KR102485543B1 - 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, furthermore excellent in dispersibility and platemaking properties, and exhibits a sufficiently low dielectric constant. The photosensitive coloring composition of the present invention contains at least (A) a colorant, (B) a dispersant, (C) an alkali-soluble resin, and (D) a photopolymerization initiator, and (A) a colorant contains (A-1) the general formula ( 1) contains an organic black pigment which is a compound represented by , a geometric isomer of the compound, a salt of the compound, or a salt of the geometric isomer of the compound, and (B) the dispersant contains a polymeric dispersant having a quaternary ammonium base group as a functional group. .

Description

Photosensitive coloring composition, black matrix, colored 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. Specifically, it relates to a photosensitive coloring composition having excellent shielding properties and plate-making properties, and uses thereof.

A black matrix for a liquid crystal display element is used to prevent leakage of light from between drive electrodes in a liquid crystal display element. In general, a black matrix is a pattern of stripe or lattice-shaped light-shielding material formed by using a photolithography method on a transparent substrate such as a glass or plastic sheet paired with a thin film transistor (TFT) element substrate.

In recent years, in order to respond to higher definition and higher luminance of color liquid crystal display elements, in an active matrix type liquid crystal display, a color filter on array system (COA system) in which color filters are provided on the TFT element substrate side is used. However, a black matrix on array method (BOA method) in which only the black matrix is formed on the TFT element substrate side has been proposed. According to this method, compared to the case where a black matrix is formed on the color filter side, since there is no need to provide a positioning margin with the active element side, the aperture ratio can be increased, and as a result, high luminance can be achieved. .

However, in the case of 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, a black matrix using a plurality of types of organic color pigments and carbon black as a pigment has been proposed (see Patent Document 1, for example).

In addition, a photosensitive composition for a black matrix using an organic black pigment as a pigment is also known, and specifically, a photosensitive composition using aniline black (see Patent Document 2) or perylene black (see Patent Document 3) It is known.

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

Japanese Unexamined Patent Publication No. 2009-75446 Japanese Unexamined Patent Publication No. 8-44049 Japanese Unexamined Patent Publication No. 2006-235153 Japanese Published Patent Publication No. 2002-528448 Japanese Patent Publication No. 2012-515240

As a result of intensive studies by the present inventors, it was found that the photosensitive composition described in Patent Literature 1 has a low shielding rate (optical density) of organic color pigments, and it is necessary to increase the film thickness in order to obtain a sufficient optical density. .

In addition, it has been found that the aniline black and perylene black described in Patent Literatures 2 and 3 have poor dispersibility and require the use of a large amount of a dispersant to disperse them, resulting in problems such as plateability. there was. Furthermore, it was found that the shielding rate (optical density) was not sufficient.

In addition, Patent Documents 4 and 5 do not describe or suggest the use of a bis-oxodihydro-indolylene-benzofuran colorant as a shielding agent used in an image display device. It is also unclear about its properties, such as optical density, dispersibility and plateability of the stain.

The present invention has been made in view of the above conventional situation, and has as its object to provide a photosensitive coloring composition that is excellent in light-shielding properties, excellent in dispersibility and platemaking properties, and exhibits a sufficiently low dielectric constant.

As a result of the inventors of the present invention conducting intensive studies in order to solve the above problems, they found that the above problems can be solved by using an organic black pigment having a specific structure as the color material in the photosensitive coloring composition and using a specific dispersing agent, and the present came up with an invention.

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

[1] A photosensitive coloring composition containing at least (A) a colorant, (B) a dispersant, (C) an alkali-soluble resin, and (D) a photopolymerization initiator, wherein the (A) colorant is represented by the following general formula A photosensitive coloring composition comprising an organic black pigment which is a compound represented by (1), a geometric isomer thereof, a salt thereof, or a salt of a geometric isomer thereof, and further comprising a polymer dispersant in which the dispersant (B) has a quaternary ammonium base 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 , They may be directly bonded to each other or bonded to each other by an oxygen atom, a sulfur atom, NH or NR ¹¹ bridge; R ¹¹ and R ¹² are each independently an alkyl group of 1 to 12 carbon atoms, a cycloalkyl group of 3 to 12 carbon atoms, an alkenyl group of 2 to 12 carbon atoms, a cycloalkenyl group of 3 to 12 carbon atoms, or an alkynyl group of 2 to 12 carbon atoms. ]

[2] In the above general formula (1),

In the formula, 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, and 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 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 polymeric 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 alkali-soluble resin (C) contains at least one of the following alkali-soluble resin (c1) and the following alkali-soluble resin (c2) .

<Alkali-soluble resin (c1)>

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

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

[6] (A-2) The photosensitive coloring composition according to [5], wherein the organic color 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) relative to 100 mass% of the color material, the content of the organic black pigment (A-1) is 30 to 90 mass%, (A-2) the content of the organic color pigment is 10 to 70 mass% , [5] or the photosensitive coloring composition as described in [6].

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

[9] (A) With respect to 100 mass% of the colorant, the content rate of the organic black pigment (A-1) is 50 to 90 mass%, (A-3) the content rate of carbon black is 10 to 50 mass%, The photosensitive coloring composition described in [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 dispersant, wherein the color material (A) is (A-1) a compound represented by the following general formula (1), a geometric isomer thereof, a salt thereof, or a compound thereof A pigment dispersion liquid containing an organic black pigment that is a salt of a geometric isomer, and further containing a polymeric dispersant in which the dispersant (B) has a quaternary ammonium base group as a functional group.

[Formula 2]

[In the formula, 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 , They may be directly bonded to each other or bonded to each other by an oxygen atom, a sulfur atom, NH or NR ¹¹ bridge; R ¹¹ and R ¹² are each independently an alkyl group of 1 to 12 carbon atoms, a cycloalkyl group of 3 to 12 carbon atoms, an alkenyl group of 2 to 12 carbon atoms, a cycloalkenyl group of 3 to 12 carbon atoms, or an alkynyl group of 2 to 12 carbon atoms. ]

[16] In the above general formula (1),

In the formula, 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, and 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 The same as ⁹ , R ⁵ is the same as R ¹⁰ , the pigment dispersion described in [15].

[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 preparing the pigment dispersion, so that it exhibits excellent plate-making properties and is also excellent in dispersibility. Accordingly, the black matrix formed from the photosensitive coloring composition of the present invention exhibits excellent light-shielding properties. Further, the black matrix and the colored spacer of the present invention exhibit a sufficiently low relative permittivity so as not to cause a short circuit or malfunction even when formed on a TFT element substrate. The image display device having a black matrix of the present invention has no problems such as TFT failure or liquid crystal drive hunting, and is excellent in reliability.

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

EMBODIMENT OF THE INVENTION Hereinafter, although embodiment of this invention is described concretely, this invention is not limited to the following embodiment, Within the range of the summary, it can be variously changed and implemented.

In the present invention, "(meth)acryl" means "acryl and/or methacryl", and the same applies to "(meth)acrylate" and "(meth)acryloyl".

"(Co)polymer" means containing both a homopolymer (homopolymer) and a copolymer (copolymer), and includes "acid (anhydride)", "(anhydride)... "Acid" means containing both an acid and its anhydride. In the present invention, "acrylic resin" means a (co)polymer containing (meth)acrylic acid and a (co)polymer containing (meth)acrylic acid ester having a carboxyl group.

In the present invention, "monomer" is a term relative to so-called high molecular substances (polymers), and is meant to include dimers, trimers, oligomers, and the like in addition to monomers (monomers) in a narrow sense.

In the present invention, "total solid content" shall mean all components other than the solvent contained in the photosensitive coloring composition or in the ink described 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).

Incidentally, in the present invention, "amine value" represents the amine value in terms of effective solid content, unless otherwise specified, and is a value expressed by the amount of base per 1 g of solid content of the dispersant and the mass of equivalent KOH. In addition, the measuring method is mentioned later. On the other hand, "acid value" shows an acid value in terms of effective solid content unless otherwise specified, and is calculated by neutralization titration.

In addition, in this specification, the percentage or part expressed by "mass" has the same meaning as the percentage or part expressed by "weight".

[Photosensitive Coloring Composition]

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

(A) coloring material

(B) dispersant

(C) alkali soluble resin

(D) photopolymerization initiator

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

<(A) coloring material>

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

[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 , They may be directly bonded to each other or bonded to each other by an oxygen atom, a sulfur atom, NH or NR ¹¹ bridge;

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

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

[Formula 4]

When the compound represented by the general formula (1) is anionic, its charge can be transferred to any known suitable cation, for example, a metal, organic, inorganic or metal-organic cation, specifically an alkali metal, an alkaline earth metal, or a transition metal. , primary ammonium, secondary ammonium, tertiary ammonium such as trialkyl ammonium, quaternary ammonium such as tetraalkyl ammonium, or salts compensated with organometallic complexes are preferred. Moreover, when the geometric isomer of the compound represented by General formula (1) is anionic, it is preferable that it is the same salt.

Since there exists a tendency for a shielding rate to become high in the substituent of General formula (1) and their definition, the following is preferable. This is because the following substituents do not absorb and are considered not to affect the hue of the pigment.

R ² , R ⁴ , R ⁵ , R ⁷ , R ⁹ and R ¹⁰ are each independently 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 hydrogen atom or SO ₃ H.

R ¹ and R ⁶ are each independently preferably a hydrogen atom, CH ₃ or CF ₃ , 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 Specifically, R ¹ is the same as R ⁶ , R ² is the same as R ⁷ , R ³ is the same as R ⁸ , R ⁴ is the same as R ⁹ , and R ⁵ is the same as R ¹⁰ .

Examples of the C1-C12 alkyl group include methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, 2-methylbutyl, 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- It is 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 trimethyl group, a norbornyl group, and a bornyl group. , norcaryl group, caryl group, menthyl group, norphinyl group, phynyl 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, a 1,3-butadien-2 -Diyl 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, for example, 2-cyclobuten-1-yl group, 2-cyclopenten-1-yl group, 2-cyclohexen-1-yl group, 3-cyclohexen-1-yl group, 2,4-cyclohexadien-1-yl group, 1-p-menthen-8-yl group, 4(10)-tuzen-10-yl group, 2-norbornen-1-yl group, 2,5-norbornadiene an en-1-yl group, a 7,7-dimethyl-2,4-norcaradien-3-yl group or a camphenyl group.

An alkynyl group having 2 to 12 carbon atoms, 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-pentadiene-3-yl group, 1,3-pentadiene-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-hexadin-5-yl group, 1-octyn-8-yl group, 1-nonin-9-yl group, 1-decyn-10 -Diary or 1-dodecyn-12-yl.

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

The organic black pigment of preferable (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 (registered trademark) Black S 0100 CF (manufactured by BASF) is exemplified as a trade name.

The organic black pigment of (A-1) is preferably used after being dispersed in a dispersing agent or solvent according to the method described below. In addition, when the sulfonic acid derivative of the general formula (2) is present at the time of dispersion, the dispersibility and storage properties may be improved.

