KR102356749B1 - Photosensitive coloring composition, black matrix, coloring spacer, image display device, and pigment dispersion - Google Patents

Abstract

An object of the present invention is to provide a photosensitive coloring composition that is excellent in light-shielding properties, is excellent in dispersibility and plate-making properties, and exhibits a sufficiently low dielectric constant. The photosensitive coloring composition of this invention contains (A) a color material, (B) a dispersing agent, (C) alkali-soluble resin, and (D) a photoinitiator at least, (A) a color material contains (A-1) general formula ( 1) contains a compound represented by, a geometric isomer of the compound, a salt of the compound, or an organic black pigment that is a salt of a geometric isomer of the compound, and (B) the dispersing agent contains a polymer dispersing agent having a quaternary ammonium base as a functional group .

Description

A photosensitive coloring composition, a black matrix, a coloring spacer, an image display apparatus, and a pigment dispersion {PHOTOSENSITIVE COLORING COMPOSITION, BLACK MATRIX, COLORING SPACER, IMAGE DISPLAY DEVICE, AND PIGMENT DISPERSION}

The present invention relates to a photosensitive coloring composition, a black matrix, a colored spacer, and an image display device. In detail, it is related with the photosensitive coloring composition excellent in shielding property and plate making characteristic, and its use.

The black matrix for liquid crystal display elements is used in order to prevent leakage of light from between drive electrodes in a liquid crystal display element. In general, the black matrix is a pattern of a light-shielding material in a stripe shape or a grid shape formed using a photolithography method on a transparent substrate such as a glass or plastic sheet that is paired with a TFT (Thin Film Transistor) device substrate.

In recent years, in order to cope with higher resolution and higher luminance of color liquid crystal display elements, in an active matrix liquid crystal display, a color filter on array method in which a color filter is provided on the TFT element substrate side (COA method) However, a black matrix on array method (BOA method) in which only a black matrix is formed on the TFT element substrate side has been proposed. According to this method, compared to the case where the black matrix is formed on the color filter side, it is not necessary to provide an alignment margin with the active element side, so that the aperture ratio can be increased, and as a result, high luminance can be achieved. .

However, in the case of adopting such a structure, the black matrix is required to have a volume resistivity above a certain level or a relative permittivity below a certain level so as not to cause a short circuit in an electric circuit even when directly mounted on a TFT element.

As such a black matrix, the black matrix which used multiple types of organic coloring pigment and carbon black for a pigment is proposed (for example, refer patent document 1).

Moreover, the photosensitive composition for black matrices using the organic black pigment as a pigment is also known, Specifically, the photosensitive composition using aniline black (for example, refer patent document 2) or perylene black (for example, refer patent document 3) is is known

On the other hand, a bis-oxodihydro-indolylene-benzofuran colorant is known as an organic pigment (see, for example, Patent Document 4). In this document, it is described that the pigment is used for forming the red layer, the blue layer and the green layer of a color filter. Moreover, it is known that the pigment is used also as an organic black pigment for electrophoretic displays (refer patent document 5, for example).

Japanese Patent Application Laid-Open No. 2009-75446 Japanese Patent Laid-Open No. 8-44049 Japanese Laid-Open Patent Publication No. 2006-235153 Japanese Patent Publication No. 2002-528448 Japanese Patent Publication No. 2012-515240

As a result of the present inventors' earnest examination, the photosensitive composition described in patent document 1 has a low shielding rate (optical density) of an organic colored pigment, and it turns out that it is necessary to thicken the film thickness in order to obtain sufficient optical density. .

In addition, it can be seen that the aniline black and perylene black described in Patent Documents 2 and 3 have poor dispersibility, and it is necessary to use a large amount of a dispersant for dispersing, resulting in problems in plate making properties and the like. there was. In addition, it was found that the shielding ratio (optical density) was not sufficient.

In addition, in Patent Documents 4 and 5, there is no description or suggestion about the use of a bis-oxodihydro-indolylene-benzofuran colorant as a shielding agent used in an image display device, and it is used as a shielding agent used in an image display device. Properties such as optical density, dispersibility, and plate making properties are also unclear.

The present invention has been made in view of the above conventional circumstances, and an object of the present invention is to provide a photosensitive coloring composition which is excellent in light-shielding property, is excellent in dispersibility and plate-making property, and exhibits a sufficiently low dielectric constant.

As a result of the present inventors earnestly examining in order to solve the said subject, it finds that the said subject can be solved by using the organic black pigment which has a specific structure as a color material in a photosensitive coloring composition, and also using a specific dispersing agent, came to the invention.

That is, the present invention has the following structures [1] to [17].

[1] A photosensitive coloring composition containing at least (A) a color material, (B) a dispersing agent, (C) an alkali-soluble resin, and (D) a photoinitiator, wherein the (A) color material has the following general formula (A-1) A photosensitive coloring composition comprising a compound represented by (1), a geometric isomer thereof, a salt thereof, or an organic black pigment that is a salt of the geometric isomer, and the dispersing agent (B) contains a polymer dispersing agent having a quaternary ammonium salt group as a functional group.

[Formula 1]

[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 are independently of each other 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 ; In addition, at least one combination selected from the group consisting of ^{R 2} and R ³ , 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 is,} They may be directly bonded to each other, or may be bonded to each other via an oxygen atom, a sulfur atom, NH or NR ^{11 bridge;} R ¹¹ and R ¹² each independently represent an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms, an alkenyl group having 2 to 12 carbon atoms, a cycloalkenyl group having 3 to 12 carbon atoms, or an alkynyl group having 2 to 12 carbon atoms. ]

[2] In the general formula (1),

wherein R ² , R ⁴ , R ⁵ , R ⁷ , R ⁹ and R ¹⁰ are each independently a hydrogen atom, a fluorine atom or a chlorine atom, R ³ and R ⁸ are each independently a 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, SO ₃ H or SO ₃ ^- , 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 R ⁹ The photosensitive coloring composition according to [1], wherein ^{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 includes at least any one of the following alkali-soluble resin (c1) and the following alkali-soluble resin (c2). .

<Alkali-soluble resin (c1)>

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

<Alkali-soluble resin (c2)>

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

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

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

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

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

Purple: Color Index Pigment Violet 23, or 29

Orange: Color Index Pigment Orange 43, 64, or 72

[7] (A) With respect to 100 mass % of the color material, the content rate of the (A-1) organic black pigment is 30 to 90 mass %, (A-2) the content rate of the organic color pigment is 10 to 70 mass % , the photosensitive coloring composition according to [5] or [6].

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

[9] (A) With respect to 100 mass% of the color material, the content rate of the (A-1) organic black pigment is 50 to 90 mass%, (A-3) the content rate of carbon black is 10 to 50 mass%; The photosensitive coloring composition according to [8].

[10] (D) The photosensitive coloring composition according to any one of [1] to [9], wherein the 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 from the cured product according to [11].

[13] A colored spacer formed from the cured product according to [11].

[14] An image display device comprising the black matrix according to [12] or the colored spacer according to [13].

[15] A pigment dispersion containing (A) a color material and (B) a dispersing agent, wherein the (A) color material is (A-1) a compound represented by the following general formula (1), its geometric isomer, its salt, or its A pigment dispersion comprising an organic black pigment that is a salt of a geometric isomer, and further comprising a polymer dispersing agent in which the (B) dispersing agent has a quaternary ammonium base as a functional group.

[Formula 2]

[wherein, 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 are independently of each other 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 ; In addition, at least one combination selected from the group consisting of ^{R 2} and R ³ , 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 is,} They may be directly bonded to each other, or may be bonded to each other via an oxygen atom, a sulfur atom, NH or NR ^{11 bridge;} R ¹¹ and R ¹² each independently represent an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms, an alkenyl group having 2 to 12 carbon atoms, a cycloalkenyl group having 3 to 12 carbon atoms, or an alkynyl group having 2 to 12 carbon atoms. ]

[16] In the general formula (1),

wherein R ² , R ⁴ , R ⁵ , R ⁷ , R ⁹ and R ¹⁰ are each independently a hydrogen atom, a fluorine atom, or a chlorine atom, R ³ and R ⁸ are each independently a 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, SO ₃ H or SO ₃ ^- , 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 R ^The pigment dispersion liquid according to [15], wherein it is the same as ^{9 and R 5 is the same as R 10 .}

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

The photosensitive coloring composition of the present invention contains an organic black pigment having a specific structure, so that the amount of the dispersant can be reduced at the time of producing the pigment dispersion, so it exhibits excellent plate making properties and is also excellent in dispersibility. Therefore, the black matrix formed from the photosensitive coloring composition of this invention shows the outstanding light-shielding property. Moreover, even if the black matrix and the colored spacer of this invention are formed on a TFT element board|substrate, it shows a dielectric constant low enough so that a short circuit, malfunction, etc. do not arise. The image display apparatus which has a black matrix of this invention does not have problems, such as a TFT malfunction and the hunting of a liquid crystal drive, and is excellent in reliability.

BRIEF DESCRIPTION OF THE DRAWINGS It is a cross-sectional schematic which shows an example of an organic electroluminescent element.

EMBODIMENT OF THE INVENTION Hereinafter, although embodiment of this invention is described concretely, this invention is not limited to the following embodiment, It can change variously and implement within the range of the summary.

In addition, in this invention, "(meth)acryl" means "acryl and/or methacryl", and it is the same also about "(meth)acrylate" and "(meth)acryloyl."

"(co)polymer" means including both a homopolymer (homopolymer) and a copolymer (copolymer), and "acid (anhydride)", "(anhydride)... "acid" means containing both an acid and its anhydride. In addition, in this invention, "acrylic resin" means the (co)polymer containing the (co)polymer containing (meth)acrylic acid, and the (meth)acrylic acid ester which has a carboxyl group.

In addition, in this invention, "monomer" is a term relative to what is called a high molecular substance (polymer), and is a meaning including a dimer, a trimer, an oligomer, etc. in addition to the narrow monomer (monomer).

In this invention, "total solid content" shall mean all components other than a solvent contained in the photosensitive coloring composition or the ink mentioned later.

In this invention, a weight average molecular weight refers to the weight average molecular weight (Mw) of polystyrene conversion by GPC (gel permeation chromatography).

In addition, in this invention, unless otherwise indicated, "amine titer" represents an amine value in terms of effective solid content, and is a value represented by the amount of base per 1 g of solid content of the dispersing agent and the mass of equivalent KOH. In addition, a measurement method is mentioned later. In addition, unless otherwise indicated, an "acid value" shows an acid value in terms of effective solid content, and is computed by neutralization titration.

In addition, in this specification, the percentage and part represented by "mass" have the same meaning as the percentage and part represented by "weight".

[Photosensitive Coloring Composition]

The photosensitive coloring composition (henceforth "photosensitive coloring composition" or "coloring resin composition" may be called) of this invention,

(A) Color material

(B) dispersant

(C) alkali-soluble resin

(D) photoinitiator

as an essential component, and, if necessary, additionally organic solvents, adhesion improvers such as silane coupling agents, coating properties improvers, development improvers, ultraviolet absorbers, antioxidants, surfactants, pigment derivatives, etc. It contains other compounding components. , it is usually used in a state in which each compounding component is dissolved or dispersed in an organic solvent.

<(A) color material>

The (A) color material 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 the geometric isomer.

[Formula 3]

[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 are independently of each other 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 ;

In addition, at least one combination selected from the group consisting of ^{R 2} and R ³ , 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 is,} They may be directly bonded to each other, or may be bonded to each other via an oxygen atom, a sulfur atom, NH or NR ^{11 bridge;}

R ¹¹ and R ¹² each independently represent an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms, an alkenyl group having 2 to 12 carbon atoms, a cycloalkenyl group having 3 to 12 carbon atoms, or an alkynyl group having 2 to 12 carbon atoms. ]

The geometric isomer of the compound represented by the general formula (1) has the following core structure (however, the substituents in the structural formula are omitted), and the trans-trans isomer is most likely the most stable.

[Formula 4]

When the compound represented by the general formula (1) is anionic, its charge is transferred to any known suitable cation, for example a metal, organic, inorganic or metal organic cation, specifically an alkali metal, alkaline earth metal, transition metal , tertiary ammonium such as primary ammonium, secondary ammonium, trialkylammonium, quaternary ammonium such as tetraalkylammonium, or a salt compensated with an organometallic complex. Moreover, when the geometrical isomer of the compound represented by General formula (1) is anionic, it is preferable that it is the same salt.

In the substituent of general formula (1) and their definition, since there exists a tendency for a shielding rate to become high, the following are preferable. This is because the following substituents do not absorb and it is thought that the hue of a pigment is not affected.

R ² , R ⁴ , R ⁵ , R ⁷ , R ⁹ and R ¹⁰ each independently represent preferably a hydrogen atom, a fluorine atom, or a chlorine atom, more preferably a hydrogen atom.

R ³ and R ⁸ are each independently preferably a hydrogen atom, NO ₂ , OCH ₃ , OC ₂ H ₅ , a bromine atom, a 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, SO ₃ H or SO ₃ ⁻ , more preferably a hydrogen atom or SO ₃ H .

R ¹ and R ⁶ are each independently preferably a hydrogen atom, CH ₃ or CF ₃ , and more 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} preferably R ¹ is identical to ^{R 6 , R 2} is identical to ^{R 7 , R 3} is identical to ^{R 8 , R 4} is identical to ^{R 9 , and R 5} is identical to ^{R 10 .}

The C1-C12 alkyl group is, for example, a methyl group, an ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, isobutyl group, tert-butyl group, 2-methylbutyl group, n -pentyl group, 2-pentyl group, 3-pentyl group, 2,2-dimethylpropyl group, n-hexyl group, heptyl group, n-octyl group, 1,1,3,3-tetramethylbutyl group, 2- an ethylhexyl group, a nonyl group, a decyl group, an undecyl group, or a dodecyl group.

The cycloalkyl group having 3 to 12 carbon atoms is, for example, a cyclopropyl group, a cyclopropylmethyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cyclohexylmethyl group, a trimethylcyclohexyl group, a tozyl group, a norbornyl group, a bornyl group. , norcaryl group, caryl group, menthyl group, norphinyl group, pinyl group, 1-adamantyl group or 2-adamantyl group.

The alkenyl group having 2 to 12 carbon atoms is, for example, a vinyl group, an allyl group, a 2-propen-2-yl group, a 2-buten-1-yl group, a 3-buten-1-yl group, and 1,3-butadiene-2. -yl group, 2-penten-1-yl group, 3-penten-2-yl group, 2-menthyl-1-buten-3-yl group, 2-methyl-3-buten-2-yl group, 3-methyl-2-butene -1-yl group, 1,4-pentadien-3-yl group, hexenyl group, octenyl group, nonenyl group, decenyl group or dodecenyl group.

The cycloalkenyl group having 3 to 12 carbon atoms is, for example, a 2-cyclobuten-1-yl group, a 2-cyclopenten-1-yl group, a 2-cyclohexen-1-yl group, a 3-cyclohexen-1-yl group, 2,4-cyclohexadien-1-yl group, 1-p-menten-8-yl group, 4(10)-tuzen-10-yl group, 2-norbornen-1-yl group, 2,5-norbornadi en-1-yl group, 7,7-dimethyl-2,4-norkaradien-3-yl group, or campenyl group.

The C2-C12 alkynyl group is, for example, 1-propyn-3-yl group, 1-butyn-4-yl group, 1-pentyn-5-yl group, 2-methyl-3-butyn-2-yl group, 1 ,4-pentadiyn-3-yl group, 1,3-pentadiyn-5-yl group, 1-hexyn-6-yl group, cis-3-methyl-2-penten-4-yn-1-yl group, trans -3-methyl-2-penten-4-yn-1-yl group, 1,3-hexadiin-5-yl group, 1-octyne-8-yl group, 1-nonin-9-yl group, 1-decyne-10 -diyl or 1-dodecin-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).

[Formula 5]

As a specific example of such an organic black pigment, Irgaphor (trademark) Black S 0100 CF (made by BASF) is mentioned by a brand name.

The organic black pigment of (A-1) is preferably used by dispersing it in a dispersing agent and a solvent according to the method mentioned later. Moreover, when the sulfonic acid derivative of the said General formula (2) exists at the time of dispersion|distribution, dispersibility and storage property may improve.

The photosensitive coloring composition of this invention may contain color materials other than (A-1) as (A) color material. Although a salt pigment can be used as the color material, a pigment is preferable from points, such as heat resistance and light resistance. In particular, (A-2) organic coloring pigments and/or (A-3) carbon black are preferably used. In addition, in this specification, an organic coloring pigment is a powder which has as a component the organic compound used for coloring, and means what is insoluble in water and oil.

(A-2) Examples of the organic color pigment include blue pigments, green pigments, red pigments, yellow pigments, purple pigments, orange pigments, brown pigments, and black pigments other than (A-1) and (A-3). Organic pigments may be used. In addition, in addition to organic pigments such as azo-based, phthalocyanine-based, quinacridone-based, benzimidazolone-based, isoindolinone-based, dioxazine-based, and indanthrene-based pigments, various inorganic pigments and the like can be used as the structure thereof. In addition, in this specification, unless there is a description in particular, the color of a pigment means the color shown when using this pigment independently as a color material and forming a photosensitive coloring composition. That is, for example, when a black pigment is used independently as a color material and the said pigment is used and the photosensitive coloring composition is formed, the color shown is meaning the pigment used as black.

Below, the specific example of the pigment which can be used for this invention is shown by a pigment number. In addition, "C. Terms such as "I. Pigment Red 2" mean a color index (C. I.).

As a red pigment,

Among these, preferably CI pigment red 48:1, 122, 168, 177, 202, 206, 207, 209, 224, 242, 254, more preferably CI pigment red 177, 209, 224, 254 can be heard In addition, it is preferable to use CI Pigment Red 177, 254, and 272 from the point of dispersibility and light-shielding property, and when hardening the photosensitive coloring composition of this invention with ultraviolet-ray, as a red pigment, a thing with a low ultraviolet-absorption rate is used It is preferable to do, and from this viewpoint, it is more preferable to use CI Pigment Red 254 and 272.

As a blue pigment,

Among these, 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. Moreover, it is preferable to use CI Pigment Blue 15:6,16,60 from the point of dispersibility and light-shielding property, and when hardening the photosensitive coloring composition of this invention with ultraviolet-ray, as a blue pigment, ultraviolet-ray absorption is low. It is preferable to use one, and from this viewpoint, it is more preferable to use CI Pigment Blue 60.

Examples of the green pigment include CI Pigment Green 1, 2, 4, 7, 8, 10, 13, 14, 15, 17, 18, 19, 26, 36, 45, 48, 50, 51, 54, 55 can Among these, Preferably, C.I. Pigment Green 7 and 36 are mentioned.

As a yellow pigment,

Among these, Preferably CI Pigment Yellow 83, 117, 129, 138, 139, 150, 154, 155, 180, 185, More preferably, CI Pigment Yellow 83, 138, 139, 150, 180 is mentioned have.

