ is an alkylene group having 1 to 4 carbon atoms , a divalent alicyclic hydrocarbon group having 3 to 6 carbon atoms, or a divalent hydrocarbon having 6 to 10 carbon atoms. Any one selected from aromatic hydrocarbon groups, R ⁶ and R ⁷ are each independently an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, and an alicyclic hydrocarbon group having 3 to 6 carbon atoms. And any one selected from aromatic hydrocarbon groups having 6 to 10 carbon atoms.)

(Wherein R ⁸ represents a hydrogen atom or a methyl group, R ⁹ is an alkylene group having 1 to 4 carbon atoms, a divalent alicyclic hydrocarbon group having a carbon number of 3-6, a divalent aromatic of 6 to 10 carbon atoms R ¹⁰ , R ¹¹ , and R ¹² are each independently selected from an aromatic hydrocarbon group, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, and an alicyclic carbon atom having 3 to 6 carbon atoms. Any one selected from a hydrogen group and an aromatic hydrocarbon group having 6 to 10 carbon atoms, X represents any one of bromine, chlorine, iodine, hydrogen sulfate and hydroxide.)

（式中Ｒ¹³は水素原子又はメチル基、ｎは０〜６の整数を表し、単一でも複数のｎの混合形でもよい。） (2) The acrylic copolymer according to (1), wherein the structure (D) having the carboxyl group is represented by the following structural formula (D1).

(In the formula, R ¹³ represents a hydrogen atom or a methyl group, n represents an integer of 0 to 6, and may be a single or a mixed form of a plurality of n.)

（式中Ｒ¹⁴は、水素、炭素数１〜４のアルキル基、炭素数１〜４のアルコキシ基、炭素数３〜６の脂環式炭化水素基、炭素数６〜１０の芳香族炭化水素基、ハロゲン原子、エステル基、アシル基およびニトロ基から選ばれるいずれかを表す。）

（式中Ｒ¹⁵は水素原子又はメチル基、Ｒ¹⁶は、水素、炭素数１〜４のアルキル基、炭素数１〜４のアルコキシ基、炭素数３〜６の脂環式炭化水素基、炭素数６〜１０の芳香族炭化水素基、ハロゲン原子、エステル基、アシル基およびニトロ基から選ばれるいずれかを表す。） (3) The acrylic copolymer according to (1) or (2), wherein the structure (E) having the aromatic ring is represented by the following structural formula (E1) or (E2).

(In the formula, R ¹⁴ is hydrogen, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, an alicyclic hydrocarbon group having 3 to 6 carbon atoms, or an aromatic hydrocarbon having 6 to 10 carbon atoms. Represents any one selected from a group, a halogen atom, an ester group, an acyl group and a nitro group.)

(Wherein R ¹⁵ is a hydrogen atom or a methyl group, R ¹⁶ is hydrogen, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, an alicyclic hydrocarbon group having 3 to 6 carbon atoms, carbon It represents one selected from an aromatic hydrocarbon group of several 6 to 10, a halogen atom, an ester group, an acyl group and a nitro group.)

（Ｒ¹⁷は、水素原子またはメチル基、Ｒ¹⁸は、水素原子または炭素原子数２〜２０個のアルキル基、Ｒ¹⁹は炭素原子数２〜４０個のアルキル基を表す。） (4) The acrylic copolymer according to any one of (1) to (3), wherein the acrylic copolymer further has a structure represented by the following structural formula (F).

(R ¹⁷ represents a hydrogen atom or a methyl group, R ¹⁸ represents a hydrogen atom or an alkyl group having 2 to 20 carbon atoms, and R ¹⁹ represents an alkyl group having 2 to 40 carbon atoms.)

  By using the acrylic copolymer of the present invention, a colorant dispersion and a photosensitive colored resin composition excellent in alkali development solubility and heat resistance can be obtained.

  Hereinafter, the present invention will be described in more detail.

（式中Ｒ¹，Ｒ²は互いに独立に水素原子又はメチル基、Ｒ³は炭素数１〜４のアルキレン基、炭素数３〜６の２価の脂環式炭化水素基、炭素数６〜１０の２価の芳香族炭化水素基から選ばれるいずれかを表す。) The acrylic copolymer of the present invention exhibits a function of being incorporated into a crosslinking reaction when an initiator that generates radicals, anions or cations by an active energy ray such as ultraviolet rays (UV) is used in combination. Therefore, it is essential to have an acrylic unit or a methacrylic unit represented by the following formula (A) having an ethylenically unsaturated group in the molecular side chain.

(Wherein R ¹ and R ² are each independently a hydrogen atom or a methyl group, R ³ is an alkylene group having 1 to 4 carbon atoms, a divalent alicyclic hydrocarbon group having 3 to 6 carbon atoms, and 6 to 6 carbon atoms) Represents any one selected from 10 divalent aromatic hydrocarbon groups.)

In the above formula (A), R ¹ and R ² are each independently a hydrogen atom or a methyl group, and an acrylic unit when R ¹ is hydrogen and a methacryl unit when it is a methyl group. R ³ is selected from an alkylene group having 1 to 4 carbon atoms, a divalent alicyclic hydrocarbon group having 3 to 6 carbon atoms, and a divalent aromatic hydrocarbon group having 6 to 10 carbon atoms, preferably carbon number It is good in it being a C1-C3 alkylene group, a C5-C6 bivalent alicyclic hydrocarbon group, and a C6-C8 bivalent aromatic hydrocarbon group.

  The method for introducing the (meth) acrylic unit represented by the above formula (A) is not particularly limited, and can be introduced by a usual method. For example, a method of adding a glycidyl group-containing polymerizable unsaturated monomer to an acrylic copolymer obtained by copolymerizing a carboxyl group-containing unsaturated monomer can be used. In this case, examples of the carboxyl group-containing unsaturated monomer to be copolymerized include acrylic acid and methacrylic acid, and examples of the glycidyl-containing unsaturated monomer include glycidyl acrylate and glycidyl methacrylate. In the present invention, these acrylic monomers may be used alone or in a mixture of two or more.

  The acrylic copolymer of the present invention has a (meth) acryl unit represented by the following formula (B) having a tertiary amino group in the side chain and / or a quaternary side chain in order to develop a high degree of dispersion stability. It is essential to contain a (meth) acryl unit represented by the following formula (C) having an ammonium salt.

  The (meth) acryl unit represented by the formula (B) having a tertiary amino group and the (meth) acryl unit represented by the formula (C) having a quaternary ammonium salt in the side chain both Either one or both of them may be introduced in order to increase the affinity and improve the dispersion stability. In the case of application to applications where developability is required as in the present invention, the (meth) acryl unit of the formula (B) having a tertiary amino group is selected from the viewpoint of easy balance between developability and dispersion stability. It is preferable to introduce.

（式中Ｒ⁴は水素原子又はメチル基、Ｒ⁵は炭素数１〜４のアルキレン基、炭素数３〜６の２価の脂環式炭化水素基、炭素数６〜１０の２価の芳香族炭化水素基から選ばれるいずれか、Ｒ⁶，Ｒ⁷は互いに独立に炭素数１〜４のアルキル基、炭素数１〜４のアルコキシ基、炭素数３〜６の脂環式炭化水素基、炭素数６〜１０の芳香族炭化水素基から選ばれるいずれかを表す。）

(Wherein R ⁴ is a hydrogen atom or a methyl group, R ⁵ is an alkylene group having 1 to 4 carbon atoms, a divalent alicyclic hydrocarbon group having a carbon number of 3-6, a divalent aromatic of 6 to 10 carbon atoms Any one selected from group hydrocarbon groups, R ⁶ and R ⁷ are each independently an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, an alicyclic hydrocarbon group having 3 to 6 carbon atoms, It represents one selected from aromatic hydrocarbon groups having 6 to 10 carbon atoms.)