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

(A-2) organic color pigments 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) of various colors. Organic pigments may be used. In addition, as the structure, various inorganic pigments in addition to organic pigments such as azo, phthalocyanine, quinacridone, benzimidazolone, isoindolinone, dioxazine, and indanthrene may be used. In addition, in this specification, the color of a pigment means the color shown when a photosensitive coloring composition is formed using the pigment independently as a coloring material, unless otherwise specified. In short, for example, a black pigment means the pigment which the color shown when the photosensitive coloring composition is formed using the said pigment independently as a color material becomes black.

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

As a red pigment,

Among these, preferably C. I. Pigment Red 48: 1, 122, 168, 177, 202, 206, 207, 209, 224, 242, 254, more preferably C. I. Pigment Red 177, 209, 224, 254 can be heard In view of dispersibility and light-shielding properties, it is preferable to use C.I. Pigment Red 177, 254, or 272, and when the photosensitive coloring composition of the present invention is cured with ultraviolet rays, as the red pigment, those with low ultraviolet absorption are used. It is preferable, and from this point of view, it is more preferable to use C. I. Pigment Red 254, 272.

As a blue pigment,

Among these, C. I. Pigment Blue 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6 are preferred, and C. I. Pigment Blue 15: 6 is more preferred. In addition, in terms of dispersibility and light-shielding properties, it is preferable to use C. I. Pigment Blue 15: 6, 16, or 60, and when the photosensitive coloring composition of the present invention is cured with ultraviolet rays, the blue pigment has a low ultraviolet absorption rate. It is preferable to use it, and from this point of view, it is more preferable to use C. I. Pigment Blue 60.

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

As a yellow pigment,

Among these, C. I. Pigment Yellow 83, 117, 129, 138, 139, 150, 154, 155, 180, 185 are preferred, and C. I. Pigment Yellow 83, 138, 139, 150, and 180 are more preferred. there is.

As an orange (orange) pigment,

Among these, C. I. Pigment Orange 38 and 71 are preferable. In view of dispersibility and light-shielding properties, it is preferable to use C. I. Pigment Orange 43, 64, or 72, and when the photosensitive coloring composition of the present invention is cured with ultraviolet rays, as the orange pigment, those having a low ultraviolet absorption rate are used. It is preferable, and from this point of view, it is more preferable to use C. I. Pigment Orange 64, 72.

As a purple pigment, C. I. 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, C. I. Pigment Violet 19 and 23 are preferable, and C. I. Pigment Violet 23 is more preferable. In view of dispersibility and light-shielding properties, it is preferable to use C.I. Pigment Violet 23 or 29, and when the photosensitive coloring composition of the present invention is cured with ultraviolet rays, it is preferable to use those having low ultraviolet absorption as the purple pigment. It is preferable, and from this point of view, it is more preferable to use C. I. Pigment Violet 29.

Among these, it is preferable to use at least one or more 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 color combination 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 blue pigment, an orange pigment, and a purple pigment. A combination etc. are mentioned.

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

Examples of azo dyes include C. I. Acid Yellow 11, C. I. Acid Orange 7, C. I. Acid Red 37, C. I. Acid Red 180, C. I. Acid Blue 29, C. I. Direct Red 28, C. I. Direct Red 83, C. I. Direct Yellow 12, C. I. Direct Orange 26, C. I. Direct Green 28, C. I. Direct Green 59, C. I. Reactive Yellow 2, C. I. Reactive Red 17, C. I. Reactive Red 120, C. I. Reactive Black 5, C. I. Disperse Orange 5, C. I. Disperse Red 58, C. I. Disperse Blue 165, C. I. Basic Blue 41, C. I. Basic Red 18, C. I. Mordant Red 7, C. I. Mordant Yellow 5, C. I. Mordant Black 7 and the like.

Examples of anthraquinone dyes include C. I. Vat Blue 4, C. I. Acid Blue 40, C. I. Acid Green 25, C. I. Reactive Blue 19, C. I. Reactive Blue 49, C. I. Disperse Red 60, C. I. Disperse Blue 56, C. I. Disperse Blue 60 etc. are mentioned.

In addition, as phthalocyanine-based dyes, for example, C. I. Pad Blue 5, etc., as quinoneimine-based dyes, for example, C. I. Basic Blue 3, C. I. Basic Blue 9, etc., as quinoline-based dyes, for example, C. I. Solvent Yellow 33, C. I. Acid Yellow 3, C. I. Disperse Yellow 64, etc. as nitro dyes include, for example, C. I. Acid Yellow 1, C. I. Acid Orange 3, C. I. Disperse Yellow 42 and the like.

Moreover, black pigments other than (A-1) can also be used for the photosensitive coloring composition of this invention. Black pigments other than (A-1) may be used singly or in combination of red, green, blue, or the like. Moreover, these color materials can be suitably selected from inorganic or organic pigments and dyes.

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

In addition, for other pigments that can be mixed and used further, when represented by C. I. numbers, for example, C. I. Yellow Pigment 20, 24, 86, 93, 109, 110, 117, 125, 137, 138, 147, 148, 153, 154, 166, C. I. Orange Pigment 36, 43, 51, 55, 59, 61, C. I. Red Pigment 9, 97, 122, 123, 149, 168, 177, 180, 192, 215, 216, 217, 220, 223, 224, 226, 227, 228, 240, C. I. Violet Pigment 19, 23, 29, 30, 37, 40, 50, C. I. Blue Pigment 15, 15: 1, 15: 4, 22, 60, 64, C. I. Green Pigment 7, C. I. Brown pigment 23, 25, 26 etc. are mentioned.

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

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

Manufactured by Mitsubishi Chemical Corporation:

Manufactured by Degussa:

Manufactured by Cabot:

Manufactured by Columbian Carbon Co.:

As the carbon black, one coated with a resin may be used. When carbon black coated with resin is used, there is an effect of improving adhesion to a glass substrate and volume resistance value. As carbon black coated with resin, the carbon black described in Unexamined-Japanese-Patent No. 09-71733 etc. can be used suitably, for example.

It is preferable that the total content of Na and Ca is 100 ppm or less as the carbon black subjected to the coating treatment with the resin. Carbon black is usually produced from raw material oil, combustion oil (or gas), reaction stop water and granulation water, and Na, Ca, K, Mg, Al, Fe, etc. mixed from the furnace materials of the reaction furnace. The ash with the composition is contained in the order of percent. Among these, it is common that each of Na and Ca is contained in several hundred ppm or more. However, if these are present in large amounts, they may permeate the transparent electrode (ITO) or other electrodes and cause an electrical short circuit.

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

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

Moreover, it is preferable that resin-coated carbon black is so-called acidic carbon black of pH 6 or less. Since the dispersion diameter in water (agglomerate diameter) becomes small, it is possible to coat even microscopic units, which is preferable. In addition, it is preferable that the particle size is 40 nm or less and the dibutyl phthalate (DBP) absorption is 140 ml/100 g or less. When the particle diameter is larger than 40 nm and the DBP absorption amount is larger than 140 ml/100 g, the dispersibility when used as a paste is excellent, but the thickness of the coating film may not be sufficient, and the film thickness is about 1 to 2 μm. This is because there is a risk of shortage.

The method for preparing the carbon black coated with resin is not particularly limited. For example, after appropriately adjusting the amount of carbon black and resin, 1. Mixing the resin with a solvent such as cyclohexanone, toluene, or xylene, and heating A mixture of the dissolved resin solution and a suspension of carbon black and water is mixed and stirred, after separating the carbon black and water, the water is removed, heat-kneaded, and the obtained composition is molded into a sheet shape, pulverized, and then dried. Way ; 2. A method in which the resin solution and suspension prepared in the same manner as above are mixed and stirred to granulate carbon black and resin, and then the obtained granular material is separated and heated 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, add resin thereto and dry how to blend; 4. A suspension is prepared by stirring at high speed a monomer component containing a reactive group constituting the resin to be coated and water, and after polymerization, cooling is performed to obtain a resin containing a reactive group from the polymer suspension. Carbon black is added thereto, kneaded, and carbon A method of reacting black with a reactive group (grafting carbon black), cooling and grinding, and the like can be employed.

The type of resin to be coated is not particularly limited, but synthetic resins are common, and resins having a benzene nucleus in the structure have a stronger action as an amphoteric surfactant, so they are preferable in terms of dispersibility and dispersion stability.

Specific synthetic resins include thermosetting resins such as phenol resins, melamine resins, xylene resins, diallyl phthalate resins, glyptal resins, epoxy resins, and alkylbenzene resins, polystyrene, polycarbonate, polyethylene terephthalate, and polybutylene tere Thermoplastics such as phthalate, modified polyphenylene oxide, polysulfone, polyparaphenylene terephthalamide, polyamideimide, polyimide, polyaminobismaleimide, polyethersulfopolyphenylenesulfone, polyarylate, and polyetheretherketone resin can be used. The coating amount of the resin relative to the carbon black is preferably 1 to 30% by mass relative to the total amount of the carbon black and the resin, and in an amount less than 1% by mass, there is a concern that only the same dispersibility and dispersion stability as that of untreated carbon black can be obtained. there is On the other hand, when it exceeds 30% by mass, the adhesion between the resins is strong, resulting in a dumpling-like lump, and there is a risk that dispersion may not proceed.

Carbon black coated with resin in this way can be used as a light-shielding material for a black matrix by a conventional method, and a color filter containing the black matrix as a component can be produced by a conventional method. If such carbon black is used, a black matrix having a high light-shielding rate and a low surface reflectance and a thin film thickness can be achieved at low cost. It is presumed that this is because the dispersibility and dispersion stability of the carbon black in the resin or solvent constituting the black matrix liquid are remarkably improved. It is also presumed that by coating the carbon black surface with a resin, there is also an effect of blocking Ca or Na in the carbon black.

Further, barium sulfate, lead sulfate, titanium oxide, yellow lead, red ash, chromium oxide and the like can also be used as pigments.

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

Among these various pigments (A-2), pigments particularly preferably used in terms of light-shielding properties as organic color pigments include C. I. Pigment Blue 60, C. I. Pigment Blue 15:6, C. I. Pigment Red 177, C. I. Pigment Red 242, C. I. Pigment Blue 254, C. I. Pigment Violet 23, C. I. Pigment Violet 29, C. I. Pigment Orange 49, C. I. Pigment Orange 64, C. I. Pigment Orange 79. (A-2) When containing an organic color pigment, 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 carbon black (A-3), resin-coated carbon black is preferably used from the point of a volume resistivity or dielectric constant.

These pigments are preferably used after being dispersed so that the average particle diameter is usually 1 µm or less, preferably 0.5 µm or less, and more preferably 0.25 µm or less. Here, the criterion for 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 at a pigment concentration of about 0.005 to 0.2% by mass. However, if there is a concentration recommended by the measuring instrument, it is followed by the concentration), and is measured at 25 ° C. .

<(B) dispersing agent>

In the photosensitive coloring composition of the present invention, since it is important to finely disperse (A) the colorant and stabilize the dispersion state to ensure the stability of quality, (B) a dispersant is included, and in particular (A-1) From the viewpoint of the dispersibility of the organic black pigment, a polymeric dispersant having a quaternary ammonium base as a functional group is included.