As an orange (orange) pigment,

Among these, Preferably, C.I. Pigment Orange 38 and 71 are mentioned. In addition, it is preferable to use CI pigment orange 43, 64, 72 from the point of dispersibility and light-shielding property, and when hardening the photosensitive coloring composition of this invention with ultraviolet-ray, as an orange pigment, a thing with a low ultraviolet absorption is used It is preferable to do it, and it is more preferable to use CI pigment orange 64 and 72 from such a viewpoint.

As a purple pigment, 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 these, Preferably C.I. Pigment Violet 19 and 23, More preferably, C.I. Pigment Violet 23 is mentioned. In addition, it is preferable to use CI pigment violet 23 and 29 from the point of dispersibility and light-shielding property, and when hardening the photosensitive coloring composition of this invention with ultraviolet-ray, it is a purple pigment to use a thing with a low ultraviolet absorption. It is preferable, and it is more preferable to use CI pigment violet 29 from such a viewpoint.

Among these, it is preferable to set it as the thing containing at least 1 or more types of the following pigments.

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

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

Purple: Color Index Pigment Violet 23 or 29

Orange: Color Index Pigment Orange 43, 64 or 72

In addition, when using a combination of pigments of different colors, the combination of colors is not particularly limited, but from the viewpoint of light-shielding properties, for example, a combination of a red pigment and a blue pigment, or a combination of a blue pigment and an orange pigment and a purple pigment. combinations, and the like.

Moreover, dye may be used instead of (A-2) organic coloring pigment, and dye may be used further for (A-2) organic coloring pigment. Examples of the dye usable as a color material include azo dyes, anthraquinone dyes, phthalocyanine dyes, quinoneimine dyes, quinoline dyes, nitro dyes, carbonyl dyes, and methine dyes.

Examples of the azo dye 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 etc. are mentioned.

Examples of the anthraquinone dye include CI Vat 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 etc. are mentioned.

In addition, as a phthalocyanine type dye, for example, CI pad blue 5 etc., as a quinoneimine type dye, for example, CI basic blue 3, CI basic blue 9 etc., as a quinoline type dye, for example, CI solvent yellow 33, CI acid yellow 3, CI disperse yellow 64, etc. are mentioned as nitro type dye, for example, CI acid yellow 1, CI acid orange 3, CI dispers yellow 42, etc. are mentioned.

Moreover, black pigments 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 independent, or the thing by mixing of red, green, blue, etc. may be sufficient as it. Moreover, these color materials can be suitably selected from an inorganic or organic pigment, and dye.

Colorants that can be mixed to prepare black colorant include Victoria Pure Blue (42595), Oramine O (41000), Catillon Brilliant Flavin (Basic 13), Rhodamine 6GCP (45160), Rhodamine B (45170) , Safranin OK70: 100 (50240), Erioglaucine X (42080), No.120/Lionol Yellow (21090), Lionol Yellow GRO (21090), Simulator Fast Yellow 8GF (21105), Benzidine Yellow 4T-564D (21095), Simulator Fast Red 4015 (12355), Lionol Red 7B4401 (15850), Fastogen Blue TGR-L (74160), Lionol Blue SM (26150), Lionol Blue ES (Pigment Blue) 15: 6), Lyonogen Red GD (Pigment Red 168), Lionol Green 2YS (Pigment Green 36), etc. (In addition, the numbers in ( ) above mean the color index (CI)).

In addition, when expressed by CI numbers for other pigments capable of being mixed, 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 Violet Pigment 19, 23, 29, 30, 37, 40, 50, CI Blue Pigment 15, 15: 1, 15: 4, 22, 60, 64, CI Green Pigment 7, CI Brown pigment 23, 25, 26 etc. are mentioned.

Moreover, as a black color material which can be used individually, acetylene black, lamp black, bone black, graphite, iron black, aniline black, cyanine black, titanium black, perylene black, etc. are mentioned.

Moreover, as a color material other than (A-1) organic black pigment, (A-3) carbon black is used preferably from a viewpoint of a light-shielding rate and an image characteristic. Examples of carbon black include the following carbon blacks.

Manufactured by Mitsubishi Chemical Corporation:

Manufactured by Degussa:

Cabot Manufacturing:

Produced by Columbia Carbon:

As carbon black, you may use what was coat|covered with resin. When carbon black coated with resin is used, there is an effect of improving the adhesiveness to the glass substrate and the volume resistance value. As carbon black coated with resin, for example, the carbon black described in Unexamined-Japanese-Patent No. 09-71733, etc. can be used preferably.

As carbon black used for the coating process with resin, it is preferable that the total content of Na and Ca is 100 ppm or less. Carbon black usually contains Na, Ca, K, Mg, Al, Fe, etc. mixed from raw material oil, combustion oil (or gas), reaction stop water or granulated water, and further the furnace material of the reactor at the time of manufacture. Ash is contained in the order of percent. Of these, Na and Ca are generally contained in each of several hundred ppm or more, but when they exist in a large amount, they may permeate into the transparent electrode (ITO) or other electrodes and cause an electrical short circuit.

As a method of reducing the content of ash containing Na or Ca, as raw material oil or fuel oil (or gas) and reaction stop water when producing carbon black, carefully selecting those with the lowest content of these as much as possible and a structure It is possible by minimizing the addition amount of the alkali substance to adjust the . As another method, a method of dissolving and removing Na and Ca by washing the carbon black submitted from the furnace with water or hydrochloric acid or the like is mentioned.

Specifically, after mixing and dispersing carbon black in water, hydrochloric acid, or hydrogen peroxide solution, when a poorly soluble solvent is added to water, the carbon black migrates to the solvent side, is completely separated from water, and most of the Na present in the carbon black and Ca are dissolved in water or acid and removed. In order to reduce the total amount of Na and Ca to 100 ppm or less, it may be possible to use only the carbon black manufacturing process in which raw materials are carefully selected or the water or acid dissolution method alone. can be 100 ppm or less.

Moreover, it is preferable that resin-coated carbon black is so-called acidic carbon black with a pH of 6 or less. Since the dispersion diameter (agglomerate diameter) in water becomes small, it becomes possible to cover up to a fine unit, and it is preferable. Moreover, it is preferable that the particle diameter is 40 nm or less and the dibutyl phthalate (DBP) absorption amount is 140 ml/100 g or less. When the particle size is larger than 40 nm and the DBP absorption amount is larger than 140 ml/100 g, the dispersibility is excellent in the case of a paste, but the concentration of the coating film is not sufficient in some cases, and the light-shielding property is about 1 to 2 μm in thickness. This is because there is a risk of shortage.

The method for preparing the carbon black coated with the resin is not particularly limited, but for example, after appropriately adjusting the blending amount of the carbon black and the resin, 1. Mix the resin with a solvent such as cyclohexanone, toluene, and xylene and heat it The dissolved resin solution and the suspension in which carbon black and water are mixed are mixed and stirred, the carbon black and water are separated, the water is removed, and the composition obtained by heating and kneading is formed into a sheet, pulverized, and dried. Way ; 2. Method of mixing and stirring the resin solution and suspension prepared in the same manner as above to granulate carbon black and resin, then separating and heating the obtained granular material to remove residual solvent and water; 3. Dissolve carboxylic acids such as maleic acid and fumaric acid in the solvents exemplified above, add carbon black, mix and dry, remove the solvent to obtain carboxylic acid-impregnated carbon black, and add resin to this to dry How to blend; 4. The reactive group-containing monomer component constituting the resin to be coated and water are stirred at high speed to prepare a suspension, after polymerization and cooling to obtain a reactive group-containing resin from the polymer suspension, then carbon black is added thereto and kneaded; A method of reacting black with a reactive group (grafting carbon black), cooling and pulverizing, and the like can be employed.

The type of resin to be coated is not particularly limited, either, but synthetic resins are common, and resins having benzene nuclei in their structure are preferable in terms of dispersibility and dispersion stability because the amphoteric surfactant action is stronger.

Specific synthetic resins include thermosetting resins such as phenol resins, melamine resins, xylene resins, diallyl phthalate resins, glyphtal resins, epoxy resins and alkylbenzene resins, polystyrene, polycarbonate, polyethylene terephthalate, and polybutylene terephthalate. Thermoplastics such as phthalate, modified polyphenylene oxide, polysulfone, polyparaphenylene terephthalamide, polyamideimide, polyimide, polyaminobismaleimide, polyethersulfopolyphenylenesulfone, polyarylate, polyetheretherketone, etc. A resin may be used. The coating amount of the resin to carbon black is preferably 1 to 30 mass % with respect to the total amount of carbon black and resin, and an amount less than 1 mass % may result in only dispersibility and dispersion stability similar to those of untreated carbon black. there is On the other hand, when it exceeds 30 mass %, adhesiveness between resins is strong, it becomes a dump-like mass, and there exists a possibility that dispersion|distribution may not advance.

In this way, the carbon black formed by coating with resin can be used as a light-shielding material of a black matrix according to a conventional method, and the color filter which uses this black matrix as a component can be manufactured by a conventional method. When such carbon black is used, a black matrix having a high light-shielding rate, a low surface reflectance and a thin film thickness can be achieved at low cost. It is estimated that it is because the dispersibility and dispersion stability of carbon black improved remarkably with respect to resin and the solvent which comprise black matrix liquid. Moreover, it is also estimated that there exists an effect|action which block|blocks Ca and Na in carbon black by coat|covering the carbon black surface with resin.

Moreover, as a pigment, barium sulfate, lead sulfate, titanium oxide, yellow lead, bengala, chromium oxide, etc. can also be used.

These various pigments can also use multiple types together. For example, a green pigment and a yellow pigment can be used together for adjustment of chromaticity, or a blue pigment and a purple pigment can be used together.

Among these various pigments, (A-2) as an organic color pigment, particularly preferably used from the viewpoint of light-shielding properties, CI Pigment Blue 60, CI Pigment Blue 15:6, CI Pigment Red 177, CI Pigment Red 242, CI pigment blue 254, CI pigment violet 23, CI pigment violet 29, CI pigment orange 49, CI pigment orange 64, and CI pigment orange 79 are mentioned. (A-2) When an organic coloring pigment is included, it is preferable to contain at least 1 type or more of the said pigment, and it is more preferable to contain 2 or more types.

Moreover, as (A-3) carbon black, the point of a volume resistance or dielectric constant to resin-coated carbon black is used preferably.

It is preferable to disperse|distribute these pigments so that an average particle diameter may become 1 micrometer or less normally, Preferably it is 0.5 micrometer or less, More preferably, it may become 0.25 micrometer or less. Here, the standard of the average particle diameter is the number of pigment particles.

In addition, in this invention, the average particle diameter of a pigment is the value calculated|required from the pigment particle diameter measured by dynamic light scattering (DLS). Particle size measurement is carried out on a sufficiently diluted colored resin composition (usually diluted and prepared with a pigment concentration of about 0.005-0.2 mass%. However, if there is a concentration recommended by the measuring instrument, the concentration is followed), and the measurement is carried out at 25°C. .

<(B) dispersant>

In the photosensitive coloring composition of the present invention, (A) finely dispersing the color material and stabilizing the dispersed state is important for ensuring quality stability, so (B) a dispersing agent is included, particularly (A-1) A polymer dispersing agent having a quaternary ammonium base as a functional group is included from the viewpoint of dispersibility of the organic black pigment.

The polymer dispersant further comprises a carboxyl group in terms of dispersion stability; phosphate group; sulfonic acid group; or a base thereof; a primary, secondary or tertiary amino group; What further has functional groups, such as a group derived from nitrogen-containing heterocyclic rings, such as a pyridine, a pyrimidine, and a pyrazine, may be sufficient. Among them, a primary, secondary, or tertiary amino group; A polymer dispersing agent further having a basic functional group such as a group derived from a nitrogen-containing heterocyclic ring such as pyridine, pyrimidine or pyrazine is preferable from the viewpoint of dispersing the pigment with a small amount of the dispersing agent.

Among these, from a viewpoint of the dispersibility of (A-1) an organic black pigment, and a viewpoint of the dispersibility of (A-2) an organic coloring pigment and/or (A-3) carbon black, a quaternary ammonium base group and a tertiary amino group A polymer dispersing agent having as a functional group is preferable.

Further, as the polymer dispersant, for example, a urethane dispersant, an acrylic dispersant, a polyethyleneimine dispersant, a polyallylamine dispersant, a dispersant composed of a monomer having an amino group and a macromonomer, a polyoxyethylene alkyl ether dispersant, polyoxyethylene di and ester dispersants, polyether phosphate dispersants, polyester phosphate dispersants, sorbitan aliphatic ester dispersants, and aliphatic modified polyester dispersants.

Specific examples of such a dispersing agent include EFKA (registered trademark, manufactured by BASF, Inc.), DISPERBYK (registered trademark, manufactured by Bikchemi), DISPERON (registered trademark, manufactured by Kusumoto Chemicals), SOLSPERSE ( A registered trademark, manufactured by Lubrizol, Inc.), KP (manufactured by Shin-Etsu Chemical Industries, Ltd.), Polyflow (manufactured by Kyoeisha Chemical Corporation), and Azisper (registered trademark, manufactured by Ajinomoto Corporation), and the like are mentioned.

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

The weight average molecular weight (Mw) of the polymer dispersant is usually 700 or more, preferably 1000 or more, and usually 100,000 or less, preferably 50,000 or less.

Among these, from the viewpoint of adhesiveness and linearity, (B) the dispersant preferably contains a functional group-containing urethane-based polymer dispersant and/or an acrylic polymer dispersant, and particularly preferably contains an acrylic polymer dispersant.

Moreover, the polymer dispersing agent which has a basic functional group and has a polyester bond and/or a polyether bond from the point of dispersibility and storage property is preferable.

Examples of the urethane-based and acrylic polymer dispersants include DISPERBYK160 to 166 and 182 series (all of which are urethane-based), DISPERBYK2000, 2001, and LPN21116 (all of which are acrylic) (all of which are manufactured by Bikchemi).

If a chemical structure preferable as a urethane-based polymer dispersant is specifically illustrated, for example, a polyisocyanate compound, a compound having a number average molecular weight of 300 to 10,000 having one or two hydroxyl groups in the molecule, and active hydrogen and a tertiary amino group in the same molecule and dispersion resins having a weight average molecular weight of 1,000 to 200,000 obtained by reacting a compound having By treating these with a quaternizing agent such as benzyl chloride, all or part of the tertiary amino groups can be made into quaternary ammonium base groups.

Examples of the polyisocyanate compound include paraphenylene diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, naphthalene-1,5-diisocyanate, toly Aliphatic diisocyanates, such as aromatic diisocyanate, such as din diisocyanate, hexamethylene diisocyanate, lysine methyl ester diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, dimer acid diisocyanate, isophorone diisocyanate, 4,4'- Aromatic rings, such as alicyclic diisocyanate, such as methylenebis (cyclohexyl isocyanate), ω,ω'-diisocyanate, dimethylcyclohexane, xylylene diisocyanate, α,α,α',α'-tetramethylxylylene diisocyanate Aliphatic diisocyanate having triisocyanate, such as isocyanate, tris (isocyanate phenylmethane), and tris (isocyanate phenyl) thiophosphate, these trimers, water adducts, these polyol adducts, etc. are mentioned. As the polyisocyanate, preferred is a trimer of organic diisocyanate, and most preferred is a trimer of tolylene diisocyanate and trimer of isophorone diisocyanate. These may be used individually by 1 type, and may use 2 or more types together.

As a method for producing a trimer of isocyanate, the polyisocyanate is partially formed using an appropriate trimerization catalyst, for example, tertiary amines, phosphines, alkoxides, metal oxides, carboxylates, etc. After performing trimerization and stopping trimerization by addition of a catalyst poison, solvent extraction and thin film distillation remove unreacted polyisocyanate, The method of obtaining the target isocyanurate group containing polyisocyanate is mentioned. .

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

As polyether glycol, polyether diol, polyether ester diol, and these 2 or more types of mixture are mentioned. Examples of the polyetherdiol include those obtained by copolymerizing alkylene oxides alone or by copolymerization, for example, polyethylene glycol, polypropylene glycol, polyethylene-propylene glycol, polyoxytetramethylene glycol, polyoxyhexamethylene glycol, polyoxyoctamethylene glycol and A mixture of 2 or more types of them is mentioned.

As the polyether ester diol, one obtained by reacting an ether group-containing diol or a mixture with another glycol with dicarboxylic acid or anhydride thereof, or reacting an alkylene oxide with polyester glycol, for example, poly (poly oxytetramethylene) adipate and the like. The most preferable polyether glycol is polyethylene glycol, polypropylene glycol, polyoxytetramethylene glycol, or a compound in which one terminal hydroxyl group of these compounds is alkoxylated with an alkyl group having 1 to 25 carbon atoms.

Examples of the polyester glycol include dicarboxylic acids (succinic acid, glutaric acid, adipic acid, sebacic acid, fumaric acid, maleic acid, phthalic acid, etc.) or anhydrides 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 -aliphatic glycols such as hexanediol, 1,8-octamethylene glycol, 2-methyl-1,8-octamethylene glycol, 1,9-nonanediol, alicyclic glycols such as bishydroxymethylcyclohexane, and xylylene glycol , aromatic glycols such as bishydroxyethoxybenzene, N-alkyl dialkanolamines such as N-methyldiethanolamine), for example, polyethylene adipate, polybutylene adipate, poly Hexamethylene adipate, polyethylene/propylene adipate, etc., or polylactonediol or polylactone monool obtained by using the above diols or monohydric alcohols having 1 to 25 carbon atoms as an initiator, such as polycaprolactone glycol, polymethyl valerolactone and mixtures of two or more thereof. The most preferable polyester glycol is polycaprolactone glycol or polycaprolactone using an alcohol having 1 to 25 carbon atoms as an initiator.

As polycarbonate glycol, poly(1,6-hexylene) carbonate diol, poly(3-methyl-1,5-pentylene) carbonate diol, etc., as polyolefin glycol, polybutadiene glycol, hydrogenated polybutadiene glycol, hydrogen Addition-type polyisoprene glycol, etc. are mentioned.

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

The number average molecular weight of the compound which has one or two hydroxyl groups in the same molecule is 300-10,000 normally, Preferably it is 500-6,000, More preferably, it is 1,000-4,000.

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

Examples of active hydrogen, that is, a hydrogen atom directly bonded to an oxygen atom, a nitrogen atom, or a sulfur atom, include a hydrogen atom in a functional group such as a hydroxyl group, an amino group, and a thiol group, and among them, an amino group, particularly a hydrogen atom of a primary amino group is preferable do.

Although the tertiary amino group is not specifically limited, For example, the amino group which has a C1-C4 alkyl group, or a heterocyclic structure, more specifically, an imidazole ring, a triazole ring, etc. are mentioned.

If such a compound having an active hydrogen and a tertiary amino group in the same molecule is exemplified, N,N-dimethyl-1,3-propanediamine, N,N-diethyl-1,3-propanediamine, N,N-diamine Propyl-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.