In the above formula (B), R ⁴ is a hydrogen atom or a methyl group. When R ⁴ is hydrogen, it is an acrylic unit, and when it is a methyl group, it is a methacryl unit. R ⁵ is selected from an alkylene group having 1 to 4 carbon atoms, a divalent alicyclic hydrocarbon group having 3 to 6 carbon atoms, and a divalent aromatic hydrocarbon group having 6 to 10 carbon atoms, preferably carbon number It is good in it being a C1-C3 alkylene group, a C5-C6 bivalent alicyclic hydrocarbon group, and a C6-C8 bivalent aromatic hydrocarbon group.

R ⁶ and R ⁷ may be the same or different and may be the same or different, each having an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, an alicyclic hydrocarbon group having 3 to 6 carbon atoms, Selected from C6-C10 aromatic hydrocarbon groups, preferably C1-C3 alkylene groups, C1-C3 alkoxy groups, C5-C6 divalent alicyclic hydrocarbon groups And a divalent aromatic hydrocarbon group having 6 to 8 carbon atoms.

  Examples of the unsaturated monomer constituting the (meth) acrylic unit having a tertiary amino group represented by the formula (B) include acrylic acid-2-dimethylaminoethyl, acrylic acid-2-diethylaminoethyl, acrylic acid- 2-dipropylaminoethyl, 2-diphenylaminoethyl acrylate, 2-dibenzylaminoethyl acrylate, 2-dimethylaminoethyl methacrylate, 2-diethylaminoethyl methacrylate, 2-dipropyl methacrylate Aminoethyl, 2-diphenylaminoethyl methacrylate, 2-benzylaminoethyl methacrylate and the like can be exemplified, but are not particularly limited. These (meth) acrylic monomers may be used alone or in a mixture of two or more.

  The (meth) acryl unit having a tertiary amino group represented by the formula (B) can be introduced by copolymerizing an unsaturated monomer containing an amino group.

（式中Ｒ⁸は水素原子又はメチル基、Ｒ⁹は炭素数１〜４のアルキレン基、炭素数３〜６の２価の脂環式炭化水素基、炭素数６〜１０の２価の芳香族炭化水素基から選ばれるいずれか、Ｒ¹⁰，Ｒ¹¹，Ｒ¹²は互いに独立に炭素数１〜４のアルキル基、炭素数１〜４のアルコキシ基、炭素数３〜６の脂環式炭化水素基、炭素数６〜１０の芳香族炭化水素基から選ばれるいずれか、Ｘは臭素、塩素、ヨウ素、硫酸水素塩および水酸化物のいずれかを表す。)

(Wherein R ⁸ represents a hydrogen atom or a methyl group, R ⁹ is an alkylene group having 1 to 4 carbon atoms, a divalent alicyclic hydrocarbon group having a carbon number of 3-6, a divalent aromatic of 6 to 10 carbon atoms R ¹⁰ , R ¹¹ , and R ¹² are each independently selected from an aromatic hydrocarbon group, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, and an alicyclic carbon atom having 3 to 6 carbon atoms. Any one selected from a hydrogen group and an aromatic hydrocarbon group having 6 to 10 carbon atoms, X represents any one of bromine, chlorine, iodine, hydrogen sulfate and hydroxide.)

In the above formula (C), R ⁸ is a hydrogen atom or a methyl group, and when R ⁸ is hydrogen, it becomes an acrylic unit, and when it is a methyl group, it becomes a methacryl unit. R ⁹ is selected from an alkylene group having 1 to 4 carbon atoms, a divalent alicyclic hydrocarbon group having 3 to 6 carbon atoms, and a divalent aromatic hydrocarbon group having 6 to 10 carbon atoms, preferably carbon number It is good in it being a C1-C3 alkylene group, a C5-C6 bivalent alicyclic hydrocarbon group, and a C6-C8 bivalent aromatic hydrocarbon group.

R ¹⁰ , R ¹¹ and R ¹² may be the same or different and may be the same or different, and may be an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, or an alicyclic carbonization having 3 to 6 carbon atoms Selected from a hydrogen group and an aromatic hydrocarbon group having 6 to 10 carbon atoms, preferably an alkylene group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, and a divalent alicyclic group having 5 to 6 carbon atoms. It is good that it is a hydrocarbon group and a C6-C8 bivalent aromatic hydrocarbon group.

  X is selected from bromine, chlorine, iodine, hydrogen sulfate and hydroxide, and is preferably bromine or chlorine.

  Examples of the unsaturated monomer constituting the (meth) acrylic unit having a quaternary ammonium salt represented by the formula (C) include acrylic acid-dimethylaminoethylmethyl chloride salt, dimethylaminoethylbenzyl chloride acrylate salt, methacrylic acid Examples include acid-dimethylaminoethylmethyl chloride salt and dimethylaminoethylbenzyl chloride methacrylate methacrylate, but are not particularly limited. These (meth) acrylic monomers may be used alone or in a mixture of two or more.

  The (meth) acryl unit having a quaternary ammonium salt represented by the formula (C) can be introduced by copolymerizing an unsaturated monomer containing a quaternary ammonium salt.

  In order to impart alkali developability, the acrylic copolymer of the present invention needs to introduce an acidic group that is neutralized into a side chain and exhibits water solubility. Examples of the acidic group include a carboxyl group, a sulfonic acid group, and a phosphoric acid group. In the present invention, it is essential to have a structure (D) having a carboxyl group in the molecular side chain.

（式中Ｒ¹³は水素原子又はメチル基、ｎは０〜６の整数を表し、単一でも複数のｎの混合形でもよい。） The structure (D) having a carboxyl group can be introduced by copolymerizing a carboxyl group-containing unsaturated monomer. Examples of the carboxyl group-containing unsaturated monomer include acrylic acid, methacrylic acid, itaconic acid, maleic acid, maleic anhydride, phthalic acid, phthalic anhydride, and crotonic acid. In particular, in consideration of introducing a (meth) acryl unit having an ethylenically unsaturated group into the molecular side chain represented by the above formula (A), a (meth) acryl unit having a carboxyl group in the molecular side chain is preferable. In particular, a carboxy group-containing unsaturated monomer represented by the following formula (D1) is particularly preferable from the viewpoints of reaction control and stability.

(In the formula, R ¹³ represents a hydrogen atom or a methyl group, n represents an integer of 0 to 6, and may be a single or a mixed form of a plurality of n.)

In the above formula (D1), R ¹³ is a hydrogen atom or a methyl group, and when R ¹³ is hydrogen, it becomes an acryl unit, and when it is a methyl group, it becomes a methacryl unit. n is an integer of 0 to 6, preferably 0. n may be a single integer or a plurality of integers between 0-6.

  Examples of the unsaturated monomer (D1) containing a carboxyl group represented by the above structure include acrylic acid, methacrylic acid, 2-carboxyethyl acrylate oligomer, 2-carboxyethyl methacrylate oligomer and the like. These (meth) acrylic monomers may be used alone or in a mixture of two or more.

  In order for the acrylic copolymer of the present invention to exhibit high heat resistance, the structure (E) having an aromatic ring in the side chain is necessarily contained. The structure (E) having an aromatic ring in the side chain can be introduced by copolymerizing an unsaturated monomer having an aromatic ring, and a phenyl group and a derivative of the phenyl group represented by the following formula (E1), or (E2 ) And benzyl group derivatives are particularly suitable, and a higher effect of improving heat resistance can be obtained.