The polymeric dispersing agent may further include a carboxyl group in terms of dispersion stability; a phosphoric acid group; sulfonic acid group; or bases thereof; primary, secondary or tertiary amino groups; It may further have a functional group, such as a group derived from nitrogen-containing heterocycles such as pyridine, pyrimidine, and pyrazine. Among them, a primary, secondary or tertiary amino group; A polymeric dispersant further having a basic functional group such as a group derived from a nitrogen-containing heterocyclic ring such as pyridine, pyrimidine, and pyrazine is preferable from the viewpoint of being able to disperse the pigment with a small amount of the dispersant.

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

Moreover, as a polymer dispersing agent, for example, a urethane-type dispersing agent, an acrylic-type dispersing agent, a polyethyleneimine-type dispersing agent, a polyallylamine-type dispersing agent, a dispersing agent consisting of a monomer and a macromonomer having an amino group, a polyoxyethylene alkyl ether-type dispersing agent, polyoxyethylenedi Ester dispersants, polyether phosphoric acid dispersants, polyester phosphoric acid dispersants, sorbitan aliphatic ester dispersants, aliphatic modified polyester dispersants, and the like are exemplified.

Specific examples of such a dispersant include EFKA (registered trademark, manufactured by BASF), DISPERBYK (registered trademark, manufactured by Big Chemie), Disparon (registered trademark, manufactured by Kusumoto Kasei), SOLSPERSE ( (Registered trademark. Lubrizol Co., Ltd.), KP (Shin-Etsu Chemical Co., Ltd.), Polyflow (Kyoeisha Chemical Co., Ltd.), Ajispur (registered trademark. Ajinomoto Co., Ltd.), and the like.

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, in terms of adhesion and linearity, (B) the dispersant preferably contains a functional group-containing urethane polymer dispersant and/or an acrylic polymer dispersant, and particularly preferably contains an acrylic polymer dispersant.

Further, from the viewpoint of dispersibility and preservation, a polymeric dispersant having a basic functional group and having a polyester bond and/or a polyether bond is preferable.

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

If a specific chemical structure is exemplified as a urethane-based polymer dispersant, 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 an active hydrogen and a tertiary amino group in the same molecule A dispersion resin 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 converted to a quaternary ammonium base.

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 Aromatic diisocyanates such as diisocyanate, hexamethylene diisocyanate, lysine methyl ester diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, aliphatic diisocyanates such as dimer acid diisocyanate, isophorone diisocyanate, 4,4'- Methylene bis(cyclohexyl isocyanate), ω,ω'-diisocyanate, alicyclic diisocyanate such as dimethylcyclohexane, xylylene diisocyanate, α,α,α',α'-tetramethylxylylene diisocyanate, etc. aromatic ring Aliphatic diisocyanate having, lysine ester triisocyanate, 1,6,11-undecane triisocyanate, 1,8-diisocyanate-4-isocyanate methyl octane, 1,3,6-hexamethylene triisocyanate, bicycloheptane tri triisocyanates such as isocyanate, tris(isocyanate phenylmethane), and tris(isocyanate phenyl)thiophosphate, trimers thereof, water adducts, and polyol adducts thereof; and the like. As the polyisocyanate, a trimer of organic diisocyanate is preferred, and a trimer of tolylene diisocyanate and isophorone diisocyanate are most preferred. 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 from an isocyanate group using an appropriate trimerization catalyst, for example, tertiary amines, phosphines, alkoxides, metal oxides, carboxylates, etc. After performing trimerization and stopping trimerization by adding a catalyst poison, unreacted polyisocyanate is removed by solvent extraction and thin-film distillation to obtain the target isocyanurate group-containing polyisocyanate. .

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

Examples of the polyether glycol include polyether diols, polyether ester diols, and mixtures of two or more of these. As the polyetherdiol, those obtained by singly or copolymerizing alkylene oxides, for example, polyethylene glycol, polypropylene glycol, polyethylene-propylene glycol, polyoxytetramethylene glycol, polyoxyhexamethylene glycol, polyoxyoctamethylene glycol, and Mixtures of two or more of them are exemplified.

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

As polyester glycol, dicarboxylic acids (succinic acid, glutaric acid, adipic acid, sebacic acid, fumaric acid, maleic acid, phthalic acid, etc.) or their anhydrides 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, neopentylglycol, 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, and 1,9-nonanediol, alicyclic glycols such as bishydroxymethylcyclohexane, and xylylene glycol , aromatic glycols such as bishydroxyethoxybenzene, N-alkyl dialkanolamines such as N-methyldiethanolamine, etc.) obtained by polycondensation, for example, polyethylene adipate, polybutylene adipate, poly Hexamethylene adipate, polyethylene/propylene adipate, etc., or a polylactone diol or polylactone monool obtained by using the diols or a monohydric alcohol having 1 to 25 carbon atoms as an initiator, such as polycaprolactone glycol and polymethyl valerolactone and mixtures of two or more thereof. Most preferable as the polyester glycol is polycaprolactone glycol or polycaprolactone using an alcohol having 1 to 25 carbon atoms as an initiator.

Examples of polycarbonate glycol include poly(1,6-hexylene)carbonatediol and poly(3-methyl-1,5-pentylene)carbonatediol. Examples of polyolefin glycol include polybutadiene glycol, hydrogenated polybutadiene glycol, and 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 having one or two hydroxyl groups in the same molecule is usually 300 to 10,000, preferably 500 to 6,000, and more preferably 1,000 to 4,000.

Compounds having an active hydrogen and a tertiary amino group in the same molecule used in the present invention are described.

Examples of the hydrogen atom directly bonded to an active hydrogen, that is, 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 these, an amino group, particularly a primary amino group hydrogen atom is preferred Do.

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

Examples of such compounds having an active hydrogen and a tertiary amino group in the same molecule include N,N-dimethyl-1,3-propanediamine, N,N-diethyl-1,3-propanediamine, and 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, etc. are mentioned.

In addition, examples of the nitrogen-containing heterocycle in the case where the tertiary amino group has a nitrogen-containing heterocyclic structure include a pyrazole ring, an imidazole ring, a triazole ring, a tetrazole ring, an indole ring, a carbazole ring, an indazole ring, and a benzene ring. Imidazole ring, benzotriazole ring, benzoxazole ring, benzothiazole ring, nitrogen-containing hetero 5-membered ring such as benzothiadiazole ring, pyridine ring, pyridazine ring, pyrimidine ring, triazine ring, quinoline ring , nitrogen-containing hetero 6-membered rings such as an acridine ring and an isoquinoline ring. Among these nitrogen-containing heterocycles, an imidazole ring or a triazole ring is preferable.

Specific examples of 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 -Triazoles are preferred.

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

A preferable blending ratio of raw materials when producing a 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 It is preferably 20 to 190 parts by mass, more preferably 30 to 180 parts by mass, and 0.2 to 25 parts by mass, preferably 0.3 to 24 parts by mass of a compound having an active hydrogen and a tertiary amino group in the same molecule.

The preparation of the urethane-based polymer dispersant is carried out according to a known method for the preparation of polyurethane resins. As the solvent for production, usually 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, secondary 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 dimethyl sulfoxide are used. These may be used individually by 1 type, and may use 2 or more types together.

In the above production, a urethanization reaction catalyst is usually used. Examples of the catalyst include tin-based catalysts such as dibutyltin dilaurate, dioctyltin dilaurate, dibutyltin dioctoate and stannous octoate, iron-based catalysts 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 types.

The introduced amount of the compound having an active hydrogen and a tertiary amino group in the same molecule is preferably controlled within the range of 1 to 100 mgKOH/g based on the amine value after the reaction. More preferably, it is the range of 5-95 mgKOH/g. The amine value is a value obtained by titrating neutralization of a basic amino group with an acid and expressing the number of milligrams of KOH 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 dispersant in the above reaction, it is preferable to further modify the isocyanate group with an alcohol or amino compound because the stability over time of the product is increased.

The weight average molecular weight (Mw) of the urethane-based polymer dispersing agent 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. If this molecular weight is less than 1,000, dispersibility and dispersion stability are inferior, and if it exceeds 200,000, solubility decreases, and if dispersibility is inferior, control of the reaction becomes difficult at the same time.

As the acrylic polymer dispersant, a random copolymer of an unsaturated group-containing monomer having a functional group (the functional group referred to herein is a functional group described above as a functional group contained in the polymer dispersant) 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 known methods.

As the monomer containing an unsaturated group having a functional group, (meth)acrylic acid, 2-(meth)acryloyloxyethylsuccinic acid, 2-(meth)acryloyloxyethylphthalic acid, 2-(meth)acryloyloxyethylhexane 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, and unsaturated monomers having a quaternary ammonium base 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, α-methylstyrene, N-cyclohexylmaleimide, N-phenylmaleimide, N-substituted maleimides such as N-benzylmaleimide, acrylonitrile, vinyl acetate and polymethyl(meth)acryl and macromonomers such as late macromonomers, polystyrene macromonomers, poly 2-hydroxyethyl (meth)acrylate macromonomers, polyethylene glycol macromonomers, polypropylene glycol macromonomers, and polycaprolactone macromonomers. These may be used individually by 1 type, and may use 2 or more types together.

The acrylic polymer dispersant is particularly preferably an A-B or B-A-B block copolymer composed of an A block having a functional group and a B block having no functional group, but in this case, the A block contains a partial structure derived from an unsaturated group-containing monomer containing the functional group, , A partial structure derived from an unsaturated group-containing monomer that does not contain the above functional group may be included, and these may be contained in any mode of random copolymerization or block copolymerization in the A block. Further, the content in the A block of the partial structure not containing a functional group is usually 80% by mass or less, preferably 50% by mass or less, and more preferably 30% by mass or less.

The B block is composed of a partial structure derived from an unsaturated group-containing monomer containing no functional group, but partial structures derived from two or more types of monomers may be contained in one B block, and these may be random copolymerization or It may be contained in any aspect of block copolymerization.

The AB or B-A-B block copolymer is prepared, for example, by a 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 them, the anion living polymerization method is an anionic polymerization active species, and is represented by, for example, 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 greater.

In the radical living polymerization method, the polymerization active species are radicals, and are represented, 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 greater than or equal to 1, R ^a is a hydrogen atom or a monovalent organic group, and R ^b is a hydrogen atom different from R ^a or a monovalent organic group.

When synthesizing this acrylic polymer dispersant, Japanese Unexamined Patent Publication 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, Polymer Journal, 46, 189 (1989) , M. Kuroki, T. Aida, J. Am. Chem. Sic, 109, 4737 (1987), Takuzo Aida, Shohei Inoue, Synthetic Organic Chemistry, 43, 300 (1985), D. Y. Sogoh, W. R. Hertler et al, Macromolecules, 20, 1473 (1987). can do.

The acrylic polymer dispersant that can be used in the present invention may be an A-B block copolymer or a B-A-B block copolymer, and the A block/B block ratio constituting the copolymer is 1/99 to 80/20, particularly 5/95 to 60. /40 (mass ratio) is preferable, and good heat resistance and dispersibility may not be combined outside this range.

In addition, the amount of the quaternary ammonium base in 1 g of the A-B block copolymer and the B-A-B block copolymer usable in the present invention is usually preferably 0.1 to 10 mmol. 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, there are cases where amino groups generated during the production process are usually contained, but the amine value is about 1 to 100 mgKOH/g, and from the viewpoint of dispersibility, it is preferably 10 mgKOH/g or 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 /g or less.