Moreover, as the nitrogen-containing heterocyclic ring in case a tertiary amino group has a nitrogen-containing heterocyclic structure, a pyrazole ring, an imidazole ring, a triazole ring, a tetrazole ring, an indole ring, a carbazole ring, an indazole ring, benz Nitrogen-containing hetero 5-membered rings such as imidazole ring, benzotriazole ring, benzoxazole ring, benzothiazole ring and benzothiadiazole ring, pyridine ring, pyridazine ring, pyrimidine ring, triazine ring, quinoline ring , a nitrogen-containing hetero 6-membered ring, such as an acridine ring and an isoquinoline ring. Preferred among these nitrogen-containing heterocycles are an imidazole ring or a triazole ring.

Specific examples of the compounds having an imidazole ring and an amino group include 1-(3-aminopropyl)imidazole, histidine, 2-aminoimidazole and 1-(2-aminoethyl)imidazole. In addition, if a compound having a triazole ring and an amino group is specifically exemplified, 3-amino-1,2,4-triazole, 5-(2-amino-5-chlorophenyl)-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-triazole, etc. are mentioned. Among them, N,N-dimethyl-1,3-propanediamine, N,N-diethyl-1,3-propanediamine, 1-(3-aminopropyl)imidazole, 3-amino-1,2,4 - Triazole is preferred.

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

A preferred blending ratio of the raw materials for producing the urethane-based polymer dispersant is 10 to 200 parts by mass of a compound having a number average molecular weight of 300 to 10,000 having one or two hydroxyl groups in the same molecule with respect to 100 parts by mass of the polyisocyanate compound, preferably Preferably it is 20-190 mass parts, More preferably, it is 30-180 mass parts, 0.2-25 mass parts of compounds which have active hydrogen and a tertiary amino group in the same molecule, Preferably it is 0.3-24 mass parts.

The production of the urethane-based polymer dispersant is carried out according to a known method for producing a polyurethane resin. Examples of the solvent for production include ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclopentanone, cyclohexanone and isophorone; esters such as ethyl acetate, butyl acetate, and cellosolve acetate; benzene; , hydrocarbons such as toluene, xylene, and hexane, some alcohols such as diacetone alcohol, isopropanol, second butanol and tertiary butanol, chlorides such as methylene chloride and chloroform, ethers such as tetrahydrofuran and diethyl ether , aprotic polar solvents such as dimethylformamide, N-methylpyrrolidone, and dimethylsulfoxide are used. These may be used individually by 1 type, and may use 2 or more types together.

In the above preparation, a urethanation reaction catalyst is usually used. Examples of the catalyst include tin-based compounds such as dibutyltindilaurate, dioctyltindilaurate, dibutyltindioctoate, and stannus octoate, iron-based such as iron acetylacetonate and ferric chloride, and triethyl Tertiary amine systems, such as an amine and triethylenediamine, etc. are mentioned. These may be used individually by 1 type, and may be used in combination of 2 or more type.

The introduction amount of the compound having active hydrogen and a tertiary amino group in the same molecule is preferably controlled in the range of 1 to 100 mgKOH/g as the amine value after the reaction. More preferably, it is the range of 5-95 mgKOH/g. The amine value is a value expressed in mg of KOH by titration by neutralizing a basic amino group with an acid and corresponding to the acid value. When the amine value is lower than the above range, the dispersibility tends to decrease, and when the amine value exceeds the above range, developability tends to decrease.

In addition, when the isocyanate group remains in the polymer dispersing agent in the above reaction, it is preferable to further modify the isocyanate group with an alcohol or an amino compound to increase the stability of the product over time.

The weight average molecular weight (Mw) of the urethane-based polymer dispersant is usually in the range of 1,000 to 200,000, preferably 2,000 to 100,000, and more preferably 3,000 to 50,000. When this molecular weight is less than 1,000, dispersibility and dispersion stability are inferior, when it exceeds 200,000, solubility falls, and when dispersibility is inferior, control of reaction becomes difficult at the same time.

Examples of the acrylic polymer dispersant include a random copolymer of an unsaturated group-containing monomer having a functional group (the functional group referred to herein is the aforementioned functional group as a functional group contained in the polymer dispersing agent) and an unsaturated group-containing monomer having no functional group, a graft copolymer, Preference is given to using block copolymers. These copolymers can be prepared by a known method.

Examples of the unsaturated group-containing monomer having a functional group include (meth)acrylic acid, 2-(meth)acryloyloxyethylsuccinic acid, 2-(meth)acryloyloxyethylphthalic acid, and 2-(meth)acryloyloxyethylhexa Unsaturated monomers having a carboxyl group, such as hydrophthalic acid and acrylic acid dimer, tertiary amino groups, such as dimethylaminoethyl (meth)acrylate, diethylaminoethyl (meth)acrylate, and quaternary products thereof, unsaturated monomers having a quaternary ammonium salt group can be mentioned as a specific example. 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, iso Butyl (meth) acrylate, t-butyl (meth) acrylate, benzyl (meth) acrylate, phenyl (meth) acrylate, cyclohexyl (meth) acrylate, phenoxyethyl (meth) acrylate, phenoxymethyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, isobornyl (meth)acrylate, tricyclodecane (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, N-vinylpyrrolidone , styrene and its derivatives, N-substituted maleimides such as α-methylstyrene, N-cyclohexylmaleimide, N-phenylmaleimide and N-benzylmaleimide, acrylonitrile, vinyl acetate and polymethyl (meth)acryl Macromonomers, such as a late macromonomer, a polystyrene macromonomer, a poly2-hydroxyethyl (meth)acrylate macromonomer, a polyethyleneglycol macromonomer, a polypropylene glycol macromonomer, and a polycaprolactone macromonomer, etc. are mentioned. 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 comprising an A block having a functional group and a B block not having a functional group. , a partial structure derived from an unsaturated group-containing monomer not containing the functional group may be contained, and these may be contained in either random copolymerization or block copolymerization in the A block. Moreover, content in A block of the partial structure which does not contain a functional group is 80 mass % or less normally, Preferably it is 50 mass % or less, More preferably, it is 30 mass % or less.

The B block is composed of a partial structure derived from an unsaturated group-containing monomer that does not contain the functional group, but one B block may contain a partial structure derived from two or more types of monomers, and these are random copolymerized or You may contain in any aspect of block copolymerization.

The A-B or B-A-B block copolymer is prepared, for example, by the living polymerization method shown below.

The living polymerization method includes an anionic living polymerization method, a cationic living polymerization method, and a radical living polymerization method. Among these, the anionic living polymerization method is a polymerization active species an anion, and is shown, for example, by the following scheme.

[Formula 6]

In the above scheme, 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.

In the radical living polymerization method, the polymerization active species is a radical, and is shown, for example, by the following scheme.

[Formula 7]

In the above scheme, Ar ¹ is a monovalent organic group, Ar ² is a ^{monovalent organic group different from Ar 1} , j and k are each an integer of 1 or more, R ^a is a hydrogen atom or a monovalent organic group, R ^b is ^a hydrogen atom or a monovalent organic group different from R a .

When synthesizing this acrylic polymer dispersant, Japanese Patent Application Laid-Open No. 9-62002, P. Lutz, P. Masson et al, Polym. Bull. 12, 79 (1984), B. C. Anderson, G. D. Andrews et al, Macromolecules, 14, 1601 (1981), K. Hatada, K. Ute, et al, Polym. J. 17, 977 (1985), 18, 1037 (1986), Koichi Ute, Koichi Hatada, Polymer Processing, 36, 366 (1987), Toshinobu Higashimura, Mitsuo Sawamoto, Proceedings of Polymers, 46, 189 (1989) , M. Kuroki, T. Aida, J. Am. Chem. Sic, 109, 4737 (1987), Takuzo Aida, Shohei Inoue, Organic Synthetic Chemistry, 43, 300 (1985), DY Sogoh, WR Hertler et al, Macromolecules, 20, 1473 (1987), etc. are adopted. can do.

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, particularly 5/95 to 60 It is preferable that it is /40 (mass ratio), and it may not be able to have favorable heat resistance and dispersibility outside this range.

In addition, the amount of quaternary ammonium base in 1 g of the AB block copolymer and BAB block copolymer that can be used in the present invention is usually 0.1 to 10 mmol, and outside this range, good heat resistance and dispersibility can be achieved. there are cases where there is no

In addition, in such a block copolymer, an amino group generated during the production process is usually contained in some cases, but the amine value is about 1 to 100 mgKOH/g, and from the viewpoint of dispersibility, preferably 10 mgKOH/g or more, more Preferably 30 mgKOH/g or more, more preferably 50 mgKOH/g or more, and preferably 90 mgKOH/g or less, more preferably 80 mgKOH/g or less, still more preferably 75 mgKOH or more. /g or less.

Here, the amine titer of a dispersing agent, such as these block copolymers, is represented by the amount of base per 1 g of solid content excluding the solvent in a dispersing agent sample, and the mass of KOH equivalent, and is measured by the following method.

In a 100 ml beaker, 0.5 to 1.5 g of the dispersant sample is precisely weighed and dissolved with 50 ml of acetic acid. Using an automatic titrator equipped with a pH electrode, this solution is neutralized and titrated _{with a 0.1 mol/L HClO 4 acetic acid solution.} Using the inflection point of the titration pH curve as the titration end point, the amine number is calculated by the following formula.

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

[However, W: Weighing amount of dispersant sample [g], V: titration amount at the end point of titration [ml], S: shows the solid content concentration [mass %] of the dispersant sample.]

In addition, although the acid value of this block copolymer varies depending on the presence or absence and type of an acidic group that is the basis of the acid value, it is generally preferable that the acid value is lower, and is usually 10 mgKOH/g or less, and its weight average molecular weight (Mw ) is preferably in the range of 1000 to 100,000. When the weight average molecular weight of the block copolymer is less than 1000, dispersion stability tends to decrease, and when it exceeds 100,000, developability and resolution tend to decrease.

The specific structure of the polymer dispersant having a quaternary ammonium base as a functional group is not particularly limited, but from the viewpoint of dispersibility, a repeating unit represented by the following formula (i) (hereinafter sometimes referred to as “repeating unit (i)”) has it is preferable

[Formula 8]

In the 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 have a substituent, and among ^{R 31} to R ³³ Two or more may combine with each other to form a cyclic structure. R ³⁴ is a hydrogen atom or a methyl group. X is a divalent linking group, and Y ^- is a counter anion.

The formula (i) The number of carbon atoms of R ³¹ ~ of the alkyl group which may have a substituent in R ³³ is not particularly limited, but is usually 1 or more, it is yet more preferred not higher than desirable, and 610 or less. Specific examples of the alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, and an octyl group. Among them, a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, or It is preferable that it is a hexyl group, and it is more preferable that they are a methyl group, an ethyl group, a propyl group, or a butyl group. Moreover, either linear or branched type may be sufficient. Moreover, cyclic structures, such as a cyclohexyl group and a cyclohexylmethyl group, may be included.

The number of carbon atoms of the aryl group which may have a substituents at the R ³¹ ~ R ³³ in the formula (i) is not particularly limited, but is usually 6 or more, it is yet more preferred not higher than preferred, and less than or equal to 12 16. Specific examples of the aryl group include a phenyl group, a methylphenyl group, an ethylphenyl group, a dimethylphenyl group, a diethylphenyl group, a naphthyl group, and an anthracenyl group. Among them, a phenyl group, a methylphenyl group, an ethylphenyl group, a dimethylphenyl group, or a di It is preferable that it is an ethylphenyl group, and it is more preferable that it is a phenyl group, a methylphenyl group, or an ethylphenyl group.

The formula (i) The number of carbon atoms of R ³¹ ~ of, an aralkyl group which may have a substituent in R ³³ is not particularly limited, and usually 7 or higher, it is yet more preferred not higher than preferred, and less than or equal to 12 16. Specific examples of the aralkyl group include a phenylmethylene group, a phenylethylene group, a phenylpropylene group, a phenylbutylene group, and a phenylisopropylene group, and among these, a phenylmethylene group, a phenylethylene group, a phenylpropylene group, or a phenyl group It is preferable that it is a butylene group, and it is more preferable that it is a phenylmethylene group or a phenylethylene group.

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

Moreover, when the said polymer dispersing agent has a tertiary amine as a functional group, from a dispersibility viewpoint, it is preferable to have a repeating unit represented by following formula (ii) (Hereinafter, it may be referred to as "repeating unit (ii)").

[Formula 9]

In the 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 They may combine with each other to form a cyclic 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 in ^{R 35} and R ^{36 in the formula (ii), those exemplified as R 31} to R ^{33 in} the formula (i) can be preferably employed.

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

Among these ^{, it is preferable that R 35} and R ³⁶ are each independently an alkyl group which may have a substituent, and it is more preferable that they are a methyl group or an ethyl group.

As the substituent group is the formula (i) of R ³¹ ~ R ³³ and the formula (ii) of R ³⁵ and the alkyl group, aralkyl group or aryl group in R ³⁶ which may have is a halogen atom, an alkoxy group, a benzoyl group, a hydroxyl group and the like.

In the formulas (i) and (ii), the divalent linking groups X and Z include, for example, an alkylene group having 1 to 10 carbon atoms, an arylene group having 6 to 12 carbon atoms, -CONH-R ⁴³ -group, -COOR ⁴⁴ - group and the like [However, R ⁴³ and R ⁴⁴ represents a single bond, an alkylene group, or an ether group (alkyloxy group) having 2 to 10 carbon atoms having 1 to 10 carbon atoms], preferably -COO-R ⁴⁴ - is a group.

Further, in the above formula (i), the counter anion Y ^- roneun ^{Cl -, Br -, I -} , ClO 4 -, BF 4 -, CH 3 COO - , and the like ^-, PF _6.

The content ratio of the repeating unit represented by the formula (i) is not particularly limited, but from the viewpoint of dispersibility, the content ratio of the repeating unit represented by the formula (i) and the content ratio of the repeating unit represented by the formula (ii) is It is preferably 60 mol% or less, more preferably 50 mol% or less, still more preferably 40 mol% or less, particularly preferably 35 mol% or less, and preferably 5 mol% or more, More preferably, it is 10 mol% or more, More preferably, it is 20 mol% or more, Especially preferably, it is 30 mol% or more.

In addition, the content ratio of the repeating unit represented by the formula (i) in the total repeating units of the polymer dispersant is not particularly limited, but is preferably 1 mol% or more, more preferably 5 mol% or more, from the viewpoint of dispersibility, 10 It is more preferable that it is mol% or more, and it is preferable that it is 50 mol% or less, It is more preferable that it is 30 mol% or less, It is more preferable that it is 20 mol% or less, It is especially preferable that it is 15 mol% or less.

In addition, the content ratio of the repeating unit represented by the formula (ii) in the total repeating units of the polymer dispersant is not particularly limited, but is preferably 5 mol% or more, more preferably 10 mol% or more, from the viewpoint of dispersibility, 15 It is more preferably mol% or more, particularly preferably 20 mol% or more, and more preferably 60 mol% or less, more preferably 40 mol% or less, still more preferably 30 mol% or less, and particularly preferably 25 mol% or less. desirable.

In addition, the polymer dispersant is a repeating unit represented by the following formula (iii) from the viewpoint of improving compatibility with binder components such as solvents and improving dispersion stability (hereinafter referred to as "repeating unit (iii)" in some cases. ) is preferred.

[Formula 10]

In the formula (iii), R ⁴⁰ is an ethylene 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 of 1-20.

^{Although carbon number of the alkyl group which may have a substituent in R 41} of said Formula (iii) is not specifically limited, Usually, it is 1 or more, It is preferable that it is 2 or more, It is also preferable that it is 10 or less, It is more preferable that it is 6 or less. . Specific examples of the alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, and an octyl group. Among them, a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, or It is preferable that it is a hexyl group, and it is more preferable that they are a methyl group, an ethyl group, a propyl group, or a butyl group. Moreover, either linear or branched type may be sufficient. Moreover, cyclic structures, such as a cyclohexyl group and a cyclohexylmethyl group, may be included.

Further, n in the formula (iii) is preferably 1 or more, more preferably 2 or more, more preferably 10 or less, and more preferably 5 or less from the viewpoint of compatibility and dispersibility with binder components such as solvents. do.

The content of the repeating unit represented by the formula (iii) in the total repeating units of the polymer dispersant is not particularly limited, but is preferably 1 mol% or more, more preferably 2 mol% or more, and 4 mol% or more It is more preferable, and it is preferable that it is 30 mol% or less, It is more preferable that it is 20 mol% or less, It is more preferable that it is 10 mol% or less. When it is within the above range, compatibility with binder components such as solvents and dispersion stability tend to be compatible.

In addition, the polymer dispersant is a repeating unit represented by the following formula (iv) (hereinafter referred to as "repeating unit (iv)" from the viewpoint of improving the compatibility of the dispersant with a binder component such as a solvent and improving dispersion stability. It is preferable to have ).

[Formula 11]

In the formula (iv), R ³⁸ represents 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.

^{Although the number of carbon atoms of the alkyl group which may have a substituent in R 38} in the formula (iv) is not particularly limited, it 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 a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, and an octyl group. Among them, a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, or It is preferable that it is a hexyl group, and it is more preferable that they are a methyl group, an ethyl group, a propyl group, or a butyl group. Moreover, either linear or branched type may be sufficient. Moreover, cyclic structures, such as a cyclohexyl group and a cyclohexylmethyl group, may be included.

^{Although 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, it is usually 6 or more, and preferably 16 or less, more preferably 12 or less, and more preferably 8 or less. desirable. Specific examples of the aryl group include a phenyl group, a methylphenyl group, an ethylphenyl group, a dimethylphenyl group, a diethylphenyl group, a naphthyl group, and an anthracenyl group. Among them, a phenyl group, a methylphenyl group, an ethylphenyl group, a dimethylphenyl group, or a di It is preferable that it is an ethylphenyl group, and it is more preferable that they are a phenyl group, a methylphenyl group, or an ethylphenyl group.

^{Although the number of carbon atoms of the aralkyl group which may have a substituent in R 38} in the formula (iv) is not particularly limited, it is usually 7 or more, and preferably 16 or less, more preferably 12 or less, and more preferably 10 or less. desirable. Specific examples of the aralkyl group include a phenylmethylene group, a phenylethylene group, a phenylpropylene group, a phenylbutylene group, and a phenylisopropylene group, and among these, a phenylmethylene group, a phenylethylene group, a phenylpropylene group, or a phenyl group It is preferable that it is a butylene group, and it is more preferable that it is a phenylmethylene group or a phenylethylene group.

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

As a substituent which the alkyl group may have in R<^38> , a halogen atom, an alkoxy group, etc. are mentioned. Moreover, as a substituent which the aryl group or an aralkyl group may have, a linear alkyl group, a halogen atom, an alkoxy group, etc. are mentioned. In addition, the ^{linear alkyl group represented by R 38} includes both linear and branched chain types.

Further, the content ratio of the repeating unit represented by the formula (iv) in the total repeating units of the polymer dispersant is preferably 30 mol% or more, more preferably 40 mol% or more, and 50 mol% or more from the viewpoint of dispersibility. It is more preferable, and it is preferable that it is 80 mol% or less, and it is more preferable that it is 70 mol% or less.