（式中Ｒ¹⁴は、水素、炭素数１〜４のアルキル基、炭素数１〜４のアルコキシ基、炭素数３〜６の脂環式炭化水素基、炭素数６〜１０の芳香族炭化水素基、ハロゲン原子、エステル基、アシル基およびニトロ基から選ばれるいずれかを表す。）

(In the formula, R ¹⁴ is hydrogen, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, an alicyclic hydrocarbon group having 3 to 6 carbon atoms, or an aromatic hydrocarbon having 6 to 10 carbon atoms. Represents any one selected from a group, a halogen atom, an ester group, an acyl group and a nitro group.)

In the above formula (E1), R ¹⁴ is hydrogen, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, an alicyclic hydrocarbon group having 3 to 6 carbon atoms, or 6 to 10 carbon atoms. Any one selected from an aromatic hydrocarbon group, a halogen atom, an ester group, an acyl group and a nitro group, preferably hydrogen, an alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, and 5 to 6 carbon atoms These are alicyclic hydrocarbon groups and aromatic hydrocarbon groups having 6 to 8 carbon atoms.

  Examples of the unsaturated monomer containing an aromatic ring represented by the above formula (E1) include styrene, methylstyrene, 4-vinyltoluene and its structural isomer, 4-methoxystyrene and its structural isomer, 4- Examples include butoxystyrene and its structural isomer, 4-tert-butoxystyrene and its structural isomer, 4-vinylbiphenyl, 2-vinylnaphthalene and its structural isomer, 9-vinylanthracene, 9-vinylcarbazole, and the like. . In the present invention, these unsaturated monomers may be used alone or in a mixture of two or more.

（式中Ｒ¹⁵は水素原子又はメチル基、Ｒ¹⁶は、水素、炭素数１〜４のアルキル基、炭素数１〜４のアルコキシ基、炭素数３〜６の脂環式炭化水素基、炭素数６〜１０の芳香族炭化水素基、ハロゲン原子、エステル基、アシル基およびニトロ基から選ばれるいずれかを表す。）

(Wherein R ¹⁵ is a hydrogen atom or a methyl group, R ¹⁶ is hydrogen, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, an alicyclic hydrocarbon group having 3 to 6 carbon atoms, carbon It represents one selected from an aromatic hydrocarbon group of several 6 to 10, a halogen atom, an ester group, an acyl group and a nitro group.)

In the above formula (E2), R ¹⁵ is a hydrogen atom or a methyl group, and when R ¹⁵ is hydrogen, it becomes an acryl unit, and when it is a methyl group, it becomes a methacryl unit. R ¹⁶ is hydrogen, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, an alicyclic hydrocarbon group having 3 to 6 carbon atoms, an aromatic hydrocarbon group having 6 to 10 carbon atoms, a halogen atom Any one selected from an atom, an ester group, an acyl group and a nitro group, preferably hydrogen, an alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, and an alicyclic hydrocarbon group having 5 to 6 carbon atoms And an aromatic hydrocarbon group having 6 to 8 carbon atoms.

  Examples of the (meth) acrylic monomer containing the aromatic ring represented by the above formula (E2) include, but are not limited to, benzyl acrylate and benzyl methacrylate. In the present invention, these (meth) acrylic monomers may be used alone or in a mixture of two or more.

  In the acrylic copolymer of the present invention, the segment which is a structural unit represented by the above formulas (B), (C), (D1), (E1), and (E2) is usually used for solution polymerization, emulsion polymerization, bulk polymerization and the like. It can be obtained in the form of a random copolymer or a block copolymer by radical polymerization reaction. In addition, for the (meth) acrylic unit represented by the formula (A), a monomer having a functional group capable of reacting with the side chain functional group of the acrylic copolymer obtained above is subjected to addition reaction. It can introduce | transduce by the normal method introduce | transduced by.

（式中Ｒ¹，Ｒ²，Ｒ⁴は互いに独立に水素原子又はメチル基、Ｒ³は炭素数１〜４のアルキレン基、炭素数３〜６の２価の脂環式炭化水素基、炭素数６〜１０の２価の芳香族炭化水素基から選ばれるいずれか、Ｒ⁵は炭素数１〜４のアルキレン基、炭素数３〜６の２価の脂環式炭化水素基、炭素数６〜１０の２価の芳香族炭化水素基から選ばれるいずれか、Ｒ⁶，Ｒ⁷は互いに独立に炭素数１〜４のアルキル基、炭素数１〜４のアルコキシ基、炭素数３〜６の脂環式炭化水素基、炭素数６〜１０の芳香族炭化水素基から選ばれるいずれか、Ｒ¹⁴は、水素、炭素数１〜４のアルキル基、炭素数１〜４のアルコキシ基、炭素数３〜６の脂環式炭化水素基、炭素数６〜１０の芳香族炭化水素基、ハロゲン原子、エステル基、アシル基およびニトロ基から選ばれるいずれかを表す。） The acrylic copolymer of the present invention is characterized by comprising a structural unit containing a polymerizable unsaturated bond, a tertiary amino group and / or a quaternary ammonium salt, a carboxyl group, and an aromatic ring in the side chain. Among them, it is preferable to contain a (meth) acryl unit containing a tertiary amino group in the side chain, and a particularly preferable acrylic copolymer is an acrylic copolymer containing a structural unit represented by the following formula (1). If necessary, other main chain constituent units may be contained.

(Wherein R ¹ , R ² and R ⁴ are each independently a hydrogen atom or a methyl group, R ³ is an alkylene group having 1 to 4 carbon atoms, a divalent alicyclic hydrocarbon group having 3 to 6 carbon atoms, carbon any one selected from the divalent aromatic hydrocarbon group having 6 to 10, R ⁵ is an alkylene group having 1 to 4 carbon atoms, a divalent alicyclic hydrocarbon group having a carbon number of 3 to 6, carbon atoms 6 R ⁶ and R ⁷ are each independently selected from an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, and 3 to 6 carbon atoms. Any one selected from an alicyclic hydrocarbon group and an aromatic hydrocarbon group having 6 to 10 carbon atoms, R ¹⁴ is hydrogen, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, or a carbon number 3-6 alicyclic hydrocarbon groups, aromatic hydrocarbon groups having 6-10 carbon atoms, halogen atoms, ester groups, acyl groups, and nitro groups It represents any one selected et.)

  The acrylic copolymer of the present invention comprises a (meth) acryl unit of the formula (A) having an ethylenically unsaturated group in the molecular side chain and a formula (B) and / or a side chain having a tertiary amino group in the side chain. A structural unit of formula (E1) or (E2) having a (meth) acrylic unit of formula (C) having a quaternary ammonium salt, a (meth) acrylic unit of formula (D1) having a carboxyl group, and an aromatic ring In addition, by introducing a structural unit having a long chain alkyl group in the side chain, a higher degree of dispersion stability can be expressed.

（Ｒ¹⁷は、水素原子またはメチル基、Ｒ¹⁸は、水素原子または炭素原子数２〜２０個のアルキル基、Ｒ¹⁹は炭素原子数２〜４０個のアルキル基を表す。） In the present invention, the long chain alkyl group can be introduced by copolymerizing a long chain alkyl group-containing unsaturated monomer. Examples of the long-chain alkyl group-containing unsaturated monomer include octyl acrylate, octyl methacrylate, lauryl acrylate, lauryl methacrylate, stearyl acrylate, stearyl methacrylate, dodecyl acrylate, dodecyl methacrylate, and the like. Among these, unsaturated monomers having a long-chain alkyl group in the side chain having a structure represented by the following formula (F) tend to exhibit a higher degree of dispersion stability, and thus are particularly preferable.