Here, the amine value of dispersants such as these block copolymers is expressed by the amount of base per 1 g of the solid content in the dispersant sample excluding the solvent and the mass of equivalent KOH, and is measured by the following method.

0.5 to 1.5 g of the dispersant sample is precisely weighed in a 100 ml beaker, and dissolved in 50 ml of acetic acid. Using an automatic titrator equipped with a pH electrode, this solution was subjected to neutralization titration with a 0.1 mol/L HClO ₄ acetic acid solution. The inflection point of the titration pH curve is used as the titration end point, and the amine value is obtained by the following formula.

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

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

In addition, 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, but generally the lower one is preferable, 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 polymeric dispersant having a quaternary ammonium salt group as a functional group is not particularly limited, but from the viewpoint of dispersibility, it has a repeating unit represented by the following formula (i) (hereinafter sometimes referred to as "repeating unit (i)") it is desirable

[Formula 8]

In the formula (i), R ³¹ to R ³³ each independently represent a hydrogen atom, an optionally substituted alkyl group, an optionally substituted aryl group, or an optionally substituted aralkyl group, and among R ³¹ to R ³³ Two or more may be bonded to 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 number of carbon atoms in the alkyl group which may have a substituent in R ³¹ to R ³³ in the formula (i) is not particularly limited, but is usually 1 or more, preferably 10 or less, and more preferably 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, an octyl group, and the like, and among these, 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 it is a methyl group, an ethyl group, a propyl group, or a butyl group. Moreover, either a linear form or a branched form may be sufficient. Moreover, you may include cyclic structures, such as a cyclohexyl group and a cyclohexylmethyl group.

The number of carbon atoms in the aryl group which may have a substituent in R ³¹ to R ³³ in the formula (i) is not particularly limited, but is usually 6 or more, preferably 16 or less, and more preferably 12 or less. 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, an anthracenyl group, and the like, and among these, 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 number of carbon atoms in the aralkyl group which may have a substituent in R ³¹ to R ³³ in the formula (i) is not particularly limited, but is usually 7 or more, preferably 16 or less, and more preferably 12 or less. Specific examples of the aralkyl group include a phenylmethylene group, a phenylethylene group, a phenylpropylene group, a phenylbutylene group, and a phenylisopropylene group. Among these, a phenylmethylene group, a phenylethylene group, a phenylpropylene group, or a phenyl It is preferably a butylene group, and more preferably a phenylmethylene group or a phenylethylene group.

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

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

[Formula 9]

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

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

Examples of substituents that the alkyl, aralkyl or aryl groups in R ³¹ to R ³³ in the formula (i) and R ³⁵ and R ³⁶ in the formula (ii) may have include a halogen atom, an alkoxy group, a benzoyl group, and a hydroxyl group. etc. can be mentioned.

In the above formulas (i) and (ii), examples of the divalent linking group X and Z include an alkylene group of 1 to 10 carbon atoms, an arylene group of 6 to 12 carbon atoms, -CONH-R ⁴³ - group, -COOR ⁴⁴ -Group [provided that R ⁴³ and R ⁴⁴ are a single bond, an alkylene group having 1 to 10 carbon atoms, or an ether group (alkyloxyalkyl group) having 2 to 10 carbon atoms] and the like, preferably -COO-R ⁴⁴ - Ki.

In the above formula (i), Y ⁻ of the counter anion includes Cl ⁻ , Br ⁻ , I ⁻ , ClO ₄ ⁻ , BF ₄ ⁻ , CH ₃ COO ⁻ , PF ₆ ⁻ , and the like.

The content of the repeating unit represented by the formula (i) is not particularly limited, but from the viewpoint of dispersibility, the sum of the content of the repeating unit represented by the formula (i) and the content of the repeating unit represented by the formula (ii) 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, still more preferably 20 mol% or more, and particularly preferably 30 mol% or more.

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

In addition, the content ratio of the repeating unit represented by the formula (ii) in all the 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, more preferably 60 mol% or less, more preferably 40 mol% or less, still more preferably 30 mol% or less, and particularly 25 mol% or less. desirable.

In addition, the polymer dispersant is a repeating unit represented by the following formula (iii) from the viewpoint of enhancing compatibility with binder components such as solvents and improving dispersion stability (hereinafter, it may be referred to as “repeating unit (iii)”) ) is preferred.

[Formula 10]

In the formula (iii), R ⁴⁰ is an ethylene group or a propylene group, R ⁴¹ is an optionally substituted alkyl group, and R ⁴² is a hydrogen atom or a methyl group. n is an integer from 1 to 20;

The number of carbon atoms in the alkyl group which may have a substituent in R ⁴¹ in the formula (iii) is not particularly limited, but is usually 1 or more, preferably 2 or more, more preferably 10 or less, and more preferably 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, an octyl group, and the like, and among these, 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 it is a methyl group, an ethyl group, a propyl group, or a butyl group. Moreover, either a linear form or a branched form may be sufficient. Moreover, you may include cyclic structures, such as a cyclohexyl group and a cyclohexylmethyl group.

Also, n in the above 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.

In addition, the content ratio of the repeating unit represented by the formula (iii) in all the 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 preferably 30 mol% or less, more preferably 20 mol% or less, and still more preferably 10 mol% or less. 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) from the viewpoint of enhancing the compatibility of the dispersant with a binder component such as a solvent and improving dispersion stability (hereinafter referred to as "repeating unit (iv)") It is preferable to have).

[Formula 11]

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

The number of carbon atoms in the alkyl group which may have a substituent in R ³⁸ in the formula (iv) is not particularly limited, but is usually 1 or more, preferably 2 or more, more preferably 4 or more, and preferably 10 or less. , 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, an octyl group, and the like, and among these, 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 it is a methyl group, an ethyl group, a propyl group, or a butyl group. Moreover, either a linear form or a branched form may be sufficient. Moreover, you may include cyclic structures, such as a cyclohexyl group and a cyclohexylmethyl group.

The number of carbon atoms in the aryl group that may have a substituent in R ³⁸ in the formula (iv) is not particularly limited, but is usually 6 or more and preferably 16 or less, more preferably 12 or less, and still more 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, an anthracenyl group, and the like, and among these, 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 number of carbon atoms in the aralkyl group which may have a substituent in R ³⁸ in the formula (iv) is not particularly limited, but is usually 7 or more and preferably 16 or less, more preferably 12 or less, and still more 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. Among these, a phenylmethylene group, a phenylethylene group, a phenylpropylene group, or a phenyl It is preferably a butylene group, and more preferably a phenylmethylene group or a phenylethylene group.

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

As the substituent which the alkyl group in R ³⁸ may have, a halogen atom, an alkoxy group, etc. are mentioned. Moreover, as a substituent which an aryl group or an aralkyl group may have, a chain-like alkyl group, a halogen atom, an alkoxy group, etc. are mentioned. In addition, both linear and branched chain alkyl groups represented by R ³⁸ are included.

Moreover, from a dispersible viewpoint, the content rate of the repeating unit represented by the formula (iv) in all the repeating units of the polymer dispersant is preferably 30 mol% or more, more preferably 40 mol% or more, and 50 mol% or more. More preferably, it is more preferably 80 mol% or less, and more preferably 70 mol% or less.

The polymeric dispersant may have repeating units other than repeating unit (i), repeating unit (ii), repeating unit (iii), and repeating unit (iv). Examples of such repeating units include styrenic monomers such as styrene and α-methylstyrene; (meth)acrylate type monomers such as (meth)acrylic acid chloride; (meth)acrylamide 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 block having an A block having repeating unit (i) and repeating unit (ii) and a B block having no repeating unit (i) and repeating unit (ii), from the viewpoint of higher dispersibility of the polymeric dispersant. It is preferably 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 into the A block but also a tertiary amino group, the dispersing ability of the dispersant unexpectedly tends to be significantly improved. Moreover, it is preferable that the B block has a repeating unit (iii), and it is more preferable to have a repeating unit (iv).

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

Further, repeating units other than 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 above-mentioned (meth)acrylic acid ester monomers. . The content of repeating units other than repeating unit (i) and repeating unit (ii) in A block is preferably 0 to 50 mol%, more preferably 0 to 20 mol%, but these repeating units in A block It is most preferable that it does not contain.

Repeating units other than repeating units (iii) and (iv) may be contained in the B block, and examples of such repeating units include styrenic monomers such as styrene and α-methylstyrene; (meth)acrylate type monomers such as (meth)acrylic acid chloride; (meth)acrylamide 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 repeating units other than repeating unit (iii) and repeating unit (iv) in the B block is preferably 0 to 50 mol%, more preferably 0 to 20 mol%, but these repeating units in the B block It is most preferable that it does not contain.

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

<(C) alkali-soluble resin>

The (C) alkali-soluble resin used in the present invention is not particularly limited as long as it is a resin containing a carboxyl group or a hydroxyl group, and examples thereof include epoxy (meth)acrylate-based resins, acrylic resins, carboxyl-containing epoxy resins, and carboxyl-containing urethanes. resins, novolak-based resins, polyvinylphenol-based resins, and the like, but among these, epoxy (meth)acrylate-based resins and acrylic resins 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, especially the following alkali-soluble resin (c1) and / or alkali-soluble resin (c2) (hereinafter sometimes referred to as "carboxyl group-containing epoxy (meth) acrylate resin") excellent plate making It is preferably used from the point of view of gender.

<Alkali-soluble resin (c1)>

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

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

[Formula 12]

In the above general formula (C1), a represents an average value and represents a number from 0 to 10. R ¹¹¹ represents a hydrogen atom, a halogen atom, an alkyl group of 1 to 8 carbon atoms, a cycloalkyl group of 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.

[Formula 13]

In the above general formula (C2), b represents an average value and represents a number from 0 to 10. R ¹²¹ represents any one of a hydrogen atom, a halogen atom, an alkyl group of 1 to 8 carbon atoms, a cycloalkyl group of 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.

[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, one or more adamantane structures are included in the molecular structure. c represents an integer of 2 or 3;

[Formula 15]

In the general formulas (C3-1) and (C3-2), R ¹³¹ to R ¹³⁴ and R ¹³⁵ to R ¹³⁷ are each independently an adamantyl group which may have a substituent, a hydrogen atom, or a hydrogen atom which may have a substituent. An alkyl group of 1 to 12 carbon atoms or a phenyl group which may have a substituent is shown. * represents a bonding hand.

[Formula 16]

In the above general formula (C4), p and q each independently represent an integer of 0 to 4, and R ¹⁴¹ and R ¹⁴² each independently represent an alkyl group 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 greater than or equal to 0;

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

Examples of the α,β-unsaturated monocarboxylic acid or α,β-unsaturated monocarboxylic acid ester having a carboxyl group include (meth)acrylic acid, crotonic acid, o-, m- or p-vinylbenzoic acid, and (meth)acrylic acid. α-position haloalkyl, alkoxyl, halogen, nitro, monocarboxylic acids such as cyano substituents, 2-(meth)acryloyloxyethylsuccinic acid, 2-(meth)acryloyloxyethyladipic acid, 2- (meth)acryloyloxyethylphthalic 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)acryloyloxypropylmale Acid, 2-(meth)acryloyloxybutylsuccinic 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, or (anhydride) maleic acid to a monomer or hydroxyalkyl (meth)acrylate or pentaerythritol tri(meth)acrylate; (meth)acrylic acid dimer etc. are mentioned.