The polymer dispersant may have a repeating unit other than the repeating unit (i), the repeating unit (ii), the repeating unit (iii), and the repeating unit (iv). Examples of such a repeating unit include styrene-based monomers such as styrene and α-methylstyrene; (meth)acrylate-based monomers such as (meth)acrylic acid chloride; (meth)acrylamide type monomers, such as (meth)acrylamide and N-methylolacrylamide; vinyl acetate; acrylonitrile; allyl glycidyl ether, crotonic acid glycidyl ether; and repeating units derived from monomers such as N-methacryloylmorpholine.

A polymer dispersing agent is a block having an A block having a repeating unit (i) and a repeating unit (ii) and a B block having no repeating unit (i) and a repeating unit (ii) from the viewpoint of further improving the dispersibility. It is preferable that it is a copolymer. The block copolymer is preferably an A-B block copolymer or a B-A-B block copolymer. By introducing not only a quaternary ammonium base but also a tertiary amino group into the A block, the dispersing ability of the dispersant unexpectedly tends to be remarkably improved. Moreover, it is preferable that B block has a repeating unit (iii), and it is more preferable that it has a repeating unit (iv).

In the A block, the repeating unit (i) and the repeating unit (ii) may be contained in either random copolymerization or block copolymerization mode. In addition, the repeating unit (i) and the repeating unit (ii) may be contained in each of two or more types in one A block, and in that case, each repeating unit is in any aspect of random copolymerization and block copolymerization in the A block. may contain.

In addition, repeating units other than the repeating unit (i) and repeating unit (ii) may be contained in the A block, and examples of such repeating units include repeating units derived from the (meth)acrylic acid ester monomers described above. . The content of repeating units other than the repeating unit (i) and repeating unit (ii) in the A block is preferably 0 to 50 mol%, more preferably 0 to 20 mol%, but these repeating units are contained in the A block. It is most preferable not to contain it.

Repeating units other than repeating units (iii) and (iv) may be contained in the B block, and examples of such repeating units include styrene-based monomers such as styrene and α-methylstyrene; (meth)acrylate-based monomers such as (meth)acrylic acid chloride; (meth)acrylamide type monomers, such as (meth)acrylamide and N-methylolacrylamide; vinyl acetate; acrylonitrile; allyl glycidyl ether, crotonic acid glycidyl ether; and repeating units derived from monomers such as N-methacryloylmorpholine. 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 these repeating units are contained in the B block. It is most preferable not to contain it.

Moreover, it is preferable to use together the (B) dispersing agent with the pigment derivative mentioned later from the point of a dispersion stability improvement.

<(C) Alkali-soluble resin>

(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, for example, an epoxy (meth)acrylate-based resin, an acrylic resin, a carboxyl group-containing epoxy resin, a carboxyl group-containing urethane Although resin, a novolak-type resin, polyvinylphenol-type resin, etc. are mentioned, Especially, an epoxy (meth)acrylate-type resin and an acrylic resin are preferable. These can be used individually by 1 type or in mixture of multiple types.

As the alkali-soluble resin used in the present invention, particularly the following alkali-soluble resin (c1) and/or alkali-soluble resin (c2) (hereinafter sometimes referred to as "carboxyl group-containing epoxy (meth)acrylate resin") is excellent in plate making It is preferably used from the viewpoint of gender.

<Alkali-soluble resin (c1)>

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

<Alkali-soluble resin (c2)>

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 with a polyhydric alcohol and a polybasic acid and/or anhydride thereof.

As an epoxy resin used as a raw material, for example, a bisphenol A epoxy resin (For example, Mitsubishi Chemical Co., Ltd. "Epicoat (registered trademark. hereinafter the same.) 828", "Epicoat 1001", "Epicoat 1002", "Epicoat 1004" etc.), an epoxy obtained by reaction of an alcoholic hydroxyl group of a bisphenol A epoxy resin with epichlorhydrin (for example, "NER-1302" manufactured by Nippon Kayaku Co., Ltd. (epoxy equivalent 323, softening point 76 ° C.) )), bisphenol F-type resin (for example, "Epicoat 807", "EP-4001", "EP-4002", "EP-4004", "EP-4004" manufactured by Mitsubishi Chemical Corporation), alcoholic hydroxyl group of bisphenol F-type epoxy resin Epoxy resin obtained by reaction of with epichlorhydrin (for example, Nippon Kayaku Co., Ltd. "NER-7406" (epoxy equivalent 350, softening point 66°C)), bisphenol S-type epoxy resin, biphenyl glycidyl ether (For example, "YX-4000" manufactured by Mitsubishi Chemical Corporation), a phenol novolak type epoxy resin (eg, "EPPN-201" manufactured by Nippon Kayaku Corporation, "EP-152" manufactured by Mitsubishi Chemical Corporation, "EP -154", "DEN-438" manufactured by Dow Chemical Co., Ltd.), (o,m,p-)cresol novolak-type epoxy resin (for example, "EOCN (registered trademark, hereinafter the same)" manufactured by Nippon Kayaku Corporation. -102S", "EOCN-1020", "EOCN-104S"), triglycidyl isocyanurate (eg, "TEPIC (registered trademark)" manufactured by Nissan Chemical Corporation), trisphenolmethane type epoxy resin (eg For example, "EPPN (registered trademark, hereinafter the same.)-501", "EPN-502", "EPPN-503" manufactured by Nippon Kayaku Co., Ltd.), an alicyclic epoxy resin ("Celoxide 2021P manufactured by Daicel Chemical Industry Co., Ltd.") ', "Celoxide (registered trademark, hereinafter the same.) EHPE"), an epoxy resin obtained by glycidylating a phenol resin by reaction of dicyclopentadiene and phenol (for example, "EXA-7200" manufactured by DIC Corporation) , of the Nippon Kayaku company " NC-7300"), an epoxy resin represented by the following general formulas (C1) to (C4), etc. can be used preferably. Specifically, as an epoxy resin represented by the following general formula (C1), "XD-1000" manufactured by Nippon Kayaku Corporation, "NC-3000" manufactured by Nippon Kayaku Corporation as an epoxy resin represented by the following general formula (C2), the following general As an epoxy resin represented by Formula (C4), "ESF-300" by a Shin-Nitetsu Chemical Company, etc. are mentioned.

[Formula 12]

In the said general formula (C1), a represents an average value and represents the number of 0-10. R ¹¹¹ represents 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 ¹¹¹ present in one molecule may be the same or different, respectively.

[Formula 13]

In the said general formula (C2), b represents an average value and represents the number of 0-10. R ¹²¹ represents 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 present in one molecule may be the same or different, respectively.

[Formula 14]

In the above general formula (C3), X represents a linking group represented by the following general formula (C3-1) or (C3-2). However, at least one adamantane structure is included in the molecular structure. c represents the integer of 2 or 3.

[Formula 15]

In the formulas (C3-1) and (C3-2), R ¹³¹ to R ¹³⁴ and R ¹³⁵ to R ¹³⁷ each independently represent an adamantyl group optionally having a substituent, a hydrogen atom, or a substituent A C1-C12 alkyl group or the phenyl group which may have a substituent is shown. * indicates a bond.

[Formula 16]

In the 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 having 1 to 4 carbon atoms or a halogen atom. 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 the epoxy resin represented by any one of the general formulas (C1) to (C4).

As α,β-unsaturated monocarboxylic acid or α,β-unsaturated monocarboxylic acid ester having a carboxyl group, (meth)acrylic acid, crotonic acid, o-, m- or p-vinylbenzoic acid, (meth)acrylic acid Monocarboxylic acids such as α-position haloalkyl, alkoxyl, halogen, nitro and cyano substituents, 2-(meth)acryloyloxyethylsuccinic acid, 2-(meth)acryloyloxyethyladipic acid, 2- (meth)acryloyloxyethyl phthalic acid, 2-(meth)acryloyloxyethylhexahydrophthalic acid, 2-(meth)acryloyloxyethylmaleic acid, 2-(meth)acryloyloxypropylsuccinic acid, 2 -(meth)acryloyloxypropyladipic acid, 2-(meth)acryloyloxypropyltetrahydrophthalic acid, 2-(meth)acryloyloxypropylphthalic acid, 2-(meth)acryloyloxypropylmalee Acid, 2-(meth)acryloyloxybutyl succinic acid, 2-(meth)acryloyloxybutyladipic acid, 2-(meth)acryloyloxybutylhydrophthalic acid, 2-(meth)acryloyloxy Lactones such as ε-caprolactone, β-propiolactone, γ-butyrolactone and δ-valerolactone are added to butylphthalic acid, 2-(meth)acryloyloxybutylmaleic acid, and (meth)acrylic acid A monomer obtained by adding an acid (anhydride) such as (anhydride) succinic acid, (anhydride) phthalic acid, (anhydride) maleic acid, (meth)acrylic acid dimer etc. are mentioned.

Among these, (meth)acrylic acid is particularly preferable from the viewpoint of sensitivity.

As a method of adding α,β-unsaturated monocarboxylic acid or α,β-unsaturated monocarboxylic acid ester having a carboxyl group to the epoxy resin, a known method can be used. For example, in the presence of an esterification catalyst, at a temperature of 50 to 150° C., 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. . Examples of the esterification catalyst used herein include tertiary amines such as triethylamine, trimethylamine, benzyldimethylamine, and benzyldiethylamine, and quaternary ammonium salts such as tetramethylammonium chloride, tetraethylammonium chloride and dodecyltrimethylammonium chloride. etc. can be used.

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

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, more preferably 0.7 with respect to 1 equivalent of the epoxy group of the epoxy resin. -1.1 equivalents. When the amount of the α,β-unsaturated monocarboxylic acid or α,β-unsaturated monocarboxylic acid ester having a carboxyl group is small, the amount of unsaturated group introduced becomes insufficient, and the subsequent reaction with the polybasic acid and/or its anhydride becomes insufficient. Moreover, it is also not advantageous that a large amount of epoxy groups remain|survive. On the other hand, when the amount used is large, α,β-unsaturated monocarboxylic acid or α,β-unsaturated monocarboxylic acid ester having a carboxyl group remains as an unreacted product. In either case, the tendency for hardening characteristics to deteriorate is seen.

Examples of the polybasic acid and/or its anhydride include maleic acid, succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, pyromellitic acid, trimellitic acid, benzophenonetetracarboxylic acid, methylhexahydrophthalic acid, and endomethylenetetra. 1 type(s) or 2 or more types selected from hydrophthalic acid, chlorendic acid, methyltetrahydrophthalic acid, biphenyltetracarboxylic acid, and these anhydrides, etc. are mentioned.

Preferably, they are maleic acid, succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, pyromellitic acid, trimellitic acid, biphenyltetracarboxylic acid, or an anhydride thereof. Particularly preferably, they are tetrahydrophthalic acid, biphenyltetracarboxylic acid, tetrahydrophthalic anhydride, or biphenyltetracarboxylic dianhydride.

A known method can also be used for the addition reaction of a polybasic acid and/or anhydride thereof, and the addition reaction of α,β-unsaturated monocarboxylic acid or α,β-unsaturated monocarboxylic acid ester having a carboxyl group to an epoxy resin The target product can be obtained by continuing the reaction under the same conditions. The addition amount of the polybasic acid and/or its anhydride component is preferably such that the acid value of the resulting carboxyl group-containing epoxy (meth)acrylate resin is in the range of 10 to 150 mgKOH/g, and further, 20 to 140 mgKOH/g It is preferable that it is a grade used as the range of g. When the acid value of the carboxyl group-containing epoxy (meth)acrylate resin is less than the above range, alkali developability tends to be insufficient, and when it exceeds the above range, the curing performance tends to be inferior.

Moreover, at the time of the addition reaction of this polybasic acid and/or its anhydride, polyfunctional alcohols, such as trimethylol propane, a pentaerythritol, and dipentaerythritol, are added, and it is good also as what introduce|transduced the multi-branched structure.

A carboxyl group-containing epoxy (meth)acrylate resin is usually a reaction product of an epoxy resin and an α,β-unsaturated monocarboxylic acid or an α,β-unsaturated monocarboxylic acid ester having a carboxyl group, a polybasic acid and/or an anhydride thereof is mixed After mixing the polybasic acid and/or its anhydride and polyfunctional alcohol with the reaction product of the epoxy resin and the α,β-unsaturated monocarboxylic acid or α,β-unsaturated monocarboxylic acid ester having a carboxyl group, heating obtained by doing In this case, there is no restriction|limiting in particular in the mixing order of a polybasic acid and/or its anhydride, and a polyfunctional alcohol. By heating, polybasic acid and / or The anhydride undergoes an addition reaction.

The weight average molecular weight (Mw) of the carboxyl group-containing epoxy (meth)acrylate resin in terms of polystyrene measured by gel permeation chromatography (GPC) is usually 1000 or more, preferably 1500 or more, and usually 10000 or less, preferably It is 8000 or less, More preferably, it is 6000 or less. When this weight average molecular weight is small, the solubility with respect to a developing solution is high, and when too large, the solubility with respect to a developing solution is low.

Carboxyl group containing epoxy (meth)acrylate resin may be used individually by 1 type, and may mix and use 2 or more types of resin.

Moreover, (C) alkali-soluble resin used by this invention may substitute another binder resin for a part of carboxyl group containing epoxy (meth)acrylate resin mentioned above, unless the performance of this invention is impaired. That is, you may use together carboxyl group-containing epoxy (meth)acrylate resin and other binder resin. In this case, it is preferable that the ratio of the carboxyl group-containing epoxy (meth)acrylate resin in (C) alkali-soluble resin shall be 50 mass % or more, and especially be 80 mass % or more.

As long as the performance of the present invention is not impaired, there is no limitation on other binder resins that can be used in combination with the carboxyl group-containing epoxy (meth)acrylate resin, and may be selected from resins normally used for the photosensitive coloring composition. For example, the binder resin of Unexamined-Japanese-Patent No. 2007-271727, Unexamined-Japanese-Patent No. 2007-316620, Unexamined-Japanese-Patent No. 2007-334290, etc. are mentioned.

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

<(D) Photoinitiator>

(D) A photoinitiator is a component which has a function which absorbs light directly, raises a decomposition reaction or a hydrogen extraction reaction, and generate|occur|produces a polymerization active radical. You may use, adding additives, such as a polymerization accelerator (chain transfer agent) and a sensitizing dye, as needed.

As a photoinitiator, For example, the metallocene compound containing the titanocene compound of Unexamined-Japanese-Patent No. 59-152396 and Unexamined-Japanese-Patent No. 61-151197 each; The hexaarylbiimidazole derivatives described in Unexamined-Japanese-Patent No. 2000-56118; N-aryl-α-amino acids and N-aryl-α-amino acids such as halomethylated oxadiazole derivatives, halomethyl-s-triazine derivatives, and N-phenylglycine described in Japanese Patent Laid-Open No. 10-39503 , radical activators such as N-aryl-α-amino acid esters, α-aminoalkylphenone derivatives; The oxime ester derivatives etc. described in Unexamined-Japanese-Patent No. 2000-80068, Unexamined-Japanese-Patent No. 2006-36750, etc. are mentioned.

Specifically, for example, as the titanocene derivatives, dicyclopentadienyl titanium dichloride, dicyclopentadienyl titanium bisphenyl, 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- Trifluoropheny-1-yl), dicyclopentadienyl titanium di (2,6-difluorophenyl-1-yl), dicyclopentadienyl titanium di (2,4-difluoropheny-1) -yl), di (methylcyclopentadienyl) titanium bis (2,3,4,5,6-pentafluorophenyl-1-yl), di (methylcyclopentadienyl) titanium bis (2,6- difluorophenyl-1-yl), dicyclopentadienyl titanium [2,6-di-fluoro-3-(pyrro-1-yl)-phenyl-1-yl], and the like.

In addition, as biimidazole derivatives, 2-(2'-chlorophenyl)-4,5-diphenylimidazole dimer, 2-(2'-chlorophenyl)-4,5-bis(3' -Methoxyphenyl) imidazole dimer, 2- (2'-fluorophenyl) -4,5-diphenylimidazole dimer, 2- (2'-methoxyphenyl) -4,5-diphenyl An imidazole dimer, (4'-methoxyphenyl) -4,5-diphenyl imidazole dimer, etc. are mentioned.

Also, examples of the halomethylated oxadiazole derivatives include 2-trichloromethyl-5-(2'-benzofuryl)-1,3,4-oxadiazole, 2-trichloromethyl-5-[β-( 2'-benzofuryl)vinyl]-1,3,4-oxadiazole, 2-trichloromethyl-5-[β-(2'-(6''-benzofuryl)vinyl)]-1,3, 4-oxadiazole, 2-trichloromethyl-5-furyl-1,3,4-oxadiazole, etc. are mentioned.

In addition, as halomethyl-s-triazine derivatives, 2-(4-methoxyphenyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(4-methoxynaphthyl) -4,6-bis(trichloromethyl)-s-triazine, 2-(4-ethoxynaphthyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(4-e and oxycarbonylnaphthyl)-4,6-bis(trichloromethyl)-s-triazine.

Further, α-aminoalkylphenone derivatives include 2-methyl-1[4-(methylthio)phenyl]-2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1-( 4-morpholinophenyl)-butanone-1, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butan-1-one, 4-dimethylaminoethylbenzoate, 4-dimethylamino Isoamylbenzoate, 4-diethylaminoacetophenone, 4-dimethylaminopropiophenone, 2-ethylhexyl-1,4-dimethylaminobenzoate, 2,5-bis(4-diethylaminobenzal)cyclohexa Non, 7-diethylamino-3-(4-diethylaminobenzoyl)coumarin, 4-(diethylamino)chalcone, etc. are mentioned.

As the photopolymerization initiator, oxime derivatives (oxime-based and ketoxime-based compounds) are particularly effective in terms of sensitivity and plate-making properties, and it is disadvantageous in terms of sensitivity when an alkali-soluble resin containing a phenolic hydroxyl group is used. In particular, oxime derivatives (oxime esters and ketoxime ester compounds) excellent in such sensitivity are useful.

As an oxime type compound, the compound containing the structural moiety represented by the following general formula (3) is mentioned, Preferably the oxime ester type compound represented by the following general formula (3a) is mentioned.

[Formula 17]

In the formula (3), ^{each of R 22} may be substituted, and an alkanoyl group having 2 to 12 carbon atoms, a heteroarylalkanoyl group having 1 to 20 carbon atoms, an alkenoyl group having 3 to 25 carbon atoms, or cycloal having 3 to 8 carbon atoms. A caroyl group, a C3-C20 alkoxycarbonylalkanoyl group, a C8-C20 phenoxycarbonylalkanoyl group, a C3-C20 heteroaryloxycarbonylalkanoyl group, a C2-10 aminoalkylcarbonyl group, An aryloyl group having 7 to 20 carbon atoms, a heteroaryloyl group having 1 to 20 carbon atoms, an alkoxycarbonyl group having 2 to 10 carbon atoms, or an aryloxycarbonyl group having 7 to 20 carbon atoms is shown.

