TW201832005A - Photosensitive colored composition, black matrix, colored spacer, image display device and pigment dispersion liquid - Google Patents

Abstract

An object of the present invention is to provide a photosensitive colored composition which has an excellent light-blocking property and an excellent dispersibility and plate making property, and shows a sufficiently low relative permittivity. The photosensitive colored composition of the present invention at least comprises (A) a coloring agent, (B) a dispersing agent, (C) a alkali soluble resin and (D) a photopolymerization initiator, wherein the coloring agent (A) contains (A-1) an organic black pigment that is a compound represented by the formula (1), a geometric isomer of the compound, a salt of the compound, or a salt of the geometric isomer of the compound, and the dispersing agent (B) contains a polymer dispersing agent having a quaternary ammonium base as a functional group.

Description

   Photosensitive coloring composition, black matrix, coloring spacer, image display device, and pigment dispersion liquid   

The present invention relates to a photosensitive coloring composition, a black matrix, a coloring spacer, and an image display device. Specifically, the present invention relates to a photosensitive coloring composition having excellent shielding properties and plate-making properties and uses thereof.

A black matrix system for a liquid crystal display element is used to prevent light leakage between self-driving electrodes in a liquid crystal display element. In general, a black matrix is a pattern of light-shielding materials in the form of stripes or grids formed on a transparent substrate such as a glass or plastic sheet paired with a TFT (Thin Film Transistor) substrate using a photolithography method. Recently, in order to cope with higher definition and higher brightness of color liquid crystal display elements, a color filter array (COA (color filter on array) method or a black matrix on a TFT element substrate (BOA (black matrix on array) method). According to the above-mentioned method, as compared with the case where a black matrix is formed on the color filter side, it is not necessary to provide a margin aligned with the position of the active element side, so that the aperture ratio can be increased. As a result, a high aperture ratio can be achieved. Brightness.

However, in the case where the above-mentioned structure is adopted, the black matrix is required to have a volume resistivity of a certain degree or more and a relative dielectric constant of a certain degree so as not to cause a short circuit even when directly mounted on the TFT element. As such a black matrix, a black matrix using a plurality of organic coloring pigments and carbon black in pigments has been proposed (for example, refer to Patent Document 1).

Further, a photosensitive composition for a black matrix using an organic black pigment as a pigment is also known, and specifically, an aniline black (for example, refer to Patent Document 2) or a perylene black (for example, refer to Patent Document 3) is known. Photosensitive composition. On the other hand, as an organic pigment, a bis-oxodihydro-indolyl-benzofuran colorant is known (for example, refer to Patent Document 4). This document describes a case where the pigment is used in order to form a red layer, a blue layer, and a green layer of a color filter. Moreover, it is known that this pigment can also be used as an organic black pigment for electrophoretic displays (for example, refer patent document 5).

    [Prior technical literature]         [Patent Literature]    

Patent Document 1: Japanese Patent Laid-Open No. 2009-75446

Patent Document 2: Japanese Patent Laid-Open No. 8-44049

Patent Document 3: Japanese Patent Laid-Open No. 2006-235153

Patent Document 4: Japanese Patent Publication No. 2002-528448

Patent Document 5: Japanese Patent Publication No. 2012-515240

The inventors of the present inventors conducted diligent research, and as a result, it was found that the photosensitive composition-based organic coloring pigment described in Patent Document 1 has a low shielding rate (optical density), and it is necessary to increase the film thickness in order to obtain a sufficient optical density. Further, it was found that the dispersibility of the aniline black or perylene black described in Patent Document 2 or 3 is poor, a large amount of dispersant must be used for dispersion, and problems such as plate-making properties may occur. In addition, it was found that the shielding ratio (optical density) was insufficient.

Furthermore, in Patent Document 4 or 5, there is no description or teaching about using a bis-oxodihydro-indolyl-benzofuran colorant as a masking agent for an image display device, and there is no description regarding the use as a shielding agent. The characteristics of optical density, dispersibility, or plate-making property when used as a masking agent for an image display device are also unclear. The present invention has been made in view of the above-mentioned actual situation, and an object of the present invention is to provide a photosensitive coloring composition having excellent light-shielding properties, excellent dispersibility or plate-making properties, and showing a sufficiently low relative dielectric constant.

The present inventors made diligent research in order to solve the above-mentioned problems, and as a result, they found that the above-mentioned problems can be solved by using an organic black pigment having a specific structure as a colorant in the photosensitive coloring composition and using a specific dispersant, thereby The present invention has been completed. That is, the present invention has the following structures [1] to [17].

[1] A photosensitive coloring composition comprising at least (A) a colorant, (B) a dispersant, (C) an alkali-soluble resin, and (D) a photopolymerization initiator, and the (A) color The organic black pigment (A-1) is a compound represented by the following general formula (1), a geometric isomer thereof, a salt thereof, or a salt of a geometric isomer thereof, and the dispersant (B) contains Polymer dispersant with quaternary ammonium salt as functional group,

[In formula (1), R ¹ and R ⁶ are each independently a hydrogen atom, CH ₃ , CF ₃ , a fluorine atom, or a chlorine atom; R ² , R ³ , R ⁴ , R ⁵ , R ⁷ , R ⁸ , R ⁹ and R ¹⁰ lines and all of the other independently of one another, a hydrogen atom, a halogen ^{atom, R 11, COOH, COOR 11} , COO -, CONH 2, CONHR 11, CONR 11 R 12, CN, OH, OR 11, COCR 11, OOCNH ₂ OOCNHR ¹¹ OOCNR ¹¹ R ¹² NO ₂ NH ₂ NHR ¹¹ NR ¹¹ R ¹² NHCOR ¹² NR ¹¹ COR ¹² N = CH ₂ N = CHR ¹¹ N = CR ¹¹ R ¹² SH ^{, SR 11, SOR 11, SO} 2 R 11, SO 3 R 11, SO 3 H, SO 3 -, SO 2 NH 2, SO 2 NHR 11 or SO ₂ NR ¹¹ R ^12; and selected from the group consisting of R ² and R ³ , At least one combination of R ³ and R ⁴ , R ⁴ and R ⁵ , R ⁷ and R ⁸ , R ⁸ and R ⁹ , and R ⁹ and R ¹⁰ , can be directly bonded to each other, or Bonded to each other by bridging with oxygen atom, sulfur atom, NH or NR ¹¹ ; R ¹¹ and R ¹² are independent of each other as an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms, and 2 to 12 carbon atoms Alkenyl, cycloalkenyl having 3 to 12 carbons or alkynyl having 2 to 12 carbons].

[2] The photosensitive coloring composition according to [1], wherein in the general formula (1) above, R ² , R ⁴ , R ⁵ , R ⁷ , R ^9, and R ¹⁰ are each independently a hydrogen atom , Fluorine atom or chlorine atom, and R ³ and R ⁸ are independently hydrogen atom, NO ₂ , OCH ₃ , OC ₂ H ₅ , bromine atom, chlorine atom, CH ₃ , C ₂ H ₅ , N (CH ₃ ) ₂ , the same, R ¹ and R ^6, R ² and ^{_{R - N (CH 3) (}} C 2 H 5), N (C 2 H 5) 2, α- naphthyl, β- naphthyl group, SO ₃ H or SO ₃ ^{7 is the} same, R ³ is the same as R ⁸ , R ⁴ is the same as R ⁹ , and R ⁵ is the same as R ¹⁰ .

[3] The photosensitive coloring composition according to [1] or [2], wherein the polymer dispersant further has a tertiary amine as a functional group.

[4] The photosensitive coloring composition according to any one of [1] to [3], wherein the (C) alkali-soluble resin contains the following alkali-soluble resin (c1) and the following alkali-soluble resin (c2) At least one of them is <alkaline soluble resin (c1)>. By adding an α, β-unsaturated monocarboxylic acid or an α, β-unsaturated monocarboxylic acid ester having a carboxyl group to an epoxy resin, the polyacrylic acid And / or an alkali-soluble resin obtained by reacting the anhydride; <alkali-soluble resin (c2)> by adding an α, β-unsaturated monocarboxylic acid or an α, β-unsaturated monocarboxylic acid ester having a carboxyl group to An epoxy resin, and an alkali-soluble resin obtained by reacting with a polyhydric alcohol and a polybasic acid and / or an anhydride thereof.

[5] The photosensitive coloring composition according to any one of [1] to [4], wherein the (A) colorant further contains (A-2) an organic coloring pigment.

[6] The photosensitive coloring composition according to [5], wherein the (A-2) organic coloring pigment contains at least one of the following pigments,

Blue: Chroma Index Pigment Blue 60, or 15: 6

Red: Chromaticity Index Pigment Red 177, 254, or 272

Violet: Chromaticity Index Pigment Violet 23, or 29

Orange: Chromatic Index Pigment Orange 43, 64, or 72.

[7] The photosensitive coloring composition according to [5] or [6], wherein the content ratio of the (A-1) organic black pigment is 30 to 90% by mass relative to 100% by mass of the colorant (A), (A-2) The content ratio of the organic coloring pigment is 10 to 70% by mass.

[8] The photosensitive coloring composition according to any one of [1] to [7], wherein the (A) colorant further contains (A-3) carbon black.

[9] The photosensitive coloring composition according to [8], wherein the content ratio of the (A-1) organic black pigment is 50 to 90% by mass relative to 100% by mass of the colorant (A), (A-3 The content of carbon black is 10 to 50% by mass.

[10] The photosensitive coloring composition according to any one of [1] to [9], wherein the (D) photopolymerization initiator is an oxime ester initiator and / or a ketoxime ester initiator.

[11] A cured product obtained by curing the photosensitive coloring composition according to any one of [1] to [10].

[12] A black matrix formed of the hardened body of [11].

[13] A colored spacer formed of the hardened body of [11].

[14] An image display device including the black matrix of [12] or the colored spacer of [13].

[15] A pigment dispersion liquid containing (A) a colorant and (B) a dispersant, and the (A) colorant contains (A-1) a compound represented by the following general formula (1) , An organic black pigment of a geometric isomer, a salt thereof, or a salt of a geometric isomer thereof, and the (B) dispersant contains a polymer dispersant having a quaternary ammonium salt group as a functional group,

[Wherein R ¹ and R ⁶ are each independently a hydrogen atom, CH ₃ , CF ₃ , fluorine atom or chlorine atom; R ² , R ³ , R ⁴ , R ⁵ , R ⁷ , R ⁸ , R ⁹ and R ¹⁰ lines and all of the other independently of one another, a hydrogen atom, a halogen ^{atom, R 11, COOH, COOR 11} , COO -, CONH 2, CONHR 11, CONR 11 R 12, CN, OH, OR 11, COCR 11, OOCNH 2, OOCNHR ¹¹ , OCNCR ¹¹ R ¹² , NO ₂ , NH ₂ , NHR ¹¹ , NR ¹¹ R ¹² , NHCOR ¹² , NR ¹¹ COR ¹² , N = CH ₂ , N = CHR ¹¹ , N = CR ¹¹ R ¹² , SH, SR ^{11 _{, SOR 11, SO 2 R 11}} , SO 3 R 11, SO 3 H, SO 3 -, SO 2 NH 2, SO 2 NHR 11 or SO ₂ NR ¹¹ R ^12; and selected from the group consisting of R ² and R ^3, R ³ And at least one combination of R ⁴ , R ⁴ and R ⁵ , R ⁷ and R ⁸ , R ⁸ and R ⁹ , and R ⁹ and R ¹⁰ can be directly bonded to each other, or by An oxygen atom, a sulfur atom, NH or NR ^{11 are} bridged and bonded to each other; R ¹¹ and R ¹² are independently of each other an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms, and an olefin having 2 to 12 carbon atoms Group, cycloalkenyl group having 3 to 12 carbon atoms or alkynyl group having 2 to 12 carbon atoms].

[16] The pigment dispersion liquid according to [15], wherein, in the general formula (1), in the formula, R ² , R ⁴ , R ⁵ , R ⁷ , R ^9, and R ¹⁰ are independently a hydrogen atom and fluorine Atom or chlorine atom, and R ³ and R ⁸ are independently hydrogen atom, NO ₂ , OCH ₃ , OC ₂ H ₅ , bromine atom, chlorine atom, CH ₃ , C ₂ H ₅ , N (CH ₃ ) ₂ , N ( the same, R ¹ and R ^6, the same as R ² and _{^{R 7 - CH 3) (C}} 2 H 5), N (C 2 H 5) 2, α- naphthyl, β- naphthyl group, SO ₃ H or SO ₃ R ³ is the same as R ⁸ , R ⁴ is the same as R ⁹ , and R ⁵ is the same as R ¹⁰ .

[17] The pigment dispersion liquid according to [15] or [16], wherein the polymer dispersant further has a tertiary amine as a functional group.

Since the photosensitive coloring composition of the present invention contains an organic black pigment having a specific structure, the amount of a dispersant can be reduced when a pigment dispersion is produced, and therefore, it exhibits excellent plate-making properties and excellent dispersibility. Therefore, the black matrix formed from the photosensitive coloring composition of the present invention exhibits excellent light-shielding properties. In addition, even if the black matrix and the colored spacers of the present invention are formed on a TFT element substrate, they have a sufficiently low relative dielectric constant that does not cause short circuits or malfunctions. The image display device having the black matrix of the present invention does not have problems such as TFT failure or chaos of liquid crystal driving, and has excellent reliability.

10‧‧‧ transparent support substrate

20‧‧‧ pixels

30‧‧‧ Organic protective layer

40‧‧‧ inorganic oxide film

50‧‧‧ transparent anode

51‧‧‧ Hole injection layer

52‧‧‧ Hole Transmission Layer

53‧‧‧Light-emitting layer

54‧‧‧ Electron injection layer

55‧‧‧ cathode

100‧‧‧Organic EL element

500‧‧‧Organic luminous body

FIG. 1 is a schematic cross-sectional view showing an example of an organic EL element.

Hereinafter, embodiments of the present invention will be specifically described, but the present invention is not limited to the following embodiments, and can be implemented with various modifications within the scope of the gist thereof. In the present invention, the "(meth) acryl group" means "acryl group and / or methacryl group", and "(meth) acrylate" and "(meth) acryl group" The same.

The so-called "(co) polymer" means including both homopolymers (homopolymers) and copolymers (copolymers). The so-called "acids (anhydrides)" and "(anhydrous) ... acids" include acids And its anhydride. The "acrylic resin" in the present invention means a (co) polymer containing (meth) acrylic acid and a (co) polymer containing (meth) acrylate having a carboxyl group.

In addition, the "monomer" in the present invention is a term for a so-called high molecular substance (polymer), and includes a dimer, trimer, oligomer, etc. in addition to a monomer in a narrow sense. meaning. The "total solid content" in the present invention means all components other than the solvent contained in the photosensitive coloring composition or the ink described below. The weight average molecular weight in the present invention refers to a weight average molecular weight (Mw) in terms of polystyrene obtained by GPC (gel permeation chromatography). In addition, the "amine value" in the present invention indicates an amine value in terms of effective solid content unless otherwise specified, and is a value expressed by the mass of KOH equivalent to the alkali amount per 1 g of the solid content of the dispersant. The measurement method is described below. On the other hand, the so-called "acid value" indicates the acid value in terms of effective solid content unless otherwise specified in advance, and is calculated by neutralization titration.

In addition, in this specification, the percentage or part represented by "mass" is synonymous with the percentage or part represented by "weight".

    [Photosensitive coloring composition]    

The photosensitive coloring composition of the present invention (hereinafter sometimes referred to as a "photosensitive coloring composition" or "colored resin composition") contains

(A) Pigment

(B) Dispersant

(C) Alkali soluble resin

(D) Photopolymerization initiator

As an essential component, and further containing other formulation ingredients such as an adhesion improver such as an organic solvent and a silane coupling agent, a coating improver, a development improver, an ultraviolet absorber, an antioxidant, a surfactant, and a pigment derivative, if necessary In addition, each preparation component is usually used in a state of being dissolved or dispersed in an organic solvent.

    <(A) Colorant>    

The (A) colorant used in the present invention contains (A-1) an organic black pigment which is a compound represented by the following general formula (1), a geometric isomer thereof, a salt thereof, or a salt of a geometric isomer thereof. .

[In formula (1), R ¹ and R ⁶ are each independently a hydrogen atom, CH ₃ , CF ₃ , a fluorine atom, or a chlorine atom; R ² , R ³ , R ⁴ , R ⁵ , R ⁷ , R ⁸ , R ⁹ and R ¹⁰ lines and all of the other independently of one another, a hydrogen atom, a halogen ^{atom, R 11, COOH, COOR 11} , COO -, CONH 2, CONHR 11, CONR 11 R 12, CN, OH, OR 11, COCR 11, OOCNH ₂ , OOCNHR ¹¹ , OOCNR ¹¹ R ¹² , NO ₂ , NH ₂ , NHR ¹¹ , NR ¹¹ R ¹² , NHCOR ¹² , NR ¹¹ COR ¹² , N = CH ₂ , N = CHR ¹¹ , N = CR ¹¹ R ¹² , SH ^{, SR 11, SOR 11, SO} 2 R 11, SO 3 R 11, SO 3 H, SO 3 -, SO 2 NH 2, SO 2 NHR 11 or SO ₂ NR ¹¹ R ^12; and selected from the group consisting of R ² and R ³ , At least one combination of the group consisting of, R ³ and R ⁴ , R ⁴ and R ⁵ , R ⁷ and R ⁸ , R ⁸ and R ⁹ , and R ⁹ and R ¹⁰ , can be directly bonded to each other, Or they are bonded to each other by bridging with oxygen atom, sulfur atom, NH or NR ¹¹ ; R ¹¹ and R ¹² are independent of each other as an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms, and 2 to 12 carbon atoms. 12 alkenyl, 3 to 12 carbon alkenyl or 2 to 12 alkynyl]. The geometric isomer of the compound represented by the general formula (1) has the following core structure (but the substituents in the structural formula are omitted), and the trans-trans isomer may be the most stable.

In the case where the compound represented by the general formula (1) is anionic, it is preferable to use any known appropriate cation, such as a metal, organic, inorganic, or metal organic cation, and specifically, an alkali metal, an alkaline earth metal , Transition metal, primary ammonium, secondary ammonium, trialkylammonium and other tertiary ammonium, tetraalkylammonium and other quaternary ammonium or organometallic complexes to compensate their charges. When the geometric isomer of the compound represented by the general formula (1) is anionic, the same salt is preferred.

Among the substituents of the general formula (1) and the definitions of these, the following are preferred in terms of the tendency for the shielding rate to increase. The reason for this is that the following substituents are considered to have no absorption and do not affect the hue of the pigment. R ² , R ⁴ , R ⁵ , R ⁷ , R ⁹ and R ¹⁰ are independent of each other, preferably a hydrogen atom, a fluorine atom, or a chlorine atom, and more preferably a hydrogen atom. R ³ and R ⁸ are independent of each other, preferably hydrogen atom, NO ₂ , OCH ₃ , OC ₂ H ₅ , bromine atom, chlorine atom, CH ₃ , C ₂ H ₅ , N (CH ₃ ) ₂ , N (CH _{3 ) (C 2 H 5),} N (C 2 H 5) 2, α- naphthyl, β- naphthyl group, SO ₃ H or SO ₃ ^-, further preferably a hydrogen atom or SO ₃ H.

R ¹ and R ⁶ are independent of each other, preferably a hydrogen atom, CH ₃ or CF ₃ , and further preferably a hydrogen atom. Preferably, at least one combination selected from the group consisting of R ¹ and R ⁶ , R ² and R ⁷ , R ³ and R ⁸ , R ⁴ and R ⁹ , and R ⁵ and R ¹⁰ is the same, more preferably R ¹ is the same as R ⁶ , R ² is the same as R ⁷ , R ³ is the same as R ⁸ , R ⁴ is the same as R ⁹ , and R ⁵ is the same as R ¹⁰ .

Examples of the alkyl group having 1 to 12 carbon atoms include methyl, ethyl, n-propyl, isopropyl, n-butyl, second butyl, isobutyl, third butyl, 2-methylbutyl, and n-butyl. Amyl, 2-pentyl, 3-pentyl, 2,2-dimethylpropyl, n-hexyl, heptyl, n-octyl, 1,1,3,3-tetramethylbutyl, 2-ethyl Hexyl, nonyl, decyl, undecyl or dodecyl.

Cycloalkyl groups having 3 to 12 carbon atoms are, for example, cyclopropyl, cyclopropylmethyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclohexylmethyl, trimethylcyclohexyl, thujyl, norbornel base, , Norcaryl, caryl, Group, norpinyl, pinyl, 1-adamantyl or 2-adamantyl.

Alkenyl groups having 2 to 12 carbon atoms are, for example, vinyl, allyl, 2-propen-2-yl, 2-buten-1-yl, 3-buten-1-yl, 1,3-butadiene 2-yl, 2-penten-1-yl, 3-penten-2-yl, 2- 1-butene-3-yl, 2-methyl-3-buten-2-yl, 3-methyl-2-buten-1-yl, 1,4-pentadien-3-yl , Hexenyl, octenyl, nonenyl, decenyl or dodecenyl.

The cycloalkenyl group having 3 to 12 carbon atoms is, for example, 2-cyclobuten-1-yl, 2-cyclopenten-1-yl, 2-cyclohexen-1-yl, 3-cyclohexen-1-yl , 2,4-cyclohexadien-1-yl, 1-pair Ene-8-yl, 4 (10) -thuberene-10-yl, 2-nor En-1-yl, 2,5-nor Dien-1-yl, 7,7-dimethyl-2,4-norbornadien-3-yl or camphenyl.

Examples of the alkynyl group having 2 to 12 carbon atoms are 1-propyn-3-yl, 1-butyn-4-yl, 1-pentyn-5-yl, and 2-methyl-3-butyn-2-yl. , 1,4-pentadiyn-3-yl, 1,3-pentadiyn-5-yl, 1-hexyne-6-yl, cis-3-methyl-2-pentene-4-yne- 1-yl, trans-3-methyl-2-pentene-4-yn-1-yl, 1,3-hexadiyn-5-yl, 1-octyne-8-yl, 1-nonynyl- 9-yl, 1-decyne-10-yl or 1-dodecyne-12-yl.

The halogen atom is, for example, a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom.