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

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

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

The amount of 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 to 1 equivalent of the epoxy group of the epoxy resin. to 1.1 equivalents. When the amount of α,β-unsaturated monocarboxylic acid or α,β-unsaturated monocarboxylic acid ester having a carboxyl group is small, the amount of unsaturated group introduced is insufficient, and the subsequent reaction with the polybasic acid and/or its anhydride becomes insufficient. It is also not advantageous that a large amount of epoxy groups remain. 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 substance. In either case, the curing properties tend to deteriorate.

Examples of polybasic acids and/or their anhydrides include maleic acid, succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, pyromellitic acid, trimellitic acid, benzophenone tetracarboxylic acid, methylhexahydrophthalic acid, and endomethylenetetra. One or two or more selected from hydrophthalic acid, chlorendic acid, methyltetrahydrophthalic acid, biphenyltetracarboxylic acid, and anhydrides thereof.

Preferably, it is maleic acid, succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, pyromellitic acid, trimellitic acid, biphenyltetracarboxylic acid, or an anhydride thereof. Particularly preferred 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 its anhydride, and an addition reaction of an α,β-unsaturated monocarboxylic acid or an α,β-unsaturated monocarboxylic acid ester having a carboxyl group to an epoxy resin Under the same conditions, the reaction can be continued to obtain the desired product. The addition amount of the polybasic acid and/or its anhydride component is preferably such that the acid value of the produced carboxyl group-containing epoxy (meth)acrylate resin is in the range of 10 to 150 mgKOH/g, and is preferably 20 to 140 mgKOH/g. It is preferable that it is about 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.

In the case of addition reaction of this polybasic acid and/or its anhydride, polyfunctional alcohols such as trimethylolpropane, pentaerythritol, and dipentaerythritol may be added to introduce a multibranched structure.

The carboxyl group-containing epoxy (meth)acrylate resin is usually a mixture of a polybasic acid and/or its anhydride with 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. After heating obtained by doing In this case, the order of mixing the polybasic acid and/or its anhydride with the polyfunctional alcohol is not particularly limited. By heating, a polybasic acid and/or a polybasic acid and/or a polybasic acid and/or a polybasic acid and/or The anhydride undergoes an addition reaction.

The weight average molecular weight (Mw) in terms of polystyrene measured by gel permeation chromatography (GPC) of the carboxyl group-containing epoxy (meth)acrylate resin 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, solubility in a developing solution is high, and when it is too large, solubility in a developing solution is low.

A 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 a part of the above-mentioned carboxyl group-containing epoxy (meth)acrylate resin with another binder resin, as long as the performance of this invention is not impaired. That is, you may use together the carboxyl group-containing epoxy (meth)acrylate resin and another binder resin. In this case, it is preferable to make the ratio of carboxyl group-containing epoxy (meth)acrylate resin in (C) alkali-soluble resin 50 mass % or more, especially 80 mass % or more.

As long as the performance of the present invention is not impaired, other binder resins that can be used in combination with the carboxyl group-containing epoxy (meth)acrylate resin are not limited, and may be selected from resins commonly used in photosensitive coloring compositions. 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 resins may be used individually by 1 type, or may be used in combination of 2 or more type.

<(D) photopolymerization initiator>

(D) The photopolymerization initiator is a component having a function of directly absorbing light, causing a decomposition reaction or a hydrogen withdrawal reaction, and generating polymerization active radicals. You may add and use additives, such as a polymerization accelerator (chain transfer agent) and a sensitizing dye, as needed.

As a photoinitiator, Metallocene compounds containing the titanocene compound of Unexamined-Japanese-Patent No. 59-152396 and each publication of Unexamined-Japanese-Patent No. 61-151197, for example; Hexaarylbiimidazole derivatives described in Japanese Unexamined Patent Publication 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 Unexamined Patent Publication No. 10-39503 , radical activators such as N-aryl-α-amino acid esters, and α-aminoalkylphenone derivatives; The oxime ester derivative described in Unexamined-Japanese-Patent No. 2000-80068, Unexamined-Japanese-Patent No. 2006-36750, etc. are mentioned.

Specifically, for example, as titanocene derivatives, dicyclopentadienyltitanium dichloride, dicyclopentadienyltitanium bisphenyl, dicyclopentadienyltitanium bis(2,3,4,5,6- pentafluorophenyl-1-yl), dicyclopentadienyltitanium bis(2,3,5,6-tetrafluorophenyl-1-yl), dicyclopentadienyltitanium bis(2,4,6- trifluorophenyl-1-yl), dicyclopentadienyltitaniumdi(2,6-difluorophenyl-1-yl), dicyclopentadienyltitaniumdi(2,4-difluorophenyl-1 -yl), di (methylcyclopentadienyl) titanium bis (2,3,4,5,6-pentafluorophenyl-1-yl), di (methylcyclopentadienyl) titanium bis (2,6- difluorophenyl-1-yl), dicyclopentadienyltitanium [2,6-di-fluoro-3-(pyro-1-yl)-phenyl-1-yl], and the like.

Further, as the 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 imidazole dimer, (4'-methoxyphenyl)-4,5-diphenylimidazole dimer, etc. are mentioned.

Further, as halomethylated oxadiazole derivatives, 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.

Further, 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-ethoxynaphthyl)-4,6-bis(trichloromethyl)-s-triazine Toxycarbonyl naphthyl) -4,6-bis (trichloromethyl) -s-triazine, etc. are mentioned.

Further, as α-aminoalkylphenone derivatives, 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 and ketoxime compounds) are particularly effective in terms of sensitivity and plateability, and when an alkali-soluble resin containing a phenolic hydroxyl group is used, it is disadvantageous in terms of sensitivity. Therefore, oxime derivatives (oxime ester and ketoxime ester compounds) having such excellent sensitivity are particularly useful.

As an oxime type compound, the compound containing the structural part 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 Formula (3), R ²² , each optionally substituted, is selected from an alkanoyl group of 2 to 12 carbon atoms, a heteroarylalkanoyl group of 1 to 20 carbon atoms, an alkenoyl group of 3 to 25 carbon atoms, and a cycloal group of 3 to 8 carbon atoms. Kanoyl group, C3-C20 alkoxycarbonylalkanoyl group, C8-C20 phenoxycarbonylalkanoyl group, C3-C20 heteroaryloxycarbonylalkanoyl group, C2-C10 aminoalkylcarbonyl group, An aryloyl group of 7 to 20 carbon atoms, a heteroaryloyl group of 1 to 20 carbon atoms, an alkoxycarbonyl group of 2 to 10 carbon atoms, or an aryloxycarbonyl group of 7 to 20 carbon atoms.

[Formula 18]

In formula (3a), R ^21a is a hydrogen atom, or an optionally substituted alkyl group of 1 to 20 carbon atoms, an alkenyl group of 2 to 25 carbon atoms, a heteroarylalkyl group of 1 to 20 carbon atoms, or an alkoxycarb group of 3 to 20 carbon atoms. Carbonylalkyl group, C8-C20 phenoxycarbonylalkyl group, C1-C20 heteroaryloxycarbonylalkyl group or heteroarylthioalkyl group, C1-C20 aminoalkyl group, C2-C12 alkanoyl group, C3 Alkenoyl group of 25 to 25, cycloalkanoyl group of 3 to 8 carbon atoms, aryloyl group of 7 to 20 carbon atoms, heteroaryloyl group of 1 to 20 carbon atoms, alkoxycarbonyl group of 2 to 10 carbon atoms, aryloxy group of 7 to 20 carbon atoms A carbonyl group or a cycloalkylalkyl group having 1 to 10 carbon atoms is shown. R ^21b represents an arbitrary substituent containing an aromatic ring or a heterocyclic 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, each of which may have a substituent, a polyethylene group (-(CH=CH) _r -), a polyethynylene group ( -(C≡C) _r -) or a group formed by combining these (in addition, r is an integer of 0 to 3).

In formula (3a), R ^22a is selected from an optionally substituted alkanoyl group of 2 to 12 carbon atoms, a heteroarylalkanoyl group of 1 to 20 carbon atoms, an alkenoyl group of 3 to 25 carbon atoms, and a cycloal group of 3 to 8 carbon atoms. Kanoyl group, alkoxycarbonylalkanoyl group of 3 to 20 carbon atoms, phenoxycarbonylalkanoyl group of 8 to 20 carbon atoms, heteroaryloxycarbonylalkanoyl group of 3 to 20 carbon atoms, aminocarbonyl group of 2 to 10 carbon atoms, carbon atoms An aryloyl group of 7 to 20, a heteroaryloyl group of 1 to 20 carbon atoms, an alkoxycarbonyl group of 2 to 10 carbon atoms, or an aryloxycarbonyl group of 7 to 20 carbon atoms.

As R ²² in the general formula (3) and R ^22a in the general formula (3a), preferably an alkanoyl group having 2 to 12 carbon atoms, a heteroarylalkanoyl group having 1 to 20 carbon atoms, or a carbon number 3 to 8 cycloalkanoyl groups.

Examples of R ^21a in the general formula (3a) include preferably an unsubstituted methyl group, an ethyl group, a propyl group, and a propyl group substituted with an N-acetyl-N-acetoxyamino group.

Moreover, as ^R21b in the said General formula (3a), Preferably, an optionally substituted carbazoyl group, an optionally substituted thioxanthonyl group, and an optionally substituted phenyl sulfide group 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.

As an oxime ester type compound suitable for this invention, although the compound illustrated below is specifically mentioned, It is not limited to these compounds at all.

[Formula 19]

[Formula 20]

An oxime ester initiator having a carbazole group having a nitro group is also effective.

As a ketoxime type compound, the compound containing the structural part 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 above general formula (5), R ^23a is selected from an optionally substituted phenyl group, an alkyl group of 1 to 20 carbon atoms, an alkenyl group of 2 to 25 carbon atoms, a heteroarylalkyl group of 1 to 20 carbon atoms, and an alkoxy group of 3 to 20 carbon atoms. Carbonylalkyl group, phenoxycarbonylalkyl group of 8 to 20 carbon atoms, alkylthioalkyl group of 2 to 20 carbon atoms, heteroaryloxycarbonylalkyl group or heteroarylthioalkyl group of 1 to 20 carbon atoms, aminoalkyl group of 1 to 20 carbon atoms, carbon atoms Alkanoyl group of 2 to 12, alkenoyl group of 3 to 25 carbon atoms, cycloalkanoyl group of 3 to 8 carbon atoms, aryloyl group of 7 to 20 carbon atoms, heteroaryl group of 1 to 20 carbon atoms, heteroaryl group of 2 to 10 carbon atoms An alkoxycarbonyl group, a C7-C20 aryloxycarbonyl group, or a C1-C10 cycloalkylalkyl group is shown.

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

In addition, R ^23a may form a ring together with R ^23b , and the linking group is an alkylene group having 1 to 10 carbon atoms, which each may have a substituent, a polyethylene group (-(CH=CH) _r -), or a polyethynylene group. (-(C≡C) _r -) or a group formed by combining these (in addition, r is an integer of 0 to 3).