[Formula 18]

In the formula (3a), R ^21a is a hydrogen atom or an optionally substituted alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 25 carbon atoms, a heteroarylalkyl group having 1 to 20 carbon atoms, or an alkoxycar having 3 to 20 carbon atoms. A bornylalkyl group, a phenoxycarbonylalkyl group having 8 to 20 carbon atoms, a heteroaryloxycarbonylalkyl group or heteroarylthioalkyl group having 1 to 20 carbon atoms, an aminoalkyl group having 1 to 20 carbon atoms, an alkanoyl group having 2 to 12 carbon atoms, 3 carbon atoms Alkenoyl group having to 25 carbon atoms, cycloalkanoyl group having 3 to 8 carbon atoms, aryl group having 7 to 20 carbon atoms, heteroaryloyl group having 1 to 20 carbon atoms, alkoxycarbonyl group having 2 to 10 carbon atoms, aryloxy group having 7 to 20 carbon atoms. A carbonyl group or a C1-C10 cycloalkylalkyl group is represented. R ^21b represents an arbitrary substituent including an aromatic ring or a heteroaromatic ring.

In addition, R ^21a may ^{form a ring together with R 21b,} and the linking group is an alkylene group having 1 to 10 carbon atoms which may each have a substituent, a polyethylene group (-(CH=CH) _r- ), a polyethynylene group ( -(C≡C) _r- ) or a group formed by combining them (in addition, r is an integer of 0 to 3).

In formula (3a), R ^22a is each optionally substituted alkanoyl group having 2 to 12 carbon atoms, heteroarylalkanoyl group having 1 to 20 carbon atoms, alkenoyl group having 3 to 25 carbon atoms, cycloal having 3 to 8 carbon atoms. A caroyl group, a C3-C20 alkoxycarbonylalkanoyl group, a C8-C20 phenoxycarbonylalkanoyl group, a C3-C20 heteroaryloxycarbonylalkanoyl group, a C2-C10 aminocarbonyl group, carbon number A 7-20 aryl group, a C1-C20 heteroaryl group, a C2-C10 alkoxycarbonyl group, or a C7-20 aryloxycarbonyl group is represented.

R ^{22 in} the general formula (3) and R ^22a in the general formula (3a) are preferably an alkanoyl group having 2 to 12 carbon atoms, a heteroarylalkanoyl group having 1 to 20 carbon atoms, or 3 carbon atoms. - The cycloalkanoyl group of 8 is mentioned.

^{R 21a} in the general formula (3a) preferably includes an unsubstituted methyl group, an ethyl group, a propyl group, or a propyl group substituted with an N-acetyl-N-acetoxyamino group.

^{Moreover, as R 21b} in the said General formula (3a), Preferably, the carbazoyl group which may be substituted, the thioxanthonyl group which may be substituted, and the phenyl sulfide group which may be substituted are mentioned.

Moreover, as an arbitrary substituent in the said General formula (3) and (3a), an alkyl group, an aryl group, an alicyclic group, a heterocyclic group, a halogen group, a hydroxyl group, a carboxyl group, an amino group, an amide group, etc. are mentioned.

Although the compound specifically illustrated below is mentioned as an oxime ester type compound preferable for this invention, it is not limited to these compounds at all.

[Formula 19]

[Formula 20]

Moreover, the oxime ester initiator which has a carbazole group which has a nitro group is also effective.

As a ketoxime type compound, the compound containing the structural moiety represented by the following general formula (4) is mentioned, Preferably the oxime ester type compound represented by the following general formula (5) is mentioned.

[Formula 21]

In the general formula (4), R ²⁴ has the same meaning ^{as R 22} in the general formula (3).

[Formula 22]

In the general formula (5), R ^23a is each optionally substituted phenyl group, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 25 carbon atoms, a heteroarylalkyl group having 1 to 20 carbon atoms, or alkoxy having 3 to 20 carbon atoms. A carbonylalkyl group, a C8-C20 phenoxycarbonylalkyl group, a C2-C20 alkylthioalkyl group, a C1-C20 heteroaryloxycarbonylalkyl group or heteroarylthioalkyl group, a C1-C20 aminoalkyl group, carbon number alkanoyl group having 2 to 12 carbon atoms, alkanoyl group having 3 to 25 carbon atoms, cycloalkanoyl group having 3 to 8 carbon atoms, aryloyl group having 7 to 20 carbon atoms, heteroaryloyl group having 1 to 20 carbon atoms, heteroaryl group having 2 to 10 carbon atoms An alkoxycarbonyl group, an aryloxycarbonyl group having 7 to 20 carbon atoms, or a cycloalkylalkyl group having 1 to 10 carbon atoms is shown.

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

In addition, R ^23a may ^{form a ring together with R 23b,} and the coupling group is a C1-C10 alkylene group which may each have a substituent, a polyethylene group (-(CH=CH) _r- ), a polyethynylene group. (-(C≡C) _r- ) or a group formed by combining them (in addition, r is an integer of 0 to 3).

In the general formula (5), R ^24a is an optionally substituted alkanoyl group having 2 to 12 carbon atoms, an alkenoyl group having 3 to 25 carbon atoms, a cycloalkanoyl group having 4 to 8 carbon atoms, or a benzoyl group having 7 to 20 carbon atoms. , a heteroaryloyl group having 3 to 20 carbon atoms, an alkoxycarbonyl group having 2 to 10 carbon atoms, an aryloxycarbonyl group having 7 to 20 carbon atoms, a heteroaryl group having 2 to 20 carbon atoms, or an alkylaminocarbonyl group having 2 to 20 carbon atoms.

^{R 24} in the general formula (4) ^{and R 24a} in the general formula (5) are preferably an alkanoyl group having 2 to 12 carbon atoms, a heteroarylalkanoyl group having 1 to 20 carbon atoms, or 3 carbon atoms. - A cycloalkanoyl group of 8 and a C7-20 aryl group are mentioned.

^{R 23a} in the general formula (5) preferably includes an unsubstituted ethyl group, a propyl group, a butyl group, or an ethyl group or a propyl group substituted with a methoxycarbonyl group.

^{Moreover, as R 23b} in the said General formula (5), Preferably, the optionally substituted carbazoyl group and the optionally substituted phenyl sulfide group are mentioned.

Moreover, as an arbitrary substituent in the said General formula (4) and (5), an alkyl group, an aryl group, an alicyclic group, a heterocyclic group, a halogen group, a hydroxyl group, a carboxyl group, an amino group, an amide group, etc. are mentioned.

Although the compound specifically illustrated below is mentioned as a ketoxime ester type compound preferable for this invention, it is not limited to these compounds at all.

[Formula 23]

[Formula 24]

These oximes and ketoxime ester compounds are compounds known per se, and are, for example, a kind of a series of compounds described in JP-A-2000-80068 and JP-A-2006-36750. In this invention, it is preferable that (D) photoinitiator is an oxime ester initiator and/or a ketoxime ester initiator.

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

The ratio of the photoinitiator in the photosensitive coloring composition of this invention is 0.4-15 mass % normally with respect to total solid, Preferably it is 0.5-10 mass %. When there are too many ratios of a photoinitiator from this range, there exists a tendency for developability to fall, On the other hand, when there are too few, formation of the preferable shape of colored hardened|cured material and the level|step difference may not be carried out.

In addition, benzoin alkyl ethers, such as benzoin methyl ether, benzoin phenyl ether, benzoin isobutyl ether, and benzoin isopropyl ether; anthraquinone derivatives such as 2-methylanthraquinone, 2-ethylanthraquinone, 2-t-butylanthraquinone, and 1-chloroanthraquinone; benzophenone derivatives such as benzophenone, Michler's ketone, 2-methylbenzophenone, 3-methylbenzophenone, 4-methylbenzophenone, 2-chlorobenzophenone, 4-bromobenzophenone, and 2-carboxybenzophenone; 2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxyacetophenone, 1-hydroxycyclohexylphenylketone, α-hydroxy-2-methylphenylpropanone, 1-hydroxy-1-methyl Ethyl-(p-isopropylphenyl)ketone, 1-hydroxy-1-(p-dodecylphenyl)ketone, 2-methyl-(4'-methylthiophenyl)-2-morpholino-1-propanone , acetophenone derivatives such as 1,1,1-trichloromethyl-(p-butylphenyl)ketone; Thioxanthone, 2-ethylthioxanthone, 2-isopropylthioxanthone, 2-chlorothioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2,4-di thioxanthone derivatives such as isopropyl thioxanthone; benzoic acid ester derivatives such as ethyl p-dimethylaminobenzoate and ethyl p-diethylaminobenzoate; acridine derivatives such as 9-phenylacridine and 9-(p-methoxyphenyl)acridine; phenazine derivatives such as 9,10-dimethylbenzphenazine; Anthrone derivatives, such as benzanthrone, etc. are mentioned.

In these photoinitiators, the point of a sensitivity to oxime ester derivatives (oxime ester type compound) is especially preferable.

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

[Formula 25]

Here, R ^23a and R ^24a have the same meaning as in the general formula (5).

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

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. A - R a hydrogen atom of the substituent represented by ^25c is, and may be further substituted with a halogen atom, the alkylene portion of the substituent represented by R ^25c is -O-, -S-, -COO-, -OCO- or -NR ^25d It may be interrupted 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 part of the substituent represented by R ^25c may have a branched side chain, and cyclopentyl or cyclohexyl may be sufficient as it.

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

[Formula 26]

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 arylene group having 6 to 30 carbon atoms, or an arylene alkylene group having 7 to 30 carbon atoms.

The ^{alkylene moiety of the substituent represented by R 26b} may be interrupted 1 to 5 times by -O-, -S-, -COO- or -OCO-. The ^{alkylene moiety of the substituent represented by R 26b} may have a branched side chain or may be cyclohexylene.

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

* indicates a bond.

A photoinitiator may be used individually by 1 type, and may be used in combination of 2 or more type.

A sensitizing dye according to the wavelength of an image exposure light source and a polymerization accelerator can be mix|blended with a photoinitiator for the purpose of raising a sensitivity sensitivity as needed. As a sensitizing dye, the xanthene dye described in Unexamined-Japanese-Patent No. 4-221958 and Unexamined-Japanese-Patent No. 4-219756, Unexamined-Japanese-Patent No. 3-239703, Unexamined-Japanese-Patent No. 5-289335 A coumarin dye having a heterocyclic ring as described, a 3-ketocoumarin compound described in Japanese Patent Application Laid-Open No. Hei 3-239703 and Hei 5-289335, a pyromethene dye described in Japanese Unexamined Patent Publication No. Hei 6-19240 , Other Japanese Unexamined Patent Publication No. 47-2528, Japanese Unexamined Patent Publication No. 54-155292, Japanese Patent Publication No. 45-37377, Japanese Unexamined Patent Publication No. 48-84183, Japanese Unexamined Patent Publication No. 52-112681 No., Japanese Unexamined Patent Publication No. 58-15503, Japanese Unexamined Patent Publication No. 60-88005, Japanese Unexamined Patent Publication No. 59-56403, Japanese Unexamined Patent Publication No. 2-69, Japanese Unexamined Patent Publication No. 57-168088 The pigment|dye etc. which have dialkylamino benzene skeleton of Unexamined-Japanese-Patent No. 5-107761, Unexamined-Japanese-Patent No. 5-210240, and Unexamined-Japanese-Patent No. 4-288818 are mentioned.

Among these sensitizing dyes, an amino group-containing sensitizing dye is preferable, and a compound having an amino group and a phenyl group in the same molecule is more preferable. Particularly preferred are, for example, 4,4'-dimethylaminobenzophenone, 4,4'-diethylaminobenzophenone, 2-aminobenzophenone, 4-aminobenzophenone, 4,4'-diaminobenzophenone, benzophenone compounds such as 3,3'-diaminobenzophenone and 3,4-diaminobenzophenone; 2-(p-dimethylaminophenyl)benzoxazole, 2-(p-diethylaminophenyl)benzoxazole, 2-(p-dimethylaminophenyl)benzo[4,5]benzoxazole, 2-(p -Dimethylaminophenyl)benzo[6,7]benzoxazole, 2,5-bis(p-diethylaminophenyl)-1,3,4-oxadiazole, 2-(p-dimethylaminophenyl)benzothia Sol, 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-diethylaminophenyl)pyridine, (p-dimethylaminophenyl)quinoline, (p-diethyl p-dialkylaminophenyl group-containing compounds, such as aminophenyl)quinoline, (p-dimethylaminophenyl)pyrimidine, and (p-diethylaminophenyl)pyrimidine. Among them, 4,4'-dialkylaminobenzophenone is most preferred.

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

Examples of the polymerization accelerator include aromatic amines such as p-dimethylaminobenzoate ethyl and 2-dimethylaminoethyl benzoate, aliphatic amines such as n-butylamine and N-methyldiethanolamine, and mercapto compounds described later. do. A polymerization accelerator may be used individually by 1 type, and may be used in combination of 2 or more type.

<Photopolymerizable monomer>

In the photosensitive coloring composition of this invention, it is preferable from points, such as a sensitivity, that a photopolymerizable monomer (photopolymerizable compound) is further included.

As a photopolymerizable monomer used for this invention, the compound (Hereinafter, it may call an "ethylenic monomer") which has at least 1 ethylenically unsaturated group in a molecule|numerator is mentioned. Specific examples include (meth)acrylic acid, (meth)acrylic acid alkylester, acrylonitrile, styrene, and monoester of carboxylic acid having one ethylenically unsaturated bond and polyhydric or monohydric alcohol. have.

In this invention, it is especially preferable to use the polyfunctional ethylenic monomer which has 2 or more of ethylenically unsaturated groups in 1 molecule.

As an example of such a polyfunctional ethylenic monomer, For example, ester of an aliphatic polyhydroxy compound and unsaturated carboxylic acid; Ester of aromatic polyhydroxy compound and unsaturated carboxylic acid; The ester etc. obtained by the esterification reaction of polyhydric hydroxy compounds, such as an aliphatic polyhydroxy compound and an aromatic polyhydroxy compound, and unsaturated carboxylic acid and polybasic carboxylic acid are mentioned.

Examples of the ester of the aliphatic polyhydroxy compound and the unsaturated carboxylic acid include ethylene glycol diacrylate, triethylene glycol diacrylate, trimethylolpropane triacrylate, trimethylolethane triacrylate, pentaerythritol diacrylate, Acrylic acid of aliphatic polyhydroxy compounds, such as pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, and glycerol acrylate Ester, methacrylic acid ester in which the acrylate of these exemplary compounds is changed to methacrylate, itaconic acid ester similarly changed to itaconate, crotonic acid ester changed to crotonate, or maleic acid ester changed to maleate and the like.

Examples of the ester of the aromatic polyhydroxy compound and the unsaturated carboxylic acid include aromatic polyacrylates such as hydroquinone diacrylate, hydroquinone dimethacrylate, resorcinol diacrylate, resorcinol dimethacrylate, and pyrogallol triacrylate. Acrylic acid ester of a hydroxy compound, methacrylic acid ester, etc. are mentioned.

The ester obtained by the esterification reaction of a polybasic carboxylic acid and an unsaturated carboxylic acid with a polyhydric hydroxy compound is not necessarily a single substance, but representative specific examples include a condensate of acrylic acid, phthalic acid, and ethylene glycol, acrylic acid, maleic acid and a condensate of diethylene glycol, a condensate of methacrylic acid, terephthalic acid and pentaerythritol, and a condensate of acrylic acid, adipic acid, butanediol and glycerin.

In addition, examples of the polyfunctional ethylenic monomer used in the present invention include urethane (meth) obtained by reacting a polyisocyanate compound with a hydroxyl group-containing (meth)acrylic acid ester or a polyisocyanate compound with a polyol and a hydroxyl group-containing (meth)acrylic acid ester acrylates; Epoxy acrylates like the addition reaction product of a polyhydric epoxy compound and hydroxy (meth)acrylate or (meth)acrylic acid; acrylamides such as ethylenebisacrylamide; allyl esters such as diallyl phthalate; Vinyl group-containing compounds, such as divinyl phthalate, etc. are useful.

Examples of the urethane (meth) acrylates 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 (manufactured by Shin-Nakamura Chemical Co., Ltd.), UA-306H, UA-510H, UF-8001G (manufactured by Kyoeisha Chemical Co., Ltd.), UV-1700B, UV-7600B, UV-7605B, UV-7630B, UV7640B (made by Nippon Synthetic Chemical Company), etc. are mentioned.

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

<Other compounding components of the photosensitive coloring composition>

In the photosensitive coloring composition of the present invention, in addition to the above components, organic solvents, adhesion improvers such as silane coupling agents, coating properties improvers, development improvers, ultraviolet absorbers, antioxidants, surfactants, pigment derivatives, etc. can be appropriately blended. .

(1) organic solvents

The photosensitive coloring composition of the present invention usually contains (A) a color material, (B) a dispersant, (C) an alkali-soluble resin, (D) a photoinitiator, and optionally used photopolymerizable monomers and other various materials. It is used in a dissolved or dispersed state in a solvent.

As an organic solvent, it is preferable to select the thing of the range of 100-300 degreeC with a boiling point. More preferably, it is a solvent which has a boiling point of 120-280 degreeC.

As such an organic solvent, the following are mentioned, for example.

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-t- 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 glycol monoalkyl ethers such as -3-methoxybutanol, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, and tripropylene glycol methyl ether;

Glycol dialkyl ethers such as ethylene glycol dimethyl ether, ethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, and dipropylene glycol dimethyl ether ;

Ethylene glycol 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, 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 mono glycol alkyl ether acetates such as methyl ether acetate, triethylene glycol monomethyl ether acetate, triethylene glycol monoethyl ether acetate, and 3-methyl-3-methoxybutyl acetate;

glycol diacetates such as ethylene glycol diacetate, 1,3-butylene glycol diacetate, and 1,6-hexanol diacetate;

alkyl acetates such as cyclohexanol acetate;

ethers such as amyl ether, diethyl ether, dipropyl ether, diisopropyl ether, dibutyl ether, diamyl ether, ethyl isobutyl ether, and dihexyl ether;

Acetone, methyl ethyl ketone, methyl amyl ketone, methyl isopropyl ketone, methyl isoamyl ketone, diisopropyl ketone, diisobutyl ketone, methyl isobutyl ketone, cyclohexanone, ethyl amyl ketone, methyl butyl ketone, methylhexyl ketones such as ketone, methyl nonyl ketone, and methoxymethyl pentanone;

Monohydric or polyhydric alcohols such as ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, propylene glycol, butanediol, diethylene glycol, dipropylene glycol, triethylene glycol, methoxymethylpentanol, glycerin, and benzyl alcohol Ryu ;

aliphatic hydrocarbons such as n-pentane, n-octane, diisobutylene, n-hexane, hexene, isoprene, dipentene and dodecane;

alicyclic hydrocarbons such as cyclohexane, methylcyclohexane, methylcyclohexene and bicyclohexyl;

aromatic hydrocarbons such as benzene, toluene, xylene, and cumene;

Amyl formate, ethyl formate, ethyl acetate, butyl acetate, propyl acetate, amyl acetate, methyl isobutylate, ethylene glycol acetate, ethyl propionate, propyl propionate, butyl butyrate, isobutyl butyrate, methyl isobutyrate, Ethyl caprylate, butyl stearate, ethyl benzoate, 3-ethoxy methyl propionate, 3-ethoxy ethyl propionate, 3-methoxy methyl propionate, 3-methoxy ethyl propionate, 3-methoxy propyl propionate, 3- chain or cyclic esters such as butyl methoxypropionate and γ-butyrolactone;

alkoxycarboxylic acids such as 3-methoxypropionic acid and 3-ethoxypropionic acid;

halogenated hydrocarbons such as butyl chloride and amyl chloride;

ether ketones such as methoxymethylpentanone;

nitriles such as acetonitrile and benzonitrile.