The preferable organic black pigment of (A-1) is a compound represented by the following general formula (2).

Specific examples of such an organic black pigment include Irgaphor (registered trademark) Black S 0100 CF (manufactured by BASF) as a trade name. The organic black pigment (A-1) is preferably used by being dispersed by a dispersant, a solvent, and a method described below. In addition, if a sulfonic acid derivative of the general formula (2) is present at the time of dispersion, the dispersibility or storage stability may be improved.

The photosensitive coloring composition of the present invention may contain a colorant other than (A-1) as the (A) colorant. As the colorant, a dye pigment can be used, but in terms of heat resistance, light resistance, and the like, a pigment is preferred. In particular, (A-2) an organic coloring pigment and / or (A-3) carbon black can be preferably used. In addition, the so-called organic coloring pigment in the present specification is a powder containing an organic compound used for coloring as a component, and means that it is insoluble in water or oil.

As the (A-2) organic coloring pigment, blue pigment, green pigment, red pigment, yellow pigment, purple pigment, orange pigment, brown pigment, black pigment other than (A-1) and (A-3), etc. can be used. Organic pigments of various colors. In addition, as the structure, azo-based, phthalocyanine-based, quinacridone-based, benzimidazolone-based, isoindolinone-based, or In addition to organic pigments, such as cyanide and indanthrene, various inorganic pigments can also be used. In addition, in this specification, unless specifically stated in advance, the color of a pigment means the color which appears when using this pigment as a coloring material alone to form a photosensitive coloring composition. That is, for example, a black pigment means a pigment whose color is black when a photosensitive coloring composition is formed by using the pigment alone as a colorant.

In the following, specific examples of pigments which can be used in the present invention are represented by pigment numbers. The terms "C.I. Pigment Red 2" and the like listed below mean the chromaticity index (C.I.). Examples of the red pigment include CI Pigment Red 1, 2, 3, 4, 5, 6, 7, 8, 9, 12, 14, 15, 16, 17, 21, 22, 23, 31, 32, 37, 38, 41, 47, 48, 48: 1, 48: 2, 48: 3, 48: 4, 49, 49: 1, 49: 2, 50: 1, 52: 1, 52: 2, 53, 53: 1, 53: 2, 53: 3, 57, 57: 1, 57: 2, 58: 4, 60, 63, 63: 1, 63: 2, 64, 64: 1, 68, 69, 81, 81: 1, 81: 2, 81: 3, 81: 4, 83, 88, 90: 1, 101, 101: 1, 104, 108, 108: 1, 109, 112, 113, 114, 122, 123, 144, 146, 147, 149, 151, 166, 168, 169, 170, 172, 173, 174, 175, 176, 177, 178, 179, 181, 184, 185, 187, 188, 190, 193, 194, 200, 202, 206, 207, 208, 209, 210, 214, 216, 220, 221, 224, 230, 231, 232, 233, 235, 236, 237, 238, 239, 242, 243, 245, 247, 249, 250, 251, 253, 254, 255, 256, 257, 258, 259, 260, 262, 263, 264, 265, 266, 267, 268, 269, 270, 271, 272, 273, 274, 275, 276. Among them, preferred examples include CI Pigment Red 48: 1, 122, 168, 177, 202, 206, 207, 209, 224, 242, and 254. Further preferred examples include CI Pigment Red 177, 209, 224, and 254. . In terms of dispersibility or light-shielding properties, it is preferable to use CI Pigment Red 177, 254, and 272. When the photosensitive coloring composition of the present invention is hardened by ultraviolet rays, it is preferable to use a red pigment. In order to use those having a low ultraviolet absorption rate, it is more preferable to use CI Pigment Red 254 and 272 from this viewpoint.

Examples of the blue pigment include CI Pigment Blue 1, 1: 2, 9, 14, 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, 16, 17, 19, 25 , 27, 28, 29, 33, 35, 36, 56, 56: 1, 60, 61, 61: 1, 62, 63, 66, 67, 68, 71, 72, 73, 74, 75, 76, 78 , 79. Among them, preferably, C.I. Pigment Blue 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, and more preferably C.I. Pigment Blue 15: 6. Furthermore, in terms of dispersibility or light-shielding properties, it is preferable to use CI Pigment Blue 15: 6, 16, 60. When the photosensitive coloring composition of the present invention is hardened by ultraviolet rays, it is used as a blue pigment. It is preferable to use the one having a lower ultraviolet absorption rate. From this viewpoint, it is more preferable to use CI Pigment Blue 60.

Examples of the green pigment include C.I. Pigment Green 1, 2, 4, 7, 8, 10, 13, 14, 15, 17, 18, 19, 26, 36, 45, 48, 50, 51, 54, 55. Among them, C.I. Pigment Green 7, 36 is preferable. Examples of the yellow pigment include: CI Pigment Yellow 1, 1: 1, 2, 3, 4, 5, 6, 9, 10, 12, 13, 14, 16, 17, 24, 31, 32, 34, 35, 35: 1, 36, 36: 1, 37, 37: 1, 40, 41, 42, 43, 48, 53, 55, 61, 62, 62: 1, 63, 65, 73, 74, 75, 81, 83, 87, 93, 94, 95, 97, 100, 101, 104, 105, 108, 109, 110, 111, 116, 117, 119, 120, 126, 127, 127: 1, 128, 129, 133, 134, 136, 138, 139, 142, 147, 148, 150, 151, 153, 154, 155, 157, 158, 159, 160, 161, 162, 163, 164, 165, 166, 167, 168, 169, 170, 172, 173, 174, 175, 176, 180, 181, 182, 183, 184, 185, 188, 189, 190, 191, 191: 1, 192, 193, 194, 195, 196, 197, 198, 199, 200, 202, 203, 204, 205, 206, 207, 208. Among them, preferably, C.I. Pigment Yellow 83, 117, 129, 138, 139, 150, 154, 155, 180, 185, and more preferably, C.I. Pigment Yellow 83, 138, 139, 150, 180.

Examples of orange pigments include CI pigment orange 1, 2, 5, 13, 16, 17, 19, 20, 21, 22, 23, 24, 34, 36, 38, 39, 43, 46, 48. , 49, 61, 62, 64, 65, 67, 68, 69, 70, 71, 72, 73, 74, 75, 77, 78, 79. Among them, preferred examples include C.I. pigment oranges 38 and 71. In terms of dispersibility or light-shielding properties, it is preferable to use CI pigment oranges 43, 64, and 72. When the photosensitive coloring composition of the present invention is hardened by ultraviolet rays, it is preferable as an orange pigment. In order to use those having a lower ultraviolet absorption rate, it is more preferable to use CI pigment oranges 64 and 72 from this viewpoint.

Examples of the purple pigment include CI Pigment Violet 1, 1: 1,2, 2: 2, 3, 3: 1, 3: 3, 5, 5: 1, 14, 15, 16, 19, 23, 25, 27, 29, 31, 32, 37, 39, 42, 44, 47, 49, 50. Among them, C.I. Pigment Violet 19 and 23 are preferred, and C.I. Pigment Violet 23 is further preferred. Furthermore, in terms of dispersibility or light-shielding properties, CI pigment violets 23 and 29 are preferably used. When the photosensitive coloring composition of the present invention is hardened by ultraviolet rays, it is preferably used as a purple pigment. From this viewpoint, it is more preferable to use CI Pigment Violet 29 from the viewpoint of lower ultraviolet absorption.

Among these, it is preferred to contain at least one or more of the following pigments.

Blue: Chroma Index Pigment Blue 60, or 15: 6

Red: Chromaticity Index Pigment Red 177, 254, or 272

Violet: Chromaticity Index Pigment Violet 23 or 29

Orange: Chromaticity Index Pigment Orange 43, 64 or 72

In addition, when using pigments of different colors in combination, the combination of colors is not particularly limited. From the viewpoint of light-shielding properties, examples include a combination of a red pigment and a blue pigment, or a blue pigment. In combination with orange and purple pigments.

A dye may be used instead of the (A-2) organic coloring pigment, and a dye may be used in addition to the (A-2) organic coloring pigment. Examples of dyes that can be used as colorants include azo dyes, anthraquinone dyes, phthalocyanine dyes, quinimine dyes, quinoline dyes, nitro dyes, carbonyl dyes, and methine groups. Department of dyes and so on. Examples of the azo dyes include CI Acid Yellow 11, CI Acid Orange 7, CI Acid Red 37, CI Acid Red 180, CI Acid Blue 29, CI Direct Red 28, CI Direct Red 83, CI Direct Yellow 12, CI Direct Orange 26, CI Direct Green 28, CI Direct Green 59, CI Reactive Yellow 2, CI Reactive Red 17, CI Reactive Red 120, CI Reactive Black 5, CI Disperse Orange 5, CI Disperse Red 58, CI Disperse Blue 165, CI Basic Blue 41, CI Basic Red 18, CI Mordant Red 7, CI Mordant Yellow 5, CI Mordant Black 7, and the like.

Examples of the anthraquinone-based dye include CI reduction blue 4, CI acid blue 40, CI acid green 25, CI reactive blue 19, CI reactive blue 49, CI disperse red 60, CI disperse blue 56, CI disperse blue 60 and so on. In addition, examples of the phthalocyanine dye include CI reduction blue 5 and the like, and examples of the quinone imine dye include CI basic blue 3 and CI basic blue 9 as the quinoline dye. Examples include CI solvent yellow 33, CI acid yellow 3, CI disperse yellow 64, and the like. Examples of the nitro dye include CI acid yellow 1, CI acid orange 3, and CI disperse yellow 42.

Moreover, a black pigment other than (A-1) can also be used for the photosensitive coloring composition of this invention. The black pigment other than (A-1) may be a single black pigment, or may be a mixture of red, green, and blue. These colorants can be appropriately selected from inorganic or organic pigments and dyes.

Examples of colorants that can be mixed for use in the preparation of black colorants include Victoria Pure Blue (42595), Aumine O (41000), Catilon Luflavin (basic 13), and Rose Red 6GCP. (45160), Rose B (45170), Saffron OK70: 100 (50240), Wool Poppy X (42080), No. 120 / Leonor Yellow (21090), Leonor Yellow GRO (21090), West Symuler Fast Yellow 8GF (21105), benzidine Yellow 4T-564D (21095), Symuler Fast Red 4015 (12355), Leonor 7B4401 (15850), Fast Gen Blue TGR -L (74160), Leonor Blue SM (26150), Leonor Blue ES (Pigment Blue 15: 6), Lionogen Red GD (Pigment Red 168), Leonor Green 2YS (Pigment Green 36), etc. (re Or, the number in the above () means chromaticity index (CI)).

Furthermore, regarding other pigments that can be used in combination, if they are represented by CI numbers, for example, CI yellow pigments 20, 24, 86, 93, 109, 110, 117, 125, 137, 138, 147, 148, 153, 154, 166; CI orange pigment 36, 43, 51, 55, 59, 61; CI red pigment 9, 97, 122, 123, 149, 168, 177, 180, 192, 215, 216, 217, 220, 223, 224, 226, 227, 228, 240; CI purple pigments 19, 23, 29, 30, 37, 40, 50; CI blue pigments 15, 15: 1, 15: 4, 22, 60, 64; CI Green pigment 7; CI brown pigment 23, 25, 26, etc.

Examples of the black colorant that can be used alone include acetylene black, lamp black, bone black, graphite, iron black, aniline black, cyan black, titanium black, and black.

From the standpoint of light shielding rate and image characteristics, it is preferable to use (A-3) carbon black as a colorant other than (A-1) an organic black pigment. Examples of the carbon black include the following carbon blacks.

Manufactured by Mitsubishi Chemical Corporation: MA7, MA8, MA11, MA77, MA100, MA100R, MA100S, MA220, MA230, MA600, MCF88, # 5, # 10, # 20, # 25, # 30, # 32, # 33, # 40 # 44, # 45, # 47, # 50, # 52, # 55, # 650, # 750, # 850, # 900, # 950, # 960, # 970, # 980, # 990, # 1000, # 2200, # 2300, # 2350, # 2400, # 2600, # 2650, # 3030, # 3050, # 3150, # 3250, # 3400, # 3600, # 3750, # 3950, # 4000, # 4010, OIL7B, OIL9B , OIL11B, OIL30B, OIL31B

Made by Degussa: Printex (registered trademark, the same below) 3, Printex3OP, Printex30, Printex30OP, Printex40, Printex45, Printex55, Printex60, Printex75, Printex80, Printex85, Printex90, Printex A, Printex L, Printex G, Printex P, Printex U , Printex V, PrintexG, SpecialBlack550, SpecialBlack350, SpecialBlack250, SpecialBlack100, SpecialBlack6, SpecialBlack5, SpecialBlack4, Color Black FW1, Color Black FW2, Color Black FW2V, Color Black FW18, Color Black FW18, Color Black FW200, Color Black S160, Color Black S170

Manufactured by Cabot: Monarch (registered trademark, the same below) 120, Monarch280, Monarch460, Monarch800, Monarch880, Monarch900, Monarch1000, Monarch1100, Monarch1300, Monarch1400, Monarch4630, REGAL (registered trademark, the same below) 99, REGAL99R, REGAL415, REGAL415R, REGAL250, REGAL250R, REGAL330, REGAL400R, REGAL55R0, REGAL660R, BLACK PEARLS480, PEARLS130, VULCAN (registered trademark, the same below) XC72R, ELFTEX (registered trademark) -8

Made by Columbia Carbon: RAVEN (registered trademark, the same below) 11, RAVEN14, RAVEN15, RAVEN16, RAVEN22, RAVEN30, RAVEN35, RAVEN40, RAVEN410, RAVEN420, RAVEN450, RAVEN500, RAVEN780, RAVEN850, RAVEN890H, RAVEN1000, RAVENI020, RAVEN1040, RAVEN1060U , RAVEN1080U, RAVENI170, RAVEN1190U, RAVEN1250, RAVEN1500, RAVEN2000, RAVEN2500U, RAVEN3500, RAVEN5000, RAVEN5250, RAVEN5750, RAVEN7000

Carbon black can also be used as a resin coating. If carbon black coated with a resin is used, it has the effect of improving the adhesion to the glass substrate or the volume resistance value. As the carbon black coated with a resin, for example, the carbon black described in Japanese Patent Application Laid-Open No. 09-71733 can be preferably used.

As the carbon black to be used for the coating treatment with the resin, the total content of Na and Ca is preferably 100 ppm or less. Carbon black usually contains Na, or Ca, K, Mg, Al mixed with the raw material oil or combustion oil (or gas), the reaction termination water or the granulated water, and the furnace material of the reaction furnace. , Fe, etc. as the composition of the ash. Among them, Na or Ca usually contains hundreds of ppm or more, respectively. The reason is that if such a large amount is present, it may penetrate into a transparent electrode (ITO) or other electrodes and become an electrical short circuit.

As a method to reduce the content of such ash containing Na or Ca, it is possible to strictly select those with very low content as the raw material oil or fuel oil (or gas) and the reaction termination water when producing carbon black; and minimize the adjustment of the structure The amount of alkaline substances added. Other methods include a method of washing carbon black produced from a furnace with water or hydrochloric acid, and dissolving and removing Na or Ca.

Specifically, if carbon black is mixed and dispersed in water, hydrochloric acid, or hydrogen peroxide water, and a solvent that is hardly soluble in water is added, the carbon black migrates to the solvent side and is completely separated from the water. Most of the Na or Ca is dissolved in water or acid and removed. In order to reduce the total amount of Na and Ca to less than 100 ppm, although the carbon black manufacturing process of strictly selected raw materials can be achieved alone, or water or acid dissolving methods can be separately achieved, but by using the above two methods in combination, Further, the total amount of Na and Ca can be easily set to 100 ppm or less.

The resin-coated carbon black is preferably a so-called acidic carbon black having a pH of 6 or less. Since the dispersion diameter (agglomeration diameter) in water becomes smaller, it becomes possible to cover fine cells, which is preferable. It is more preferable that the particle diameter is 40 nm or less and the absorption amount of dibutyl phthalate (DBP) is 140 ml / 100 g or less. The reason is that if the particle diameter is greater than 40nm and the DBP absorption is greater than 140ml / 100g, the dispersibility when it is made into a paste is excellent, but the concentration feeling of the coating film is not sufficient. If the film thickness is about 1 ~ 2μm, it may be The light-shielding property may become insufficient.

There is no particular limitation on the method for preparing carbon black coated with resin. For example, after the carbon black and the amount of the resin are appropriately adjusted, 1. a mixed resin with a solvent such as cyclohexanone, toluene, xylene and the like The resin solution prepared by heating and dissolving is mixed with a suspension of carbon black and water, and the carbon black is separated from water. Then, the composition obtained by removing water and heating and kneading is formed into a sheet shape. A method of drying after pulverization; 2. mixing and stirring the resin solution and the suspension prepared in the same manner as above to granulate carbon black and the resin, and separating the obtained granules, Method for removing residual solvent and water by heating; 3. Dissolving carboxylic acids such as maleic acid and fumaric acid in the solvents exemplified above, adding carbon black, mixing and drying, and removing the solvent to obtain After adding carbon black with carboxylic acid, add a resin to it and dry-blend it; 4. High-speed stirring of the monomer component containing the reactive group-containing monomer constituting the coated resin with water to prepare a suspension, and polymerization is carried out Cooling, since After the assembly suspension is obtained containing reactive group of the resin, in which carbon black is added and kneaded, so that reaction with the reactive group of carbon black (carbon black to make grafting), a method for cooling and grinding of the like.

The type of the resin to be coated is not particularly limited. Usually, it is a synthetic resin. In terms of dispersibility and dispersion stability, a resin having a benzene nucleus in the structure is preferred because the resin is Amphoteric surfactants have a stronger effect.

As specific synthetic resins, thermosetting resins such as phenol-based resins, melamine resins, xylene resins, diallyl phthalate resins, glycine resins, epoxy resins, and alkylbenzene resins; or polybenzenes can be used. Ethylene, polycarbonate, polyethylene terephthalate, polybutylene terephthalate, modified polyphenylene ether, polyfluorene, poly (p-xylylene) p-phenylenediamine, poly (fluorene) imide , Polyimide, polyaminobismaleimide, polyether, polyphenylene, polyarylate, polyetheretherketone and other thermoplastic resins. The coating amount of the resin relative to the carbon black is preferably 1 to 30% by mass relative to the total amount of the carbon black and the resin. If the amount is less than 1% by mass, only the same amount as the untreated carbon black is obtained. Dispersion or dispersion stability. On the other hand, if it exceeds 30% by mass, there is a possibility that the resins have strong adhesiveness with each other, and become agglomerates without being dispersed.

The carbon black obtained by coating the resin with the above-mentioned method can be used as a black matrix light-shielding material according to a conventional method, and a color filter including the black matrix as a constituent element can be produced by a conventional method. If such carbon black is used, a black matrix with a high light shielding rate, a low surface reflectance, and a small film thickness can be achieved at a low cost. The reason is presumably that the dispersibility or dispersion stability of carbon black is significantly improved for the resin or solvent constituting the black matrix liquid. It is also speculated that by covering the surface of the carbon black with a resin, Ca or Na has a function of sealing the carbon black.

Also, as the pigment, barium sulfate, lead sulfate, titanium oxide, Huang Dan, iron Dan, chromium oxide, and the like can be used.

These various pigments may be used in combination. For example, in order to adjust the chromaticity, a green pigment and a yellow pigment may be used in combination, or a blue pigment and a purple pigment may be used in combination.

Among these various pigments, pigments used as (A-2) organic coloring pigments are particularly preferable in terms of light-shielding properties. Examples include CI Pigment Blue 60, CI Pigment Blue 15: 6, and CI Pigment Red 177. , CI Pigment Red 242, CI Pigment Blue 254, CI Pigment Purple 23, CI Pigment Purple 29, CI Pigment Orange 49, CI Pigment Orange 64, CI Pigment Orange 79. When (A-2) an organic coloring pigment is contained, it is preferable to contain at least 1 type (s) of the said pigment, and it is more preferable to contain 2 or more types of the said pigment.

As the (A-3) carbon black, a resin-coated carbon black can be preferably used in terms of volume resistance or dielectric constant.

These pigments are preferably used in a manner such that the average particle diameter is usually 1 μm or less, preferably 0.5 μm or less, and more preferably 0.25 μm or less. Here, the reference of the average particle diameter is the number of pigment particles.

In addition, in this invention, the average particle diameter of a pigment is a value calculated | required from the particle diameter of the pigment measured by dynamic light scattering (DLS). The particle size measurement is based on a fully diluted colored resin composition (usually diluted to prepare a pigment concentration of about 0.005 to 0.2% by mass. However, if it is the concentration recommended by the measuring device, it is based on this concentration), and is measured at 25 The measurement was performed at ℃.

    <(B) Dispersant>    

In the photosensitive coloring composition of the present invention, to ensure the stability of quality, it is important to finely disperse the (A) colorant and stabilize the dispersed state. Therefore, it contains (B) a dispersant, especially (A-1) From the viewpoint of dispersibility of an organic black pigment, a polymer dispersant having a quaternary ammonium salt group as a functional group is contained.

In terms of dispersion stability, the above-mentioned polymer dispersant may further have a carboxyl group; a phosphate group; a sulfonic acid group; or such a base; a primary, secondary, or tertiary amine group; pyridine, pyrimidine, pyridine Derived from functional groups such as nitrogen-containing heterocyclic groups. Among them, from the viewpoint of dispersing the pigment with a small amount of dispersant when dispersing the pigment, it is particularly preferred that it further has a primary, secondary, or tertiary amine group; pyridine, pyrimidine, pyridine Polymer dispersants derived from basic functional groups such as nitrogen-containing heterocyclic groups.

Among these, from the viewpoint of the dispersibility of the (A-1) organic black pigment, and from the viewpoint of the dispersibility of the (A-2) organic color pigment and / or (A-3) carbon black, A polymer dispersant having a quaternary ammonium salt group and a tertiary amine group as functional groups is preferred.

Examples of the polymer dispersant include a urethane-based dispersant, an acrylic-based dispersant, a polyethyleneimine-based dispersant, a polyallylamine-based dispersant, a monomer having an amine group, and a macromolecular dispersant. Monomer-based dispersant, polyoxyethylene alkyl ether-based dispersant, polyoxyethylene diester-based dispersant, polyether phosphoric acid-based dispersant, polyester phosphoric acid-based dispersant, sorbitan fatty acid ester-based dispersant, Aliphatic modified polyester-based dispersant.