(R ¹⁷ represents a hydrogen atom or a methyl group, R ¹⁸ represents a hydrogen atom or an alkyl group having 2 to 20 carbon atoms, and R ¹⁹ represents an alkyl group having 2 to 40 carbon atoms.)

In the above formula (F), R ¹⁷ is a hydrogen atom or a methyl group, and when R ¹⁷ is hydrogen, it becomes an acrylic unit, and when it is a methyl group, it becomes a methacryl unit. R ¹⁸ is hydrogen or an alkyl group having 2 to 20 carbon atoms, preferably hydrogen or an alkyl group having 2 to 6 carbon atoms. R ¹⁹ is an alkyl group having 2 to 40 carbon atoms, preferably an alkyl group having 2 to 18 carbon atoms.

  Examples of the unsaturated monomer containing a long-chain alkyl group represented by the formula (F) include 2-ethylhexyl acrylate and 2-ethylhexyl methacrylate, but are not particularly limited. These acrylic monomers may be used alone or in a mixture of two or more.

  The acrylic copolymer of the present invention can be copolymerized with any (meth) acrylic acid ester as a monomer in addition to the structural units listed above, if necessary. Specifically, methyl acrylate, ethyl acrylate, propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, t-butyl acrylate, cyclohexyl acrylate, isobornyl acrylate, methyl methacrylate, methacrylic acid Examples include, but are not limited to, ethyl, propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, t-butyl methacrylate, cyclohexyl methacrylate, and isobornyl methacrylate. In the present invention, these (meth) acrylic acid ester monomers may be used alone or in a mixture of two or more.

  The production method of the acrylic copolymer of the present invention can be obtained by a usual polymerization method such as solution polymerization, emulsion polymerization, bulk polymerization, etc., but solution polymerization using an organic solvent is easy to remove heat during the reaction. Is preferred.

  Although it does not specifically limit as an organic solvent which can be used for solution polymerization, An aliphatic hydrocarbon, carboxylic acid ester, a ketone, ethers, and alcohol can be illustrated. Among these, carboxylic acid esters, ketones, and ethers can be preferably used from the viewpoint of solubility. Specifically, benzyl acetate, ethyl benzoate, γ-butyrolactone, methyl benzoate, diethyl malonate, 2-ethylhexyl acetate, 2-butoxyethyl acetate, diethyl oxalate, ethyl acetoacetate, cyclohexyl acetate, 3-methoxy-butyl acetate , Methyl acetoacetate, ethyl-3-ethoxypropionate, 2-ethylbutyl acetate, isopentylpropionate, pentyl acetate, 3-methoxy-3-methyl-butyl acetate, propylene glycol monoethyl ether acetate, propylene glycol monomethyl Examples include ether propionate and propylene glycol monomethyl ether acetate. Among them, 3-methoxy-butyl acetate, 3-methoxy-3-methyl- Chill acetate, propylene glycol monoethyl ether acetate, propylene glycol monomethyl ether propionate, propylene glycol monomethyl ether acetate is particularly preferably used.

  Further, as solvents other than the above, aliphatic ethers such as propylene glycol derivatives such as propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol tertiary butyl ether, dipropylene glycol monomethyl ether, aliphatic esters other than the above, For example, ethyl acetate, butyl acetate, isopentyl acetate, aliphatic alcohols such as butanol, 3-methyl-2-butanol and 3-methyl-3-methoxybutanol, ketones such as cyclopentanone and cyclohexanone, xylene, A solvent such as ethylbenzene or solvent naphtha can be used in combination.

  In the present invention, it is important that the acid value, base value, and weight average molecular weight of the acrylic copolymer are within appropriate ranges. The acrylic copolymer is copolymerized so that its base number is 5 to 70 mmol / 100 g, preferably 5 to 50 mmol / 100 g, more preferably 10 to 30 mmol / 100 g, and still more preferably 10 to 20 mmol / 100 g. If the base value of the acrylic copolymer is less than 5 mmol / 100 g, the pigment dispersion stability tends to deteriorate, and if it exceeds 70 mmol / 100 g, the developability tends to deteriorate. The base number can be set within a predetermined range by adjusting the composition ratio of the structural units of the acrylic copolymer, particularly the composition ratio of the structural units of the formulas (B) and (C). The base number of the acrylic copolymer is defined as the number of moles of perchloric acid required to neutralize 100 g of the acrylic copolymer (unit: mmol / 100 g).

  The acrylic copolymer is copolymerized so that its acid value is 50 to 120 mg, preferably 60 to 120 mg, more preferably 70 to 110 mg, and still more preferably 70 to 100 mg. When the acid value of the acrylic copolymer exceeds 120 mg, the dispersion stability tends to deteriorate, and when it is less than 50 mg, the alkali development tends to deteriorate. The acid value can be set within a predetermined range by adjusting the composition ratio of the structural units of the acrylic copolymer. The acid value of the acrylic copolymer is defined as the number of mg of potassium hydroxide required to neutralize 1 g of the acrylic copolymer (unit: mgKOH / g).

  The weight average molecular weight (Mw) of the acrylic copolymer of the present invention is 5,000 to 30,000, preferably 5,000 to 20,000. When the weight average molecular weight is less than 5,000, the dispersion stability tends to decrease, and when the weight average molecular weight is more than 30,000, the developability tends to deteriorate. The weight average molecular weight (Mw) of the acrylic copolymer is measured by gel permeation chromatography using tetrahydrofuran as a carrier, and converted using a standard polystyrene calibration curve.

  EXAMPLES Hereinafter, although this invention is demonstrated further in detail using an Example and a comparative example, this invention is not limited to a following example. In addition, the analytical value and characteristic of the acrylic copolymer were measured by the following method.

<Evaluation method>
"Acid value"
The number of potassium hydroxide required to neutralize 1 g of the acrylic copolymer was defined as the acid value (unit: mg KOH / g).
"Base number"
The number of moles of perchloric acid required to neutralize 100 g of the acrylic copolymer was defined as the base number (unit: mmol / 100 g).
"Weight average molecular weight"
Using gel permeation chromatography (GPC) “HLC-8220GPC” (test equipment of Tosoh Corporation), the carrier was tetrahydrofuran, and the weight average molecular weight (Mw) was measured using polystyrene as the molecular weight standard.
"viscosity"
Using a viscometer (RE105L manufactured by Toki Sangyo Co., Ltd.), set the temperature to 25.0 ± 0.2 ° C. and set the value measured at 100 rpm as the viscosity value.
"Dispersion stability"
For the colorant dispersions prepared in the examples, the initial viscosity, the viscosity after one week were measured by the above measuring method, and the dispersion state was comprehensively evaluated as follows by the change in the viscosity after one week. . Although it is desirable that the viscosity increase with time is small, the viscosity may increase due to the interaction between the finely dispersed pigments.
○: Viscosity in one week of production is 50% or less, and the dispersion state is very good.
(Triangle | delta): Thickening in preparation 1 week is 50 to 100%, and a dispersed state is favorable.
X: Thickening in one week of production exceeds 100%, and the dispersion state is unstable.
"Developability"
From the viewpoint of industrial use, an acceptable standard was evaluated as follows for the dissolution time of the non-photosensitive portion of the coating film developed with 0.045% potassium hydroxide aqueous solution. Acceptance criteria are as follows.
○: Developability is extremely good (resist coating film unexposed portion dissolution is completed within 50 seconds)
(Triangle | delta): Developability is favorable (resist coating film unexposed part melt | dissolution completion in 50 to 100 second)
X: Developability is poor (requires more than 100 seconds to complete dissolution of resist film unexposed area)
"Heat-resistant"
The black matrix produced in the example was pre-baked at 150 ° C. for 30 minutes with a thermogravimetric analyzer (TA Instruments Q50), and then heated in a procedure of post-baking at 280 ° C. for 60 minutes. Evaluated by change. From the viewpoint of industrial use, the heat resistance tolerance standard was evaluated as follows. Acceptance criteria are as follows.
○: Very good heat resistance (weight change of 1.5% or less)
Δ: Good heat resistance (weight change of more than 1.5% and not more than 2.0%)
X: Heat resistance is poor (weight change exceeding 2.0%)