Commercially available solvents corresponding to the above include Mineral Spirit, Barsol #2, Apco #18 Solvent, Apco Thinner, Socal Solvent No.1 and No.2, Solvesso #150, Shell TS28 Solvent, Carbitol, Ethylcarbitol, butylcarbitol, methylcellosolve (“Cellosolve” is a registered trademark; hereinafter the same), ethylcellosolve, ethylcellosolve acetate, methylcellosolve acetate, diglyme (all trade names), etc. can be heard

These organic solvents may be used independently and may use 2 or more types together.

When forming the pixel or black matrix of a color filter by the photolithography method, the organic solvent having a boiling point in the range of 100 to 200 ° C (under the pressure of 1013.25 [hPa]. Hereinafter, the boiling point is all the same.) It is preferable to do More preferably, it has a boiling point of 120-170 degreeC.

Among the above organic solvents, the glycol alkyl ether acetates are preferable from the viewpoint of good balance of coating properties and surface tension, and relatively high solubility of the constituent components in the composition.

Moreover, although glycol alkyl ether acetate may be used independently, they may use other organic solvents together. Especially preferable as an organic solvent used together are glycol monoalkyl ethers. Among them, propylene glycol monomethyl ether is particularly preferable from the viewpoint of solubility of the constituents in the composition. In addition, glycol monoalkyl ethers have high polarity, and when there is too much added amount, pigments tend to aggregate, and storage stability tends to decrease, such as increasing the viscosity of the colored resin composition obtained later, so the ratio of glycol monoalkyl ethers in the solvent 5 mass % - 30 mass % of silver are preferable, and 5 mass % - 20 mass % are more preferable.

Moreover, it is also preferable to use together the organic solvent (Hereinafter, it may call a "high boiling point solvent") which has a boiling point of 150 degreeC or more. By using such a high boiling point solvent together, although a colored resin composition becomes difficult to dry, it is effective in preventing that the uniform dispersion state of the pigment in a composition is destroyed by rapid drying. That is, for example, there is an effect of preventing the occurrence of a foreign material defect due to precipitation and solidification of the color material at the tip of the slit nozzle. From the viewpoint of such a high effect, diethylene glycol mono-n-butyl ether, diethylene glycol mono-n-butyl ether acetate, and diethylene glycol monoethyl ether acetate are particularly preferred among the various solvents described above.

3 mass % - 50 mass % are preferable, as for the content rate of the high boiling point solvent in an organic solvent, 5 mass % - 40 mass % are more preferable, 5 mass % - 30 mass % are especially preferable. If the amount of the high boiling point solvent is too small, for example, there is a possibility that a color material or the like will precipitate and solidify at the tip of the slit nozzle to cause foreign matter defects. We are concerned about causing problems, such as a tact defect of a reduced pressure drying process in this, and a pin trace of a prebaking.

In addition, glycol alkyl ether acetates may be sufficient as the high boiling point solvent of 150 degreeC or more boiling point, and glycol alkyl ethers may be sufficient as it, In this case, it is not cared about without separately containing the high boiling point solvent of 150 degreeC or more boiling point.

As preferred high boiling point solvents, for example, among the various solvents described above, diethylene glycol mono-n-butyl ether acetate, diethylene glycol monoethyl ether acetate, dipropylene glycol methyl ether acetate, and 1,3-butylene glycol diacetate , 1,6-hexanol diacetate, triacetin, and the like.

(2) Adhesion enhancer

In the photosensitive coloring composition of this invention, in order to improve adhesiveness with a board|substrate, you may make it contain a close_contact|adherence improving agent. As a close_contact|adherence improving agent, a silane coupling agent, a phosphoric acid group containing compound, etc. are preferable.

As a kind of a silane coupling agent, various things, such as an epoxy type, a (meth)acrylic type, and an amino type, can be used individually by 1 type or in mixture of 2 or more types.

As a preferable silane coupling agent, For example, (meth)acryloxysilanes, such as 3-methacryloxypropylmethyldimethoxysilane and 3-methacryloxypropyl trimethoxysilane, 2-(3,4-epoxycyclohexyl) ) Epoxysilanes such as ethyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, and 3-glycidoxypropyltriethoxysilane, 3-ureidopropyl Although ureidosilanes, such as triethoxysilane, and isocyanate silanes, such as 3-isocyanate propyl triethoxysilane, are mentioned, Especially preferably, it is the silane coupling agent of epoxysilanes.

As a phosphoric acid group containing compound, (meth)acryloyl group containing phosphates are preferable, and what is represented by the following general formula (g1), (g2) or (g3) is preferable.

[Formula 27]

In the formulas (g1), (g2) and (g3), R ⁵¹ represents a hydrogen atom or a methyl group, l and l' are an integer of 1 to 10, and m is 1, 2 or 3.

These phosphoric acid group containing compounds may be used individually by 1 type, and may be used in combination of 2 or more type.

(3) surfactant

You may make the photosensitive coloring composition of this invention contain surfactant for an applicability|paintability improvement.

As surfactant, various things, such as an anionic, cationic, nonionic, and amphoteric surfactant, can be used, for example. Among them, it is preferable to use a nonionic surfactant from the viewpoint of having a low possibility of adversely affecting various properties, and among them, a fluorine-based surfactant or a silicone-based surfactant is effective in terms of applicability.

Examples of such surfactants include TSF4460 (manufactured by Toshiba Silicone Co., Ltd.), DFX-18 (manufactured by Neos Corp.), BYK-300, BYK-325, BYK-330 (manufactured by Bikchemi Co., Ltd.), KP340 (Shin-Etsu Silicone Co., Ltd.) manufactured by), F-470, F-475, F-478, F-559 (manufactured by DIC Corporation), SH7PA (manufactured by Toray Silicon Corporation), DS-401 (manufactured by Daikin Corporation), L-77 (manufactured by Nippon Unika Corporation) , FC4430 (manufactured by Sumitomo 3M), and the like.

In addition, 1 type may be used for surfactant and may use 2 or more types together by arbitrary combinations and a ratio.

(4) pigment derivatives

You may make the photosensitive coloring composition of this invention contain a pigment derivative as a dispersing auxiliary agent in order to improve dispersibility and storage stability.

Pigment derivatives include azo, phthalocyanine, quinacridone, benzimidazolone, quinophthalone, isoindolinone, dioxazine, anthraquinone, indanthrene, perylene, perinone, diketopy Although derivatives, such as a rolopyrrole type and a dioxazine type, are mentioned, Among them, a phthalocyanine type and a quinophthalone type are preferable.

As a substituent of the pigment derivative, a sulfonic acid group, a sulfonamide group and its quaternary salt, a phthalimidomethyl group, a dialkylaminoalkyl group, a hydroxyl group, a carboxyl group, an amide group, etc. What couple|bonded through it is mentioned, Preferably it is a sulfonic acid group. Moreover, two or more of these substituents may be substituted by one pigment frame|skeleton.

Specific examples of the pigment derivative include phthalocyanine sulfonic acid derivatives, quinophthalone sulfonic acid derivatives, anthraquinone sulfonic acid derivatives, quinacridone sulfonic acid derivatives, diketopyrrolopyrrole sulfonic acid derivatives, dioxazine sulfonic acid derivatives, and the like. . These may be used individually by 1 type, and may use 2 or more types together.

(5) photoacid generator

A photo-acid generator is a compound which can generate|occur|produce an acid by ultraviolet-ray, and a crosslinking reaction advances by the action of the acid which generate|occur|produces when it exposes, for example, when crosslinking agents, such as a melamine compound, exist. Among these photo-acid generators, those having high solubility in solvents, particularly solvents used for photosensitive coloring compositions, are preferable, for example, diphenyliodonium, ditolyliodonium, phenyl(p-anisyl)iodonium. , bis(m-nitrophenyl)iodonium, bis(p-tert-butylphenyl)iodonium, bis(p-chlorophenyl)iodonium, bis(n-dodecyl)iodonium, p-isobutylphenyl (p Chloride, bromide, or borofluoride salt, hexafluorophosphate salt of diaryliodonium such as tolyl)iodonium and p-isopropylphenyl(p-tolyl)iodonium, or triarylsulfonium such as triphenylsulfonium , hexafluoroarsenate salt, aromatic sulfonate salt, tetrakis (pentafluorophenyl) borate salt, or sulfonium organoboron complexes such as diphenylphenacyl sulfonium (n-butyl) triphenyl borate, or 2 Triazine compounds, such as -methyl-4,6-bistrichloromethyltriazine and 2-(4-methoxyphenyl)-4,6-bistrichloromethyltriazine, etc. are mentioned, However, It is not limited to this.

(6) crosslinking agent

A crosslinking agent can be further added to the photosensitive coloring composition of this invention, For example, a melamine or a guanamine type compound can be used. Examples of these crosslinking agents include melamine or guanamine compounds represented by the following general formula (6).

[Formula 28]

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

Here, the C6-C12 aryl group is typically a phenyl group, 1-naphthyl group, or 2-naphthyl group, Substituent groups, such as an alkyl group, an alkoxy group, and a halogen atom, may couple|bond with these phenyl group or a naphthyl group. 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, among the above.

In the melamine-based compound corresponding to the general formula (6), that is, the compound of the following general formula (6-1), hexamethylolmelamine, pentamethylolmelamine, tetramethylolmelamine, hexamethoxymethylmelamine, pentamethoxymethyl melamine, tetramethoxymethylmelamine, hexaethoxymethylmelamine, and the like.

[Formula 29]

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 is -CH ₂ OR ⁶⁸ , and ^{the remainder of 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, wherein R ⁶⁸ represents a hydrogen atom or an alkyl group.

Moreover, in the guanamine type compound corresponded to General formula (6), ie, R<^61> in General formula (6) is aryl, tetramethylolbenzoguanamine, tetramethoxymethylbenzoguanamine, trimethoxymethylbenzo guanamine, tetraethoxymethylbenzoguanamine, and the like.

Moreover, the crosslinking agent which has a methylol group or a methylol alkyl ether group can also be used. An example is 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-triazin-2-one (common name: N-ethyldimethyloltriazone) or its dimethyl ether, dimethyloltrimethyleneurea or its dimethyl ether, 3,5-bis(hydroxymethyl) Perhydro-1,3,5-oxadiazin-4-one (common name dimethyloluron) or its dimethyl ether, tetramethylolglyoxaldiurein or its tetramethyl ether.

In addition, these crosslinking agents may be used individually by 1 type, and may be used in combination of 2 or more type. As for the quantity at the time of using a crosslinking agent, 0.1-15 mass % is preferable with respect to the total solid of the photosensitive coloring composition, Especially preferably, it is 0.5-10 mass %.

(7) mercapto compounds

As a polymerization accelerator, a mercapto compound can also be added in order to improve the adhesiveness to a board|substrate.

Examples of the mercapto compound include 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, 2-mercaptobenzoimidazole, hexanedithiol, decanedithiol, 1,4-dimethylmercaptobenzene, butanediol. Bisthiopropionate, butanediol bisthioglycolate, ethylene glycol bisthioglycolate, trimethylolpropane tristhioglycolate, butanediol bisthiopropionate, trimethylolpropane tristhiopropionate, trimethylolpropane tristhioglycolate , pentaerythritol tetrakisthiopropionate, pentaerythritol tetrakisthioglycolate, trishydroxyethyl tristhiopropionate, ethylene glycol bis(3-mercaptobutylate), butanediol bis(3-mercaptobutyl rate), 1,4-bis (3-mercaptobutyryloxy) butane, trimethylolpropane tris (3-mercapto butyrate), pentaerythritol tetrakis (3-mercapto butyrate), pentaerythritol tris (3-mercaptobutyrate), ethylene glycol bis(3-mercaptoisobutylate), butanediolbis(3-mercaptoisobutylate), trimethylolpropanetris(3-mercaptoisobutylate) , 1,3,5-tris (3-mercaptobutyloxyethyl) -1,3,5-triazine-2,4,6 (1H, 3H, 5H) - mercapto having a heterocyclic ring, such as trione compound or an aliphatic polyfunctional mercapto compound; and the like. These can be used individually by 1 type or in mixture of 2 or more types of various things.

<Ingredient compounding quantity in photosensitive coloring composition>

The photosensitive coloring composition of this invention WHEREIN: It is preferable that content of (A) color material is 10 mass % or more and 20 mass % or more normally with respect to the total solid amount in the photosensitive coloring composition, and it is 50 mass % or less normally. When the content of the color material (A) is too small, a sufficient optical density (OD) may not be obtained. Conversely, if the content of the color material (A) is too large, sufficient image formability may not be obtained. Moreover, the content rate of (A-1) organic black pigment is 10 mass % or more normally with respect to (A) 100 mass % of color material, Preferably it is 30 mass % or more, and is 100 mass % or less normally. (A) When there are too few content rates of the (A-1) organic black pigment in a color material, sufficient optical density (OD) may not be obtained.

The photosensitive coloring composition of this invention WHEREIN: (A-2) organic coloring pigment may be contained with (A-1) organic black pigment in (A) color material. In that case, the content rate of (A-1) organic black pigment is 10 mass % or more normally with respect to 100 mass % of (A) color material, Preferably it is 20 mass % or more, More preferably, 30 mass % or more, and 90 mass % or more normally. % or less, preferably 80 mass% or less, and more preferably 60 mass% or less. Moreover, the content rate of (A-2) organic coloring pigment is 10 mass % or more normally, Preferably it is 20 mass % or more, More preferably, it is 40 mass % or more, And it is 90 mass % or less normally, Preferably it is 80 mass %. % or less, more preferably 70 mass% or less. (A-2) When there is too much content of an organic coloring pigment, sufficient optical density may not be obtained. Moreover, the content ratio of (A-1) organic black pigment with respect to (A-2) 100 mass parts of organic coloring pigments is 15 mass parts or more normally, Preferably it is 20 mass parts or more, Usually 900 mass parts or less, Preferably 800 mass parts or less, More preferably, it is 500 mass parts or less, More preferably, it is 200 mass parts or less.

The photosensitive coloring composition of this invention WHEREIN: (A-3) carbon black may be contained with (A-1) organic black pigment in (A) color material. In that case, the content rate of (A-1) organic black pigment is 50 mass % or more normally with respect to 100 mass % of (A) color material, Preferably it is 60 mass % or more, And it is 95 mass % or less normally, Preferably 90 mass %. is below. Moreover, the content rate of (A-3) carbon black is 5 mass % or more normally, Preferably it is 10 mass % or more, Furthermore, it is 50 mass % or less normally, Preferably it is 40 mass % or less. (A-3) When there is too much content of carbon black, a volume resistance value may fall or a dielectric constant may become large. Moreover, the content ratio of (A-1) organic black pigment with respect to (A-3) 100 mass parts of carbon black is 100 mass parts or more normally, Preferably it is 150 mass parts or more, Usually 2000 mass parts or less, Preferably 1000 It is less than a mass part.

Moreover, the photosensitive coloring composition of this invention WHEREIN: (A-2) organic coloring pigment and (A-3) carbon black may be contained with (A-1) organic black pigment in (A) color material. In that case, the content rate of (A-1) organic black pigment is 10 mass % or more normally with respect to 100 mass % of (A) color material, Preferably it is 20 mass % or more, And 80 mass % or less normally, Preferably it is 70 mass %. is below. Moreover, the content rate of (A-2) organic coloring pigment is 10 mass % or more normally, Preferably it is 20 mass % or more, Moreover, it is 60 mass % or less normally, Preferably it is 50 mass % or less. Moreover, the content rate of (A-3) carbon black is 5 mass % or more normally, Preferably it is 10 mass % or more, And it is 50 mass % or less normally, Preferably it is 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 color pigment is usually 15 parts by mass or more, preferably 20 parts by mass or more, usually 800 parts by mass or less, preferably is 700 parts by mass or less. Moreover, the content ratio of (A-1) organic black pigment with respect to (A-3) 100 mass parts of carbon black is 40 mass parts or more normally, Preferably it is 50 mass parts or more, Usually 1000 mass parts or less, Preferably it is 900 It is less than a mass part.

(B) Content of a dispersing agent is 1 mass % or more normally in solid content of the photosensitive coloring composition, 3 mass % or more is preferable, 5 mass % or more is more preferable, and 30 mass % or less and 20 mass % or less normally It is preferable, and 15 mass % or less is especially preferable. Moreover, content of (B) dispersing agent is especially 5 mass % or more and 10 mass % or more are especially preferable normally with respect to 100 mass % of (A) color material, and it is preferable that it is usually 50 mass % or less, and especially 30 mass % or less. (B) When the content of the dispersant is too small, sufficient dispersibility may not be obtained.

(C) Content of alkali-soluble resin is 5 mass % or more normally with respect to the total solid of the photosensitive coloring composition of this invention, Preferably it is 10 mass % or more, Usually 85 mass % or less, Preferably it is 80 mass % or less . (C) When there is remarkably little content of alkali-soluble resin, the solubility with respect to the developing solution of an unexposed part will fall and it will become easy to cause poor image development. Conversely, when there is too much content of (C) alkali-soluble resin, there exists a tendency for the permeability of the developing solution to an exposure part to become high, and the sharpness and adhesiveness of a pixel may fall.

(D) Content of a photoinitiator is 0.1 mass % or more normally with respect to the total solid of the photosensitive coloring composition of this invention, Preferably it is 0.5 mass % or more, More preferably, it is 1 mass % or more, Usually 15 mass % or less. , Preferably it is 10 mass % or less. (D) When there is too little content of a photoinitiator, a sensitivity fall may be caused, and when there is too much conversely, the solubility with respect to the developing solution of an unexposed part falls, and it is easy to cause poor image development.

(D) When a polymerization accelerator is used together with a photoinitiator, content of a polymerization accelerator with respect to the total solid of the photosensitive coloring composition of this invention becomes like this. Preferably it is 0.05 mass % or more, Usually 10 mass % or less, Preferably It is 5 mass % or less, and it is preferable to use a polymerization accelerator in the ratio of 0.1-50 mass parts normally with respect to 100 mass parts of (D) photoinitiators, especially 0.1-20 mass parts.

(D) If the mixing ratio of the photopolymerization initiator-based component comprising the photopolymerization initiator and the polymerization accelerator is remarkably low, it may cause the sensitivity to the exposure light to decrease. The solubility with respect to this may fall, and may cause poor image development.

Moreover, the compounding ratio of the sensitizing dye which occupies in the photosensitive coloring composition of this invention is 20 mass % or less normally in the total solid in the photosensitive coloring composition from a sensitivity viewpoint, Preferably it is 15 mass % or less, More preferably, it is 10 mass % or less. to be.