Specific examples of such dispersants include EFKA (registered trademark, manufactured by BASF), DISPERBYK (registered trademark, manufactured by BYK-Chemie), Disparlon (registered trademark, manufactured by Kusumoto Chemical Co., Ltd.), and SOLSPERSE by trade name. (Registered trademark, manufactured by Lubrizol), KP (made by Shin-Etsu Chemical Industry Co., Ltd.), Polyflow (made by Kyoeisha Chemical Co., Ltd.), Ajisper (registered trademark, manufactured by Ajinomoto Co., Ltd.), and the like.

These polymer dispersants can be used alone or in combination of two or more.

The weight average molecular weight (Mw) of the polymer dispersant is usually 700 or more, preferably 1,000 or more, and usually 100,000 or less, preferably 50,000 or less.

Among these, in terms of adhesion and linearity, the (B) dispersant is preferably a urethane-based polymer dispersant and / or an acrylic polymer dispersant including a functional group, and particularly preferably It contains an acrylic polymer dispersant.

In terms of dispersibility and storage properties, a polymer dispersant having a basic functional group and having a polyester bond and / or a polyether bond is preferred.

Examples of the urethane-based and acrylic polymer dispersants include: DISPERBYK 160 to 166, 182 series (both urethane-based), DISPERBYK 2000, 2001, LPN21116, etc. (both acrylic-based) (above) (All manufactured by BYK-Chemie).

Specific examples of the preferred chemical structure of the urethane-based polymer dispersant include, for example, a polyisocyanate compound having a number average molecular weight of 300 to 10,000 with a number of one or two hydroxyl groups in the molecule. Compounds, dispersing resins having a weight average molecular weight of 1,000 to 200,000 obtained by reacting with compounds having active hydrogen and tertiary amine groups in the same molecule. By treating these with a quaternizing agent such as benzyl chloride, all or part of the tertiary amine group can be made into a quaternary ammonium salt group.

Examples of the polyisocyanate compound include p-phenylene diisocyanate, 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, 4,4'-diphenylmethane diisocyanate, and naphthalene-1,5- Aromatic diisocyanates such as diisocyanate, ditoluidine diisocyanate; hexamethylene diisocyanate, methyl lyme diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, dimer acid diisocyanate And other aliphatic diisocyanates; isophorone diisocyanate, 4,4'-methylenebis (cyclohexyl isocyanate), ω, ω'-diisocyanate dimethylcyclohexane and other alicyclic diisocyanates; Aliphatic diisocyanates with aromatic rings such as methyl diisocyanate, α, α, α ', α'-tetramethylxylylene diisocyanate; triamine isocyanate, 1,6,11-undecane Triisocyanate, 1,8-diisocyanate-4-isocyanate methyloctane, 1,3,6-hexamethylenetriisocyanate, dicycloheptane triisocyanate, tris (isocyanatephenylmethane), tris ( Isocyanate phenyl) phosphorothioate and other triisocyanates; and terpolymers, water Adducts, and polyol adducts thereof. As the polyisocyanate, a terpolymer of an organic diisocyanate is preferable, and a terpolymer of a toluene diisocyanate and a terpolymer of an isophorone diisocyanate are most preferable. These may be used individually by 1 type, and may use 2 or more types together.

As a method for producing an isocyanate trimer, an appropriate trimerization catalyst, such as a tertiary amine, a phosphine, an alkoxide, a metal oxide, or a carboxylate, can be used. Isocyanates are partially trimerized with isocyanate groups. After the trimerization is stopped by adding catalyst poisons, unreacted polyisocyanates are solvent-extracted and removed by thin-film distillation to obtain the target isocyanuric acid. Polyester isocyanate.

Examples of compounds having a number average molecular weight of 300 to 10,000 having one or two hydroxyl groups in the same molecule include polyether diol, polyester diol, polycarbonate diol, polyolefin diol, and the like Those having a single terminal hydroxyl group alkoxylated with an alkyl group having 1 to 25 carbon atoms and a mixture of two or more of these.

Examples of the polyether diol include polyether diol, polyether ester diol, and a mixture of two or more of these. Examples of the polyether diol include those obtained by polymerizing alkylene oxide alone or by copolymerization, such as polyethylene glycol, polypropylene glycol, ethylene glycol-propylene glycol copolymer, polyoxytetramethylene glycol, and polyoxyhexamethylene. Methylene glycol, polyoxyoctyl glycol, and a mixture of two or more of these.

Examples of the polyetherester diol include a reaction of an ether group-containing diol or a mixture with another diol with a dicarboxylic acid or an anhydride thereof, or an alkylene oxide with a polyester diol. The recipient is, for example, poly (polyoxytetramethylene) adipate. As the polyether diol, polyethylene glycol, polypropylene glycol, polyoxytetramethylene glycol, or a compound in which a single terminal hydroxyl group of these compounds is alkoxylated with an alkyl group having 1 to 25 carbon atoms is preferable.

Examples of the polyester diol include a dicarboxylic acid (succinic acid, glutaric acid, adipic acid, sebacic acid, fumaric acid, maleic acid, phthalic acid, etc.) or an acid anhydride thereof and Glycols (ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 2 , 3-butanediol, 3-methyl-1,5-pentanediol, neopentyl glycol, 2-methyl-1,3-propanediol, 2-methyl-2-propyl-1,3- Propanediol, 2-butyl-2-ethyl-1,3-propanediol, 1,5-pentanediol, 1,6-hexanediol, 2-methyl-2,4-pentanediol, 2,2 , 4-trimethyl-1,3-pentanediol, 2-ethyl-1,3-hexanediol, 2,5-dimethyl-2,5-hexanediol, 1,8-octanediol Aliphatic diols such as alcohols, 2-methyl-1,8-octanediol, 1,9-nonanediol; alicyclic diols such as dimethylolcyclohexane; benzyl alcohol, bishydroxyethoxylate Aromatic diols such as benzene; N-alkyldialkanolamines such as N-methyldiethanolamine, etc.) obtained by polycondensation, such as polyethylene adipate, polybutylene adipate, polyhexamethylene adipate Adipic acid diacid, polyethylene adipate / propylene glycol, etc .; or use the above-mentioned diols or a carbon number of 1 to 25 yuan A polylactone diol or a polylactone monool obtained by using an alcohol as a starter, such as polycaprolactone diol, polymethylvalerolactone, and a mixture of two or more of these. As the polyester diol, polycaprolactone diol or polycaprolactone with an alcohol having 1 to 25 carbon atoms as a starter is most preferred.

Examples of the polycarbonate diol include poly (1,6-hexyl) carbonate and poly (3-methyl-1,5-pentyl) carbonate. Examples of the polyolefin diol include: Polybutadiene glycol, hydrogenated polybutadiene glycol, hydrogenated polyisoprene glycol, and the like.

These may be used individually by 1 type, and may use 2 or more types together.

The number average molecular weight of a compound having one or two hydroxyl groups in the same molecule is usually 300 to 10,000, preferably 500 to 6,000, and more preferably 1,000 to 4,000.

The compound having an active hydrogen and a tertiary amine group in the same molecule used in the present invention will be described.

Active hydrogen, that is, a hydrogen atom directly bonded to an oxygen atom, a nitrogen atom, or a sulfur atom, includes a hydrogen atom in a functional group such as a hydroxyl group, an amine group, or a thiol group. Among them, an amine group is preferred, and an amine group is particularly preferred. It is a hydrogen atom of a primary amine group.

The tertiary amine group is not particularly limited, and examples thereof include an amine group having an alkyl group having 1 to 4 carbon atoms or a heterocyclic structure, and more specifically, an imidazole ring or a triazole ring.

Examples of such compounds having active hydrogen and tertiary amine groups in the same molecule include N, N-dimethyl-1,3-propanediamine, N, N-diethyl-1, 3-propanediamine, N, N-dipropyl-1,3-propanediamine, N, N-dibutyl-1,3-propanediamine, N, N-dimethylethylenediamine, N , N-diethylethylenediamine, N, N-dipropylethylenediamine, N, N-dibutylethylenediamine, N, N-dimethyl-1,4-butanediamine, N, N-diethyl-1,4-butanediamine, N, N-dipropyl-1,4-butanediamine, N, N-dibutyl-1,4-butanediamine, and the like.

Examples of the nitrogen-containing heterocyclic ring when the tertiary amino group has a nitrogen-containing heterocyclic structure include a pyrazole ring, an imidazole ring, a triazole ring, a tetrazole ring, an indole ring, a carbazole ring, and an indazole. Ring, benzimidazole ring, benzotriazole ring, benzo Nitrogen heterocyclic five-membered rings such as azole ring, benzothiazole ring, benzothiadiazole ring; pyridine ring, Ring, pyrimidine ring, three Ring, quinoline ring, acridine ring, isoquinoline ring and other nitrogen-containing six-membered rings. Among these nitrogen-containing heterocyclic rings, an imidazole ring or a triazole ring is preferred.

Specific examples of such compounds having an imidazole ring and an amino group include 1- (3-aminopropyl) imidazole, histidine, 2-aminoimidazole, and 1- (2-amino group). (Ethyl) imidazole and the like. Moreover, if the compound which has a triazole ring and an amino group is specifically illustrated, 3-amino-1,2,4-triazole, 5- (2-amino-5-chlorophenyl) may be mentioned. 3-phenyl-1H-1,2,4-triazole, 4-amino-4H-1,2,4-triazole-3,5-diol, 3-amino-5-phenyl- 1H-1,3,4-triazole, 5-amino-1,4-diphenyl-1,2,3-triazole, 3-amino-1-benzyl-1H-2,4-tri Azole and so on. Among these, N, N-dimethyl-1,3-propanediamine, N, N-diethyl-1,3-propanediamine, 1- (3-aminopropyl) imidazole, 3 -Amino-1,2,4-triazole.

These may be used individually by 1 type, and may use 2 or more types together.

The preferred compounding ratio of the raw materials when manufacturing the urethane-based polymer dispersant is 10 for a compound having one or two hydroxyl groups in the same molecule with an average molecular weight of 300 to 10,000 relative to 100 parts by mass of the polyisocyanate compound. ~ 200 parts by mass, preferably 20 to 190 parts by mass, and further preferably 30 to 180 parts by mass. The compound having active hydrogen and a tertiary amine group in the same molecule is 0.2 to 25 parts by mass, preferably 0.3 to 24. Parts by mass.

The production of the urethane-based polymer dispersant is performed in accordance with a known method for producing a polyurethane resin. As the solvent during production, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclopentanone, cyclohexanone, and isophorone can be generally used; ethyl acetate, butyl acetate, and acetate Esters such as threonine; hydrocarbons such as benzene, toluene, xylene, and hexane; some alcohols such as diacetone alcohol, isopropanol, second butanol, and third butanol; chlorides such as methylene chloride and chloroform; tetrahydrofuran , Ethers such as diethyl ether; aprotic polar solvents such as dimethylformamide, N-methylpyrrolidone, and dimethylsulfinium. These may be used individually by 1 type, and may use 2 or more types together.

In the above-mentioned production, a urethane reaction catalyst can usually be used. Examples of the catalyst include tin systems such as dibutyltin dilaurate, dioctyltin dilaurate, dibutyltin dioctoate, and stannous octoate; iron systems such as iron acetamate pyruvate and iron chloride; triethyl Tertiary amines such as amine and triethylenediamine. These may be used individually by 1 type, and may use 2 or more types together.

The introduction amount of the compound having active hydrogen and tertiary amine group in the same molecule is preferably controlled in the range of 1 to 100 mgKOH / g based on the amine value after the reaction. A more preferable range is 5 to 95 mgKOH / g. The amine value is a value in which the basic amine group is neutralized and titrated by an acid to correspond to the acid value and is expressed in mg of KOH. If the amine value is lower than the above range, the dispersibility tends to decrease, and if it exceeds the above range, the developability tends to decrease.

When isocyanate groups remain in the polymer dispersant during the above reaction, if the isocyanate group is further destroyed by an alcohol or an amine compound, the stability of the product over time is improved, which is preferable.

The weight average molecular weight (Mw) of the urethane-based polymer dispersant is generally in the range of 1,000 to 200,000, preferably 2,000 to 100,000, and more preferably 3,000 to 50,000. If the molecular weight is less than 1,000, the dispersibility and dispersion stability will be poor. If it exceeds 200,000, the solubility will decrease, the dispersibility will be poor, and the control of the reaction will be difficult.

As the acrylic polymer dispersant, it is preferred to use an unsaturated group-containing monomer having a functional group (herein, a functional group, which is a functional group described as a functional group contained in the polymer dispersant), and Random copolymers, graft copolymers, and block copolymers of functional group-containing unsaturated group-containing monomers. These copolymers can be produced by a known method.

Examples of the unsaturated group-containing monomer having a functional group include (meth) acrylic acid, 2- (meth) acryloxyethylsuccinic acid, and 2- (meth) acryloxyethyl ortho Unsaturated monomers having a carboxyl group, such as phthalic acid, 2- (meth) acryloxyethylhexahydrophthalic acid, acrylic acid dimer; dimethylaminoethyl (meth) acrylate, ( Unsaturated monomers having a tertiary amine group and a quaternary ammonium salt group such as diethylaminoethyl methacrylate and the quaternary compounds thereof are taken as specific examples. These may be used individually by 1 type, and may use 2 or more types together.

Examples of the unsaturated group-containing monomer having no functional group include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, N-butyl (meth) acrylate, isobutyl (meth) acrylate, third butyl (meth) acrylate, benzyl (meth) acrylate, phenyl (meth) acrylate, (meth) acrylic acid Cyclohexyl ester, phenoxyethyl (meth) acrylate, phenoxymethyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, isopropyl (meth) acrylate Ester, tricyclodecane (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, N-vinylpyrrolidone, styrene and its derivatives, α-methylstyrene, N-cyclohexyl horse N-substituted maleimine, acrylonitrile, vinyl acetate, and poly (meth) acrylate, such as lymeimine, N-phenylmaleimide, N-benzylmaleimide, etc. Monomers, polystyrene macromonomers, 2-hydroxyethyl poly (meth) acrylate macromonomers, polyethylene glycol macromonomers, polypropylene glycol macromonomers, polycaprolactone macromonomers and other macromonomers Wait. These may be used individually by 1 type, and may use 2 or more types together.

The acrylic polymer dispersant is particularly preferably an AB or BAB block copolymer composed of an A block having a functional group and a B block having no functional group. However, in this case, the A block contains In addition to the partial structure of the unsaturated group-containing monomer having the functional group, the partial structure derived from the unsaturated group-containing monomer having no functional group may also include a partial structure derived from the unsaturated group-containing monomer having no functional group. Either the conventional copolymerization or the block copolymerization includes these. The content of the structure having no functional group in the A block is usually 80% by mass or less, preferably 50% by mass or less, and further preferably 30% by mass or less.

The B block is composed of a partial structure derived from the above-mentioned unsaturated group-containing monomer having no functional group, but one B block may contain a partial structure derived from two or more kinds of monomers, and These B blocks may be contained in any one of random copolymerization and block copolymerization.

This A-B or B-A-B block copolymer can be prepared by the living polymerization method shown below, for example.

The living polymerization method includes an anionic living polymerization method, a cationic living polymerization method, and a radical living polymerization method. The polymerization active material of the anionic living polymerization method is an anion, and is represented by the following method, for example.

[Chemical 6]

In the above method, Ar ¹ is a monovalent organic group, Ar ² is a monovalent organic group different from Ar ¹ , M is a metal atom, and s and t are each an integer of 1 or more.

The polymerization active material of the radical living polymerization method is a radical, and is represented by the following method, for example.

[Chemical 7]

In the above method, Ar ¹ is a monovalent organic group, Ar ² is a monovalent organic group different from Ar ¹ , j and k are integers of 1 or more, R ^a is a hydrogen atom or a monovalent organic group, and R ^b is ^a hydrogen atom or a monovalent organic group different from Ra.

When synthesizing the acrylic polymer dispersant, Japanese Patent Laid-Open No. 9-62002 or P. Lutz, P. Masson et al, polym. Bull. 12, 79 (1984); BCAnderson, GD Andrews et. al, Macromolecules, 14, 1601 (1981); K. Hatada, K. Ute, et al, Polym. J. 17, 977 (1985), 18, 1037 (1986); Right hand Koichi, Putian Koichi, Polymer Processing, 36,366 ( 1987); Toshimura Toshiyuki, Enomoto Mitsuo, Polymer Essays, 46,189 (1989); M. Kuroki, T. Aida, J. Am. Chem. Sic, 109, 4737 (1987); Aida Takuzo, Inoue Shoji, Organic Synthetic Chemistry, 43,300 (1985); DYSogoh, WHertler et al, Macromolouloules, 20,1473 (1987) and other known methods.

The acrylic polymer dispersant usable in the present invention may be an AB block copolymer or a BAB block copolymer, and the A block / B block ratio constituting the copolymer is 1/99 to 80/20 It is particularly preferably 5/95 to 60/40 (mass ratio). If it is out of this range, it may not be able to have both good heat resistance and dispersibility.

In addition, the amount of the quaternary ammonium salt group in 1 g of the AB block copolymer and the BAB block copolymer that can be used in the present invention is usually preferably 0.1 to 10 mmol, and if it is outside this range, it may not be good. Case of heat resistance and dispersibility.

In addition, in such a block copolymer, the amine group generated in the manufacturing process is usually contained, and its amine value is about 1 to 100 mgKOH / g. From the viewpoint of dispersibility, 10 mgKOH / g or more, more preferably 30 mgKOH / g or more, still more preferably 50 mgKOH / g or more, and more preferably 90 mgKOH / g or less, more preferably 80 mgKOH / g or less, and still more preferably 75 mgKOH / g or less.

Here, these block copolymers are equal to the amine value in the dispersant, and are represented by the mass of KOH equivalent to the amount of alkali per 1 g of the solid content of the solvent-free solvent in the dispersant sample, and are carried out by the following method Determination.

In a 100 mL beaker, accurately weigh 0.5 to 1.5 g of the dispersant sample and dissolve it in 50 mL of acetic acid. Using an automatic titration device with a pH electrode, the solution was neutralized and titrated with a 0.1 mol / L HClO ₄ acetic acid solution. The bending point of the titration pH curve was set as the end point of the titration, and the amine value was obtained by the following formula.

Amine value [mgKOH / g] = (561 × V) / (W × S)

[Where W is the dispersant sample weighing amount [g], V is the titration amount at the end of the titration [mL], and S is the solid content concentration of the dispersant sample [mass%]]

The acid value of the block copolymer depends on the presence and type of the acidic group that is the basis of the acid value. Generally, the lower value is preferred, usually 10 mgKOH / g or less, and its weight average molecular weight (Mw ) Is preferably in the range of 1000 to 100,000. If the weight average molecular weight of the block copolymer is less than 1,000, the dispersion stability tends to decrease, and if it exceeds 100,000, the developability and resolution tend to decrease.

The specific structure of the polymer dispersant having a quaternary ammonium salt group as a functional group is not particularly limited. From the viewpoint of dispersibility, it is preferable to have a repeating unit represented by the following formula (i) (hereinafter , Sometimes called "repeating unit (i)").

In the above formula (i), R ³¹ to R ³³ are each independently a hydrogen atom, an alkyl group which may have a substituent, an aryl group which may have a substituent, or an aralkyl group which may also have a substituent, and R ³¹ to R ^{In 33} , two or more may be bonded to each other to form a ring structure. R ³⁴ is a hydrogen atom or a methyl group. X is a divalent linking group, and Y ^- is a counter anion.

The number of carbon atoms of the alkyl group which may have a substituent among R ³¹ to R ³³ in the formula (i) is not particularly limited, but it is usually 1 or more, and preferably 10 or less, more preferably 6 or less. Specific examples of the alkyl group include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, and octyl. Among these, methyl, ethyl, propyl, Butyl, pentyl, or hexyl, more preferably methyl, ethyl, propyl, or butyl. Moreover, it may be either linear or branched. Furthermore, it may contain a cyclic structure such as a cyclohexyl group and a cyclohexylmethyl group.

The number of carbon atoms of the aryl group which may have a substituent among R ³¹ to R ³³ in the above formula (i) is not particularly limited, but it is usually 6 or more, and preferably 16 or less, more preferably 12 or less. Specific examples of the aryl group include phenyl, methylphenyl, ethylphenyl, dimethylphenyl, diethylphenyl, naphthyl, and anthracenyl. Among these, benzene is preferred Group, methylphenyl, ethylphenyl, dimethylphenyl, or diethylphenyl, more preferably phenyl, methylphenyl, or ethylphenyl.

The carbon number of the aralkyl group which may have a substituent among R ³¹ to R ³³ in the above formula (i) is not particularly limited, but it is usually 7 or more, preferably 16 or less, and more preferably 12 or less. Specific examples of the aralkyl group include a phenylmethylene group, a phenylene group, a phenylene group, a phenylene group, and a phenylisopropyl group. Among these, a phenylmethylene group is preferred. Phenyl, phenylene, phenylene, or phenylene, more preferably phenylmethylene or phenylene.

Among these, from the viewpoint of dispersibility, it is preferable that each of R ³¹ to R ^{33 is} independently an alkyl group or an aralkyl group, and specifically, that each of R ³¹ and R ^{33 is} independently a methyl group, or An ethyl group, and R ³² is a phenylmethylene group, or a phenyl ethylene group, more preferably R ³¹ and R ³³ are methyl groups, and R ³² is a phenylmethylene group.

When the polymer dispersant has a tertiary amine as a functional group, it is preferable from the viewpoint of dispersibility that the polymer dispersant has a repeating unit represented by the following formula (ii) (hereinafter referred to as "repeated" Unit (ii)).

In the above formula (ii), R ³⁵ and R ³⁶ are each independently a hydrogen atom, an alkyl group which may have a substituent, an aryl group which may have a substituent, or an aralkyl group which may have a substituent, and R ³⁵ and R ^{36 are} also They can be bonded to each other to form a ring structure. R ³⁷ is a hydrogen atom or a methyl group. Z is a divalent linking group.