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

As R ²⁴ in the general formula (4) and R ^24a in the general formula (5), preferably an alkanoyl group of 2 to 12 carbon atoms, a heteroarylalkanoyl group of 1 to 20 carbon atoms, or a carbon atom of 3 A cycloalkanoyl group of -8, and an aryloyl group of 7-20 carbon atoms are mentioned.

R ^23a in the general formula (5) is preferably an unsubstituted ethyl group, propyl group, or butyl group, or a methoxycarbonyl group-substituted ethyl or propyl group.

Moreover, as ^R23b in the said General formula (5), Preferably, the carbazol 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 (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.

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

[Formula 23]

[Formula 24]

These oxime and ketoxime ester-type compounds are known compounds per se, and are one of a series of compounds described in, for example, Japanese Unexamined Patent Publication No. 2000-80068 and Japanese Unexamined Patent Publication No. 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 photopolymerization initiator in the photosensitive coloring composition of the present invention is usually 0.4 to 15% by mass and preferably 0.5 to 10% by mass relative to the total solid content. When the ratio of the photopolymerization initiator exceeds this range, the developability tends to decrease, while when the ratio is too small, the desired shape of the colored cured product and formation of steps may not be achieved.

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 p-dimethylaminobenzoate ethyl and p-diethylaminobenzoate ethyl; 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.

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

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

[Formula 25]

Here, R ^23a and R ^24a have the same meaning as in the above 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 to 4.

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

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 of 1 to 20 carbon atoms, an arylene group of 6 to 30 carbon atoms, or an arylene alkylene group of 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 to 3.

* represents a bonding hand.

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

To the photopolymerization initiator, if necessary, a sensitizing dye corresponding to the wavelength of the image exposure light source and a polymerization accelerator can be blended for the purpose of increasing the sensitivity. As the sensitizing dye, the xanthene dye described in Japanese Unexamined Patent Publication No. Hei 4-221958 and Japanese Unexamined Patent Publication No. Hei 4-219756, Japanese Unexamined Patent Publication No. Hei 3-239703 and Japanese Unexamined Patent Publication No. Hei 5-289335 A coumarin dye having a heterocyclic ring described above, a 3-ketocoumarin compound described in Japanese Unexamined Patent Publication No. Hei 3-239703 and Japanese Unexamined Patent Publication Hei 5-289335, and a pyrromethene dye described in Japanese Unexamined Patent Publication No. Hei 6-19240 , etc. 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 No., Japanese Unexamined Patent Publication No. 5-107761, Unexamined-Japanese-Patent No. 5-210240, and Japanese Unexamined Patent Publication No. 4-288818, etc. which have a dialkylaminobenzene skeleton are mentioned.

Among these sensitizing dyes, amino group-containing sensitizing dyes are preferred, and compounds having an amino group and a phenyl group in the same molecule are more preferred. Particularly preferred are, for example, 4,4'-dimethylaminobenzophenone, 4,4'-diethylaminobenzophenone, 2-aminobenzophenone, 4-aminobenzophenone, 4,4'-diaminobenzophenone, 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]benzooxazole, 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 and p-dialkylaminophenyl group-containing compounds such as aminophenyl)quinoline, (p-dimethylaminophenyl)pyrimidine, and (p-diethylaminophenyl)pyrimidine. Most preferred among these is 4,4'-dialkylaminobenzophenone.

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 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.

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

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

Examples of such polyfunctional ethylenic monomers include, for example, esters of aliphatic polyhydroxy compounds and unsaturated carboxylic acids; Esters of aromatic polyhydroxy compounds and unsaturated carboxylic acids; and esters obtained by esterification of polyhydric hydroxy compounds such as aliphatic polyhydroxy compounds and aromatic polyhydroxy compounds with unsaturated carboxylic acids and polybasic carboxylic acids.

Esters of the aliphatic polyhydroxy compounds and unsaturated carboxylic acids 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 Esters, methacrylic acid esters in which acrylates of these exemplary compounds are changed to methacrylates, itaconic acid esters in the same manner changed to itaconate, crotonic acid esters changed to crotonate, or maleic acid esters changed to maleate etc. can be mentioned.

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

Esters obtained by the esterification reaction of polybasic carboxylic acids and unsaturated carboxylic acids with polyvalent hydroxy compounds are not necessarily single substances, but typical examples include condensates of acrylic acid, phthalic acid, and ethylene glycol, acrylic acid, and maleic acid. , and condensates of diethylene glycol, condensates of methacrylic acid, terephthalic acid and pentaerythritol, condensates of acrylic acid, adipic acid, butanediol and glycerin, and the like.

Other 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 addition reaction products 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 Industry 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 Co., Ltd.), etc. are mentioned.

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

<Other ingredients of photosensitive coloring composition>

In the photosensitive coloring composition of the present invention, in addition to the components described above, an organic solvent, an adhesion improver such as a silane coupling agent, a coating improver, a development improver, an ultraviolet absorber, an antioxidant, a surfactant, a pigment derivative, and the like can be appropriately blended. .

(1) organic solvent

The photosensitive coloring composition of the present invention is usually composed of (A) a colorant, (B) a dispersing agent, (C) an alkali-soluble resin, (D) a photopolymerization initiator, a photopolymerizable monomer used as necessary, and various other materials. It is used in a dissolved or dispersed state in a solvent.

As an organic solvent, it is preferable to select the thing with a boiling point in the range of 100-300 degreeC. 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, methoxymethyl pentanol, 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, methyl hexyl ketones such as ketones, methyl nonyl ketones, and methoxymethylpentanone;

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 isobutyrate, ethylene glycol acetate, ethyl propionate, propyl propionate, butyl butyrate, isobutyl butyrate, methyl isobutyrate, Ethyl caprylate, butyl stearate, ethyl benzoate, 3-ethoxymethylpropionate, 3-ethoxyethylpropionate, 3-methoxymethylpropionate, 3-methoxyethylpropionate, 3-methoxypropylpropionate, 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; and the like.

Commercially available solvents that correspond to the above include mineral spirits, Barsol #2, Afco #18 solvent, Afco thinner, Socal solvent No.1 and No.2, Solvesso #150, Shell TS28 solvent, Carbitol, Ethyl Carbitol, Butyl Carbitol, Methyl Cellosolve (“Cellosolve” is a registered trademark. The same applies hereinafter), Ethyl Cellosolve, Ethyl Cellosolve Acetate, Methyl Cellosolve Acetate, Diglyme (all trade names), etc. can be heard

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

When forming color filter pixels or black matrices by photolithography, select an organic solvent with a boiling point in the range of 100 to 200°C (under a pressure of 1013.25 [hPa]. Hereinafter, all the boiling points are the same.) It is desirable to do It has a boiling point of 120-170 degreeC more preferably.

Among the above organic solvents, glycolalkyl ether acetates are preferred in terms of good balance in coating properties, surface tension, and the like, and relatively high solubility of constituent components in the composition.

Moreover, although glycol alkyl ether acetates may be used independently, you may use other organic solvents together. As the organic solvent used in combination, glycol monoalkyl ethers are particularly preferred. Especially, propylene glycol monomethyl ether is preferable from the viewpoint of solubility of constituent components in the composition. In addition, since the polarity of glycol monoalkyl ethers is high, and when the addition amount is too large, the pigment tends to aggregate, and the storage stability such as the viscosity of the colored resin composition obtained later increases and the like tends to decrease, the ratio of glycol monoalkyl ethers in the solvent Silver is preferably 5% by mass to 30% by mass, and more preferably 5% by mass to 20% by mass.

Moreover, it is also preferable to use together the organic solvent which has a boiling point of 150 degreeC or more (it may be called a "high boiling point solvent" hereafter). By using such a high boiling point solvent together, the colored resin composition becomes difficult to dry, but there is an effect of preventing the uniform dispersion state of the pigment in the composition from being destroyed by rapid drying. That is, there is an effect of preventing the occurrence of foreign matter defects due to precipitation and solidification of coloring material or the like at the tip of the slit nozzle, for example. 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.

The content of the high boiling point solvent in the organic solvent is preferably from 3% by mass to 50% by mass, more preferably from 5% by mass to 40% by mass, particularly preferably from 5% by mass to 30% by mass. If the amount of the high boiling point solvent is too small, for example, colorant etc. may precipitate and solidify at the tip of the slit nozzle, causing foreign matter defects. There is a concern about causing problems such as tact failure in the vacuum drying process and pin marks in the prebaking process.

Further, the high boiling point solvent having a boiling point of 150°C or higher may be glycol alkyl ether acetates or glycol alkyl ethers.

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

(2) adhesion improver

The photosensitive coloring composition of the present invention may contain an adhesion improver in order to improve adhesion with a substrate. As the adhesion improver, a silane coupling agent, a phosphoric acid group-containing compound, and the like are preferable.

As a kind of silane coupling agent, various things, such as an epoxy type, a (meth)acryl 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-methacryloxypropyl methyl dimethoxysilane and 3-methacryloxypropyl trimethoxysilane, 2-(3,4-epoxycyclohexyl) ) Epoxysilanes such as ethyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-ureidopropyl Although isocyanate silanes, such as ureidosilanes, such as triethoxysilane, and 3-isocyanate propyl triethoxysilane, are mentioned, Especially preferably, they are silane coupling agents of epoxysilanes.

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

[Formula 27]

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

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

(3) surfactant

The photosensitive coloring composition of the present invention may contain a surfactant for improving the coating properties.

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

As such a surfactant, for example, TSF4460 (manufactured by Ji-Toshiba Silicone Co., Ltd.), DFX-18 (manufactured by Neos Co., Ltd.), BYK-300, BYK-325, BYK-330 (manufactured by Big Chemie Co., Ltd.), KP340 (Shin-Etsu Silicone Co., Ltd.) Manufacture), F-470, F-475, F-478, F-559 (manufactured by DIC), SH7PA (manufactured by Toray Silicon Co., Ltd.), DS-401 (manufactured by Daikin Co., Ltd.), L-77 (manufactured by Nippon Unica Co., Ltd.) , FC4430 (made by Sumitomo 3M), etc. are mentioned.

In addition, surfactant may use 1 type, and may use 2 or more types together in arbitrary combinations and ratios.

(4) pigment derivatives

The photosensitive coloring composition of the present invention may contain a pigment derivative as a dispersing aid 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, the phthalocyanine type and a quinophthalone type are preferable.

Substituents of pigment derivatives include sulfonic acid groups, sulfonamide groups and quaternary salts thereof, phthalimidomethyl groups, dialkylaminoalkyl groups, hydroxyl groups, carboxyl groups, amide groups, etc. directly on the pigment backbone, or alkyl groups, aryl groups, heterocyclic groups, etc. What was bonded through it is mentioned, Preferably it is a sulfonic acid group. In addition, these substituents may be substituted in multiple numbers on one pigment skeleton.