<Synthesis of acrylic copolymer>
The synthesis example of the acrylic copolymer in this invention is shown below. The present invention is not limited to the following method. In addition, the notation “part” in each synthesis example represents part by weight.

[Synthesis Example 1]
200 parts of propylene glycol monoethyl ether acetate solvent was charged into a pressure vessel equipped with a stirrer, thermometer, reflux condenser, and dropping pump, and the reaction vessel was filled with nitrogen, then heated to 90 ° C., and methacrylic acid- 1 part of 2-dimethylaminoethyl (MLDA), 32 parts of methyl methacrylate (MMA), 20 parts of 2-ethylhexyl methacrylate (2EHMA), 30 parts of styrene (St), 17 parts of methacrylic acid (MAA), polymerization started Acrylic copolymer prepared by adding 2.0 parts of azobisisobutyronitrile (AIBN) and 3.0 parts of normal dodecyl mercaptan (MDM) as an agent and dropping the mixture over 3 hours using a dropping pump. Got. Next, the inside of the reaction vessel was replaced with air, 0.1 part of p-methoxyphenol was used as a polymerization inhibitor, and 10 parts of glycidyl methacrylate (GMA) was used as a catalyst with N, N′-dimethylbenzylamine as a catalyst. The solution was added dropwise over 1 hour. At this stage, the addition reaction between the carboxyl group of the copolymer side chain and the epoxy group of glycidyl methacrylate was traced by a decrease in the acid value, and the reaction was completed when the disappearance of glycidyl methacrylate was 97% or more. The acrylic copolymer (P-1) which introduce | transduced the unsaturated group was obtained.

  As a result, the obtained acrylic copolymer (P-1) had a base number of 18 mmol / 100 g, an acid value of 71 mg KOH / g, and a weight average molecular weight of 7000.

[Synthesis Example 2]
Acrylic copolymer (P) was prepared in the same manner as in Synthesis Example 1 except that the amount of methyl methacrylate (MMA) was changed to 32 parts and the amount of methacrylate-2-dimethylaminoethyl (MLDA) was changed to 1 part. -2) was obtained. The base value of the acrylic copolymer (P-2) was 15 mmol / 100 g, the acid value was 75 mgKOH / g, and the weight average molecular weight was 7000.

[Synthesis Example 3]
Acrylic copolymer (P) was prepared in the same manner as in Synthesis Example 1 except that the amount of methyl methacrylate (MMA) was changed to 33 parts and the amount of methacrylate-2-dimethylaminoethyl (MLDA) was changed to 2 parts. -3) was obtained. The base value of the acrylic copolymer (P-3) was 11 mmol / 100 g, the acid value 73 mgKOH / g, and the weight average molecular weight 7000.

[Synthesis Example 4]
Acrylic copolymer (P) was prepared in the same manner as in Synthesis Example 1 except that the amount of methyl methacrylate (MMA) was changed to 31 parts and the amount of methacrylate-2-dimethylaminoethyl (MLDA) was changed to 4 parts. -4) was obtained. The base value of the acrylic copolymer (P-4) was 25 mmol / 100 g, the acid value was 78 mgKOH / g, and the weight average molecular weight was 7000.

[Synthesis Example 5]
An acrylic copolymer (P-5) was prepared in the same manner as in Synthesis Example 1 except that 3 parts of 2-dimethylaminoethyl methacrylate (MLDA) was changed to 3 parts of 2-dimethylaminoethyl acrylate (ALDA). Got. The base value of the acrylic copolymer (P-5) was 16 mmol / 100 g, the acid value was 70 mgKOH / g, and the weight average molecular weight was 7000.

[Synthesis Example 6]
Prepared in the same manner as in Synthesis Example 1 except that 3 parts of 2-dimethylaminoethyl methacrylate (MLDA) was changed to 3 parts of dimethylaminoethyl methyl chloride salt (MLDA-Cl), and an acrylic copolymer (P- 6) was obtained. The base value of the acrylic copolymer (P-6) was 15 mmol / 100 g, the acid value was 71 mgKOH / g, and the weight average molecular weight was 7000.

[Synthesis Example 7]
Acrylic copolymer (P) was prepared in the same manner as in Synthesis Example 1 except that the amount of methyl methacrylate (MMA) was changed to 26 parts and the amount of methacrylate-2-dimethylaminoethyl (MLDA) was changed to 7 parts. -7) was obtained. The acrylic copolymer (P-7) had a base number of 42 mmol / 100 g, an acid value of 67 mg KOH / g, and a weight average molecular weight of 7,000.

[Synthesis Example 8]
An acrylic copolymer (P-8) was obtained in the same manner as in Synthesis Example 1 except that the amount of methyl methacrylate (MMA) was changed to 32 parts and the amount of methacrylic acid (MAA) was changed to 10 parts. . The base value of the acrylic copolymer (P-8) was 18 mmol / 100 g, the acid value was 54 mgKOH / g, and the weight average molecular weight was 7000.

[Synthesis Example 9]
An acrylic copolymer (P-9) was obtained in the same manner as in Synthesis Example 1 except that 30 parts of methyl methacrylate (MMA) was changed to 30 parts of acrylic acid (AA). The base value of the acrylic copolymer (P-9) was 19 mmol / 100 g, the acid value was 89 mgKOH / g, and the weight average molecular weight was 7000.

[Synthesis Example 10]
14 parts of methyl methacrylate (MMA) is charged, 17 parts of methacrylic acid (MAA) is a carboxyl group-containing monomer mixture: Rhodia Nikka Co., Ltd. (β-CEA) and the amount is 33 parts. Was prepared in the same manner as in Synthesis Example 1 to obtain an acrylic copolymer (P-10). The base value of the acrylic copolymer (P-10) was 18 mmol / 100 g, the acid value was 65 mgKOH / g, and the weight average molecular weight was 7000.

[Synthesis Example 11]
An acrylic copolymer (P-11) was obtained in the same manner as in Synthesis Example 1 except that the amount of methyl methacrylate (MMA) was 27 parts and the amount of methacrylic acid (MAA) was 20 parts. The base value of the acrylic copolymer (P-11) was 18 mmol / 100 g, the acid value was 90 mgKOH / g, and the weight average molecular weight was 7000.

[Synthesis Example 12]
An acrylic copolymer (P-12) was obtained in the same manner as in Synthesis Example 1 except that the amount of methyl methacrylate (MMA) was 23 parts and the amount of methacrylic acid (MAA) was 24 parts. The base value of the acrylic copolymer (P-12) was 17 mmol / 100 g, the acid value was 114 mgKOH / g, and the weight average molecular weight was 7000.