In addition, as the alkyl group which may have a substituent among R ³⁵ and R ³⁶ in the formula (ii), those exemplified as R ³¹ to R ³³ in the formula (i) can be preferably used.

Similarly, as the aryl group which may have a substituent among R ³⁵ and R ³⁶ in the above formula (ii), those exemplified as R ³¹ to R ³³ in the above formula (i) can be preferably used. In addition, as the aralkyl group which may have a substituent among R ³⁵ and R ³⁶ in the formula (ii), those exemplified as R ³¹ to R ³³ in the formula (i) can be preferably used.

Among these, R ³⁵ and R ³⁶ are each preferably an alkyl group which may have a substituent, and more preferably a methyl group or an ethyl group.

Examples of the substituent which the alkyl group, aralkyl group, or aryl group in R ³¹ to R ^{33 in} the formula (i) and R ³⁵ and R ³⁶ in the formula (ii) may have include a halogen atom and an alkoxy group. , Benzamidine, hydroxyl, etc.

In the above formulae (i) and (ii), as the divalent linking groups X and Z, for example, an alkylene group having 1 to 10 carbon atoms, an alkylene group having 6 to 12 carbon atoms, -CONH-R ⁴³ -group, -COOR ⁴⁴ -group [wherein R ⁴³ and R ⁴⁴ are single bonds, alkylene groups having 1 to 10 carbon atoms, or ether groups (alkoxyalkyl groups) having 2 to 10 carbon atoms], etc., A -COO-R ⁴⁴ -group is preferred.

Further, in the above formula (I), as the anion Y ^{-, include: Cl -, Br -, l} -, ClO 4 -, BF 4 -, CH 3 COO -, PF 6 - and the like.

The content ratio of the repeating unit represented by the above formula (i) is not particularly limited. From the viewpoint of dispersibility, the content ratio of the repeating unit represented by the above formula (i) is the same as that represented by the above formula (ii). The total content of the repeating unit is preferably 60 mol% or less, more preferably 50 mol% or less, still more preferably 40 mol% or less, and even more preferably 35 mol% or less. 5 mol% or more, more preferably 10 mol% or more, still more preferably 20 mol% or more, and even more preferably 30 mol% or more.

The content ratio of the repeating unit represented by the formula (i) to the total repeating unit of the polymer dispersant is not particularly limited. From the viewpoint of dispersibility, it is preferably 1 mol% or more, more preferably 5 Molar% or more, and further preferably 10 Molar% or more, and preferably 50 Molar% or less, more preferably 30 Molar% or less, further preferably 20 Molar% or less, particularly preferably 15 Moore%. Ear%.

The content ratio of the repeating unit represented by the formula (ii) to the total repeating unit of the polymer dispersant is not particularly limited. From the viewpoint of dispersibility, it is preferably 5 mol% or more, and more preferably 10 Molar% or more, further preferably 15 Molar% or more, particularly preferably 20 Molar% or more, and more preferably 60 Molar% or less, more preferably 40 Molar% or less, and further preferably 30 Molar% Below ear%, particularly preferably below 25 mole%.

From the viewpoint of improving the compatibility with adhesive components such as solvents and improving dispersion stability, the polymer dispersant preferably has a repeating unit represented by the following formula (iii) (hereinafter referred to as " In the case of repeating unit (iii) ").

In the above formula (iii), R ⁴⁰ is an ethylidene group or a propylene group, R ⁴¹ is an alkyl group which may have a substituent, and R ⁴² is a hydrogen atom or a methyl group. n is an integer from 1 to 20.

The carbon number of the alkyl group which may have a substituent in R ⁴¹ in the above formula (iii) is not particularly limited, but it is usually 1 or more, preferably 2 or more, and preferably 10 or less, more preferably 6 or less. Specific examples of the alkyl group include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, and octyl. Among these, methyl, ethyl, propyl, Butyl, pentyl, or hexyl, more preferably methyl, ethyl, propyl, or butyl. Moreover, it may be either linear or branched. Furthermore, it may contain a cyclic structure such as a cyclohexyl group and a cyclohexylmethyl group.

In addition, n in the formula (iii) is preferably 1 or more, more preferably 2 or more, and more preferably 10 or less, from the viewpoint of compatibility and dispersibility of a binder component such as a solvent. It is preferably 5 or less.

The content ratio of the repeating unit represented by the above formula (iii) to the total repeating unit of the polymer dispersant is not particularly limited, but it is preferably 1 mol% or more, more preferably 2 mol% or more, and further preferably It is 4 mol% or more, and preferably 30 mol% or less, more preferably 20 mol% or less, and further preferably 10 mol% or less. When it is in the said range, there exists a tendency for compatible compatibility with a binder component, such as a solvent, and dispersion stability.

From the viewpoint of improving the compatibility of the dispersant with a binder component such as a solvent and improving the dispersion stability, the polymer dispersant preferably has a repeating unit (hereinafter referred to as a formula (iv)) In the case of "repeat unit (iv)").

In the formula (iv), R ³⁸ is an alkyl group which may have a substituent, an aryl group which may have a substituent, or an aralkyl group which may have a substituent. R ³⁹ is a hydrogen atom or a methyl group.

The number of carbons of the alkyl group which may have a substituent in R ³⁸ in the above formula (iv) is not particularly limited, but is usually 1 or more, preferably 2 or more, more preferably 4 or more, and preferably 10 or less, It is more preferably 8 or less. Specific examples of the alkyl group include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, and octyl. Among these, methyl, ethyl, propyl, Butyl, pentyl, or hexyl, more preferably methyl, ethyl, propyl, or butyl. Moreover, it may be either linear or branched. Furthermore, it may contain a cyclic structure such as a cyclohexyl group and a cyclohexylmethyl group.

The number of carbon atoms of the aryl group which may have a substituent in R ³⁸ in the formula (iv) is not particularly limited, but it is usually 6 or more, preferably 16 or less, more preferably 12 or less, and even more preferably 8 or less. Specific examples of the aryl group include phenyl, methylphenyl, ethylphenyl, dimethylphenyl, diethylphenyl, naphthyl, and anthracenyl. Among these, benzene is preferred Group, methylphenyl, ethylphenyl, dimethylphenyl, or diethylphenyl, more preferably phenyl, methylphenyl, or ethylphenyl.

The carbon number of the aralkyl group which may have a substituent in R ³⁸ in the above formula (iv) is not particularly limited, but is usually 7 or more, preferably 16 or less, more preferably 12 or less, and further preferably 10 or less. . Specific examples of the aralkyl group include a phenylmethylene group, a phenylene group, a phenylene group, a phenylene group, and a phenylisopropyl group. Among these, a phenylmethylene group is preferred. Phenyl, phenylene, phenylene, or phenylene, more preferably phenylmethylene or phenylene.

Among these, from the viewpoint of solvent compatibility and dispersion stability, R ^{38 is} preferably an alkyl group or an aralkyl group, and more preferably a methyl group, an ethyl group, or a phenylmethylene group.

Examples of the substituent which the alkyl group in R ³⁸ may have include a halogen atom and an alkoxy group. Examples of the substituent which the aryl group or aralkyl group may have include a chain alkyl group, a halogen atom, and an alkoxy group. The chain-like alkyl group represented by R ³⁸ includes either a linear or branched chain.

The content ratio of the repeating unit represented by the above formula (iv) to the total repeating unit of the polymer dispersant is preferably 30 mol% or more, and more preferably 40 mol% or more from the viewpoint of dispersibility. It is more preferably 50 mol% or more, more preferably 80 mol% or less, and more preferably 70 mol% or less.

The polymer dispersant may have repeating units other than repeating unit (i), repeating unit (ii), repeating unit (ii), and repeating unit (iv). Examples of such repeating units include styrene-based monomers such as styrene and α-methylstyrene; (meth) acrylic phosphonium salt-based monomers such as (meth) acrylic acid chloride; (methyl) ) (Meth) acrylamide-based monomers such as acrylamide, N-hydroxymethyl acrylamide; vinyl acetate; acrylonitrile; allyl epoxy propyl ether, butylene glycol propyl ether; N-methacryl A repeating unit of a monomer such as pholine.

From the viewpoint of further improving dispersibility, the polymer dispersant preferably contains an A block having repeating units (i) and repeating units (ii), and does not have repeating units (i) and repeating units (ii) ) Block copolymer of B block. The block copolymer is preferably an A-B block copolymer or a B-A-B block copolymer. Not only the quaternary ammonium salt group but also the tertiary amine group is introduced into the A block, and there is a tendency that the dispersing ability of the dispersant is obviously improved. The B block preferably has a repeating unit (iii), and more preferably has a repeating unit (iv).

The A block may contain a repeating unit (i) and a repeating unit (ii) in any of random copolymerization and block copolymerization. In addition, two or more types of repeating unit (i) and repeating unit (ii) may be contained in one A block. In this case, the A block is subjected to random copolymerization or block copolymerization. Either aspect contains each repeating unit.

Further, the A block may include repeating units other than the repeating unit (i) and the repeating unit (ii). Examples of such repeating units include the above-mentioned (meth) acrylate-based monomers. Repeating units, etc. The content of repeating units (i) and repeating units other than repeating unit (ii) in the A block is preferably 0 to 50 mol%, more preferably 0 to 20 mol%, but most preferably in the A block Such repeating units are not included.

The B block may contain repeating units other than repeating units (iii) and (iv). Examples of such repeating units include styrene-based monomers such as styrene and α-methylstyrene; (Meth) acrylic acid salt-based monomers such as (meth) acrylic acid chloride; (meth) acrylamide-based monomers such as (meth) acrylamide, N-methylol acrylamide; vinyl acetate ; Acrylonitrile; Allyl Glycidyl Ether, Butyl Acrylic Glycol; N-Methacryl A repeating unit of a monomer such as pholine. The content of the repeating unit (iii) and repeating units other than the repeating unit (iv) in the B block is preferably 0 to 50 mol%, more preferably 0 to 20 mol%, but most preferably in the B block Such repeating units are not included.

From the viewpoint of improving the dispersion stability, the (B) dispersant is preferably used in combination with a pigment derivative described below.

    <(C) Alkali soluble resin>    

The (C) alkali-soluble resin used in the present invention is not particularly limited as long as it is a resin containing a carboxyl group or a hydroxyl group, and examples thereof include epoxy (meth) acrylate resins, acrylic resins, and carboxyl group-containing resins. Among epoxy resins, carboxyl group-containing urethane resins, novolac resins, polyvinylphenol resins, and the like, epoxy (meth) acrylate resins and acrylic resins are preferred. These can be used individually by 1 type or in mixture of multiple types.

As the alkali-soluble resin used in the present invention, the following alkali-soluble resins (c1) and / or alkali-soluble resins (c2) (hereinafter referred to as "Case of carboxyl group-containing epoxy (meth) acrylate resin").

    <Alkali soluble resin (c1)>    

An alkali-soluble resin obtained by adding an α, β-unsaturated monocarboxylic acid or an α, β-unsaturated monocarboxylic acid ester having a carboxyl group to an epoxy resin and further reacting it with a polybasic acid and / or its anhydride.

    <Alkali soluble resin (c2)>    

It is obtained by adding an α, β-unsaturated monocarboxylic acid or an α, β-unsaturated monocarboxylic acid ester having a carboxyl group to an epoxy resin, and then reacting it with a polyhydric alcohol, a polybasic acid, and / or an anhydride thereof. Alkali soluble resin.

As the epoxy resin used as a raw material, for example, bisphenol A type epoxy resin (for example, "Epikote (registered trademark, the same below) 828", "Epikote 1001", "Epikote 1002", " Epikote1004, etc.), epoxy resins obtained by the reaction of alcoholic hydroxyl groups of bisphenol A epoxy resin with epichlorohydrin (for example, "NER-1302" (epoxy equivalent 323, (Softening point 76 ° C)), bisphenol F-type resin (for example, "Epikote807", "EP-4001", "EP-4002", "EP-4004, etc." manufactured by Mitsubishi Chemical Corporation), bisphenol F-type resin Epoxy resin (for example, "NER-7406" (epoxy equivalent 350, softening point 66 ° C) manufactured by Nippon Kayaku Co., Ltd.) obtained by the reaction of alcoholic hydroxyl groups of epoxy resin with epichlorohydrin, bisphenol S type Epoxy resin, biphenyl epoxy propyl ether (for example, "YX-4000" manufactured by Mitsubishi Chemical Corporation), phenol novolac-type epoxy resin (for example, "EPPN-201" manufactured by Nippon Kayaku Co., Ltd., Mitsubishi "EP-152", "EP-154" manufactured by Chemical Company, "DEN-438" manufactured by Dow Chemical Company), ( , M, p) cresol novolac epoxy resin (for example, "EOCN (registered trademark, the same below) -102S", "EOCN-1020", "EOCN-104S") manufactured by Nippon Kayaku Co., Ltd., Tricyclic Oxypropyl isocyanurate (for example, "TEPIC (registered trademark)" manufactured by Nissan Chemical Co., Ltd.), triphenol methane type epoxy resin (for example, "EPPN (registered trademark, manufactured by Nihon Chemical Co., Ltd., the same below)" -501 "," EPN-502 "," EPPN-503 "), alicyclic epoxy resin (" Celloxide 2021P "manufactured by Daicel Chemical Industries, Ltd.," Celloxide (registered trademark, the same below) EHPE "), use two Epoxy resins obtained by reacting cyclopentadiene with phenol to epoxidize phenol-based resins (for example, "EXA-7200" manufactured by DIC Corporation, "NC-7300" manufactured by Nippon Kayaku Co., Ltd.), Epoxy resins and the like represented by the following general formulae (C1) to (C4). Specific examples include "XD-1000" manufactured by Nippon Kayaku Co., Ltd. as the epoxy resin represented by the following general formula (C1), and Japan as the epoxy resin represented by the following general formula (C2). "NC-3000" manufactured by Kayaku Co., Ltd., and "ESF-300" manufactured by Nippon Steel Chemical Co., Ltd. as an epoxy resin represented by the following general formula (C4).

In the general formula (C1), a represents an average value, and represents a number from 0 to 10. R ¹¹¹ represents any of a hydrogen atom, a halogen atom, an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, a phenyl group, a naphthyl group, or a biphenyl group. Furthermore, a plurality of R ¹¹¹ present in one molecule may be the same or different.

In the general formula (C2), b represents an average value, and represents a number from 0 to 10. R ¹²¹ represents any of a hydrogen atom, a halogen atom, an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, a phenyl group, a naphthyl group, or a biphenyl group. In addition, a plurality of R ¹²¹ existing in one molecule may be the same or different.

In the general formula (C3), X represents a linking group represented by the following general formula (C3-1) or (C3-2). Among them, the molecular structure includes one or more adamantane structures. c represents an integer of 2 or 3.

In the above general formulae (C3-1) and (C3-2), R ¹³¹ to R ¹³⁴ and R ¹³⁵ to R ¹³⁷ each independently represent an adamantyl group which may have a substituent, a hydrogen atom, and a carbon number which may have a substituent 1 An alkyl group of ~ 12, or a phenyl group which may have a substituent. ＊ indicates bond-bond.

In the above general formula (C4), p and q each independently represent an integer of 0 to 4, and R ¹⁴¹ and R ¹⁴² each independently represent an alkyl group or a halogen atom having 1 to 4 carbon atoms. R ¹⁴³ and R ¹⁴⁴ each independently represent an alkylene group having 1 to 4 carbon atoms. x and y each independently represent an integer of 0 or more.

Among these, it is preferable to use an epoxy resin represented by any of the general formulae (C1) to (C4).

Examples of the α, β-unsaturated monocarboxylic acid or an α, β-unsaturated monocarboxylic acid having a carboxyl group include (meth) acrylic acid, butenoic acid, o-, m- or p-vinylbenzoic acid, (formaldehyde) Mono-carboxylic acids such as α-haloalkyl, alkoxy, halogen, nitro, and cyano substituted groups of acrylic acid, 2- (meth) acryloxyethylsuccinic acid, 2- (methyl ) Acrylic ethoxyethyl adipate, 2- (meth) acrylic ethoxyethyl phthalic acid, 2- (meth) acrylic ethoxyethyl hexahydrophthalic acid, 2- ( (Meth) acryloxyethylmaleic acid, 2- (meth) acryloxypropylsuccinic acid, 2- (meth) acryloxypropyl adipic acid, 2- (methyl) ) Acrylic acid oxytetrahydrophthalic acid, 2- (meth) acrylic acid oxypropyl phthalic acid, 2- (meth) acrylic acid oxypropyl maleic acid, 2- ( (Meth) acryloxybutyl succinic acid, 2- (meth) acryloxybutyl adipic acid, 2- (meth) acryloxybutyl hydrophthalic acid, 2- ( (Meth) acryloxybutyl phthalic acid, 2- (meth) acryloxybutyl maleic acid, ε-caprolactone, β-propiolactone, γ-butyrolactone Lactones such as δ-valerolactone are monomers produced by adding (meth) acrylic acid, or acids such as succinic acid (anhydride), phthalic acid (anhydride), and maleic acid (anhydride) ( Anhydride) is a monomer obtained by adding hydroxyalkyl (meth) acrylate, pentaerythritol tri (meth) acrylate, (meth) acrylic acid dimer, and the like.

Among these, in terms of sensitivity, (meth) acrylic acid is particularly preferred.

As a method for adding an α, β-unsaturated monocarboxylic acid or an α, β-unsaturated monocarboxylic acid ester having a carboxyl group to an epoxy resin, a known method can be used. For example, an α, β-unsaturated monocarboxylic acid or an α, β-unsaturated monocarboxylic acid ester having a carboxyl group can be reacted with an epoxy resin at a temperature of 50 to 150 ° C in the presence of an esterification catalyst. reaction. As the esterification catalyst used here, tertiary amines such as triethylamine, trimethylamine, dimethylbenzylamine, and diethylbenzylamine, tetramethylammonium chloride, tetraethylammonium chloride, and decachloride can be used. Quaternary ammonium salts such as dialkyltrimethylammonium and the like.

Furthermore, the epoxy resin, the α, β-unsaturated monocarboxylic acid or the α, β-unsaturated monocarboxylic acid ester having a carboxyl group, and the esterification catalyst may be used alone or in combination of two or more.

The amount of the α, β-unsaturated monocarboxylic acid or α, β-unsaturated monocarboxylic acid ester having a carboxyl group is preferably in the range of 0.5 to 1.2 equivalents relative to 1 equivalent of the epoxy group of the epoxy resin. The range of 0.7 to 1.1 equivalents is preferred. If the amount of α, β-unsaturated monocarboxylic acid or α, β-unsaturated monocarboxylic acid ester having a carboxyl group is small, the amount of unsaturated group introduced is insufficient, so that it is subsequently used with the polybasic acid and / or its anhydride. The response also became inadequate. Moreover, the situation where a large amount of epoxy groups remain is not favorable. On the other hand, when this amount is large, an α, β-unsaturated monocarboxylic acid or an α, β-unsaturated monocarboxylic acid ester having a carboxyl group remains as an unreacted substance. In either case, the tendency to deteriorate the hardening characteristics was found.

Examples of the polybasic acid and / or its anhydride include a member selected from the group consisting of maleic acid, succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, pyromellitic acid, and metaphthalic acid. Trimellitic acid, benzophenone tetracarboxylic acid, methylhexahydrophthalic acid, internal methylenetetrahydrophthalic acid, chlorobridged acid, methyltetrahydrophthalic acid, biphenyltetracarboxylic acid And one or more of these anhydrides.

Preferred are maleic acid, succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, pyromellitic acid, trimellitic acid, biphenyltetracarboxylic acid, Or such anhydrides. Particularly preferred is tetrahydrophthalic acid, biphenyltetracarboxylic acid, tetrahydrophthalic anhydride, or biphenyltetracarboxylic dianhydride.

Regarding the addition reaction of a polybasic acid and / or its anhydride, a known method can also be used, and it can be used for epoxy resin with α, β-unsaturated monocarboxylic acid or α, β-unsaturated monocarboxylic acid ester having carboxyl Under the same conditions of the addition reaction, the reaction is continued to obtain the target. The addition amount of the polybasic acid and / or its anhydride component is preferably such that the acid value of the carboxyl-containing epoxy (meth) acrylate resin is in a range of 10 to 150 mgKOH / g, and more preferably, such as It is in a range of 20 to 140 mgKOH / g. If the acid value of the epoxy (meth) acrylate resin containing a carboxyl group is less than the above range, the alkali developability tends to be insufficient, and if it exceeds the above range, it is considered that the hardening performance tends to be poor.

In addition, during the addition reaction of the polybasic acid and / or its anhydride, a polyfunctional alcohol such as trimethylolpropane, pentaerythritol, and dipentaerythritol may be added to prepare a multi-branched structure.

A carboxyl group-containing epoxy (meth) acrylate resin can usually be obtained by mixing a polybasic acid and / or an anhydride thereof in an epoxy resin with an α, β-unsaturated monocarboxylic acid or an α, β-unsaturated monomer having a carboxyl group. After reacting the carboxylic acid ester, either a polyacid and / or its anhydride and a polyfunctional alcohol are mixed in an epoxy resin with an α, β-unsaturated monocarboxylic acid or an α, β-unsaturated monocarboxylic acid having a carboxyl group The obtained reaction product was obtained by heating. In this case, the mixing order of the polybasic acid and / or its anhydride and the polyfunctional alcohol is not particularly limited. By heating, a mixture of a polybasic acid and / or an anhydride thereof with an epoxy resin and an α, β-unsaturated monocarboxylic acid or an α, β-unsaturated monocarboxylic acid ester having a carboxyl group, and a mixture with a polyfunctional alcohol Any hydroxyl group present in the reaction proceeds.

The polystyrene-equivalent weight average molecular weight (Mw) measured by gel permeation chromatography (GPC) of the carboxyl group-containing epoxy (meth) acrylate resin is usually 1,000 or more, and preferably 1500 or more, and It is usually 10,000 or less, preferably 8000 or less, and more preferably 6000 or less. If the weight average molecular weight is small, the solubility to the developer is high, and if the weight average molecular weight is too large, the solubility to the developer is low.

The carboxyl group-containing epoxy (meth) acrylate resin may be used alone or as a mixture of two or more resins.