When using a photopolymerizable monomer, the content is 30 mass % or less normally with respect to the total solid of the photosensitive coloring composition, Preferably it is 20 mass % or less. When there is too much content of a photopolymerizable monomer, the permeability of the developing solution to an exposure part may become high, and it may become difficult to obtain a favorable image. In addition, the minimum of content of a photopolymerizable monomer is 1 mass % or more normally, Preferably it is 5 mass % or more.

When using an adhesion improving agent, the content is 0.1-5 mass % normally with respect to the total solid in the photosensitive coloring composition, Preferably it is 0.2-3 mass %, More preferably, it is 0.4-2 mass %. When content of an adhesion improving agent is less than the said range, the adhesive improvement effect may not fully be acquired, and when it is large, a sensitivity may fall or a residue may remain after image development, and it may become a defect.

Moreover, when using surfactant, the content is 0.001-10 mass % normally with respect to the total solid in the photosensitive coloring composition, Preferably it is 0.005-1 mass %, More preferably, 0.01-0.5 mass %, Most preferably It is 0.03-0.3 mass %. When 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 expressed.

Moreover, the photosensitive coloring composition of this invention is 5-50 mass % normally using the organic solvent mentioned above, and the solid content concentration is 5-50 mass %, Preferably it is prepared so that it may be 10-30 mass %.

<Physical properties of the photosensitive coloring composition>

The photosensitive coloring composition of this invention can be used suitably for black matrix formation, It is preferable that it has shown black from this viewpoint, It is preferable that the optical density (OD) per 1 micrometer of film thickness of the coating film is 1.0 or more.

<The manufacturing method of the photosensitive coloring composition>

The photosensitive coloring composition of this invention (henceforth a "resist" may be called) is manufactured according to a conventional method.

Usually, the color material (A) is preferably dispersed in advance using a paint conditioner, a sand grinder, a ball mill, a roll mill, a stone mill, a jet mill, a homogenizer, or the like. Since the (A) color material is finely divided by the dispersion treatment, the resist coating properties are improved.

The dispersion treatment is usually preferably performed in a system in which (A) a color material, an organic solvent, and (B) a dispersing agent, and (C) some or all of the alkali-soluble resin are used in combination (hereinafter, the mixture subjected to dispersion treatment; and the composition obtained by the treatment is sometimes referred to as "ink" or "pigment dispersion"). In particular, the use of a polymer dispersing agent as the dispersing agent (B) is preferable because the time-dependent thickening of the obtained ink and resist is suppressed (excellent in dispersion stability).

Thus, in the process of manufacturing a resist, it is preferable to manufacture the pigment dispersion liquid containing at least (A) a color material, an organic solvent, and (B) a dispersing agent. As (A) color material, organic solvent, and (B) dispersing agent which can be used for a pigment dispersion liquid, what was described as what can be used for the photosensitive coloring composition, respectively can be employ|adopted preferably.

Moreover, when a dispersion process is performed with respect to the liquid containing all the components mix|blended with the colored resin composition, a highly reactive component may be modified|denatured because of the heat generation|occurrence|production at the time of a dispersion process. Therefore, it is preferable to carry out the dispersion treatment in a system containing a polymer dispersing agent.

When the (A) color material is dispersed with a sand grinder, glass beads or zirconia beads having a diameter of about 0.1 to 8 mm are preferably used. As for dispersion treatment conditions, the temperature is usually from 0°C to 100°C, preferably from room temperature to 80°C. The dispersion time is appropriately adjusted because the appropriate time varies depending on the composition of the liquid, the size of the dispersion processing apparatus, and the like. The goal of dispersion is to control the gloss of the ink so that the 20 degree specular gloss (JIS Z8741) of the resist is in the range of 50 to 300. When the glossiness of the resist is low, the dispersion treatment is not sufficient and coarse pigment (colorant) particles remain in many cases, which may result in insufficient developability, adhesiveness, resolution, and the like. In addition, if dispersion treatment is performed until the gloss value exceeds the above range, the pigment is crushed and a large number of ultrafine particles are generated, and thus dispersion stability tends to be impaired on the contrary.

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 dispersion treatment and the other components contained in the resist are mixed to obtain a uniform solution. In the resist manufacturing process, since fine dust is often mixed in a liquid, it is preferable to filter the obtained resist with a filter etc.

[Cured material]

Hardened|cured material can be obtained by hardening|curing the photosensitive coloring composition of this invention. The hardened|cured material formed by hardening|curing the photosensitive coloring composition can be used suitably as a black matrix and a colored spacer.

[Black Matrix]

Next, the black matrix using the photosensitive coloring composition of this invention is demonstrated according to the manufacturing method.

(1) support

As a support body for forming a black matrix, if it has moderate intensity|strength, the material will not be specifically limited. A transparent substrate is mainly used, but as a material, for example, a polyester-based resin such as polyethylene terephthalate, a polyolefin-based resin such as polypropylene or polyethylene, or a sheet made of a thermoplastic resin such as polycarbonate, polymethyl methacrylate or polysulfone , an epoxy resin, an unsaturated polyester resin, a thermosetting resin sheet such as a poly(meth)acrylic resin, or various kinds of glass. Among these, glass and heat resistant resin are preferable from a heat resistant viewpoint. Moreover, transparent electrodes, such as ITO and IZO, may be formed into a film on the surface of a board|substrate. It can also be formed on a TFT array other than a transparent substrate.

The support may be subjected to corona discharge treatment, ozone treatment, thin film formation treatment of various resins such as a silane coupling agent and urethane resin, etc. as necessary for improvement of surface properties such as adhesiveness.

The thickness of the transparent substrate is usually in the range of 0.05 to 10 mm, preferably 0.1 to 7 mm. Moreover, when performing the thin film formation process of various resin, the film thickness is 0.01-10 micrometers normally, Preferably it is the range of 0.05-5 micrometers.

(2) Black Matrix

In order to form the black matrix of this invention with the photosensitive coloring composition of this invention mentioned above, after apply|coating and drying the photosensitive coloring composition of this invention on a transparent substrate, a photomask is put on the photosensitive coloring composition, and the A black matrix is formed by image exposure through a photomask, image development, and thermosetting or photocuring as needed.

Moreover, although the black matrix of this invention is effective in forming on a TFT element substrate, the structure is not specifically limited in each method of COA and BOA, Correspondence to various structures is possible.

(3) formation of black matrix

(3-1) Application of photosensitive coloring composition

Application|coating on the transparent substrate of the photosensitive coloring composition for black matrices can be performed by the spinner method, the wire bar method, the flow coat method, the die coat method, the roll coat method, or the spray coat method. Especially, according to the die coating method, the amount of coating liquid used is significantly reduced, and there is no influence of mist adhering when the spin coating method is used, and the generation of foreign substances is suppressed, which is preferable from a general viewpoint.

When the thickness of the coating film is too thick, pattern development becomes difficult and gap adjustment in the liquid crystal cell-forming process becomes difficult in some cases, and when it is too thin, it becomes difficult to increase the pigment concentration, and desired color expression may not be possible. . As for the thickness of a coating film, it is preferable to make it into the range of 0.2-10 micrometers normally as a film thickness after drying, More preferably, it is the range of 0.5-6 micrometers, More preferably, it is the range of 1-4 micrometers.

(3-2) Drying of the coating film

It is preferable to perform drying of the coating film after apply|coating the photosensitive coloring composition to a board|substrate by the drying method using a hot plate, IR oven, or a convection oven. Drying conditions can be suitably selected according to the kind of the said solvent component, the performance of the dryer to be used, etc. Drying time is usually selected from the range of 15 seconds - 5 minutes at the temperature of 40-200 degreeC according to the kind of solvent component, the performance of the dryer to be used, etc., Preferably it is 30 seconds - at the temperature of 50-130 degreeC It is selected in the range of 3 minutes.

The higher the drying temperature, the better the adhesion of the coating film to the transparent substrate. However, when the drying temperature is too high, the alkali-soluble resin (C) decomposes and thermal polymerization may be induced, resulting in poor development in some cases. In addition, the reduced-pressure drying method which dries in a pressure reduction chamber without raising a temperature may be sufficient as the drying process of this coating film.

(3-3) Exposure

Image exposure overlaps a negative mask pattern on the coating film of the photosensitive coloring composition, irradiates and performs the light source of an ultraviolet-ray or visible light through this mask pattern. At this time, if necessary, in order to prevent a decrease in the sensitivity of the photopolymerizable layer by oxygen, it may be exposed after forming an oxygen barrier layer such as a polyvinyl alcohol layer on the photopolymerizable coating film. The light source used for the said image exposure is not specifically limited. Examples of the light source include lamp light sources such as 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, fluorescent lamps, argon ion lasers, YAG lasers, Laser light sources, such as an excimer laser, a nitrogen laser, a helium-cadmium laser, and a semiconductor laser, etc. are mentioned. In the case of irradiating and using light of a specific wavelength, an optical filter may be used.

(3-4) phenomenon

In the black matrix according to the present invention, after image exposure of a coating film made of a photosensitive coloring composition with the light source, an image is formed on a substrate by developing using an aqueous solution containing an organic solvent or a surfactant and an alkaline compound. It can be made by forming. The aqueous solution may further contain organic solvents, buffers, complexing agents, dyes or pigments.

Examples of the alkaline compound include sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium carbonate, potassium carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, sodium silicate, potassium silicate, sodium metasilicate, sodium phosphate, potassium phosphate, sodium hydrogen phosphate, potassium hydrogen phosphate. , inorganic alkaline compounds such as sodium dihydrogen phosphate, potassium dihydrogen phosphate and ammonium hydroxide, mono-/di- or triethanolamine, mono-/di- or trimethylamine, mono-/di- or triethylamine, mono- or organic alkaline compounds such as diisopropylamine, n-butylamine, mono-/di- or triisopropanolamine, ethyleneimine, ethylenediimine, tetramethylammonium hydroxide (TMAH), and choline. A mixture of 2 or more types may be sufficient as these alkaline compounds.

Examples of the surfactant include nonionic surfactants such as polyoxyethylene alkyl ethers, polyoxyethylene alkyl aryl ethers, polyoxyethylene alkyl esters, sorbitan alkyl esters, and monoglyceride alkyl esters; Amphoteric surfactants, such as anionic surfactants, such as benzenesulfonates, alkylnaphthalenesulfonates, alkyl sulfates, alkylsulfonates, and sulfosuccinic acid ester salts, alkylbetaines, and amino acids, are mentioned.

Examples of the organic solvent include isopropyl alcohol, benzyl alcohol, ethyl cellosolve, butyl cellosolve, phenyl cellosolve, propylene glycol, and diacetone alcohol. The organic solvent may be used independently and may be used together with aqueous solution.

The conditions of the developing treatment are not particularly limited, and the developing temperature is usually in the range of 10 to 50°C, especially 15 to 45°C, particularly preferably 20 to 40°C, and the developing method is immersion developing method, spray developing method, brush It can be carried out by any method, such as a developing method and an ultrasonic developing method.

(3-5) heat curing treatment

The substrate after image development is subjected to a thermosetting treatment or a photocuring treatment, preferably a thermosetting treatment. The thermosetting treatment condition at this time is that the temperature is in the range of 100 to 280°C, preferably in the range of 150 to 250°C, and the time is selected in the range of 5 to 60 minutes.

The line width of the black matrix formed as mentioned above is 3-50 micrometers normally, Preferably it is 4-30 micrometers, and height is 0.5-5 micrometers normally, Preferably it is 1-4 micrometers. In addition, the volume resistivity is 1×10 ¹³ Ω·cm or more, preferably 1×10 ¹⁴ Ω·cm or more, and the relative permittivity is 6 or less, preferably 5 or less, and is usually 2 or more.

Moreover, the optical density (OD) per 1 micrometer in thickness is 1.2 or more, Preferably it is 1.5 or more, More preferably, it is 1.8 or more, and is 4.0 or less normally. Here, the optical density (OD) is a value measured by the method mentioned later.

[Colored Spacer]

The photosensitive coloring composition of this embodiment can also be used as a resist for coloring spacers other than a black matrix. When a spacer is used for a TFT-type LCD, the TFT as a switching element may malfunction by light incident on the TFT in some cases, and a colored spacer is used to prevent this. It is described that the spacer is light-shielding. The colored spacer can be formed in the same manner as the black matrix described above except for using a mask for the colored spacer.

[Image display device]

The image display device of the present invention is not particularly limited as long as it is a device that displays an image or video, and a liquid crystal display device, an organic EL (Electro Luminesence) display, etc. which will be mentioned later are mentioned.

[Liquid crystal display device]

The liquid crystal display device of this invention is produced using the black matrix of this invention mentioned above, and a restriction|limiting in particular, such as the formation order and formation position of a color pixel and a black matrix, is not received.

For example, after forming the black matrix of the present invention on a TFT element substrate, forming red, green, and blue pixels, and forming an overcoat layer if necessary, ITO, IZO, etc. on an image further thereon It forms a transparent electrode of , and is used as a part of parts such as color displays and liquid crystal displays. Moreover, in some uses, such as a planar alignment type drive system (IPS mode), a transparent electrode may not be formed.

After a liquid crystal display device forms an orientation film on a color filter normally, and disperse|distributes a spacer on this orientation film, or forms a photo-spacer, it bonds with a counter board|substrate, and forms a liquid crystal cell, and formed the liquid crystal cell The liquid crystal is injected into the , and the connection to the counter electrode is completed. As the alignment film, a resin film such as polyimide is preferable. A gravure printing method and/or a flexographic printing method are normally employ|adopted for formation of an alignment film, and the thickness of an alignment film is set to several tens of nm. After hardening of an alignment film by thermal baking, it surface-treats by irradiation of an ultraviolet-ray or treatment with a rubbing cloth, and is processed to the surface state which can adjust the inclination of a liquid crystal.

If the black matrix of this invention is used, a restriction|limiting in particular, such as the formation order and formation position of a color pixel and a black matrix, will not be received.

As the spacer, a spacer having a size corresponding to the gap (gap) with the opposing substrate is used, and it is usually preferably 2 to 8 µm. On a color filter substrate, the photo-spacer PS of a transparent resin film may be formed by the photolithographic method, and this may be utilized instead of a spacer.

Although the bonding gap with a counter board|substrate changes with the use of a liquid crystal display device, it is normally selected in the range of 2-8 micrometers. After bonding with a counter board|substrate, parts other than a liquid crystal injection port are sealed with sealing materials, such as an epoxy resin. The sealing material is hardened by UV irradiation and/or heating, and the periphery of the liquid crystal cell is sealed.

After the liquid crystal cell in which the periphery was sealed is cut|disconnected by panel unit, it is made into pressure reduction in a vacuum chamber, and after immersing the said liquid crystal injection port in a liquid crystal, the inside of a chamber is leaked, and a liquid crystal is inject|poured into a liquid crystal cell. Although the pressure reduction degree in a liquid crystal cell is 1x10 ^-2 - 1x10 ^-7 Pa normally, Preferably it is 1x10 ^-3 - 1x10 ^-6 Pa. Moreover, it is preferable to heat a liquid crystal cell at the time of pressure reduction, and a heating temperature is 30-100 degreeC normally, More preferably, it is 50-90 degreeC. The heating and maintenance at the time of reduced pressure is usually in the range of 10 to 60 minutes, and then immersed in the liquid crystal. A liquid crystal display device (panel) is completed by sealing the liquid crystal cell which inject|poured liquid crystal with the UV curing resin which hardened the liquid crystal injection port.

There is no restriction|limiting in particular in the kind of liquid crystal, As a conventionally known liquid crystal, such as an aromatic type, an aliphatic type, and a polycyclic compound, any of a lyotropic liquid crystal, a thermotropic liquid crystal, etc. may be sufficient. Although a nematic liquid crystal, a smectic liquid crystal, a cholesteric liquid crystal, etc. are known as a thermotropic liquid crystal, any of them may be sufficient.

[Organic EL Display]

The organic EL display of this invention can be produced using the black matrix of this invention.

When an organic EL display is produced using the black matrix of the present invention, for example, as shown in FIG. 1 , first, a pattern formed by the colored resin composition on the transparent support substrate 10 (that is, the pixel 20 , and a black matrix (not shown) formed between adjacent pixels 20) is formed, and an organic light-emitting body ( 500), the organic EL element 100 can be produced. In addition, at least one of the pixel 20 and the black matrix is produced using the photosensitive coloring composition of this invention. A method of laminating the organic light-emitting body 500 includes a transparent anode 50, a hole injection layer 51, a hole transport layer 52, a light emitting layer 53, an electron injection layer 54, and a cathode 55 on the upper surface of the color filter. ), a method in which the organic light emitting body 500 formed on a separate substrate is laminated on the inorganic oxide film 40, and the like. Using the organic EL element 100 produced in this way, for example, by the method described in "Organic EL Display" (Omsa, published on August 20, 2004, by Shizuo Tokito, Chihaya Adachi, Hideyuki Murata) An organic EL display can be produced.

Moreover, the black matrix of this invention is applicable also to the organic electroluminescent display of a passive driving system, and an organic electroluminescent display of an active driving system.

Example

Next, although the present invention will be described more specifically with reference to Synthesis Examples, Examples and Comparative Examples, the present invention is not limited to the following Examples unless the gist thereof is exceeded.

The constituent components of the photosensitive coloring composition used in the following Examples and Comparative Examples are as follows.

<(A-1) organic black pigment>

BASF Corporation make, Irgaphor (registered trademark) Black S 0100 CF (it has a chemical structure represented by the following formula (2))

[Formula 30]

<Organic black pigment: Perylene Black>

Manufactured by BASF, Lumogen (registered trademark) Black FK4281

<Organic black pigment: aniline black>

Manufactured by BASF, Paliotol (registered trademark) Black L0080

<Alkali-soluble resin-I>

It stirred, replacing 145 mass parts of propylene glycol monomethyl ether acetate with nitrogen, and it heated up at 120 degreeC. 10 parts by mass of styrene, 85.2 parts by mass of glycidyl methacrylate, and 66 parts by mass of monoacrylate having a tricyclodecane skeleton (FA-513M manufactured by Hitachi Chemical Co., Ltd.) are added dropwise thereto, and 2,2'-azobis- 8.47 mass parts of 2-methylbutyronitrile was dripped over 3 hours, and stirring was continued at 90 degreeC for 2 hours. Next, the inside of reaction container was changed to air substitution, 0.7 mass parts of trisdimethylaminomethylphenol and 0.12 mass parts of hydroquinone were thrown into 43.2 mass parts of acrylic acid, and reaction was continued at 100 degreeC for 12 hours. Then, 56.2 mass parts of tetrahydrophthalic anhydride (THPA) and 0.7 mass parts of triethylamine were added, and it was made to react at 100 degreeC for 3.5 hours. The weight average molecular weight Mw measured by GPC of the alkali-soluble resin-I obtained in this way 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 to 6000, acid value = about 60 mg-KOH/g)

<Alkali-soluble resin-III>

[Formula 31]

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

25 parts by mass of the 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), a thermometer, a stirrer, It was placed in a flask equipped with a cooling tube, and the temperature was slowly raised to 105°C while stirring to react.

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

<Alkali-soluble resin-IV>

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

<Dispersant-I>

"DISPERBYK-LPN21116" manufactured by Bikchemi (acrylic AB block copolymer comprising an A block having a quaternary ammonium base and a tertiary amino group in the side chain, and a B block having no quaternary ammonium base and amino group. The amine value is 70 mg KOH/g. Acid value is 1 mgKOH/g or less.)