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

(5) Photoacid generator

A photoacid generator is a compound capable of generating an acid by ultraviolet rays, and a crosslinking reaction is promoted by the presence of a crosslinking agent such as a melamine compound by the action of an acid generated when exposed to light. Among these photo-acid generators, those having high solubility in solvents, particularly those having high solubility in solvents used for photosensitive coloring compositions are preferred, such as diphenyliodonium, ditolyliodonium, and phenyl(p-anisyl)iodonium. , bis (m-nitrophenyl) iodonium, bis (p-tert-butylphenyl) iodonium, bis (p-chlorophenyl) iodonium, bis (n-dodecyl) iodonium, p-isobutylphenyl (p Diaryl iodonium such as tolyl) iodonium, p-isopropylphenyl (p-tolyl) iodonium, or triaryl sulfonium such as triphenylsulfonium chloride, bromide, boric fluoride salt, or hexafluorophosphate salt , hexafluoroarsenate salt, aromatic sulfonate salt, tetrakis (pentafluorophenyl) borate salt, etc., diphenylphenacylsulfonium (n-butyl) triphenyl borate, etc., sulfonium organic boron complexes, or 2 - Although triazine compounds, such as methyl- 4, 6- bistrichloromethyltriazine and 2-(4-methoxyphenyl) -4, 6-bistrichloromethyltriazine, etc. are mentioned, it is not limited to these.

(6) cross-linking agent

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

[Formula 28]

In formula (6), R ⁶¹ represents a group -NR ⁶⁶ R ⁶⁷ or an aryl group having 6 to 12 carbon atoms, and when R ⁶¹ is a group -NR ⁶⁶ R ⁶⁷ , R ⁶² , R ⁶³ , R ⁶⁴ , R ⁶⁵ , R ⁶⁶ and R ⁶⁷ , and when R ⁶¹ is an aryl group having 6 to 12 carbon atoms, one of R ⁶² , R ⁶³ , R ⁶⁴ and R ⁶⁵ represents a —CH ₂ OR ⁶⁸ group, R ⁶² , R ⁶³ , R ⁶⁴ , The rest of R ⁶⁵ , R ⁶⁶ and R ⁶⁷ independently represent 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, and substituents such as alkyl groups, alkoxy groups, and halogen atoms may be bonded to these phenyl groups and naphthyl groups. Each of the alkyl group and the alkoxy group may have about 1 to 6 carbon atoms. Among the above, the alkyl group represented by R ⁶⁸ is preferably a methyl group or an ethyl group, particularly a methyl group.

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 are included.

[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 group, 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.

In addition, tetramethylolbenzoguanamine, tetramethoxymethylbenzoguanamine, trimethoxymethylbenzo in the guanamine-type compound corresponding to general formula (6), ie, the compound in which ^R61 is aryl in general formula (6) Guanamine, tetraethoxymethylbenzoguanamine and the like are included.

A crosslinking agent having a methylol group or a methylolalkyl 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 (commonly known as N-ethyldimethyloltriazone) or its dimethyl ether form, dimethyloltrimethylene urea or its dimethyl ether form, 3,5-bis(hydroxymethyl) Perhydro-1,3,5-oxadiazin-4-one (commonly known as dimethyloluron) or its dimethyl ether form, tetramethylolglyoxaldiurane or its tetramethyl ether form.

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

(7) Mercapto compounds

A mercapto compound can also be added as a polymerization accelerator and to improve the adhesion to the substrate.

Types of mercapto compounds include 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, 2-mercaptobenzoimidazole, hexanedithiol, decanedithiol, 1,4-dimethylmercaptobenzene, butanediol Bisthiopropionate, butanediol bisthioglycolate, ethylene glycol bisthioglycolate, trimethylolpropane trithioglycolate, butanediol bisthiopropionate, trimethylolpropane trithiopropionate, trimethylolpropane trithioglycolate , Pentaerythritol tetrakithiopropionate, pentaerythritol tetrakithioglycolate, trishydroxyethyl trithiopropionate, ethylene glycol bis (3-mercaptobutylate), butanediol bis (3-mercaptobutyl rate), 1,4-bis (3-mercaptobutyryloxy) butane, trimethylolpropanetris (3-mercaptobutylate), pentaerythritol tetrakis (3-mercaptobutyrate), pentaerythritol tris (3-mercaptobutyrate), ethylene glycol bis (3-mercaptoisobutyrate), butanediol bis (3-mercaptoisobutyrate), trimethylolpropane tris (3-mercaptoisobutyrate) , Mercapto having a heterocyclic ring such as 1,3,5-tris(3-mercaptobutyloxyethyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione compounds or aliphatic polyfunctional mercapto compounds; and the like. These can use various things individually by 1 type or in mixture of 2 or more types.

<Amount of Ingredients in Photosensitive Coloring Composition>

In the photosensitive coloring composition of the present invention, the content of the (A) colorant is usually 10% by mass or more and preferably 20% by mass or more, and usually 50% by mass or less with respect to the total solid content in the photosensitive coloring composition. (A) If the content of the color material 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 formation may not be obtained. Moreover, the content ratio of the organic black pigment (A-1) to 100 mass% of (A) colorant is usually 10 mass% or more, preferably 30 mass% or more, and is usually 100 mass% or less. (A) When the content ratio of the organic black pigment (A-1) in the color material is too small, a sufficient optical density (OD) may not be obtained.

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

In the photosensitive coloring composition of the present invention, (A-3) carbon black may be contained in the color material (A) together with the organic black pigment (A-1). At that time, the content ratio of (A-1) organic black pigment to 100 mass% of (A) colorant is usually 50 mass% or more, preferably 60 mass% or more, and usually 95 mass% or less, preferably 90 mass% below Further, (A-3) the carbon black content is usually 5% by mass or more, preferably 10% by mass or more, and usually 50% by mass or less, preferably 40% by mass or less. (A-3) When the content of carbon black is too large, the volume resistivity value may decrease or the relative permittivity may increase. The content ratio of (A-1) organic black pigment to 100 parts by mass of (A-3) carbon black is usually 100 parts by mass or more, preferably 150 parts by mass or more, and usually 2000 parts by mass or less, preferably 1000 parts by mass or less. below the mass part.

Moreover, the photosensitive coloring composition of this invention WHEREIN: In (A) color material, (A-1) organic color pigment (A-2) and (A-3) carbon black may be contained with organic black pigment. At that time, the content ratio of (A-1) organic black pigment to 100 mass% of (A) colorant is usually 10 mass% or more, preferably 20 mass% or more, and usually 80 mass% or less, preferably 70 mass% below Further, (A-2) the content of the organic color pigment is usually 10% by mass or more, preferably 20% by mass or more, and usually 60% by mass or less, preferably 50% by mass or less. (A-3) The carbon black content is usually 5% by mass or more, preferably 10% by mass or more, and usually 50% by mass or less, preferably 40% by mass or less. In this case, the content ratio of the organic black pigment (A-1) to 100 parts by mass of the organic color pigment (A-2) is usually 15 parts by mass or more, preferably 20 parts by mass or more, and usually 800 parts by mass or less, preferably is 700 parts by mass or less. The content ratio of (A-1) organic black pigment to 100 parts by mass of (A-3) carbon black is usually 40 parts by mass or more, preferably 50 parts by mass or more, and usually 1000 parts by mass or less, preferably 900 parts by mass or less. below the mass part.

(B) The content of the dispersant is usually 1% by mass or more, preferably 3% by mass or more, more preferably 5% by mass or more, and usually 30% by mass or less and 20% by mass or less in the solid content of the photosensitive coloring composition. It is preferable, and 15 mass % or less is especially preferable. In addition, the content of the dispersant (B) is usually 5% by mass or more and particularly preferably 10% by mass or more, and usually 50% by mass or less, and preferably 30% by mass or less, relative to 100% by mass of the colorant (A). (B) If the content of the dispersant is too small, sufficient dispersibility may not be obtained, and if the content is too large, the ratio of other components is relatively reduced, and sensitivity, platemaking properties, and the like may be lowered.

(C) The content of the alkali-soluble resin is usually 5% by mass or more, preferably 10% by mass or more, and usually 85% by mass or less, preferably 80% by mass or less, based on the total solid content of the photosensitive coloring composition of the present invention. . (C) When the content of the alkali-soluble resin is remarkably small, the solubility of the unexposed portion in the developing solution is lowered, and it becomes easy to cause developing defects. Conversely, when the content of (C) alkali-soluble resin is too large, the permeability of the developing solution to the exposed portion tends to increase, and the sharpness and adhesion of pixels may decrease.

(D) The content of the photopolymerization initiator is usually 0.1% by mass or more, preferably 0.5% by mass or more, more preferably 1% by mass or more, and usually 15% by mass or less with respect to the total solid content of the photosensitive coloring composition of the present invention. , Preferably it is 10 mass % or less. (D) When the content of the photopolymerization initiator is too small, a decrease in sensitivity may be caused. On the contrary, when the content is too large, the solubility of the unexposed portion in the developing solution is reduced and development defects are likely to be caused.

(D) When a polymerization accelerator is used together with a photopolymerization initiator, the content of the polymerization accelerator is preferably 0.05% by mass or more, and usually 10% by mass or less, preferably 10% by mass or less, based on the total solid content of the photosensitive coloring composition of the present invention. 5% by mass or less, and the polymerization accelerator is preferably used in an amount of usually 0.1 to 50 parts by mass, particularly 0.1 to 20 parts by mass, based on 100 parts by mass of the (D) photopolymerization initiator.

(D) If the blending ratio of the photopolymerization initiator-based component consisting of a photopolymerization initiator and a polymerization accelerator is remarkably low, it may cause a decrease in sensitivity to exposure light, and conversely, if it is remarkably high, the developer of the unexposed part The solubility to the coating is lowered, which may cause developing defects.

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

When using a photopolymerizable monomer, its content is usually 30 mass % or less with respect to the total solid content of the photosensitive coloring composition, Preferably it is 20 mass % or less. When the content of the photopolymerizable monomer is too large, the permeability of the developing solution to the exposed portion increases, and it may be difficult to obtain a good image. Moreover, the lower limit of content of a photopolymerizable monomer is 1 mass % or more normally, Preferably it is 5 mass % or more.

When using an adhesion improver, its content is usually 0.1 to 5% by mass, preferably 0.2 to 3% by mass, more preferably 0.4 to 2% by mass with respect to the total solid content in the photosensitive coloring composition. When the content of the adhesion improver is less than the above range, the effect of improving adhesion may not be sufficiently obtained.

In the case of using a surfactant, the content thereof is usually 0.001 to 10% by mass, preferably 0.005 to 1% by mass, more preferably 0.01 to 0.5% by mass, most preferably 0.01 to 0.5% by mass based on the total solid content in the photosensitive coloring composition. It is 0.03-0.3 mass %. If the content of the surfactant is less than the above range, there is a possibility that the smoothness and uniformity of the coating film cannot be expressed, and if it is too large, the smoothness and uniformity of the coating film cannot be expressed, and other characteristics may deteriorate.

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

<Physical properties of photosensitive coloring composition>

The photosensitive coloring composition of the present invention can be preferably used for forming a black matrix, and from this point of view, it is preferable to exhibit a black color, and the optical density (OD) per 1 μm of film thickness of the coating film is preferably 1.0 or more.

<Method for producing photosensitive coloring composition>

The photosensitive coloring composition (hereinafter sometimes referred to as "resist") of the present invention is prepared in accordance with a conventional method.