Moreover, as long as the (C) alkali-soluble resin used in the present invention does not impair the performance of the present invention, a part of the above-mentioned carboxyl group-containing epoxy (meth) acrylate resin may be replaced with another binder resin. That is, a carboxyl group-containing epoxy (meth) acrylate resin and another binder resin may be used together. In this case, the proportion of the carboxyl group-containing epoxy (meth) acrylate resin in the (C) alkali-soluble resin is preferably 50% by mass or more, and particularly 80% by mass or more.

As long as the performance of the present invention is not impaired, other adhesive resins that can be used in combination with a carboxyl group-containing epoxy (meth) acrylate resin are not limited, as long as it is selected from resins generally used in photosensitive coloring compositions. Examples thereof include binder resins described in Japanese Patent Laid-Open No. 2007-271727, Japanese Patent Laid-Open No. 2007-316620, and Japanese Patent Laid-Open No. 2007-334290.

In addition, other binder resins may be used individually by 1 type, and may be used in combination of 2 or more type.

    <(D) Photopolymerization initiator>    

(D) The photopolymerization initiator is a component having the following functions: directly absorbing light, causing a decomposition reaction or a hydrogen abstraction reaction, and generating a polymerization-active radical. If necessary, an addition agent such as a polymerization accelerator (chain transfer agent) or a sensitizing dye may be added and used.

Examples of the photopolymerization initiator include dimetallocene compounds containing titanocene compounds described in Japanese Patent Laid-Open No. 59-152396 and Japanese Patent Laid-Open No. 61-151197; Japanese Patent No. Hexaryl biimidazole derivatives described in Japanese Patent Publication No. 2000-56118; halomethylation described in Japanese Patent Application Laid-Open No. 10-39503 Diazole derivatives, halomethyl-mesity Free radicals such as derivatives, N-aryl-α-amino acids such as N-phenylglycine, N-aryl-α-amino acid salts, N-aryl-α-amino acid esters Active agents, α-aminoalkyl phenone derivatives; oxime ester derivatives described in Japanese Patent Laid-Open No. 2000-80068, Japanese Patent Laid-Open No. 2006-36750, and the like.

Specifically, for example, as the titanocene derivatives, dicyclopentadienyl titanium dichloride, dicyclopentadienyl biphenyl titanium, and dicyclopentadienyl titanium bis (2,3, 4,5,6-pentafluorophenyl-1-yl), dicyclopentadienyl titanium bis (2,3,5,6-tetrafluorophenyl-1-yl), dicyclopentadienyl titanium bis ( 2,4,6-trifluorophenyl-1-yl), dicyclopentadienyl titanium bis (2,6-difluorophenyl-1-yl), dicyclopentadienyl titanium bis (2,4- Difluorophenyl-1-yl), bis (methylcyclopentadienyl) titanium bis (2,3,4,5,6-pentafluorophenyl-1-yl), bis (methylcyclopentadienyl) ) Titanium bis (2,6-difluorophenyl-1-yl), titanium dicyclopentadienyl (2,6-di-fluoro-3- (pyrrole-1-yl) -benzene-1-yl), etc. .

Examples of the biimidazole derivatives include 2- (2'-chlorophenyl) -4,5-diphenylimidazole dimer and 2- (2'-chlorophenyl) -4,5- Bis (3'-methoxyphenyl) imidazole dimer, 2- (2'-fluorophenyl) -4,5-diphenylimidazole dimer, 2- (2'-methoxyphenyl) ) -4,5-diphenylimidazole dimer, (4'-methoxyphenyl) -4,5-diphenylimidazole dimer, and the like.

Also, as methyl halide Examples of diazole derivatives include 2-trichloromethyl-5- (2'-benzofuranyl) -1,3,4- Diazole, 2-trichloromethyl-5- [β- (2'-benzofuranyl) vinyl] -1,3,4- Diazole, 2-trichloromethyl-5- [β- (2 '-(6 "-benzofuranyl) vinyl)]-1,3,4- Diazole, 2-trichloromethyl-5-furanyl-1,3,4- Diazole and so on.

Also, as methyl halide Derivatives include 2- (4-methoxyphenyl) -4,6-bis (-trichloromethyl) -mesanthine , 2- (4-methoxynaphthyl) -4,6-bis (-trichloromethyl) -mesanthine , 2- (4-ethoxynaphthyl) -4,6-bis (-trichloromethyl) -mesanthine , 2- (4-ethoxycarbonylnaphthyl) -4,6-bis (-trichloromethyl) -mesanthine Wait.

Examples of the α-aminoalkyl phenone derivatives include 2-methyl-1 [4- (methylthio) phenyl] -2- Linylpropane-1-one, 2-benzyl-2-dimethylamino-1- (4- Phenylphenyl) -butanone-1, 2-benzyl-2-dimethylamino-1- (4- (Phenylphenyl) butane-1-one, 4-dimethylaminoethyl benzoate, 4-dimethylaminoisoamyl benzoate, 4-diethylaminoacetophenone, 4-dimethylamine Phenylacetone, 2-ethylhexyl-1,4-dimethylamine benzoate, 2,5-bis (4-diethylaminobenzylidene) cyclohexanone, 7-diethylamino-3- (4-Diethylaminobenzyl) coumarin, 4- (diethylamino) chalcone and the like.

As photopolymerization initiators, oxime derivatives (oxime-based and ketoxime-based compounds) are particularly effective in terms of sensitivity and plate-making properties, and the sensitivity is equal to the sensitivity when an alkali-soluble resin containing a phenolic hydroxyl group is used. In this respect, oxime derivatives (oxime esters and ketoxime ester compounds) having excellent sensitivity are particularly useful.

Examples of the oxime-based compound include compounds containing a structural moiety represented by the following general formula (3), and an oxime ester-based compound represented by the following general formula (3a) is preferred.

In formula (3), R ²² represents an alkylalkyl group having 2 to 12 carbon atoms, a heteroarylalkylfluorenyl group having 1 to 20 carbon atoms, an alkenyl group having 3 to 25 carbon atoms, and carbon number 3 each of which may be substituted. Cycloalkanoyl group of 8 to 8, alkoxycarbonylalkanoyl group of 3 to 20 carbon atoms, phenoxycarbonylalkyl alkanoyl group of 8 to 20 carbon atoms, and heteroaryloxycarbonyl alkyl group of 3 to 20 carbon atoms Group, amino alkylcarbonyl group with 2 to 10 carbon atoms, arylfluorenyl group with 7 to 20 carbon atoms, heteroarylfluorenyl group with 1 to 20 carbon atoms, alkoxycarbonyl group with 2 to 10 carbon atoms, or 7 carbon number Aryloxycarbonyl of ~ 20.

In formula (3a), R ^21a represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 25 carbon atoms, a heteroaryl alkyl group having 1 to 20 carbon atoms, and a carbon number Alkoxycarbonylalkyl with 3-20, phenoxycarbonylalkyl with 8-20 carbons, heteroaryloxycarbonylalkyl or heteroarylsulfanyl with 1-20 carbons, 1 ~ carbon 20 amino alkyl group, 2 to 12 carbon alkyl group, 3 to 25 carbon alkenyl group, 3 to 8 carbon alkyl group, 7 to 20 carbon aryl group, carbon number A heteroarylfluorenyl group having 1 to 20 carbon atoms, an alkoxycarbonyl group having 2 to 10 carbon atoms, an aryloxycarbonyl group having 7 to 20 carbon atoms, or a cycloalkylalkyl group having 1 to 10 carbon atoms. R ^21b represents an arbitrary substituent containing an aromatic ring or a heteroaromatic ring.

In addition, R ^21a may form a ring together with R ^21b . Examples of the linking group include: an alkylene group having 1 to 10 carbon atoms, which may have a substituent, and a polyethylenyl group (-(CH = CH) _r- ), Polyethynyl (-(C≡C) _r- ) or a combination of these (in addition, r is an integer from 0 to 3).

In the formula (3a), R ^22a represents an alkylfluorenyl group having 2 to 12 carbon atoms, a heteroarylalkylfluorenyl group having 1 to 20 carbon atoms, an alkenyl group having 3 to 25 carbon atoms, and carbon number 3 each of which can be substituted. Cycloalkanoyl group of 8 to 8, alkoxycarbonylalkanoyl group of 3 to 20 carbon atoms, phenoxycarbonylalkyl alkanoyl group of 8 to 20 carbon atoms, and heteroaryloxycarbonyl alkyl group of 3 to 20 carbon atoms Group, amine carbonyl group having 2 to 10 carbon atoms, aryl fluorenyl group having 7 to 20 carbon atoms, heteroaryl fluorenyl group having 1 to 20 carbon atoms, alkoxycarbonyl group having 2 to 10 carbon atoms or 7 to 20 carbon atoms Aryloxycarbonyl.

As R ^{22 in} the general formula (3) and R ^22a in the general formula (3a), preferred examples include: alkyl alkanoyl groups having 2 to 12 carbon atoms, and heteroaryl alkyl fluorenyl groups having 1 to 20 carbon atoms. 3, a cycloalkanoyl group having 3 to 8 carbon atoms.

As R ^21a in the general formula (3a), preferred examples include unsubstituted methyl, ethyl, propyl, or propyl substituted with N-ethylfluorenyl-N-ethoxymethylamino. .

In addition, as R ^21b in the general formula (3a), preferred examples include a substituted carbazolyl group and a substituted 9-oxysulfide. Radical, optionally substituted phenylthio.

Examples of the arbitrary substituents in the general formulae (3) and (3a) include an alkyl group, an aryl group, an alicyclic group, a heterocyclic group, a halo group, a hydroxy group, a carboxyl group, an amine group, and amidino group. .

Specific examples of the oxime ester compound suitable for the present invention include the compounds exemplified below, but they are not limited to these compounds.

[Chemical 19]

[Chemical 20]

In addition, a carbazolyl-containing oxime ester initiator having a nitro group is also effective.

Examples of the ketoxime-based compound include compounds containing a structural moiety represented by the following general formula (4), and preferably include an oxime ester-based compound represented by the following general formula (5).

In the general formula (4), R ²⁴ is synonymous with R ²² in the general formula (3).

In the above general formula (5), R ^23a represents a phenyl group which may be substituted, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 25 carbon atoms, a heteroaryl alkyl group having 1 to 20 carbon atoms, and carbon. Alkoxycarbonylalkyl with 3 to 20 carbon atoms, phenoxycarbonylalkyl with 8 to 20 carbon atoms, alkylsulfanyl group with 2 to 20 carbon atoms, heteroaryloxycarbonylalkane with 1 to 20 carbon atoms Or heteroarylsulfanyl group, amino alkyl group having 1 to 20 carbon atoms, alkyl alkyl group having 2 to 12 carbon atoms, alkenyl group having 3 to 25 carbon atoms, and cycloalkyl alkyl group having 3 to 8 carbon atoms , Arylene group with 7 to 20 carbon atoms, heteroaryl group with 1 to 20 carbon atoms, alkoxycarbonyl group with 2 to 10 carbon atoms, aryloxycarbonyl group with 7 to 20 carbon atoms, or 1 to 10 carbon atoms Its cycloalkylalkyl.

R ^23b represents an arbitrary substituent containing an aromatic ring or a heteroaromatic ring.

In addition, R ^23a may form a ring together with R ^23b . Examples of the linking group include: an alkylene group having 1 to 10 carbon atoms which may each have a substituent, and a polyethylenyl group (-(CH = CH) _r- ), Polyethynyl (-(C≡C) _r- ) or a combination of these (in addition, r is an integer from 0 to 3).

In general formula (5), R ^24a represents an alkylalkyl group having 2 to 12 carbon atoms, an alkenyl group having 3 to 25 carbon atoms, a naphthene alkyl group having 4 to 8 carbon atoms, and 7 to 8 carbon atoms that can be substituted. Benzamidine group of 20, heteroarylfluorenyl group of 3 to 20 carbon atoms, alkoxycarbonyl group of 2 to 10 carbon atoms, aryloxycarbonyl group of 7 to 20 carbon atoms, heteroaryl group of 2 to 20 carbon atoms, Or an alkylaminocarbonyl group having 2 to 20 carbon atoms.

Preferred examples of R ^{24 in} the general formula (4) and R ^24a in the general formula (5) include: alkyl alkanoyl groups having 2 to 12 carbon atoms, and heteroaryl alkyl fluorenyl groups having 1 to 20 carbon atoms. 3, a cycloalkane group having 3 to 8 carbon atoms, and an arylene group having 7 to 20 carbon atoms.

Preferred examples of R ^23a in the general formula (5) include unsubstituted ethyl, propyl, butyl, and ethyl or propyl substituted with a methoxycarbonyl group.

In addition, as R ^23b in the general formula (5), preferred examples include a substituted carbazolyl group and a substituted phenylthio group.

Examples of the arbitrary substituents in the general formulae (4) and (5) include an alkyl group, an aryl group, an alicyclic group, a heterocyclic group, a halo group, a hydroxyl group, a carboxyl group, an amine group, and amidino group. .

Specific examples of the ketoxime ester compound suitable for the present invention include the compounds exemplified below, but they are not limited to these compounds.

[Chemical 24]

These oxime and ketoxime ester compounds are well-known compounds, for example, one of a series of compounds described in Japanese Patent Laid-Open No. 2000-80068 or Japanese Patent Laid-Open No. 2006-36750. In the present invention, the (D) photopolymerization initiator is preferably an oxime ester initiator and / or a ketoxime ester initiator.

These photopolymerization initiators may be used individually by 1 type, and may use 2 or more types together.

The proportion of the photopolymerization initiator in the photosensitive coloring composition of the present invention is usually 0.4 to 15% by mass, and preferably 0.5 to 10% by mass relative to the total solid content. If the proportion of the photopolymerization initiator is too much than this range, the developability tends to decrease. On the other hand, if the proportion of the photopolymerization initiator is too small, it may not be possible to form a better shape and step of the colored hardened material.

In addition, benzoin alkyl ethers such as benzoin methyl ether, benzoin phenyl ether, benzoin isobutyl ether, and benzoin isopropyl ether can also be listed; 2-methylanthraquinone, 2-ethylanthraquinone, 2-third Anthraquinone derivatives such as butylanthraquinone and 1-chloroanthraquinone; benzophenone, Michelin, 2-methylbenzophenone, 3-methylbenzophenone, 4-methyldione Benzophenone derivatives such as benzophenone, 2-chlorobenzophenone, 4-bromobenzophenone, and 2-carboxybenzophenone; 2,2-dimethoxy-2-phenylbenzene Ethyl ketone, 2,2-diethoxyacetophenone, 1-hydroxycyclohexylphenyl ketone, α-hydroxy-2-methylphenylacetone, 1-hydroxy-1-methylethyl- (p-iso Propylphenyl) ketone, 1-hydroxy-1- (p-dodecylphenyl) ketone, 2-methyl- (4'-methylthienyl) -2- Acetophenone derivatives such as phosphono-1-acetone, 1,1,1-trichloromethyl- (p-butylphenyl) ketone; 9-oxysulfur 2-ethyl 9-oxysulfur , 2-isopropyl-9-oxysulfur , 2-chloro9-oxysulfur 2,4-dimethyl 9-oxosulfur , 2,4-diethyl 9-oxysulfur 2,4-diisopropyl 9-oxysulfur 9-oxysulfur Derivatives; benzoate derivatives such as ethyl p-dimethylaminobenzoate and ethyl p-diethylaminobenzoate; 9-phenylacridine, 9- (p-methoxyphenyl) acyl Acridine derivatives such as pyridine; 9,10-dimethylbenzophene Isorphine Derivatives; anthrone derivatives such as benzoxanthone.

Among these photopolymerization initiators, in terms of sensitivity, oxime ester derivatives (oxime ester compounds) are particularly preferred.

Among the oxime ester derivatives, from the viewpoint of solvent resistance, a photopolymerization initiator having a diphenyl sulfide skeleton is preferred, and for example, those represented by the following general formula (5-1) can be used.

Here, R ^23a and R ^24a are synonymous with the general formula (5).

R ^25a and R ^25b each independently represent R2 ^5c , OR ^25c , CN, OH, or a halogen atom, f represents an integer from 0 to 5, and g represents an integer from 0 to 4.

R ^25c represents an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, or an arylalkyl group having 7 to 30 carbon atoms. The hydrogen atom of the substituent represented by R ^25c may be further substituted by a halogen atom, and the alkylene portion of the substituent represented by R ^25c may also be replaced by -O-, -S-, -COO-, -OCO-, or- NR ^25d -Cut off 1 to 5 times. R ^25d represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, or an arylalkyl group having 7 to 30 carbon atoms. The alkyl portion of the substituent represented by R ^25c may be a branched side chain, or may be cyclopentyl or cyclohexyl.

R ²⁶ represents OH, COOH, or a base represented by the following general formula (5-2), and h represents an integer of 0 to 5.

In formula (5-2), R ^26a represents -O-, -S-, -OCO-, or -COO-.

R ^26b represents an alkylene group having 1 to 20 carbon atoms, an alkylene group having 6 to 30 carbon atoms, or an alkylene group having 7 to 30 carbon atoms.

The alkylene part of the substituent represented by R ^26b may be cut off by -O-, -S-, -COO-, or -OCO- 1 to 5 times. The alkylene portion of the substituent represented by R ^26b may be a branched side chain or a cyclohexyl group.

R ^26c represents OH or COOH, and i represents an integer of 1 to 3.

* Indicates a bond key.

The photopolymerization initiator may be used singly or in combination of two or more kinds.

As the photopolymerization initiator, a sensitizing dye and a polymerization accelerator corresponding to the wavelength of an image exposure light source can be blended for the purpose of improving the sensitivity of the photosensitivity. Examples of the sensitizing dye include those described in Japanese Patent Laid-Open No. 4-221958 and Japanese Patent Laid-Open No. 4-219756. Pigments; Coumarin pigments with heterocyclic rings described in Japanese Patent Laid-Open No. 3-239703 and Japanese Patent Laid-Open No. 5-289335; Japanese Patent Laid-Open No. 3-239703 and Japanese Patent Laid-Open No. 5-289335 Documented 3-ketocoumarin compounds; in addition to the pyrrole methylene pigment described in Japanese Patent Laid-Open No. 6-19240, Japanese Patent Laid-Open No. 47-2528, Japanese Patent Laid-Open No. 54- 155292, Japanese Patent Publication No. 45-37377, Japanese Patent Publication No. 48-84183, Japanese Patent Publication No. 52-112681, Japanese Patent Publication No. 58-15503, Japanese Patent Publication No. 60-88005 No., Japanese Patent Laid-Open No. 59-56403, Japanese Patent Laid-Open No. 2-69, Japanese Patent Laid-Open No. 57-168088, Japanese Patent Laid-Open No. 5-107761, Japanese Patent Laid-Open No. 5-210240, Japan A pigment having a dialkylaminobenzene skeleton and the like described in Japanese Patent Application Laid-Open No. 4-288818.

Among these sensitizing dyes, amine-containing sensitizing dyes are preferred, and compounds having amine and phenyl groups in the same molecule are more preferred. Particularly preferred are, for example, 4,4'-dimethylaminobenzophenone, 4,4'-diethylaminobenzophenone, 2-aminobenzophenone, 4-aminobenzophenone, 4,4'-diaminobenzophenone, 3,3'-diaminobenzophenone, 3,4-diaminobenzophenone, and other benzophenone compounds; 2- (p-diphenyl Methylaminophenyl) benzo Azole, 2- (p-diethylaminophenyl) benzo Azole, 2- (p-dimethylaminophenyl) benzo [4,5] benzo Azole, 2- (p-dimethylaminophenyl) benzo [6,7] benzo Azole, 2,5-bis (p-diethylaminophenyl) -1,3,4- Azole, 2- (p-dimethylaminophenyl) benzothiazole, 2- (p-diethylaminophenyl) benzothiazole, 2- (p-dimethylaminophenyl) benzimidazole, 2- ( P-diethylaminophenyl) benzimidazole, 2,5-bis (p-diethylaminophenyl) -1,3,4-thiadiazole, (p-dimethylaminophenyl) pyridine, (p-dimethylaminophenyl) Diethylaminophenyl) pyridine, (p-dimethylaminophenyl) quinoline, (p-diethylaminophenyl) quinoline, (p-dimethylaminophenyl) pyrimidine, (p-diethylamino) (Phenyl) pyrimidine and other compounds containing p-dialkylaminophenyl. Among them, 4,4'-dialkylaminobenzophenone is the best.

A sensitizing dye may be used individually by 1 type, and may use 2 or more types together.

As the polymerization accelerator, for example, aromatic amines such as p-dimethylaminobenzoate, 2-dimethylaminoethyl benzoate, aliphatic amines such as n-butylamine, and N-methyldiethanolamine, and the following can be used. Mercapto compounds and so on. A polymerization accelerator may be used individually by 1 type, and may be used in combination of 2 or more type.

    <Photopolymerizable monomer>    

The photosensitive coloring composition of the present invention preferably further contains a photopolymerizable monomer (photopolymerizable compound) in terms of sensitivity and the like.

Examples of the photopolymerizable monomer used in the present invention include compounds having at least one ethylenically unsaturated group in the molecule (hereinafter, sometimes referred to as "ethylenic monomer"). Specific examples include (meth) acrylic acid, (meth) acrylic acid alkyl esters, acrylonitrile, styrene, carboxylic acids having one ethylenically unsaturated bond, and monoesters with polyhydric or monohydric alcohols. Wait.

In the present invention, a polyfunctional ethylenic monomer having two or more ethylenically unsaturated groups in one molecule is particularly preferably used.

Examples of such a polyfunctional ethylenic monomer include an ester of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid; an ester of an aromatic polyhydroxy compound and an unsaturated carboxylic acid; and an aliphatic polyhydroxy compound, Polyhydroxy compounds such as aromatic polyhydroxy compounds, esters obtained by esterification reaction with unsaturated carboxylic acids and polycarboxylic acids, and the like.

Examples of the ester of the aliphatic polyhydroxy compound and the unsaturated carboxylic acid include ethylene glycol diacrylate, triethylene glycol diacrylate, trimethylolpropane triacrylate, and trimethylolethane triacrylate. Acrylates of aliphatic polyhydroxy compounds such as esters, pentaerythritol diacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, glyceryl acrylate, etc. The acrylates of the exemplified compounds are replaced by the methacrylates of the methacrylates, the same by the Iconates of the Iconates, the butenoates of the Butenoates or the maleates Maleate etc.