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

[Formula 32]

<Dispersant-II>

"DISPERBYK-2000" manufactured by Bikchemi (acrylic A-B block copolymer comprising an A block having a quaternary ammonium base in a side chain and a B block not having a quaternary ammonium base)

<Dispersant-III>

"EFKA-4300" by EFKA company (Acryl-type polymer dispersing agent which has a tertiary amino group and a butyl group in a side chain. It does not have a quaternary ammonium base group in a side chain.)

<Pigment derivative>

"Solsperse12000" manufactured by Lubrizol

<Solvent-I>

PGMEA: Propylene glycol monomethyl ether acetate

<Solvent-II>

MB: 3-methoxybutanol

<Photoinitiator-I>

[Formula 33]

Compound 1 (0.98 g, 5 mmol) and methylene chloride (17 mL) were added to a 50 mL three neck flask under nitrogen atmosphere. After cooling this to 3 degreeC, o-toluoyl chloride (0.77 g, 5 mmol) was dripped. Aluminum chloride (0.67 g, 5 mmol) was slowly added thereto over 1 hour. After completion of the addition, the mixture was further stirred at 3°C for 2 hours, and methylene chloride (8 ml) was added. Next, 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 completion of the addition, the mixture was further stirred at 3°C for 2 hours, and the reaction solution was poured into ice water (400 ml) little by little. Sodium chloride (80 g) was added to the aqueous layer, and extraction was performed 5 times with methylene chloride (50 ml). The organic layer was washed with a saturated aqueous sodium chloride solution, and dried over anhydrous magnesium sulfate. After filtering anhydrous magnesium sulfate, the solvent was distilled off with the evaporator, and the compound 2 (2.13 g, 100% of crude yield) was obtained. This was used for the next reaction without purification.

[Formula 34]

In a nitrogen atmosphere, the compound 2 (2.13 g, 5 mmol), methanol (22 ml), and concentrated sulfuric acid (5 mg) were put into a 50 ml three neck flask, and the mixture was heated and refluxed for 3 hours. After cooling, the solvent was concentrated, and water (10 mL) and ethyl acetate (30 mL) were added.

The organic layer was washed sequentially with a saturated aqueous sodium hydrogen carbonate solution and a saturated aqueous sodium chloride solution, and dried over anhydrous magnesium sulfate. After filtering anhydrous magnesium sulfate, the solvent was distilled off with the evaporator, and the compound 3 (1.72 g, crude yield 78%) was obtained. It was used for the next reaction without purification.

[Formula 35]

In a nitrogen atmosphere, the compound 3 (1.00 g, 2.26 mmol) and methylene chloride (10 mL) were put in a 50 mL three neck flask, and it cooled at 10 degreeC. To this was added a 1N solution of hydrogen chloride in diethyl ether (4.68 ml). Next, amyl nitrite (0.36 g, 3.04 mmol) was added, and it was made to react at 10 degreeC for 4 hours. After adding water (10 ml), the mixture was washed sequentially with a saturated aqueous sodium hydrogencarbonate solution and a saturated aqueous sodium chloride solution, and dried by adding anhydrous magnesium sulfate. After filtration of anhydrous magnesium sulfate, the solvent was distilled off with the evaporator, and the pale yellow solid (0.88g) was obtained. This was subjected to recrystallization purification with toluene (3.5 ml) to obtain compound 4 (0.45 g, yield 42%).

[Formula 36]

In a nitrogen atmosphere, the compound 4 (3.50 g, 7.44 mmol) and methylene chloride (35 mL) were put in a 50 mL three neck flask, and it cooled at 4 degreeC. Triethylamine (1.50 g, 14.9 mmol) was added to this. Next, after adding acetyl chloride (0.70 g, 8.93 mmol), it was made to react as it is for 1 hour. After adding a saturated aqueous sodium hydrogencarbonate solution (10 ml), the organic layer was separated, further washed with a saturated aqueous sodium hydrogencarbonate solution and a saturated aqueous sodium chloride solution in this order, and dried by adding anhydrous magnesium sulfate. After filtering anhydrous magnesium sulfate, the solvent was distilled off with the evaporator, and the yellow oily thing (3.65 g) was obtained. This was purified by column chromatography (ethyl acetate/hexane = 1/1) to obtain compound 5 (3.12 g, yield 82%, photoinitiator-I). The chemical shift of compound 5 is shown below.

<Photoinitiator-II>

[Formula 37]

<Photopolymerizable Monomer-I>

DPHA: dipentaerythritol hexaacrylate manufactured by Nippon Kayaku Co., Ltd.

<Photopolymerizable Monomer-II>

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

<Additive-I>

Manufactured by Nippon Kayaku Co., Ltd., KAYAMER PM-21 (Phosphate containing methacryloyl group)

<Surfactant-I>

Megapack F-559 manufactured by DIC Co., Ltd.

<Preparation of Pigment Dispersion Liquids-1 to 7>

The pigment, dispersing agent, dispersing aid, alkali-soluble resin, and solvent shown in Table 1 were mixed so that it might become the mass ratio shown in Table 1. The dispersion process was performed for this solution in the range of 25-45 degreeC with a paint shaker for 3 hours. As the beads, 0.5 mm phi zirconia beads were used, and 2.5 times the mass of the dispersion was added. After completion of the dispersion, the beads and the dispersion were separated with a filter to prepare pigment dispersions -1 to 7.

Here, when the perylene black was dispersed under the same conditions as that of the pigment dispersion-1, the viscosity of the perylene black was greatly increased. Therefore, in order to disperse these pigments, it was necessary to greatly increase the amount of the dispersant as in the pigment dispersion liquid-6.

<Coating carbon black dispersion>

Carbon black was manufactured by the usual oil furnace method. However, as raw material oil, ethylene bottom oil with a small amount of Na, Ca, and S was used, and coke oven gas was used for combustion. In addition, as the reaction stop water, pure water treated with an ion exchange resin was used. 540 g of the obtained carbon black was stirred with 14500 g of pure water at 5,000 to 6,000 rpm using a homomixer for 30 minutes to obtain a slurry. 600 g of toluene in which 60 g of epoxy resin "Epicoat 828" (manufactured by Mitsubishi Chemical Co., Ltd.) was dissolved was added little by little while transferring this slurry to a container with a screw stirrer and mixing at about 1,000 rpm. In about 15 minutes, the carbon black dispersed in water migrated to the toluene side in the entire amount, and became granules of about 1 mm.

Next, after draining the water with a 60 mesh wire mesh, it put in a vacuum dryer, and it dried at 70 degreeC for 7 hours, and toluene and water were completely removed.

With respect to 90 parts by mass of the obtained coating carbon black, 20 parts by mass of DISPERBYK-167 (manufactured by Bikchemi Co., Ltd.) as a dispersant and 4.5 parts by mass of Solsperse12000 (manufactured by Lubrizol) as a pigment derivative are added so that the solid content concentration is 25 mass% Propylene glycol monomethyl ether acetate (PGMEA) was added.

This was fully stirred with a stirrer, and premixing was performed. Next, dispersion processing was performed in the range of 25-45 degreeC with a paint shaker for 6 hours. As beads, 0.5 mm phi zirconia beads were used and the same mass as the dispersion was added. After completion of the dispersion, the beads and the dispersion liquid were separated and prepared by a filter.

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

Using the pigment dispersion and coating carbon black dispersion prepared above, each component is added so that the ratio in the solid content becomes the blending ratio in Table 2, and PGMEA is further added so that the solid content is 17 mass%, stirred and dissolved, and photosensitivity A coloring composition was prepared. Examples 1-8 and Comparative Examples 1, 2 and 4 made the pigment density|concentration in solid content 40 mass %, and Comparative Example 3 made the pigment density|concentration in solid content 30 mass %. Moreover, in all the photosensitive coloring compositions, the mass ratio of alkali-soluble resin (including resin in dispersion liquid) with respect to a photopolymerizable monomer is set to 3, 4 mass % of photoinitiators in solid content, 0.5 mass % of additives, The surfactant was 0.1 mass %. The method mentioned later evaluated using the obtained photosensitive coloring composition.

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

The prepared photosensitive coloring composition was apply|coated to the glass substrate with a spin coater so that the final film thickness might be set to 2 micrometers, and after drying under reduced pressure for 1 minute, it dried at 100 degreeC for 90 second with a hotplate. By heating at 230 degreeC for 30 minutes, the resist-coated board|substrate (substrate-1) was obtained. The optical density (OD) of the obtained substrate was measured with a transmission densitometer Gretac Macbeth D200-II, and the film thickness was measured with a non-contact surface/layer cross-sectional shape measuring system VertScan(R) 2.0 manufactured by Ryoka Systems Co., Ltd. Table 3 shows the optical density (OD) per 1 µm of the film thickness.

[Measurement of dielectric constant]

In the manufacturing method of the board|substrate-1, it carried out similarly except having used the glass substrate which has a chromium vapor deposition film instead of the glass substrate, and produced the board|substrate (substrate-2). Using the chromium film of this sample as the main electrode, a gold counter electrode was formed on the resist coating film by vapor deposition. Moreover, the dielectric constant in 1 kHz*1V was measured using "LCR meter 4284A" by HP (now Agilent). A result is shown in Table 3.

[Engraving Characteristics]

Drying with a hot plate was performed in the same manner as in substrate-1. This sample was image-exposed with a high-pressure mercury lamp through a negative type mask having a linear pattern having an opening of 20 µm (illuminance 30 mW/cm 2 , exposure amount 20 mJ/cm 2 ). At this time, the distance between the sample and the mask was set to 200 µm. Then, spray development was carried out at the temperature of 25 degreeC using the developing solution with a KOH concentration of 0.05 mass %. The development time was 1.5 times the dissolution time of the unexposed part. Table 3 shows the result of the line width of the obtained linear pattern. However, when the resists of Comparative Examples 1 and 2 were used, no pattern was obtained even after 10 minutes of development.

From the comparison of Example 1 and Comparative Examples 1, 2 and 4, if it was the same pigment density|concentration, the direction of the board|substrate obtained from the photosensitive coloring composition of this invention has high OD, and it was confirmed that shielding property is high. Moreover, in Comparative Examples 1 and 2, even if it developed for 10 minutes, the linear pattern was not obtained. Although Comparative Examples 1 and 2 contained perylene black as a pigment, it is necessary to use a large amount of a dispersant when dispersing perylene black, and it is considered that this adversely affected the plate making characteristics. Moreover, although the line width shows that a sensitivity is so high that a value is large, it is Example 4 that the sensitivity can be raised without lowering|hanging OD significantly by using (A-1) organic black pigment and (A-2) organic coloring pigment together. and 5.

In Comparative Example 3, the pigment was only coated carbon black, and although it showed high OD, it turns out that the dielectric constant becomes high. By using together the (A-1) organic black pigment used by this invention, and (A-3) carbon black, it was confirmed from Examples 6 and 7 that OD was high and a dielectric constant could be kept low.

[Dispersibility Assessment]

<Preparation of Pigment Dispersion Liquids-8 to 11>

The pigment, dispersing agent, dispersing aid, alkali-soluble resin, and solvent shown in Table 4 were mixed so that it might become the mass ratio shown in Table 4. The dispersion process was performed for this solution in the range of 25-45 degreeC with a paint shaker for 3 hours. As the beads, 0.5 mm phi zirconia beads were used, and 2.5 times the mass of the dispersion was added. After completion of the dispersion, beads and dispersions were separated with a filter to prepare pigment dispersions 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 in the solid content became the blending ratio of Table 5, and PGMEA was further added so that the solid content was 17 mass%, stirred and dissolved, and a photosensitive coloring composition was prepared. .

Moreover, about each obtained photosensitive coloring composition, the viscosity was measured with the Toki Sangyo Co., Ltd. product RC80L type|mold viscometer (measurement conditions: 23 degreeC, 50 rpm). A result is shown in Table 5.

Generally, in order to disperse an organic pigment in a photosensitive coloring composition, a basic polymer dispersing agent having a quaternary ammonium base group and a basic polymer dispersing agent not having a quaternary ammonium base group are treated equally, and it is known that they exhibit equivalent dispersibility. In fact, in Comparative Examples 6 and 7 of Table 5, there is no significant difference in the viscosity of the photosensitive coloring composition in the case of using dispersant I or dispersant III for perylene black as an organic black pigment.

Surprisingly (A-1) in the photosensitive coloring composition containing the organic black pigment, from the comparison of Example 9 and Comparative Example 5 in Table 5, by using a polymer dispersing agent (dispersant I) having a quaternary ammonium base as a functional group, 4 Compared with the case where the polymer dispersing agent (dispersing agent III) which does not have a primary ammonium base group as a functional group was used, the viscosity of the photosensitive coloring composition became about half, and (A-1) organic black pigment became what disperse|distributed uniformly.

Moreover, the value of the viscosity measured by the method similar to Example 9 about the photosensitive coloring composition of Examples 1-8 in Table 6 is shown.

As shown in Table 6, not only Examples 1 and 2 in which (A-1) organic black pigment was used alone as the pigment, but also (A-1) organic black pigment and (A-2) organic colored pigment were used in combination. Examples 3 to 5 and 8, (A-1) Example 6 in which an organic black pigment and (A-3) carbon black were used together, (A-1) an organic black pigment and (A-2) an organic colored pigment ( A-3) In any of Example 7 which used carbon black together, it became the viscosity equivalent to Examples 1 and 2, and also in any photosensitive coloring composition, it became what disperse|distributed the pigment uniformly.

Although this invention was detailed also demonstrated with reference to the specific embodiment, it is clear for those skilled in the art that various changes and correction can be added without deviating from the mind and range of this invention. This application is based on the JP Patent application (Japanese Patent Application No. 2013-198425) for which it applied on September 25, 2013, The content is taken in here as a reference.

10: transparent support substrate
20: pixel
30: organic protective layer
40: inorganic oxide film
50: transparent anode
51: hole injection layer
52: hole transport layer
53: light emitting layer
54: electron injection layer
55: cathode
100: organic EL device
500: organic light emitting material

Claims (18)

A photosensitive coloring composition containing at least (A) a color material, (B) a dispersant, (C) an alkali-soluble resin, and (D) a photoinitiator,
The (A) color material 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 the geometric isomer;
The photosensitive coloring composition in which the said (B) dispersing agent contains the polymer dispersing agent which has a quaternary ammonium base 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 are independently of each other 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 ; In addition, at least one combination selected from the group consisting of ^{R 2} and R ³ , 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 is,} They may be directly bonded to each other, or may be bonded to each other through an ^{oxygen atom, a sulfur atom, NH or NR 11 bridge;} R ¹¹ and R ¹² are each independently an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms, an alkenyl group having 2 to 12 carbon atoms, a cycloalkenyl group having 3 to 12 carbon atoms, or an alkynyl group having 2 to 12 carbon atoms. ] The method of claim 1,
In the general formula (1),
R ² , R ⁴ , R ⁵ , R ⁷ , R ⁹ and R ¹⁰ are each independently a hydrogen atom, a fluorine atom or a chlorine atom, R ³ and R ⁸ are each independently a 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, SO ₃ H or SO ₃ ^- , 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 photosensitive coloring composition as ^{R 10 .} The method of claim 1,
The photosensitive coloring composition in which the said polymer dispersing agent further has a tertiary amine as a functional group. The method of claim 1,
The photosensitive coloring composition in which said (C) alkali-soluble resin contains at least any one of following alkali-soluble resin (c1) and following alkali-soluble resin (c2).
<Alkali-soluble resin (c1)>
Alkali-soluble resin obtained by adding α,β-unsaturated monocarboxylic acid or α,β-unsaturated monocarboxylic acid ester having a carboxyl group to an epoxy resin, and further reacting a polybasic acid and/or anhydride thereof.
<Alkali-soluble resin (c2)>
Alkali-soluble resin obtained by adding α,β-unsaturated monocarboxylic acid or α,β-unsaturated monocarboxylic acid ester having a carboxyl group to an epoxy resin, and further reacting with a polyhydric alcohol and a polybasic acid and/or anhydride thereof. The method of claim 1,
The photosensitive coloring composition whose content of the said (A) color material is 20 mass % or more with respect to the total solid amount in the photosensitive coloring composition. The method of claim 1,
The photosensitive coloring composition in which the said (A) color material further contains the (A-2) organic coloring pigment. 7. The method of claim 6,
The photosensitive coloring composition in which the said (A-2) organic coloring pigment contains at least 1 or more types of the following pigments.
Blue: Color Index Pigment Blue 60, or 15: 6
Red: Color Index Pigment Red 177, 254, or 272
Purple: Color Index Pigment Violet 23, or 29
Orange: Color Index Pigment Orange 43, 64, or 72 7. The method of claim 6,
Photosensitive coloring whose content rate of said (A-1) organic black pigment is 30-90 mass %, (A-2) content rate of organic coloring pigment is 10-70 mass % with respect to said (A) 100 mass % of color material composition. The method of claim 1,
The photosensitive coloring composition in which the said (A) color material further contains (A-3) carbon black. 10. The method of claim 9,
The photosensitive coloring composition whose content rate of the said (A-1) organic black pigment is 50-90 mass %, and the content rate of (A-3) carbon black is 10-50 mass % with respect to said (A) 100 mass % of color materials . The method of claim 1,
The photosensitive coloring composition whose said (D) photoinitiator is an oxime ester initiator and/or a ketoxime ester initiator. Hardened|cured material obtained by hardening|curing the photosensitive coloring composition in any one of Claims 1-11. The black matrix formed from the hardened|cured material of Claim 12. The colored spacer formed from the hardened|cured material of Claim 12. An image display device comprising a black matrix formed from the cured product according to claim 12 or a colored spacer formed from the cured product according to claim 12 . A pigment dispersion comprising (A) a colorant and (B) a dispersing agent, the pigment dispersion comprising:
The (A) color material 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 the geometric isomer;
The pigment dispersion liquid in which the said (B) dispersing agent contains the polymer dispersing agent which has a quaternary ammonium base 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 are independently of each other 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 ; In addition, at least one combination selected from the group consisting of ^{R 2} and R ³ , 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 is,} They may be directly bonded to each other, or may be bonded to each other through an ^{oxygen atom, a sulfur atom, NH or NR 11 bridge;} R ¹¹ and R ¹² are each independently an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms, an alkenyl group having 2 to 12 carbon atoms, a cycloalkenyl group having 3 to 12 carbon atoms, or an alkynyl group having 2 to 12 carbon atoms. ] 17. The method of claim 16,
In the general formula (1),
R ² , R ⁴ , R ⁵ , R ⁷ , R ⁹ and R ¹⁰ are each independently a hydrogen atom, a fluorine atom, or a chlorine atom, R ³ and R ⁸ are each independently a 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-naph tyl, β-naphthyl, SO ₃ H or SO ₃ ^— , 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 pigment dispersion as ^{R 10 .} 18. The method according to claim 16 or 17,
The pigment dispersion liquid in which the said polymer dispersing agent further has a tertiary amine as a functional group.

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