[Synthesis Example 13]
An acrylic copolymer (P-13) was obtained in the same manner as in Synthesis Example 1 except that 20 parts of 2-ethylhexyl methacrylate (2EHMA) was changed to 20 parts of acrylic acid-2-ethylhexyl (2EHA). The base value of the acrylic copolymer (P-13) was 20 mmol / 100 g, the acid value was 73 mgKOH / g, and the weight average molecular weight was 7000.

[Synthesis Example 14]
An acrylic copolymer (P-14) was obtained in the same manner as in Synthesis Example 1 except that 20 parts of 2-ethylhexyl methacrylate (2EHMA) was changed to 20 parts of dodecyl acrylate (DOA). The base value of the acrylic copolymer (P-14) was 20 mmol / 100 g, the acid value was 70 mgKOH / g, and the weight average molecular weight was 7000.

[Synthesis Example 15]
An acrylic copolymer (P-15) was obtained in the same manner as in Synthesis Example 1 except that 20 parts of 2-ethylhexyl methacrylate (2EHMA) was changed to 20 parts of stearyl acrylate (SLA). The acrylic copolymer (P-15) had a base number of 20 mmol / 100 g, an acid value of 72 mgKOH / g, and a weight average molecular weight of 7,000.

[Synthesis Example 16]
An acrylic copolymer (P-16) was obtained in the same manner as in Synthesis Example 1 except that methyl methacrylate (MMA) was charged to 50 parts without using 2-ethylhexyl methacrylate (2EHMA). It was. The acrylic copolymer (P-16) had a base number of 20 mmol / 100 g, an acid value of 71 mg KOH / g, and a weight average molecular weight of 7,000.

[Synthesis Example 17]
An acrylic copolymer (P-17) was obtained in the same manner as in Synthesis Example 1 except that the amount of normal dodecyl mercaptan (MDM) charged was 5.0 parts. The acrylic copolymer (P-17) had a base number of 17 mmol / 100 g, an acid value of 72 mgKOH / g, and a weight average molecular weight of 5,000.

[Synthesis Example 18]
An acrylic copolymer (P-18) was obtained in the same manner as in Synthesis Example 1 except that the amount of normal dodecyl mercaptan (MDM) charged was 2.0 parts. The base value of the acrylic copolymer (P-18) was 18 mmol / 100 g, the acid value was 73 mgKOH / g, and the weight average molecular weight was 11000.

[Synthesis Example 19]
An acrylic copolymer (P-19) was obtained in the same manner as in Synthesis Example 1 except that the amount of normal dodecyl mercaptan (MDM) charged was 1.0 part. The acrylic copolymer (P-19) had a base number of 18 mmol / 100 g, an acid value of 73 mg KOH / g, and a weight average molecular weight of 16000.

[Synthesis Example 20]
An acrylic copolymer (P-20) was obtained in the same manner as in Synthesis Example 1 except that normal dodecyl mercaptan (MDM) was not used. The base value of the acrylic copolymer (P-20) was 17 mmol / 100 g, the acid value was 73 mgKOH / g, and the weight average molecular weight was 20000.

[Synthesis Example 21]
An acrylic copolymer (P-21) was obtained in the same manner as in Synthesis Example 1 except that 30 parts of styrene (St) was changed to 30 parts of 4-methylstyrene (4MSt). The base value of the acrylic copolymer (P-21) was 17 mmol / 100 g, the acid value was 72 mgKOH / g, and the weight average molecular weight was 7000.

[Synthesis Example 22]
An acrylic copolymer (P-22) was obtained in the same manner as in Synthesis Example 1 except that 30 parts of styrene (St) was changed to 30 parts of benzyl methacrylate (BzMA). The acrylic copolymer (P-22) had a base number of 18 mmol / 100 g, an acid value of 73 mg KOH / g, and a weight average molecular weight of 7,000.

[Synthesis Example 23]
An acrylic copolymer (P-23) was prepared in the same manner as in Synthesis Example 1 except that the amount of methyl methacrylate (MMA) was changed to 33 parts without using 2-dimethylaminoethyl methacrylate (MLDA). Got. The acrylic copolymer (P-23) had a base number of 0 mmol / 100 g, an acid value of 75 mgKOH / g, and a weight average molecular weight of 7,000.

[Synthesis Example 24]
This was prepared in the same manner as in Synthesis Example 1 except that the amount of methyl methacrylate (MMA) was 17 parts and the amount of 2-dimethylaminoethyl methacrylate (MLDA) was 16 parts, and an acrylic copolymer (P- 24) was obtained. The acrylic copolymer (P-24) had a base number of 95 mmol / 100 g, an acid value of 65 mgKOH / g, and a weight average molecular weight of 7,000.

[Synthesis Example 25]
An acrylic copolymer (P-25) was obtained in the same manner as in Synthesis Example 1 except that the amount of methyl methacrylate (MMA) was changed to 47 parts without using methacrylic acid (MAA). The base value of the acrylic copolymer (P-25) was 20 mmol / 100 g, the acid value was 0 mgKOH / g, and the weight average molecular weight was 7000.

[Synthesis Example 26]
An acrylic copolymer (P-26) was obtained in the same manner as in Synthesis Example 1 except that the amount of methyl methacrylate (MMA) was 40 parts and the amount of methacrylic acid (MAA) was 7 parts. The acrylic copolymer (P-26) had a base number of 18 mmol / 100 g, an acid value of 14 mg KOH / g, and a weight average molecular weight of 7,000.

[Synthesis Example 27]
An acrylic copolymer (P-27) was obtained in the same manner as in Synthesis Example 1 except that the amount of methyl methacrylate (MMA) was 15 parts and the amount of methacrylic acid (MAA) was 32 parts. The acrylic copolymer (P-27) had a base number of 17 mmol / 100 g, an acid value of 157 mg KOH / g, and a weight average molecular weight of 7,000.

[Synthesis Example 28]
An acrylic copolymer (P-28) was obtained in the same manner as in Synthesis Example 1 except that the amount of azobisisobutyronitrile (AIBN) charged was 6.0 parts. The acrylic copolymer (P-28) had a base number of 18 mmol / 100 g, an acid value of 74 mgKOH / g, and a weight average molecular weight of 3000.

[Synthesis Example 29]
An acrylic copolymer (P-29) was prepared in the same manner as in Synthesis Example 1 except that the amount of azobisisobutyronitrile (AIBN) was changed to 0.8 part without using normal dodecyl mercaptan (MDM). Got. The acrylic copolymer (P-29) had a base number of 18 mmol / 100 g, an acid value of 74 mgKOH / g, and a weight average molecular weight of 39000.

[Synthesis Example 30]
An acrylic copolymer (P-30) was obtained in the same manner as in Synthesis Example 1 except that styrene (St) was not used and the amount of methyl methacrylate (MMA) was changed to 60 parts. The base value of the acrylic copolymer (P-30) was 18 mmol / 100 g, the acid value was 73 mgKOH / g, and the weight average molecular weight was 7000.

<Evaluation of acrylic copolymer>
A colorant dispersion and a photosensitive colored resin composition using the acrylic copolymer synthesized as described above were prepared and evaluated.