Examples of the ester of an aromatic polyhydroxy compound and an unsaturated carboxylic acid include hydroquinone diacrylate, hydroquinone dimethacrylate, resorcinol diacrylate, and resorcinol dimethyl. Acrylic esters and methacrylic esters of aromatic polyhydroxy compounds, such as acrylate and pyrogallol triacrylate.

As the ester obtained by the esterification reaction of a polycarboxylic acid, an unsaturated carboxylic acid, and a polyhydroxy compound, it is not necessarily a single substance. If representative specific examples are listed, acrylic acid, phthalic acid, And condensation products of ethylene glycol; condensation products of acrylic acid, maleic acid, and diethylene glycol; condensation products of methacrylic acid, terephthalic acid, and pentaerythritol; condensation of acrylic acid, adipic acid, butanediol, and glycerol Things.

In addition to the above, examples of the polyfunctional ethylenic monomer used in the present invention include a polyisocyanate compound and a hydroxyl-containing (meth) acrylate, or a polyisocyanate compound and a polyol and a hydroxyl-containing (meth) ) (Meth) acrylic acid urethanes obtained by reacting acrylates; such as epoxy acrylates of polyvalent epoxy compounds and addition reactions of hydroxy (meth) acrylates or (meth) acrylic acid; Acrylamines such as ethylene bisacrylamide; allyl esters such as diallyl phthalate; vinyl-containing compounds such as divinyl phthalate are useful.

Examples of the (meth) acrylic acid urethanes include DPHA-40H, UX-5000, UX-5002D-P20, UX-5003D, UX-5005 (manufactured by Nippon Kayaku Co., Ltd.), U-2PPA, U-6LPA, U-10PA, U-33H, UA-53H, UA-32P, UA-1100H (made by Shin Nakamura Chemical Industry Co., Ltd.), UA-306H, UA-510H, UF-8001G (made by Kyoeisha Chemical Co., Ltd. ), UV-1700B, UV-7600B, UV-7605B, UV-7630B, UV7640B (manufactured by Nippon Synthetic Chemical Co., Ltd.), and the like.

These may be used individually by 1 type, and may use 2 or more types together.

    <Other Blending Ingredients of Photosensitive Coloring Composition>    

In the photosensitive coloring composition of the present invention, in addition to the above-mentioned components, it is also possible to appropriately mix an adhesion improver such as an organic solvent and a silane coupling agent, a coating improver, a development improver, an ultraviolet absorber, an antioxidant, and an interface. Active agents, pigment derivatives, etc.

    (1) Organic solvents    

The photosensitive coloring composition of the present invention generally comprises (A) a color material, (B) a dispersant, (C) an alkali-soluble resin, (D) a photopolymerization initiator, and a photopolymerizable monomer used as needed, Various other materials are used in a state of being dissolved or dispersed in an organic solvent.

As the organic solvent, it is preferable to select a boiling point in the range of 100 to 300 ° C. More preferably, the solvent has a boiling point of 120 to 280 ° C.

Examples of such an organic solvent include the following.

Ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-n-butyl ether, propylene glycol-tertiary butyl ether, Diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol mono-n-butyl ether, methoxymethylpentanol, dipropylene glycol monoethyl ether, dipropylene glycol monomethyl ether, 3-methyl-3 -Glycol monoalkyl ethers such as methoxybutanol, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, and tripropylene glycol methyl ether; ethylene glycol dimethyl ether, ethylene glycol diethyl ether , Diethylene glycol dimethyl ethers such as diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, dipropylene glycol dimethyl ether; ethylene glycol Alcohol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol mono-n-butyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate Ester, propylene glycol monobutyl ether acetate, methoxybutyl acetate, 3-methoxybutyl acetate, methoxypentyl acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether Acetate Diethylene glycol mono-n-butyl ether acetate, dipropylene glycol monomethyl ether acetate, triethylene glycol monomethyl ether acetate, triethylene glycol monoethyl ether acetate, 3-methyl-3 acetate -Glycol alkyl ether acetates such as methoxybutyl ester; ethylene glycol diacetate, 1,3-butanediol diacetate, 1,6-hexanol diacetate, etc. Alcohol diacetates; alkyl acetates such as cyclohexanol acetate; pentyl ether, diethyl ether, dipropyl ether, diisopropyl ether, dibutyl ether, dipentyl ether, ethyl isobutyl ether, dihexane Ethers such as ethers; acetone, methyl ethyl ketone, methyl amyl ketone, methyl isopropyl ketone, methyl isoamyl ketone, diisopropyl ketone, diisobutyl ketone, methyl isopropyl Ketones such as butyl ketone, cyclohexanone, ethylpentyl ketone, methylbutyl ketone, methylhexyl ketone, methyl nonyl ketone, methoxymethylpentanone; ethanol, propanol, butyl One or more of alcohols, hexanol, cyclohexanol, ethylene glycol, propylene glycol, butylene glycol, diethylene glycol, dipropylene glycol, triethylene glycol, methoxymethylpentanol, glycerol, benzyl alcohol Alcohols; n-pentane, n-octane, diisobutylene, n-hexane, hexene, iso Aliphatic hydrocarbons such as pentadiene, dipentene, dodecane; cycloaliphatic hydrocarbons such as cyclohexane, methylcyclohexane, methylcyclohexene, bicyclohexane; benzene, Aromatic hydrocarbons such as toluene, xylene, cumene; amyl formate, ethyl formate, ethyl acetate, butyl acetate, propyl acetate, amyl acetate, methyl isobutyrate, ethylene glycol Acid ester, ethyl propionate, propyl propionate, butyl butyrate, isobutyl butyrate, methyl isobutyrate, ethyl octoate, butyl stearate, ethyl benzoate, 3-ethoxy Methyl propionate, ethyl 3-ethoxypropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, propyl 3-methoxypropionate, 3-methoxy Chain or cyclic esters such as butyl propionate, γ-butyrolactone; alkoxycarboxylic acids such as 3-methoxypropionic acid, 3-ethoxypropionic acid; chlorobutane, chlorine Halogenated hydrocarbons such as pentane; ether ketones such as methoxymethylpentanone; nitriles such as acetonitrile and benzonitrile.

Examples of commercially available solvents that comply with the above include mineral spirits, APSOL # 2, Apco # 18 Solvent, Apco thinner, Socal Solvent No.1 and No.2, Solvesso # 150, Shell TS28 solvent, Carbitol, Ethyl Carbitol, Butyl Carbitol, Methyl cellosolve ("cellosolve" is a registered trademark, the same applies hereinafter), Ethyl cellosolve, Ethyl cellosolve acetate, Methyl cellosolve acetate, Diglyme (all are trade names), etc.

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

In the case of forming a pixel or a black matrix of a color filter by a photolithography method, it is preferable to select a boiling point of 100 to 200 ° C. (at a pressure of 1013.25 [hPa] as the organic solvent. Hereinafter, the boiling points are all the same) Range of those. More preferably, it has a boiling point of 120 to 170 ° C.

Among the above-mentioned organic solvents, glycol alkyl ether acetates are preferred in terms of a good balance in coatability, surface tension, and the like, and relatively high solubility of constituent components in the composition.

The glycol alkyl ether acetates may be used alone, but other organic solvents may be used in combination. As the organic solvent used in combination, glycol monoalkyl ethers are particularly preferred. Among these, propylene glycol monomethyl ether is preferred in terms of the solubility of the constituents in the composition. In addition, glycol monoalkyl ethers have high polarity. If the amount is too large, the pigment tends to aggregate, and the coloring resin composition obtained afterwards tends to decrease in storage stability, such as an increase in viscosity. The ratio of the diol monoalkyl ethers is preferably 5 to 30% by mass, and more preferably 5 to 20% by mass.

Further, it is also preferable to use an organic solvent having a boiling point of 150 ° C. or higher (hereinafter referred to as a “high boiling point solvent”). By using such a high-boiling-point solvent in combination, although the colored resin composition becomes difficult to dry, it has the effect of preventing the uniform dispersion state of the pigment in the composition from being rapidly dried and destroyed. That is, for example, there is an effect of preventing foreign matter defects caused by precipitation and solidification of color materials and the like at the tip of the slit nozzle. In terms of such a high effect, among the above-mentioned various solvents, diethylene glycol mono-n-butyl ether, diethylene glycol mono-n-butyl ether acetate, and diethylene glycol monoethyl ether acetate are particularly preferable. ester.

The content of the high-boiling-point solvent in the organic solvent is preferably 3% to 50% by mass, more preferably 5% to 40% by mass, and even more preferably 5% to 30% by mass. If the amount of the high boiling point solvent is too small, for example, there may be foreign matter defects caused by the precipitation and solidification of color materials at the front end of the slit nozzle, and if it is too much, the drying time of the composition will be slowed down, resulting in the following black color. Concerns about problems such as poor touch in the vacuum drying process in the matrix manufacturing step, or pre-baked pore marks.

In addition, the high-boiling point solvent having a boiling point of 150 ° C or higher may be a glycol alkyl ether acetate or a glycol alkyl ether. In this case, a high-boiling point solvent having a boiling point of 150 ° C or higher may not be additionally contained. .

As a preferable high boiling point solvent, for example, among the above-mentioned various solvents, diethylene glycol mono-n-butyl ether acetate, diethylene glycol monoethyl ether acetate, dipropylene glycol methyl ether acetate, 1, 3-butanediol diacetate, 1,6-hexanol diacetate, glycerol triacetate, and the like.

    (2) Adhesive improver    

In the photosensitive coloring composition of the present invention, in order to improve the adhesion to the substrate, an adhesion improver may be contained. As the adhesion improving agent, a silane coupling agent, a phosphate group-containing compound, and the like are preferable.

As the type of the silane coupling agent, one type of epoxy type, (meth) acrylic type, and amine type may be used alone, or two or more types may be used in combination.

Examples of preferred silane coupling agents include (meth) acrylic acid such as 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, and the like. Oxysilanes; 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldi Epoxy silanes such as ethoxysilane, 3-glycidoxypropyltriethoxysilane; ureidosilanes such as 3-ureidopropyltriethoxysilane; 3-isocyanatepropyltriethyl Isocyanate-based silanes such as oxysilanes, and particularly preferably silane coupling agents of epoxy silanes.

The phosphate group-containing compound is preferably a (meth) acrylfluorenyl group-containing phosphate ester, and is preferably represented by the following general formula (g1), (g2), or (g3).

In the general formulae (g1), (g2), and (g3), R ⁵¹ represents a hydrogen atom or a methyl group, l and l ′ are integers of 1 to 10, and m is 1, 2 or 3.

These phosphate group-containing compounds may be used singly or in combination of two or more kinds.

    (3) Surfactant    

In the photosensitive coloring composition of the present invention, a surfactant may be contained in order to improve coating properties.

As the surfactant, for example, various anionic, cationic, nonionic, and amphoteric surfactants can be used. Among them, non-ionic surfactants are preferably used because of the low possibility of adversely affecting various characteristics. Among them, fluorine-based or silicon-based surfactants are effective in terms of coatability.

Examples of such a surfactant include TSF4460 (manufactured by GE Toshiba Silicone), DFX-18 (manufactured by NEOS), BYK-300, BYK-325, BYK-330 (by BYK-Chemie), and KP340 ( Shin-Etsu Silicone), F-470, F-475, F-478, F-559 (manufactured by DIC), SH7PA (manufactured by Toray Silicone), DS-401 (manufactured by Daikin), L-77 (Japan Unicar (Manufactured by the company), FC4430 (manufactured by Sumitomo 3M), etc.

The surfactant may be used singly or in combination of two or more in any combination and ratio.

    (4) Pigment derivatives    

In the photosensitive coloring composition of the present invention, in order to improve dispersibility and storage stability, a pigment derivative may be contained as a dispersing aid.

Examples of the pigment derivative include azo-based, phthalocyanine-based, quinacridone-based, benzimidazolone-based, quinoline yellow-based, isoindolinone-based, and System, anthraquinone system, indanthrene system, actinide system, Perynone system, diketopyrrolopyrrole system, two Among these derivatives, phthalocyanine and quinoline yellow are preferred.

Examples of the substituent of the pigment derivative include a sulfonic acid group, a sulfonamido group and a quaternary salt thereof, a phthalimidomethyl group, a dialkylamino group, a hydroxyl group, a carboxyl group, and a fluorenyl group. Those bonded to the pigment skeleton directly or via an alkyl group, an aryl group, a heterocyclic group and the like are preferably a sulfonic acid group. Moreover, these substituents may be plurally substituted in one pigment skeleton.

Specific examples of the pigment derivative include sulfonic acid derivatives of phthalocyanine, sulfonic acid derivatives of quinoline yellow, sulfonic acid derivatives of anthraquinone, sulfonic acid derivatives of quinacridone, and diketopyrrolo Pyrrole sulfonic acid derivatives, two Sulfonic acid derivatives. These may be used individually by 1 type, and may use 2 or more types together.

    (5) Photoacid generator    

The photoacid generator is a compound capable of generating an acid by ultraviolet rays, and the action of an acid generated upon exposure, for example, a crosslinking reaction is performed by the presence of a crosslinking agent such as a melamine compound. Among such photoacid generators, those having a high solubility in a solvent, particularly a solvent used in a photosensitive coloring composition, are preferred, and examples thereof include diphenylphosphonium, xylylhydrazone, Phenyl (p-anisyl) 錪, bis (m-nitrophenyl) 錪, bis (p-thirdbutylphenyl) 錪, bis (p-chlorophenyl) 錪, bis (n-dodecyl) 錪, Chloride, bromide, or fluoroboron of diarylfluorene such as p-isobutylphenyl (p-tolyl) fluorene, p-isopropylphenyl (p-tolyl) fluorene, or triarylfluorene such as triphenylfluorene Salt, hexafluorophosphate, hexafluoroarsenate, aromatic sulfonate, tetrakis (pentafluorophenyl) borate, etc., or diphenylbenzylmethylsulfonium (n-butyl) triphenylboronic acid Organoboronium complexes such as salts, or 2-methyl-4,6-bis-trichloromethyltris , 2- (4-methoxyphenyl) -4,6-bis-trichloromethyltri Wait three Compounds and the like, but are not limited thereto.

    (6) Crosslinking agent    

A cross-linking agent may be further added to the photosensitive coloring composition of the present invention. For example, a melamine or guanamine-based compound may be used. Examples of such a crosslinking agent include melamine or guanamine-based compounds represented by the following general formula (6).

In formula (6), R ⁶¹ represents a -NR ⁶⁶ R ⁶⁷ group or an aryl group having 6 to 12 carbon atoms. When R ⁶¹ is a -NR ⁶⁶ R ⁶⁷ group, R ⁶² , R ⁶³ , R ⁶⁴ , R ⁶⁵ One of R, R ⁶⁶ and R ⁶⁷ , and when R ⁶¹ is an aryl group having 6 to 12 carbon atoms, one of R ⁶² , R ⁶³ , R ⁶⁴ and R ⁶⁵ represents a -CH ₂ OR ⁶⁸ group, and the remainder R ⁶² , R ⁶³ , R ⁶⁴ , R ⁶⁵ , R ⁶⁶ and R ⁶⁷ independently represent a hydrogen or -CH ₂ OR ⁶⁸ group, and here, R ⁶⁸ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.

Here, the aryl group having 6 to 12 carbon atoms is typically a phenyl group, a 1-naphthyl group, or a 2-naphthyl group, and substituents such as an alkyl group, an alkoxy group, and a halogen atom may be bonded to the phenyl groups. Or naphthyl. The alkyl group and the alkoxy group may each have about 1 to 6 carbon atoms. The alkyl group represented by R ⁶⁸ is preferably a methyl group or an ethyl group, particularly a methyl group.

The melamine-based compound corresponding to the general formula (6), that is, the compound system of the following general formula (6-1) includes hexamethylolmelamine, pentamethylolmelamine, tetramethylolmelamine, hexamethoxymethylmelamine , Pentamethoxymethyl melamine, tetramethoxymethyl melamine, hexaethoxymethyl melamine, etc.

In formula (6-1), when one of R ⁶² , R ⁶³ , R ⁶⁴ , R ⁶⁵ , R ⁶⁶ and R ⁶⁷ is an aryl group, one of R ⁶² , R ⁶³ , R ⁶⁴ and R ⁶⁵ represents -CH ₂ OR ⁶⁸ group, and the remaining R ⁶² , R ⁶³ , R ⁶⁴ , R ⁶⁵ , R ⁶⁶ and R ⁶⁷ independently represent a hydrogen atom or a -CH ₂ OR ⁶⁸ group, here, R ⁶⁸ represents a hydrogen atom or an alkyl group .

In addition, the melamine diamine compound corresponding to the general formula (6), that is, the compound system in which R ⁶¹ in the general formula (6) is an aryl group includes tetramethylolbenzoguanamine and tetramethoxymethylbenzene Guanidine, trimethoxymethylbenzoguanamine, tetraethoxymethylbenzoguanamine, and the like.

Furthermore, a crosslinking agent having a methylol group or a methylol alkyl ether group may be used. Examples are given below.

2,6-bis (hydroxymethyl) -4-methylphenol, 4-tert-butyl-2,6-bis (hydroxymethyl) phenol, 5-ethyl-1,3-bis (hydroxymethyl) Perhydro-1,3,5-tri -2-one (commonly known as N-ethyldimethyloltriol Ketone) or its dimethyl ether body, dimethyloltrimethylene urea or its dimethyl ether body, 3,5-bis (hydroxymethyl) perhydro-1,3,5- two -4-ketone (commonly known as dimethylol urea) or its dimethyl ether body, tetramethylol glyoxal dialkyl urea or its dimethyl ether body.

In addition, these crosslinking agents may be used individually by 1 type, and may be used in combination of 2 or more type. The amount when the crosslinking agent is used is preferably 0.1 to 15% by mass, and particularly preferably 0.5 to 10% by mass, with respect to the total solid content of the photosensitive coloring composition.

    (7) Mercapto compounds    

In order to improve the adhesion to the substrate, a mercapto compound may be added as a polymerization accelerator.

Examples of the type of the mercapto compound include 2-mercaptobenzothiazole and 2-mercaptobenzo Azole, 2-mercaptobenzimidazole, hexamethanedithiol, decanedithiol, 1,4-dimethylmercaptobenzene, butanediol dimercaptopropionate, butanediol dimercaptoglycolate, ethylene glycol Dimercaptoglycolate, trimethylolpropane trimercaptoglycolate, butanediol bismercaptopropionate, trimethylolpropane trimercaptopropionate, trimethylolpropane trimercaptoglycolate, pentaerythritol tetra Mercaptopropionate, pentaerythritol tetramercaptoglycolate, trihydroxyethyltrimercaptopropionate, ethylene glycol bis (3-mercaptobutyrate), butanediol bis (3-mercaptobutyrate), 1, 4-bis (3-mercaptobutyryloxy) butane, trimethylolpropane tri (3-mercaptobutyrate), pentaerythritol tetra (3-mercaptobutyrate), pentaerythritol tri (3-mercaptobutyrate) ), Ethylene glycol bis (3-mercaptoisobutyrate), butanediol bis (3-mercaptoisobutyrate), trimethylolpropane tri (3-mercaptoisobutyrate), 1, 3, 5-tris (3-mercaptobutoxyethyl) -1,3,5-tri -2,4,6 (1H, 3H, 5H) -trione and other heterocyclic mercapto compounds or aliphatic polyfunctional mercapto compounds. These can be used individually by 1 type or in mixture of 2 or more types.

    <Component blending amount in the photosensitive coloring composition>    

In the photosensitive coloring composition of the present invention, the content of the (A) color material is usually 10% by mass or more, preferably 20% by mass or more, with respect to the total solid content of the photosensitive coloring composition. It is 50% by mass or less. If the content of (A) color material is too small, sufficient optical density (OD) may not be obtained. On the other hand, if the content of (A) color material is too large, sufficient image formability may not be obtained. . The content of the (A-1) organic black pigment relative to 100% by mass of the (A) color material is usually 10% by mass or more, preferably 30% by mass or more, and usually 100% by mass or less. If the content of the (A-1) organic black pigment in the (A) color material is too small, a sufficient optical density (OD) may not be obtained.

In the photosensitive coloring composition of the present invention, (A) an organic coloring pigment and (A-1) an organic black pigment may be contained in the (A) coloring material. At this time, the content of the (A-1) organic black pigment with respect to 100% by mass of the (A) color material is usually 10% by mass or more, preferably 20% by mass or more, more preferably 30% by mass or more, and usually It is 90% by mass or less, preferably 80% by mass or less, and more preferably 60% by mass or less. The content ratio of the (A-2) organic colored pigment is usually 10% by mass or more, preferably 20% by mass or more, more preferably 40% by mass or more, and usually 90% by mass or less, preferably 80% by mass. The content is preferably 70% by mass or less. If the content of the (A-2) organic coloring pigment is too large, a sufficient optical density may not be obtained. The content ratio of the (A-1) organic black pigment to 100 parts by mass of the (A-2) organic coloring pigment is usually 15 parts by mass or more, preferably 20 parts by mass or more, and usually 900 parts by mass or less, It is preferably 800 parts by mass or less, more preferably 500 parts by mass or less, and still more preferably 200 parts by mass or less.

The photosensitive coloring composition of the present invention may contain (A-3) carbon black together with (A-1) an organic black pigment in the (A) color material. At this time, the content of the (A-1) organic black pigment relative to 100% by mass of the (A) color material is usually 50% by mass or more, preferably 60% by mass or more, and usually 95% by mass or less, preferably It is 90% by mass or less. The content ratio of (A-3) carbon black is usually 5 mass% or more, preferably 10 mass% or more, and usually 50 mass% or less, and preferably 40 mass% or less. If the content of (A-3) carbon black is too large, the volume resistance value may decrease or the relative dielectric constant may increase. The content of the (A-1) organic black pigment with respect to 100 parts by mass of (A-3) carbon black is usually 100 parts by mass or more, preferably 150 parts by mass or more, and usually 2000 parts by mass or less, It is preferably 1,000 parts by mass or less.

The photosensitive coloring composition of the present invention also contains (A-2) an organic coloring pigment and (A-3) carbon black together with (A-1) an organic black pigment in the (A) coloring material. Situation. At this time, the content of the (A-1) organic black pigment relative to 100% by mass of the (A) color material is usually 10% by mass or more, preferably 20% by mass or more, and usually 80% by mass or less, preferably It is 70% by mass or less. The content ratio of the (A-2) organic coloring pigment is usually 10% by mass or more, preferably 20% by mass or more, and usually 60% by mass or less, and preferably 50% by mass or less. Furthermore, the content ratio of (A-3) carbon black is usually 5 mass% or more, preferably 10 mass% or more, and usually 50 mass% or less, and preferably 40 mass% or less. In this case, the content ratio of the (A-1) organic black pigment to 100 parts by mass of the (A-2) organic coloring pigment is usually 15 parts by mass or more, preferably 20 parts by mass or more, and usually 800 parts by mass It is preferably 700 parts by mass or less. The content ratio of (A-1) organic black pigment to 100 parts by mass of (A-3) carbon black is usually 40 parts by mass or more, preferably 50 parts by mass or more, and usually 1,000 parts by mass or less, It is preferably 900 parts by mass or less.

(B) The content of the dispersant in the solid content of the photosensitive coloring composition is usually 1% by mass or more, preferably 3% by mass or more, more preferably 5% by mass or more, and usually 30% by mass or less, preferably It is 20% by mass or less, particularly preferably 15% by mass or less. The content of the (B) dispersant with respect to 100% by mass of the (A) color material is usually 5 mass% or more, particularly preferably 10 mass% or more, and usually 50 mass% or less, particularly preferably 30 mass% or less. . If the content of the (B) dispersant is too small, sufficient dispersibility may not be obtained. If the content of the (B) dispersant is too large, the proportion of other components may be relatively reduced, and the sensitivity and plate-making properties may be reduced.

(C) The content of the alkali-soluble resin relative to the total solids content of the photosensitive coloring composition of the present invention is usually 5 mass% or more, preferably 10 mass% or more, and usually 85% by mass or less, preferably 80% by mass or less. If the content of the (C) alkali-soluble resin is remarkably small, the solubility of the unexposed portion in the developing solution is reduced, and it becomes easy to cause poor development. Conversely, if the content of the (C) alkali-soluble resin is too large, the permeability of the developer to the exposed portion tends to be high, and the sharpness or adhesion of the pixel may decrease.

The content of the (D) photopolymerization initiator is usually 0.1% by mass or more, preferably 0.5% by mass or more, and more preferably 1% by mass or more with respect to the total solid content of the photosensitive coloring composition of the present invention. And is usually 15% by mass or less, preferably 10% by mass or less. If the content of the (D) photopolymerization initiator is too small, the sensitivity may be reduced. On the other hand, if the content of the photopolymerization initiator is too large, the solubility of the unexposed portion in the developing solution may decrease, which may cause poor development.

When a polymerization accelerator is used together with the (D) photopolymerization initiator, the content of the polymerization accelerator is preferably 0.05% by mass or more with respect to the total solid content of the photosensitive coloring composition of the present invention, and it is usually It is 10% by mass or less, preferably 5% by mass or less. The polymerization accelerator is preferably 100 parts by mass relative to the (D) photopolymerization initiator, usually 0.1 to 50 parts by mass, especially 0.1 to 20 parts. Used in proportion by mass.

If the blending ratio of the photopolymerization initiator-based components composed of the (D) photopolymerization initiator and the polymerization accelerator is significantly lower, it may be the cause of the decrease in the sensitivity to the exposure light, and if it is significantly higher, , There is a case where the solubility of the unexposed portion to the developing solution is lowered, resulting in poor development.

In addition, the blending ratio of the sensitizing dye to the photosensitive coloring composition of the present invention is usually 20% by mass or less, preferably 15% of the total solid content in the photosensitive coloring composition from the viewpoint of sensitivity. Mass% or less, more preferably 10 mass% or less.

When using a photopolymerizable monomer, its content is 30 mass% or less with respect to the total solid content in a photosensitive coloring composition, Preferably it is 20 mass% or less. When the content of the photopolymerizable monomer is too large, the permeability of the developer to the exposed portion may become high, and it may become difficult to obtain a good image. The lower limit of the content of the photopolymerizable monomer is usually 1% by mass or more, and preferably 5% by mass or more.

In the case of using an adhesion improving agent, its content is usually 0.1 to 5% by mass, preferably 0.2 to 3% by mass, and more preferably 0.4 to 2 with respect to the total solid content in the photosensitive coloring composition. quality%. If the content of the adhesion improving agent is less than the above range, the effect of improving the adhesion may not be sufficiently obtained. If the content is more than the above range, the sensitivity may be reduced, or residues after development may become defects.

When a surfactant is used, its content is usually 0.001 to 10% by mass, preferably 0.005 to 1% by mass, and more preferably 0.01 to total solids in the photosensitive coloring composition. 0.5% by mass, preferably 0.03 to 0.3% by mass. If the content of the surfactant is less than the above range, there is a possibility that the smoothness and uniformity of the coating film cannot be exhibited. If the content is more than the above range, in addition to the smoothness and uniformity of the coating film, other characteristics may not be exhibited. There are also cases of deterioration.

Furthermore, the photosensitive coloring composition of the present invention is prepared by using the above-mentioned organic solvent so that the solid content concentration thereof is usually 5 to 50% by mass, preferably 10 to 30% by mass.

    <Physical properties of photosensitive coloring composition>    

The photosensitive coloring composition of the present invention can be preferably used for forming a black matrix. From this point of view, it is preferable to exhibit black, and the optical density (OD) per coating film thickness is preferably 1.0. the above.

    <Method for manufacturing photosensitive coloring composition>    

The photosensitive coloring composition of the present invention (hereinafter, sometimes referred to as a "resist") is produced by a conventional method.

Usually (A) the color material is preferably dispersed in advance using a paint conditioner, a sand mill, a ball mill, a roll mill, a stone mill, a jet mill, a homogenizer, or the like. By dispersing the (A) color material into fine particles, the coating characteristics of the resist are improved.

The dispersion treatment is preferably performed in a system in which a part or all of (A) a color material, an organic solvent, and (B) a dispersant, and (C) an alkali-soluble resin are usually used in combination (hereinafter, there are When the mixture and the composition obtained by the treatment are called "ink" or "pigment dispersion"). In particular, if a polymer dispersant is used as the (B) dispersant, it is preferable that the obtained ink and resist are thickened with time (the dispersion stability is excellent).

As described above, in the step of producing the resist, it is preferable to produce a pigment dispersion liquid containing at least (A) a color material, an organic solvent, and (B) a dispersant. As the (A) color material, the organic solvent, and the (B) dispersant which can be used in the pigment dispersion liquid, those described as those which can be used in the photosensitive coloring composition can be preferably used.

Furthermore, in the case of performing a dispersion treatment on a liquid containing all the components formulated in the colored resin composition, there is a possibility that the highly reactive component may be modified due to heat generated during the dispersion treatment. Therefore, it is preferable to perform the dispersion treatment in a system containing a polymer dispersant.

When using a sand mill to disperse the color material (A), glass beads or zirconia beads having a diameter of about 0.1 to 8 mm can be preferably used. The conditions of the dispersion treatment are usually in the range of 0 ° C to 100 ° C, preferably room temperature to 80 ° C. The dispersing time and the reasonable time differ depending on the composition of the liquid and the size of the dispersing processing device, etc., so it is appropriately adjusted. The standard of dispersion is to control the gloss of the ink so that the 20-degree specular gloss of the resist (JIS Z8741) becomes a range of 50 to 300. When the gloss of the resist is low, the dispersion treatment may be insufficient, and chaotic pigment (color material) particles may remain, and the developability, adhesion, and resolution may be insufficient. . In addition, if the dispersing treatment is performed until the gloss value exceeds the above-mentioned range, the pigment is broken and a large amount of ultrafine particles are generated, and therefore the dispersion stability tends to be impaired.

The dispersed particle diameter of the pigment dispersed in the ink is usually 0.03 to 0.3 μm, and is measured by a dynamic light scattering method or the like.

Next, the ink obtained by the above-mentioned dispersion treatment is mixed with the above-mentioned other components contained in the resist to form a uniform solution. In the production steps of the resist, fine dirt is often mixed into the liquid, so the obtained resist is preferably subjected to filtering treatment by a filter or the like.

    [Hardened matter]    

The cured product can be obtained by curing the photosensitive coloring composition of the present invention. The hardened | cured material which hardened the photosensitive coloring composition can be used suitably as a black matrix or a coloring spacer.

    [Black matrix]    

Next, a black matrix using the photosensitive coloring composition of the present invention will be described according to its manufacturing method.

    (1) Support    

As a support for forming a black matrix, the material is not particularly limited as long as it has an appropriate strength. A transparent substrate is mainly used, but examples of the material include polyester resins such as polyethylene terephthalate, polyolefin resins such as polypropylene and polyethylene, polycarbonate, polymethyl methacrylate, Sheets made of thermoplastic resins such as polyfluorene, thermosetting resin sheets such as epoxy resins, unsaturated polyester resins, poly (meth) acrylic resins, and various glasses. Among them, glass and a heat-resistant resin are preferred from the viewpoint of heat resistance. In addition, a transparent electrode such as ITO or IZO may be formed on the surface of the substrate. In addition to a transparent substrate, it may be formed on a TFT array.

The support may be subjected to corona discharge treatment, ozone treatment, a silane coupling agent, or a thin film forming treatment of various resins such as a urethane resin to improve surface physical properties such as adhesion.

The thickness of the transparent substrate is usually in the range of 0.05 to 10 mm, preferably 0.1 to 7 mm. When a thin film forming process is performed on various resins, the film thickness is usually in the range of 0.01 to 10 μm, and preferably in the range of 0.05 to 5 μm.

    (2) Black matrix    

The black matrix of the present invention is formed from the photosensitive coloring composition of the present invention described above. After the photosensitive coloring composition of the present invention is coated on a transparent substrate and dried, a photomask is provided on the photosensitive coloring composition. A black matrix is formed by carrying out image exposure, development, and thermal curing or light curing as needed on the photomask.

Furthermore, the black matrix of the present invention is effectively formed on a TFT element substrate, but its structure is not particularly limited in each of the COA and BOA modes, and it can correspond to various structures.

    (3) Formation of black matrix         (3-1) Coating of photosensitive coloring composition    

The application of the photosensitive colored composition for the black matrix on the transparent substrate can be performed by a spin coating method, a bar coating method, a shower coating method, a mold coating method, a roll coating method, or a spray coating method. Among them, if the die coating method is used, the amount of coating liquid used is drastically reduced, and the influence of mist or the like attached when the spin coating method is not used at all is preferred from the comprehensive viewpoint of suppressing the generation of foreign matter.

If the thickness of the coating film is too thick, it may be difficult to develop the pattern, and it may be difficult to adjust the gap in the liquid crystal unitization step. Invisible situation. The thickness of the coating film is preferably in the range of 0.2 to 10 m, more preferably in the range of 0.5 to 6 m, and further preferably in the range of 1 to 4 m as the film thickness after drying.

    (3-2) Drying of the coating film    

The drying of the coating film after coating the photosensitive coloring composition on the substrate is preferably performed by a drying method using a hot plate, an IR oven, or a convection oven. The drying conditions can be appropriately selected according to the type of the above-mentioned solvent components, the performance of the dryer used, and the like. The drying time is selected according to the type of the solvent component and the performance of the dryer used, and is usually selected from a range of 15 seconds to 5 minutes at a temperature of 40 to 200 ° C, and preferably a temperature of 50 to 130 ° C. Select from 30 seconds to 3 minutes.

The higher the drying temperature, the higher the adhesion of the coating film to the transparent substrate. However, if it is too high, the (C) alkali-soluble resin may be decomposed, which may cause thermal polymerization and cause poor development. Furthermore, the drying step of the coating film may be a reduced-pressure drying method for drying in a reduced-pressure chamber without increasing the temperature.

    (3-3) Exposure    

The image exposure is performed by superposing a negative mask pattern on the coating film of the photosensitive coloring composition, and irradiating a light source of ultraviolet or visible light through the mask pattern. At this time, in order to prevent a decrease in the sensitivity of the photopolymerizable layer caused by oxygen, an oxygen shielding layer such as a polyvinyl alcohol layer may be formed on the photopolymerizable coating film and then exposed as necessary. The light source used for the above image exposure is not particularly limited. Examples of the light source include: xenon lamps, halogen lamps, tungsten lamps, high-pressure mercury lamps, ultra-high-pressure mercury lamps, metal halide lamps, medium-pressure mercury lamps, low-pressure mercury lamps, carbon arcs, and fluorescent lamps; or argon ion lasers , YAG laser, excimer laser, nitrogen laser, helium-cadmium laser, semiconductor laser and other laser light sources. In the case of using light of a specific wavelength, an optical filter may be used.

    (3-4) Development    

The black matrix of the present invention can be formed on a substrate after image exposure of a coating film based on a photosensitive coloring composition by the above-mentioned light source, and development using an organic solvent or an aqueous solution containing a surfactant and a basic compound. Video. The aqueous solution may further contain an organic solvent, a buffering agent, a complexing agent, a dye, or a pigment.

Examples of the basic compound include sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, sodium silicate, potassium silicate, sodium metasilicate, sodium phosphate, Inorganic basic compounds such as potassium phosphate, sodium hydrogen phosphate, potassium hydrogen phosphate, sodium dihydrogen phosphate, potassium dihydrogen phosphate, ammonium hydroxide; or mono, di or triethanolamine, mono, di or trimethylamine, mono, di or tri Organic basic compounds such as ethylamine, mono or diisopropylamine, n-butylamine, mono, di or triisopropanolamine, ethyleneimine, ethylenediamine, tetramethylammonium hydroxide (TMAH), and choline. These basic compounds may be a mixture of two or more kinds.

Examples of the surfactant include polyoxyethylene alkyl ethers, polyoxyethylene alkylaryl ethers, polyoxyethylene alkyl esters, sorbitan alkyl esters, and monoglyceride alkyl esters. And other nonionic surfactants; anionic interfacial activities such as alkylbenzenesulfonates, alkylnaphthalenesulfonates, alkylsulfates, alkylsulfonates, sulfosuccinates, etc. Agents; amphoteric surfactants such as alkyl betaines and amino acids.

Examples of the organic solvent include isopropyl alcohol, benzyl alcohol, ethyl cyrus, butyl cyrus, phenyl cyrus, propylene glycol, and diacetone alcohol. The organic solvent may be used alone or in combination with an aqueous solution.

There are no particular restrictions on the conditions of the development process. Usually, the development temperature is in the range of 10 to 50 ° C, of which 15 to 45 ° C, particularly preferably 20 to 40 ° C. The development method can be immersion development method, jet development method, and brush development. Any one of the methods, such as the ultrasonic imaging method and the ultrasonic imaging method.

    (3-5) heat hardening treatment    

The substrate after development is subjected to a thermosetting treatment or a photohardening treatment, preferably a thermosetting treatment. The heat curing treatment conditions at this time are selected within the range of 100 to 280 ° C, preferably 150 to 250 ° C, and selected within the range of 5 to 60 minutes.

The line width of the black matrix formed in the above manner is usually 3 to 50 μm, preferably 4 to 30 μm, and the height is usually 0.5 to 5 μm, preferably 1 to 4 μm. The volume resistivity is 1 × 10 ¹³ Ω · cm or more, preferably 1 × 10 ¹⁴ Ω · cm or more, the relative permittivity is 6 or less, preferably 5 or less, and usually 2 or more.

Furthermore, the optical density (OD) per thickness of 1 μm is 1.2 or more, preferably 1.5 or more, more preferably 1.8 or more, and usually 4.0 or less. Here, the optical density (OD) is a value measured by the following method.

    [Coloring spacer]    

In addition to the black matrix, the photosensitive coloring composition of this embodiment can also be used as a resist for a coloring spacer. When a spacer is used in a TFT-type LCD, the TFT as a switching element may malfunction due to light incident on the TFT. The colored spacer is used to prevent the above. For example, Japanese Patent Laid-Open No. 8-234212 The publication describes a case where the spacer is made light-shielding. The colored spacers can be formed by the same method as the black matrix except that a mask for the colored spacers is used.

    [Image display device]    

The image display device of the present invention is not particularly limited as long as it is a device that displays images or images, and examples thereof include a liquid crystal display device or an organic EL (Electro Luminesence) display described below.

    [Liquid crystal display device]    

The liquid crystal display device of the present invention is produced by using the black matrix of the present invention, and the formation order or formation position of the color pixels or the black matrix is not particularly limited.

For example, the black matrix of the present invention is provided on a TFT element substrate to form red, green, and blue pixels, and a protective layer is formed as needed, and then transparent electrodes such as ITO and IZO are formed on the image to serve as a color display , Liquid crystal display devices and other parts. In addition, there are cases where a transparent electrode is not formed in applications such as a planar alignment drive method (IPS mode).

A liquid crystal display device is generally an alignment film formed on a color filter. A spacer or a photosensitive spacer is formed on the alignment film, and then a liquid crystal cell is formed by bonding with a counter substrate. The liquid crystal is injected and the wiring is completed on the counter electrode. As the alignment film, a resin film such as polyimide is preferred. The alignment film is usually formed by a gravure printing method and / or a quick-drying printing method, and the thickness of the alignment film is set to several tens of nm. After the hardening treatment of the alignment film is performed by thermal calcination, the surface treatment is performed by the irradiation of ultraviolet rays or the treatment with a rubbing cloth, and the surface state can be adjusted to adjust the slope of the liquid crystal.

As long as the black matrix of the present invention is used, the formation order and formation position of the color pixels or the black matrix are not particularly limited.

As the spacer, a size corresponding to the gap of the counter substrate can be used, and usually 2 to 8 μm is preferred. It is also possible to form a photosensitive spacer (PS) of a transparent resin film on a color filter substrate by a photolithography method, and use it instead of the spacer.

The gap between the substrate and the opposing substrate depends on the application of the liquid crystal display device, and is usually selected within a range of 2 to 8 μm. After bonding to the counter substrate, portions other than the liquid crystal injection port are sealed with a sealing material such as epoxy resin. The sealing material is hardened by UV irradiation and / or heating to seal the periphery of the liquid crystal cell.

After the peripheral sealed liquid crystal cell is cut into panel units, the pressure is reduced in a vacuum chamber, the liquid crystal injection port is immersed in the liquid crystal, and the liquid crystal is injected into the liquid crystal cell by leaking the chamber. The degree of decompression in the liquid crystal cell is usually 1 × 10 ^-2 to 1 × 10 ^-7 Pa, but preferably 1 × 10 ^-3 to 1 × 10 ^-6 Pa. The liquid crystal cell is preferably heated under reduced pressure, and the heating temperature is usually 30 to 100 ° C, and more preferably 50 to 90 ° C. The heating and maintaining during decompression is usually set in a range of 10 to 60 minutes, and then immersed in liquid crystal. A liquid crystal cell into which a liquid crystal is injected, and a liquid crystal injection port is sealed with a hardened UV curable resin, thereby completing a liquid crystal display device (panel).

The type of the liquid crystal is not particularly limited, and it may be a conventionally known liquid crystal such as an aromatic system, an aliphatic system, and a polycyclic compound, and is any of a lyotropic liquid crystal and a thermotropic liquid crystal. As the thermotropic liquid crystal, a nematic liquid crystal, a smectic liquid crystal, a cholesteric liquid crystal, and the like are known, but any of them may be used.

    [Organic EL display]    

The black matrix of the present invention can be used to produce the organic EL display of the present invention.

When an organic EL display is manufactured using the black matrix of the present invention, for example, as shown in FIG. 1, a pattern made of a colored resin composition is first formed on a transparent support substrate 10 (that is, provided in the pixels 20, and A color filter formed by a black matrix (not shown) between adjacent pixels 20, and an organic light emitting body 500 is laminated on the color filter with an organic protective layer 30 and an inorganic oxide film 40 interposed therebetween. The organic EL element 100 can be manufactured. In addition, at least one of the pixel 20 and the black matrix was produced using the photosensitive coloring composition of the present invention. As a method for laminating the organic light emitting body 500, a transparent anode 50, a hole injection layer 51, a hole injection layer 52, a light emitting layer 53, an electron injection layer 54, and a cathode 55 are sequentially formed on the upper surface of the color filter. A method of bonding the organic light-emitting body 500 formed on another substrate to the inorganic oxide film 40 and the like. The organic EL element 100 manufactured in the above manner can be used, for example, by the method described in "Organic EL Display" (Ohm Corporation, issued on August 20, 2004, by Jing Shi, Anda Chiba, and Hideki Murata). Production of organic EL displays.

Furthermore, the black matrix of the present invention can be applied to an organic EL display using a passive driving method, and can also be applied to an organic EL display using an active driving method.

    [Example]    

Next, the present invention will be described more specifically by citing synthesis examples, examples, and comparative examples. The present invention is not limited to the following examples, as long as it does not exceed the gist thereof.

The constituents of the photosensitive coloring composition used in the following examples and comparative examples are as follows.

    <(A-1) Organic Black Pigment>    

Manufactured by BASF, Irgaphor (registered trademark) Black S 0100 CF (having a chemical structure represented by the following formula (2))

    <Organic Black Pigment: Dark Black>    

Made by BASF, Lumogen (registered trademark) Black FK4281

    <Organic black pigment: aniline black>    

Made by BASF, Paliotol (registered trademark) Black L0080

    <Alkali soluble resin-I>    

145 parts by mass of propylene glycol monomethyl ether acetate was stirred while being replaced with nitrogen, and the temperature was raised to 120 ° C. 10 parts by mass of styrene, 85.2 parts by mass of propylene methacrylate, and 66 parts by mass of a monoacrylate (FA-513M manufactured by Hitachi Chemical Co., Ltd.) having a cyclodecane skeleton were added dropwise thereto, and the dropwise addition was performed over 3 hours. 8.47 parts by mass of 2,2'-azo-2-methylbutyronitrile was further stirred at 90 ° C for 2 hours. Next, the inside of the reaction vessel was replaced with air, 0.7 parts by mass of tris-dimethylaminomethylphenol and 0.12 parts by mass of hydroquinone were added to 43.2 parts by mass of acrylic acid, and the reaction was continued at 100 ° C. for 12 hours. Thereafter, 56.2 parts by mass of tetrahydrophthalic anhydride (THPA) and 0.7 parts by mass of triethylamine were added, and the mixture was reacted at 100 ° C for 3.5 hours. The weight-average molecular weight Mw of the alkali-soluble resin-I obtained in the above manner measured by GPC was about 8400, and the acid value was 80 mgKOH / g.