[Example 1]
Preparation of Colorant Dispersion Liquid 200 g of titanium nitride particles (manufactured by Nissin Engineering Co., Ltd.) produced by a thermal plasma method, and 114 g of a 35% by weight solution of an acrylic copolymer (P-1) in propylene glycol monoethyl ether acetate As a polymer dispersant, 25 g of Dispersic LPN-21116 (DP-1, manufactured by BYK Chemie) having a tertiary amino group and a quaternary ammonium salt and 661 g of propylene glycol monoethyl ether acetate were charged in a tank, and a homomixer (Primics) The mixture was stirred for 20 minutes to obtain a preliminary dispersion. Thereafter, the pre-dispersed liquid was supplied to an ultra apex mill (manufactured by Kotobuki Kogyo Co., Ltd.) equipped with a centrifugal separator filled with 75% 0.05 mmφ zirconia beads (manufactured by Neturen, YTZ ball), and rotated at 8 m / s for 3 hours. Dispersion was performed to obtain a colorant dispersion 1 having a solid content concentration of 25% by weight and a colorant / resin (weight ratio) = 80/20.

  The obtained colorant dispersion 1 had a viscosity immediately after production of 4.2 mPa · s, a viscosity after lapse of 1 week of 4.6 mPa · s, and the dispersion stability was determined to be ◯.

Preparation of photosensitive colored resin composition 33.00 g of this colorant dispersion 1 and 7.53 g of a propylene glycol monoethyl ether acetate 35 wt% solution of acrylic copolymer (P-1), propylene glycol monoethyl ether acetate 55.36 g, “ADEKA (registered trademark) Optomer” N-1919 (Asahi Denka Kogyo Co., Ltd.) 0.99 g, dipentaerythritol hexaacrylate (DHPA, Nippon Kayaku Co., Ltd.) 2.64 g, 3-acrylic A photosensitive colored resin composition was prepared by mixing 0.45 g of roxypropyltrimethoxysilane and 0.04 g of BYK333 (manufactured by Big Chemie Co., Ltd.).

  The resulting photosensitive colored resin composition was applied onto a non-alkali glass (Corning “1737 material”) substrate with a spin coater and prebaked at 90 ° C. for 10 minutes. Thereafter, exposure was performed through a gray tone mask using an exposure machine “XG-5000” manufactured by Dainippon Screen Co., Ltd., and a negative resist was developed using a 0.045% aqueous potassium hydroxide solution. The development time was 33 seconds, and the developability was judged as ◯.

  Furthermore, it was cured at 230 ° C. for 30 minutes to prepare a black matrix having a thickness of 1.0 μm and evaluated for heat resistance. The weight change rate was 1.1%, and it was determined to be “good”.

[Examples 2 to 22 and Comparative Examples 1 to 8]
Instead of the acrylic copolymer (P-1), the acrylic copolymer (P-2 to P-30) in which the characteristic value of the acid value, the base value, and the weight average molecular weight and the partially unsaturated monomer are changed are used. A colorant dispersion and a photosensitive colored resin composition were prepared and evaluated in the same manner as in Example 1 except that they were used.

  Tables 1 to 4 show monomer compositions, analytical values, and evaluation results of the acrylic copolymers used in Examples 1 to 22 and Comparative Examples 1 to 8. The column of “base monomer MMA” in the table represents the charged amount of methyl methacrylate in parts by weight. The column “(A) Introduced Monomer GMA” represents the charged amount of glycidyl methacrylate added in order to introduce a (meth) acrylic unit having an ethylenically unsaturated group in the molecular side chain of the formula (A) in parts by weight. . The column “(C) Monomer MLDA-Cl” indicates the amount of dimethylaminoethyl methyl chloride methacrylate charged in the (meth) acrylic unit having a quaternary ammonium salt in the molecular side chain of the formula (C). Expressed in parts.

  The column of “(B) monomer” represents the kind of monomer added to constitute a (meth) acryl unit having a tertiary amino group in the molecular side chain of the formula (B) and the charged amount in parts by weight. The column of “(D) monomer” represents the type of monomer added to constitute a (meth) acryl unit having a carboxyl group in the molecular side chain of formula (D) and the charged amount in parts by weight. The column of “(E) monomer” represents the type of monomer added to constitute the structure (E) having an aromatic ring in the molecular side chain and the charged amount in parts by weight. The column “(F) monomer” represents the type of monomer added to constitute a (meth) acrylic unit having a long-chain alkyl group in the molecular side chain of formula (F) and the charged amount in parts by weight.

Example 23
High resistance carbon black (manufactured by Cabot Corp.) (150 g), propylene glycol monoethyl ether acetate 35 wt% solution (80 g) of acrylic copolymer (P-1), Dispersic LPN-21116 (polymer dispersant) 23 g) and propylene glycol monoethyl ether acetate (440 g) were charged into a tank and stirred with a homomixer (manufactured by PRIMIX) for 20 minutes to obtain a preliminary dispersion. Thereafter, the pre-dispersed liquid was supplied to an ultra apex mill (manufactured by Kotobuki Industries) equipped with a centrifugal separator filled with 75% 0.05 mmφ zirconia beads (manufactured by Neturen, YTZ balls), and dispersed for 3 hours at a rotational speed of 8 m / s. The pigment dispersion 23 having a solid content concentration of 25% by weight and a pigment / resin (weight ratio) of 70/30 was obtained. The viscosity of the obtained pigment dispersion 23 was 3.3 mPa · s, and no change was observed in the viscosity even after 1 week of preparation.

Example 24
Red pigment (Pigment Red 177) (150 g), propylene glycol monoethyl ether acetate 35 wt% solution (190 g) of acrylic copolymer (P-1), Dispersic 2000 (manufactured by Big Chemie) as a polymer dispersant (150 g) and propylene glycol monoethyl ether acetate (600 g) were charged into a tank and stirred with a homomixer (manufactured by PRIMIX) for 20 minutes to obtain a preliminary dispersion. Thereafter, the preliminary dispersion was supplied to an ultra apex mill (manufactured by Kotobuki Industries) equipped with a centrifugal separator filled with 75% 0.03 mmφ zirconia beads (manufactured by Neturen, YTZ balls), and dispersed for 3 hours at a rotational speed of 8 m / s. The pigment dispersion R1 having a solid content concentration of 25% by weight and a pigment / resin (weight ratio) = 60/40 was obtained. The viscosity of the obtained pigment dispersion R1 was 6.7 mPa · s, and the viscosity one week after production was 6.9 mPa · s.

  33 g of this pigment dispersion R1, 55 g of propylene glycol monoethyl ether acetate, 2 g of “ADEKA (registered trademark) Optomer” N-1919 (manufactured by Asahi Denka Kogyo Co., Ltd.), dipentaerythritol hexaacrylate (Nippon Kayaku Co., Ltd.) A resist composition was prepared by mixing 3 g of M520), 0.5 g of 3-acryloxypropyltrimethoxysilane, and 0.5 g of BYK333 (manufactured by BYK Chemie).

  The obtained resist composition was applied onto a non-alkali glass (“1737 material” manufactured by Corning) substrate using a spin coater and prebaked at 90 ° C. for 10 minutes. Thereafter, exposure is performed through a photomask using an exposure machine “XG-5000” manufactured by Dainippon Screen Co., Ltd., and the negative resist is developed using a 0.1% TMAH aqueous solution. Cure at 30 ° C. for 30 minutes. In this way, a colored coating film R1 having a thickness of 1.0 μm was prepared. The development time of the colored coating film R1 was 36 seconds.

Example 25
Except for changing the acrylic copolymer (P-1) used in Example 24 to the acrylic copolymer (P-2), the same operation as in Example 24 was performed to obtain a pigment dispersion R2 and a colored coating film R2. It was. The viscosity of the obtained pigment dispersion R2 was 5.4 mPa · s, and no change was observed in the viscosity even after 1 week of preparation. The development time of the colored coating film R2 was 27 seconds.