    <Alkali soluble resin-II>    

`` ZCR-1664H '' manufactured by Nippon Kayaku Co., Ltd. (weight average molecular weight Mw = 5000 ~ 6000, acid value = about 60mg-KOH / g)

    <Alkali-soluble resin-III>    

[Chemical 31]

50 g of the epoxy compound (epoxy equivalent 247) having the above structure, 14.3 g of acrylic acid, 59.5 g of methoxybutyl acetate, 1.29 g of triphenylphosphine, and 0.05 g of p-methoxyphenol were placed in a thermometer and a stirrer. In a flask with a cooling tube, the reaction was carried out at 90 ° C. with stirring until the acid value became 5 mgKOH / g or less. The reaction required 12 hours to obtain an epoxy acrylate solution.

25 parts by mass of the above epoxy acrylate solution, 0.8 parts by mass of trimethylolpropane (TMP), 4.1 parts by mass of biphenyltetracarboxylic dianhydride (BPDA), and 2.8 parts by mass of tetrahydrophthalic anhydride (THPA) The reaction mixture was placed in a flask equipped with a thermometer, a stirrer, and a cooling tube, and the temperature was gradually raised to 105 ° C. while stirring to perform a reaction.

When the resin solution becomes transparent, it is diluted with methoxybutyl acetate and prepared so that the solid content becomes 50% by mass, to obtain an acid value of 131 mgKOH / g and a weight average molecular weight in terms of polystyrene measured by GPC. (Mw) 4000 carboxyl group-containing epoxy acrylate resin (c1).

    <Alkali soluble resin-IV>    

"ZCR-1642H" (MW = 6500, acid value = 98mg-KOH / g) manufactured by Nippon Kayaku Co., Ltd.

    <Dispersant-I>    

"DISPERBYK-LPN21116" manufactured by BYK-Chemie (acrylic system consisting of A block with quaternary ammonium salt group and tertiary amine group on the side chain and B block without quaternary ammonium salt group and amine group AB block copolymer. The amine value is 70 mgKOH / g. The acid value is 1 mgKOH / g or less).

The content ratios of the repeating units of the following formulae (1a), (2a), and (3a) to the total repeating units of the dispersant-I are 11.1 mole%, 22.2 mole%, and 6.7 mole%, respectively.

    <Dispersant-II>    

"DISPERBYK-2000" manufactured by BYK-Chemie (acrylic A-B block copolymer composed of A block having a quaternary ammonium salt group on the side chain and B block having no quaternary ammonium salt group)

    <Dispersant-III>    

"EFKA-4300" (acrylic polymer dispersant with a tertiary amine group and a butyl side chain. The side chain does not have a quaternary ammonium salt group) manufactured by EFKA.

    <Pigment derivative>    

"Solsperse12000" manufactured by Lubrizol

    <Solvent-I>    

PGMEA: propylene glycol monomethyl ether acetate

    <Solvent-II>    

MB: 3-methoxybutanol

    <Photopolymerization initiator-I>    

Under a nitrogen atmosphere, Compound 1 (0.98 g, 5 mmol) and dichloromethane (17 mL) were added to a 50 mL three-necked flask. After it was cooled to 3 ° C, o-toluene chloride (0.77 g, 5 mmol) was added dropwise. To this, aluminum chloride (0.67 g, 5 mmol) was slowly added over 1 hour. After the addition was completed, the mixture was further stirred at 3 ° C for 2 hours, and dichloromethane (8 mL) was added. Then, after adding glutaric anhydride (0.68 g, 6 mmol) over 30 minutes, aluminum chloride (1.90 g, 14 mmol) was added over 30 minutes.

After the addition was completed, the mixture was further stirred at 3 ° C for 2 hours, and the reaction solution was slowly poured into ice water (400 mL). Sodium chloride (80 g) was added to the aqueous layer, and extraction was performed 5 times with dichloromethane (50 mL). The organic layer was washed with a saturated sodium chloride aqueous solution, and dried over anhydrous magnesium sulfate. After filtering anhydrous magnesium sulfate, the solvent was distilled off by an evaporator to obtain compound 2 (2.13 g, crude yield 100%). It was used in the next reaction without purification.

In a nitrogen environment, compound 2 (2.13 g, 5 mmol), methanol (22 mL), and concentrated sulfuric acid (5 mg) were added to a 50 mL three-necked flask, and the mixture was heated under reflux for 3 hours. After cooling, the solvent was concentrated, and water (10 mL) and ethyl acetate (30 mL) were added.

The organic layer was sequentially washed with a saturated sodium bicarbonate aqueous solution and a saturated sodium chloride aqueous solution, and anhydrous magnesium sulfate was added to dry it. After filtering anhydrous magnesium sulfate, the solvent was distilled off by an evaporator to obtain compound 3 (1.72 g, crude yield 78%). It was used in the next reaction without purification.

In a nitrogen environment, compound 3 (1.00 g, 2.26 mmol) and dichloromethane (10 mL) were added to a 50 mL three-necked flask, and the mixture was cooled to 10 ° C. A 1N hydrogen chloride in diethyl ether solution (4.68 mL) was added thereto. Then, amyl nitrite (0.36 g, 3.04 mmol) was added, and the mixture was reacted at 10 ° C for 4 hours. After adding water (10 mL), washing was performed sequentially with a saturated sodium bicarbonate aqueous solution and a saturated sodium chloride aqueous solution, and anhydrous magnesium sulfate was added to dry it. After filtering anhydrous magnesium sulfate, the solvent was distilled off by an evaporator to obtain a pale yellow solid (0.88 g). This was purified again with toluene (3.5 mL) to obtain compound 4 (0.45 g, yield 42%).

Under a nitrogen atmosphere, compound 4 (3.50 g, 7.44 mmol) and dichloromethane (35 mL) were added to a 50 mL three-necked flask, and the mixture was cooled to 4 ° C. To this was added triethylamine (1.50 g, 14.9 mmol). Acetyl chloride (0.70 g, 8.93 mmol) was then added, and the reaction was carried out for 1 hour. After adding a saturated sodium bicarbonate aqueous solution (10 mL), the organic layer was separated, and the organic layer was washed with a saturated sodium bicarbonate aqueous solution and a saturated sodium chloride aqueous solution in this order, and dried over anhydrous magnesium sulfate. After filtering anhydrous magnesium sulfate, the solvent was distilled off by an evaporator to obtain a yellow oil (3.65 g). This was purified by column chromatography (ethyl acetate / hexane: 1/1) to obtain compound 5 (3.12 g, yield 82%, photopolymerization initiator-I). The chemical shift of Compound 5 is shown below.

¹ H-NMR δ [ppm] (CDCl ₃ ) 1.49 (t, 3H), 2.29 (s, 3H), 2.36 (s, 3H), 2.73 (t, 2H), 3.14 (t, 2H), 3.60 (s , 3H), 4.43 (q, 2H), 7.3 ~ r7.5 (m, 6H), 8.06 (dd, 1H), 8.29 (dd, 1H), 8.59 (d, 1H), 8.83 (dd, 1H)

    <Photopolymerization initiator-II>    

    <Photopolymerizable monomer-I>    

DPHA: manufactured by Nippon Kayaku Co., Ltd.

    <Photopolymerizable monomer II>    

DPHA-40H: manufactured by Nippon Kayaku Co., Ltd.

    <Additive-I>    

Manufactured by Nippon Kayaku Co., Ltd., KAYAMER PM-21 (methacrylic acid-containing phosphate ester)

    <Surfactant-I>    

Made by DIC (shares) MEGAFAC F-559

    <Preparation of Pigment Dispersions-1 ~ 7>    

The pigments, dispersants, dispersing aids, alkali-soluble resins, and solvents described in Table 1 were mixed so as to have a mass ratio described in Table 1. This solution was subjected to a dispersion treatment in a range of 25 to 45 ° C. for 3 hours by a paint shaker. As beads, use 0.5mm Zirconia beads, and add 2.5 times the mass of the dispersion. After the dispersion was completed, the beads and the dispersion liquid were separated by a filter to prepare pigment dispersion liquids 1 to 7.

Here, the viscosity of the black is greatly increased when the black is dispersed under the same conditions as the pigment dispersion liquid-1. Therefore, in dispersing these pigments, it is necessary to greatly increase the amount of the dispersant like the pigment dispersion liquid-6.

    <Coated carbon black dispersion>    

The carbon black is produced by a common oil furnace method. Among them, as a raw material oil, an ethylene base oil having a small amount of Na, Ca, and S is used, and a gas coke oven is used for combustion. Further, as the reaction termination water, pure water treated with an ion exchange resin was used. Using a homomixer, 540 g of the obtained carbon black and 14,500 g of pure water were stirred for 30 minutes at 5,000 to 6,000 rpm to obtain a slurry. This slurry was transferred to a container equipped with a spiral mixer, and 600 g of toluene in which 60 g of epoxy resin "Epikote 828" (manufactured by Mitsubishi Chemical Corporation) was dissolved was added little by little while mixing at about 1,000 rpm. Within about 15 minutes, all the carbon black dispersed in the water moved to the toluene side, and became about 1 mm in size.

Then, the water was removed using a 60-mesh metal wire mesh, and then placed in a vacuum dryer and dried at 70 ° C. for 7 hours to completely remove toluene and water.

With respect to 90 parts by mass of the obtained coated carbon black, 20 parts by mass of DISPERBYK-167 (manufactured by BYK-Chemie) as a dispersant, 4.5 parts by mass of Solsperse 12000 (manufactured by Lubrizol Co., Ltd.) as a pigment derivative were added, and the solid content concentration was added. Propylene glycol monomethyl ether acetate (PGMEA) was added so that it might become 25 mass%.

This was fully stirred by a blender, and pre-mixing was performed. Then, a paint shaker was used to perform a dispersion treatment in a range of 25 to 45 ° C for 6 hours. As beads, use 0.5mm Zirconia beads, and add the same quality as the dispersion. After the dispersion is completed, the beads and the dispersion are separated by a filter to prepare the dispersion.

    [Examples 1 to 8 and Comparative Examples 1 to 4]    

Using the pigment dispersion liquid and the coated carbon black dispersion liquid prepared above, each component was added so that the ratio of the solid content became the blending ratio in Table 2, and then PGMEA was added so that the solid content became 17% by mass, stirred and dissolved. To prepare a photosensitive coloring composition. In Examples 1 to 8 and Comparative Examples 1, 2, and 4, the pigment concentration in the solid content was set to 40% by mass, and Comparative Example 3 was the pigment concentration in the solid content to be set to 30% by mass. In addition, in all the photosensitive coloring compositions, the mass ratio of the alkali-soluble resin (including the resin in the dispersion) to the photopolymerizable monomer was set to 3, and the photopolymerization initiator was set to the solid content. 4% by mass, 0.5% by mass of the additive, and 0.1% by mass of the surfactant. The obtained photosensitive coloring composition was evaluated by the following method.

    [Measurement of optical density (OD) per 1 μm]    

The prepared photosensitive coloring composition was applied to a glass substrate with a spin coater so that the final film thickness became 2 μm, and dried under reduced pressure for 1 minute, and then dried at 100 ° C. for 90 seconds using a hot plate. A resist-coated substrate (Substrate-1) was obtained by heating at 230 ° C for 30 minutes. The optical density (OD) of the obtained substrate was measured with a penetration concentration meter Gretag Macbeth D200-II, and a non-contact surface and layer profile measurement system VertScan (R) manufactured by Rhombus Systems was used. The thickness was measured at 2.0. Table 3 shows the optical density (OD) per film thickness.

    [Determination of Relative Dielectric Constant]    

In the production method of the substrate-1, a substrate (substrate-2) was produced in the same manner except that a glass substrate having a chromium vapor deposition film was used instead of the glass substrate. The chromium film of this sample was set as a main electrode, and a gold counter electrode was formed on the resist coating film by a vapor deposition method. The relative dielectric constant at 1 kHz and 1 V was measured using an "LCR meter 4284A" manufactured by HP (now Agilent). The results are shown in Table 3.

    [Platemaking characteristics]    

Drying using a hot plate was performed in the same manner as for the substrate-1. Using a high-pressure mercury lamp, image exposure was performed on the sample (illuminance 30 mW / cm ² , exposure amount 20 mJ / cm ² ) through a negative mask having a linear pattern with an opening of 20 μm. At this time, the distance between the sample and the mask was set to 200 μm. Thereafter, jet development was performed using a developer having a KOH concentration of 0.05% by mass at a temperature of 25 ° C. The development time was set to 1.5 times the dissolution time of the unexposed portion. The result of the line width of the obtained linear pattern is shown in Table 3. However, in the case of using the resists of Comparative Examples 1 and 2, even if development was performed for 10 minutes, a pattern could not be obtained.

It is confirmed from the comparison between Example 1 and Comparative Examples 1, 2, and 4 that if the pigment concentration is the same, the OD of the substrate obtained from the photosensitive coloring composition of the present invention is high, and the shielding property is high. In Comparative Examples 1 and 2, even if development was performed for 10 minutes, a linear pattern could not be obtained. The reason is considered to be that Comparative Examples 1 and 2 are those containing black pigment as a pigment, but a large amount of dispersant is required to disperse the black pigment, which adversely affects plate-making properties. Also, it is confirmed from Examples 4 and 5 that the larger the line width value, the higher the sensitivity. However, by using (A-1) organic black pigment and (A-2) organic coloring pigment in combination, the OD can not be greatly reduced. And increase sensitivity.

In Comparative Example 3, it was found that the pigment only covered carbon black and showed a high OD, but the relative dielectric constant became high. From Examples 6 and 7, it was confirmed that by using the (A-1) organic black pigment and (A-3) carbon black used in the present invention in combination, the OD is high and the relative dielectric constant can be maintained low.

    [Dispersion evaluation]         <Preparation of Pigment Dispersion Liquid-8 ~ 11>    

The pigments, dispersants, dispersing aids, alkali-soluble resins, and solvents described in Table 4 were mixed so as to have a mass ratio described in Table 4. This solution was subjected to a dispersion treatment in a range of 25 to 45 ° C. for 3 hours by a paint shaker. As beads, use 0.5mm Zirconia beads, and add 2.5 times the mass of the dispersion. After the dispersion was completed, the beads and the dispersion liquid were separated by a filter to prepare a pigment dispersion liquid-8 to 11.

    [Example 9 and Comparative Examples 5 to 7]    

Using the pigment dispersion prepared above, each component was added so that the ratio of the solid content became the blending ratio of Table 5, and then PGMEA was added so that the solid content became 17% by mass, and the mixture was stirred and dissolved to prepare a photosensitive color组合 物。 Composition.

Moreover, the viscosity of each of the obtained photosensitive coloring compositions was measured with a RC80L-type viscometer (measurement conditions: 23 ° C, 50 rpm) manufactured by Toki Sangyo Co., Ltd. The results are shown in Table 5.

In general, in order to disperse an organic pigment in a photosensitive coloring composition, it is known whether it is a basic polymer dispersant having a quaternary ammonium salt group or a basic polymer dispersant having no quaternary ammonium salt group. , Are used equally and show the same dispersibility. In fact, in Comparative Examples 6 and 7 of Table 5, the blackness of the organic black pigment belongs to the viscosity of the photosensitive coloring composition, regardless of whether the dispersant I or the dispersant III is used. No significant difference.

Surprisingly, from the comparison between Example 9 and Comparative Example 5 in Table 5, the photosensitive coloring composition containing (A-1) an organic black pigment is the following, that is, the use of a photosensitive coloring composition that does not have a quaternary ammonium salt group as Compared with the case of a functional polymer dispersant (dispersant III), by using a polymer dispersant (dispersant I) having a quaternary ammonium salt group as a functional group, the viscosity of the photosensitive coloring composition becomes half. Left and right, while (A-1) the organic black pigment is uniformly dispersed.

Table 6 shows the viscosity values obtained by measuring the photosensitive coloring compositions of Examples 1 to 8 by the same method as in Example 9.

As shown in Table 6, not only in Examples 1 and 2 in which (A-1) an organic black pigment is used alone as a pigment, but also in Examples in which (A-1) an organic black pigment and (A-2) an organic coloring pigment are used in combination 3 ~ 5 and 8, Example 6 using (A-1) organic black pigment and (A-3) carbon black together, (A-1) organic black pigment and (A-2) organic coloring pigment and (A- 3) In any of Example 7 of carbon black, the viscosity is the same as that of Examples 1 and 2, and any of the photosensitive coloring compositions becomes a pigment uniformly dispersed.

The present invention has been described in detail and with reference to specific embodiments, but those skilled in the art will understand that various changes or modifications can be made without departing from the spirit and scope of the present invention. This application is based on a Japanese patent application filed on September 25, 2013 (Japanese Patent Application No. 2013-198425), and the contents are incorporated herein by reference.

Claims (11)

A photosensitive coloring composition comprising at least (A) a color material, (B) a dispersant, (C) an alkali-soluble resin, and (D) a photopolymerization initiator, wherein the (A) color material contains (A) -1) an organic black pigment, (A-2) an organic coloring pigment, and (A-3) a compound represented by the following general formula (1), a geometric isomer thereof, a salt thereof, or a salt of a geometric isomer thereof; ) Carbon black, with respect to 100% by mass of the color material (A), the content ratio of the (A-1) organic black pigment is 10% by mass or more and 80% by mass or less, and the content of the (A-2) organic color pigment The proportion is 10% by mass or more and 60% by mass or less, and the (B) dispersant contains a polymer dispersant having a quaternary ammonium salt group as a functional group, [In formula (1), R ¹ and R ⁶ are each independently a hydrogen atom, CH ₃ , CF ₃ , a fluorine atom, or a chlorine atom; R ² , R ³ , R ⁴ , R ⁵ , R ⁷ , R ⁸ , R ⁹ and R ¹⁰ lines and all of the other independently of one another, a hydrogen atom, a halogen ^{atom, R 11, COOH, COOR 11} , COO -, CONH 2, CONHR 11, CONR 11 R 12, CN, OH, OR 11, COCR 11, OOCNH ₂ OOCNHR ¹¹ OOCNR ¹¹ R ¹² NO ₂ NH ₂ NHR ¹¹ NR ¹¹ R ¹² NHCOR ¹² NR ¹¹ COR ¹² N = CH ₂ N = CHR ¹¹ N = CR ¹¹ R ¹² SH ^{, SR 11, SOR 11, SO} 2 R 11, SO 3 R 11, SO 3 H, SO 3 -, SO 2 NH 2, SO 2 NHR 11 or SO ₂ NR ¹¹ R ^12; and selected from the group consisting of R ² and R ³ , At least one combination of the group consisting of, R ³ and R ⁴ , R ⁴ and R ⁵ , R ⁷ and R ⁸ , R ⁸ and R ⁹ , and R ⁹ and R ¹⁰ , can be directly bonded to each other, Or they are bonded to each other by bridging oxygen atom, sulfur atom, NH or NR ¹¹ ; R ¹¹ and R ¹² are independent of each other, alkyl group having 1 to 12 carbon atoms, cycloalkyl group having 3 to 12 carbon atoms, and 2 to 12 carbon atoms 12 alkenyl, 3 to 12 carbon alkenyl or 2 to 12 alkynyl]. The photosensitive coloring composition according to claim 1, wherein in the general formula (1) above, R ² , R ⁴ , R ⁵ , R ⁷ , R ^9, and R ¹⁰ are independently a hydrogen atom or a fluorine atom. Or a chlorine atom, and R ³ and R ⁸ are independently hydrogen atom, NO ₂ , OCH ₃ , OC ₂ H ₅ , bromine atom, chlorine atom, CH ₃ , C ₂ H ₅ , N (CH ₃ ) ₂ , N (CH the same, R ¹ and R ^6, R ² and R ⁷ the ^{_{same, - 3) (C 2 H}} 5), N (C 2 H 5) 2, α- naphthyl, β- naphthyl group, SO ₃ H or SO ₃ R ³ is the same as R ⁸ , R ⁴ is the same as R ⁹ , and R ⁵ is the same as R ¹⁰ .     The photosensitive coloring composition according to claim 1 or 2, wherein the polymer dispersant further has a tertiary amine as a functional group.         The photosensitive coloring composition according to any one of claims 1 to 3, wherein the (C) alkali-soluble resin contains at least one of the following alkali-soluble resin (c1) and the following alkali-soluble resin (c2), <Alkali-soluble resin (c1)> By adding an α, β-unsaturated monocarboxylic acid or an α, β-unsaturated monocarboxylic acid ester having a carboxyl group to an epoxy resin, it is further added to a polybasic acid and / or its anhydride Alkali-soluble resin obtained by the reaction; <Alkali-soluble resin (c2)> By adding an α, β-unsaturated monocarboxylic acid or an α, β-unsaturated monocarboxylic acid ester having a carboxyl group to an epoxy resin, further An alkali-soluble resin obtained by reacting with a polyhydric alcohol and a polybasic acid and / or its anhydride.         The photosensitive coloring composition according to any one of claims 1 to 4, wherein the (A-2) organic coloring pigment contains at least one of the following pigments, blue: chromaticity index pigment blue 60, or 15: 6 Red: Chroma Index Pigment Red 177, 254, or 272 Violet: Chroma Index Pigment Purple 23, or 29 Orange: Chroma Index Pigment Orange 43, 64, or 72.         The photosensitive coloring composition according to any one of claims 1 to 5, wherein the content ratio of the (A-3) carbon black is 5 mass% or more and 50 masses relative to 100 mass% of the (A) color material. %the following.         The photosensitive coloring composition according to any one of claims 1 to 6, wherein the (D) photopolymerization initiator is an oxime ester initiator and / or a ketoxime ester initiator.         A cured product obtained by curing the photosensitive coloring composition according to any one of claims 1 to 7.         A black matrix formed from the hardened material of claim 8.         A colored spacer formed of the hardened material of claim 8.         An image display device includes a black matrix of claim 9 or a colored spacer of claim 10.