Example 26
In Example 24, a red pigment (Pigment Red 177) (150 g), a charge amount of a 35% by weight propylene glycol monoethyl ether acetate solution of an acrylic copolymer (P-1) was 190 to 230 g, and Dispersic as a polymer dispersant The same procedure as in Example 24 was performed, except that the charged amount of 2000 was changed from 150 g to 100 g, and the charged amount of propylene glycol monoethyl ether acetate was changed from 600 g to 620 g, and the charged amount of the composition was changed. A colored coating film 3 was obtained. The viscosity of the obtained pigment dispersion R3 was 7.0 mPa · s, and the viscosity one week after production was 7.7 mPa · s. The development time of the colored coating film R3 was 27 seconds.

Example 27
A pigment dispersion G1 and a colored coating film G1 were obtained in the same manner as in Example 24 except that the pigment of Example 24 was changed from a red pigment (Pigment Red 177) to a green pigment (Pigment Green 36). The viscosity of the obtained pigment dispersion G1 was 5.4 mPa · s, and the viscosity one week after production was 6.0 mPa · s. The development time for the colored coating G1 was 28 seconds.

Example 28
A pigment dispersion B1 and a colored coating film B1 were obtained in the same manner as in Example 24 except that the pigment of Example 24 was changed from a red pigment (Pigment Red 177) to a blue pigment (Pigment View 15: 3). It was. The viscosity of the obtained pigment dispersion B1 was 7.0 mPa · s, and the viscosity one week after production was 7.3 mPa · s. The development time of the colored coating film B1 was 20 seconds.

[Comparative Example 9]
In Example 1, the acrylic copolymer (P-1) was changed to the acrylic copolymer (P-23), and 71 g of a 35 wt% solution of the acrylic copolymer (P-23) in propylene glycol monoethyl ether acetate was used. Dispersic LPN-21116 (DP-1) 63 g, propylene glycol monoethyl ether acetate 666 g, and a colorant dispersion and a black matrix were prepared in the same manner as in Example 1 except that the amount charged was changed. The obtained colorant dispersion had a viscosity immediately after production of 3.4 mPa · s, and the viscosity after one week elapsed was 3.6 mPa · s. Development time was 111 seconds.

[Comparative Example 10]
In Example 24, except that the acrylic copolymer was changed to (P-23), the same operation as in Example 24 was performed to obtain a pigment dispersion R4. The viscosity of the obtained pigment dispersion was 5.0 mPa · s. However, the pigment dispersion R4 aggregated after 24 hours from the dispersion.

  The colorant dispersions produced in Examples 1 to 22 are compatible with both the dispersion stability and the developability and heat resistance when made into a black matrix as compared with the colorant dispersions produced in Comparative Examples 1 to 8. It can be seen that the acrylic copolymer needs to have characteristic values of a base number, an acid value, and a weight average molecular weight within a specific range. In addition, in order to obtain sufficient heat resistance, it is necessary to introduce an aromatic ring into the side chain, and by introducing a long-chain acrylic group into the side chain, the stability of the pigment dispersion is higher. It turns out that it is.

  In addition, from the results of Comparative Example 9, it is possible to improve the dispersion stability of the acrylic copolymer having no base number by increasing the amount of the polymer dispersant used. The colorant dispersion produced in Examples 1 to 22 using an acrylic copolymer having a tertiary amine or quaternary ammonium salt structure in the side chain was found to impair the developability, and was very effective in performance balance. You can see that

  Further, from the results of Examples 23 to 28, the present invention is not limited to metal pigments such as titanium black, but also to carbon black pigments and organic pigments, as in the case of titanium black, the colorant dispersion having excellent storage stability and plate making characteristics. It can be seen that liquids and photosensitive colored resin compositions can be provided.

  The colorant dispersion and the photosensitive colored resin composition using the acrylic copolymer of the present invention are particularly useful in the field of electronic information materials. However, the acrylic copolymer is also used in coatings, adhesives, and optical materials. It is useful in a wide variety of industrial applications.

Claims (4)

A structure represented by the following formula (A) having an ethylenically unsaturated group in the molecular side chain, a structure represented by the following formula (B) having a tertiary amino group in the side chain, and / or a quaternary in the side chain. An acrylic copolymer having a structure represented by the following formula (C) having an ammonium salt, a structure (D) having a carboxyl group, and a structure (E) having an aromatic ring, and the base of the acrylic copolymer An acrylic copolymer having a valence of 5 to 70 mmol / 100 g, an acid value of 50 to 120 mg KOH / g, and a weight average molecular weight in terms of polystyrene by gel permeation chromatography of 5,000 to 30,000.

(Wherein R ¹ and R ² are each independently a hydrogen atom or a methyl group, R ³ is an alkylene group having 1 to 4 carbon atoms, a divalent alicyclic hydrocarbon group having 3 to 6 carbon atoms, and 6 to 6 carbon atoms) Represents any one selected from 10 divalent aromatic hydrocarbon groups.)

(Wherein R ⁴ is a hydrogen atom or a methyl group, R ⁵ is an alkylene group having 1 to 4 carbon atoms, a divalent alicyclic hydrocarbon group having a carbon number of 3-6, a divalent aromatic of 6 to 10 carbon atoms Any one selected from group hydrocarbon groups, R ⁶ and R ⁷ are each independently an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, an alicyclic hydrocarbon group having 3 to 6 carbon atoms, It represents any one selected from aromatic hydrocarbon groups having 6 to 10 carbon atoms.)

(Wherein R ⁸ represents a hydrogen atom or a methyl group, R ⁹ is an alkylene group having 1 to 4 carbon atoms, a divalent alicyclic hydrocarbon group having a carbon number of 3-6, a divalent aromatic of 6 to 10 carbon atoms R ¹⁰ , R ¹¹ , and R ¹² are each independently selected from an aromatic hydrocarbon group, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, and an alicyclic carbon atom having 3 to 6 carbon atoms. Any one selected from a hydrogen group and an aromatic hydrocarbon group having 6 to 10 carbon atoms, X represents any one of bromine, chlorine, iodine, hydrogen sulfate and hydroxide.) The acrylic copolymer according to claim 1, wherein the structure (D) having the carboxyl group is represented by the following structural formula (D1).

(In the formula, R ¹³ represents a hydrogen atom or a methyl group, n represents an integer of 0 to 6, and may be a single or a mixture of a plurality of n.) The acrylic copolymer according to claim 1 or 2, wherein the structure (E) having the aromatic ring is represented by the following structural formula (E1) or (E2).

(In the formula, R ¹⁴ is hydrogen, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, an alicyclic hydrocarbon group having 3 to 6 carbon atoms, or an aromatic hydrocarbon having 6 to 10 carbon atoms. Represents any one selected from a group, a halogen atom, an ester group, an acyl group and a nitro group.)

(Wherein R ¹⁵ is a hydrogen atom or a methyl group, R ¹⁶ is hydrogen, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, an alicyclic hydrocarbon group having 3 to 6 carbon atoms, carbon It represents one selected from an aromatic hydrocarbon group of several 6 to 10, a halogen atom, an ester group, an acyl group and a nitro group.) The acrylic copolymer according to claim 1, wherein the acrylic copolymer has a structure represented by the following structural formula (F).

(R ¹⁷ represents a hydrogen atom or a methyl group, R ¹⁸ represents a hydrogen atom or an alkyl group having 2 to 20 carbon atoms, and R ¹⁹ represents an alkyl group having 2 to 40 carbon atoms.)