Usually, it is preferable to carry out dispersion treatment of (A) the coloring material in advance using a paint conditioner, sand grinder, ball mill, roll mill, stone mill, jet mill, homogenizer or the like. Since the colorant (A) is finely divided by the dispersion treatment, the coating properties of the resist are improved.

The dispersion treatment is preferably carried out in a system in which a part or all of (A) a colorant, an organic solvent, (B) a dispersant, and (C) an alkali-soluble resin are used in combination (hereinafter, a mixture used for dispersion treatment, And the composition obtained by the treatment is sometimes referred to as "ink" or "pigment dispersion"). In particular, use of a polymeric dispersant as the dispersant (B) is preferable because the resulting ink and resist thicken over time (excellent in dispersion stability).

In this way, in the step of producing a resist, it is preferable to prepare a pigment dispersion containing at least (A) a color material, an organic solvent, and (B) a dispersant. As the (A) colorant, organic solvent, and (B) dispersant that can be used for the pigment dispersion, those described as those that can be used for the photosensitive coloring composition can be preferably employed.

Further, when a dispersion treatment is performed on a liquid containing all components to be blended in the colored resin composition, there is a possibility that the highly reactive component is denatured due to heat generated during the dispersion treatment. Therefore, it is preferable to carry out the dispersion treatment in a system containing a polymeric dispersant.

When dispersing (A) the coloring material with a sand grinder, glass beads or zirconia beads having a diameter of about 0.1 to 8 mm are preferably used. As for the dispersion treatment conditions, the temperature is usually in the range of 0°C to 100°C, preferably room temperature to 80°C. The dispersing time is appropriately adjusted since the appropriate time differs depending on the composition of the liquid and the size of the dispersing treatment device. The goal of dispersion is to control the gloss of the ink so that the 20 degree specular gloss of the resist (JIS Z8741) is in the range of 50 to 300. When the gloss of the resist is low, the dispersion treatment is not sufficient and coarse pigment (colorant) particles often remain, which may result in insufficient developability, adhesion, resolution, and the like. In addition, if the 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, so the dispersion stability tends to be rather impaired.

In addition, the dispersion particle size 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 form a uniform solution. In the resist manufacturing process, since fine dust is often mixed into the liquid, it is preferable to filter the resulting resist with a filter or the like.

[cured material]

A cured product can be obtained by curing the photosensitive coloring composition of the present invention. A cured product formed by curing the photosensitive coloring composition can be suitably used as a black matrix or 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 the support for forming the black matrix, the material is not particularly limited as long as it has adequate strength. A transparent substrate is mainly used, but as a material, for example, a sheet made of a polyester-based resin such as polyethylene terephthalate, a polyolefin-based resin such as polypropylene or polyethylene, or a thermoplastic resin sheet such as polycarbonate, polymethyl methacrylate, or polysulfone. , thermosetting resin sheets such as epoxy resins, unsaturated polyester resins, and poly(meth)acrylic resins, or various types of glass. Among these, from a viewpoint of heat resistance, glass and heat-resistant resin are preferable. In some cases, a transparent electrode such as ITO or IZO is formed on the surface of the substrate. Other than the transparent substrate, it can also be formed on a TFT array.

The support may be subjected to corona discharge treatment, ozone treatment, silane coupling agent, thin film formation treatment of various resins such as urethane-based resin, etc., as necessary, in order to improve surface properties such as adhesiveness.

The thickness of the transparent substrate is usually in the range of 0.05 to 10 mm, preferably in the range of 0.1 to 7 mm. Further, when performing thin film formation treatment of various resins, the film thickness is usually in the range of 0.01 to 10 µm, preferably 0.05 to 5 µm.

(2) Black Matrix

In order to form the black matrix of the present invention with the above-described photosensitive coloring composition of the present invention, the photosensitive coloring composition of the present invention is applied onto a transparent substrate, dried, and then a photomask is placed on the photosensitive coloring composition. A black matrix is formed through image exposure, image development, and heat-curing or photo-curing as needed through a photomask.

In addition, the black matrix of the present invention is effective for forming on a TFT element substrate, but its configuration is not particularly limited in each of COA and BOA systems, and it is possible to respond to various configurations.

(3) formation of black matrix

(3-1) Application of photosensitive coloring composition

Coating of the photosensitive coloring composition for a black matrix onto a transparent substrate can be performed by a spinner method, a wire bar method, a flow coating method, a die coating method, a roll coating method, or a spray coating method. Among them, the die coating method is preferable from a comprehensive viewpoint, in that the amount of the coating solution used is significantly reduced, there is no influence of mist or the like that adheres when the spin coating method is applied, and the generation of foreign substances is suppressed.

If the thickness of the coating film is too thick, pattern development may be difficult, and gap adjustment in the liquid crystal cell forming step may be difficult. . The thickness of the coated film, as the film thickness after drying, is usually preferably in the range of 0.2 to 10 µm, more preferably in the range of 0.5 to 6 µm, and still more preferably in the range of 1 to 4 µm.

(3-2) Drying of the coating film

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

The higher the drying temperature, the better the adhesion of the coating film to the transparent substrate, but if it is too high, (C) the alkali-soluble resin is decomposed, causing thermal polymerization, which may cause developing defects. In addition, the drying process of this coating film may be a reduced pressure drying method in which drying is performed in a reduced pressure chamber without raising the temperature.

(3-3) Exposure

Image exposure is performed by overlapping a negative mask pattern on the coating film of the photosensitive coloring composition and irradiating a light source of ultraviolet rays or visible rays through the mask pattern. At this time, exposure may be performed after forming an oxygen barrier layer such as a polyvinyl alcohol layer on the photopolymerizable coating film, if necessary, in order to prevent a decrease in the sensitivity of the photopolymerizable layer due to oxygen. A light source used for the image exposure is not particularly limited. As the light source, for example, a lamp light source such as a xenon lamp, a halogen lamp, a tungsten lamp, a high-pressure mercury lamp, an ultra-high pressure mercury lamp, a metal halide lamp, a medium-pressure mercury lamp, a low-pressure mercury lamp, a carbon arc, a fluorescent lamp, an argon ion laser, a YAG laser, 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, an image is formed on a substrate by subjecting a coating film of a photosensitive coloring composition to image exposure using the light source, and then developing using an organic solvent or an aqueous solution containing a surfactant and an alkaline compound. can be formed and produced. This aqueous solution may further contain an organic solvent, buffer, complexing agent, dye or pigment.

As the alkaline compound, 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. 2 or more types of mixtures 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, alkyl Anionic surfactants, such as benzene sulfonates, alkylnaphthalene sulfonates, alkyl sulfates, alkyl sulfonates, and sulfosuccinic acid ester salts; and amphoteric surfactants, such as alkyl betaines and amino acids.

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 alone or in combination with an aqueous solution.

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

(3-5) Heat curing treatment

The substrate after development is subjected to a thermal curing treatment or a photo curing treatment, preferably a thermal curing treatment. Regarding the thermal curing treatment conditions at this time, the temperature is selected from the range of 100 to 280°C, preferably from 150 to 250°C, and the time is selected from the range of 5 to 60 minutes.

The line width of the black matrix formed as described above is usually 3 to 50 μm, preferably 4 to 30 μm, and the height is usually 0.5 to 5 μm, preferably 1 to 4 μm. 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 μm of thickness is 1.2 or more, preferably 1.5 or more, more preferably 1.8 or more, and usually 4.0 or less. Here, the optical density (OD) is a value measured by the method described later.

[Colored Spacer]

The photosensitive coloring composition of this embodiment can also be used as a resist for colored spacers other than a black matrix. When a spacer is used for a TFT-type LCD, the TFT as a switching element may malfunction due to light incident on the TFT, and a colored spacer is used to prevent this, for example, Japanese Unexamined Patent Publication No. 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 colored spacer mask.

[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, but a liquid crystal display device described later, an organic EL (Electro Luminesence) display, and the like are exemplified.

[liquid crystal display device]

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

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 as necessary, ITO, IZO, etc. It forms a transparent electrode of and is used as a part of parts such as color displays and liquid crystal display devices. Moreover, in some applications, such as a planar alignment drive system (IPS mode), there are cases where a transparent electrode is not formed.

In a liquid crystal display device, an alignment film is usually formed on a color filter, spacers are spread on the alignment film, or photo spacers are formed, and then bonded to a counter substrate to form a liquid crystal cell. Liquid crystal is injected into and connected to the opposite electrode to complete. As the alignment film, a resin film such as polyimide is preferable. For formation of the alignment film, a gravure printing method and/or a flexographic printing method is usually employed, and the thickness of the alignment film is several tens of nm. After curing the alignment film by thermal firing, the surface is treated by irradiation of ultraviolet rays or treatment with a rubbing cloth, and the surface is processed into a surface state in which the inclination of the liquid crystal can be adjusted.

As long as the black matrix of the present invention is used, there are no particular restrictions on the formation order or formation position of the color pixels or black matrix.

As the spacer, a spacer having a size corresponding to the gap (gap) with the counter substrate is used, and a spacer having a size of usually 2 to 8 μm is preferable. On the color filter substrate, a photo spacer (PS) of a transparent resin film is formed by photolithography, and this may be used instead of the spacer.

Although the bonding gap with a counter substrate differs according to the use of a liquid crystal display device, it is normally selected from the range of 2-8 micrometers. After bonding with the counter substrate, portions other than the liquid crystal inlet are sealed with a sealing material such as an epoxy resin. The sealing material is cured by UV irradiation and/or heating, and the periphery of the liquid crystal cell is sealed.

After the liquid crystal cell sealed around the periphery is cut into panel units, the pressure is reduced in a vacuum chamber, and the liquid crystal is injected into the liquid crystal cell by immersing the liquid crystal injection hole in the liquid crystal and leaking the inside of the chamber. The degree of pressure reduction in the liquid crystal cell is usually 1 × 10 ^-2 to 1 × 10 ^-7 Pa, but preferably 1 × 10 ^-3 to 1 × 10 ^-6 Pa. Moreover, it is preferable to heat the liquid crystal cell at the time of pressure reduction, and the warming temperature is 30-100 degreeC normally, More preferably, it is 50-90 degreeC. The temperature maintenance at the time of pressure reduction 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 into which liquid crystal is injected with a UV curable resin in which the liquid crystal injection port is cured.

The type of the liquid crystal is not particularly limited, and conventionally known liquid crystals such as aromatic, aliphatic, and polycyclic compounds may be any of lyotropic liquid crystals and thermotropic liquid crystals. Although nematic liquid crystals, smectic liquid crystals, cholesteric liquid crystals, and the like are known as thermotropic liquid crystals, any of them may be used.

[Organic EL display]

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

When producing an organic EL display using the black matrix of the present invention, as shown in Fig. 1, for example, a pattern (ie, pixels 20, and a black matrix (not shown) formed between adjacent pixels 20 is produced, and an organic light emitting element ( 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 the present invention. As a method of laminating the organic light emitting body 500, 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 are formed on the upper surface of the color filter. ) in order, a method of bonding the organic light emitting body 500 formed on another substrate onto 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" (Ohm Corporation, published on August 20, 2004, by Shizuo Tokito, Chihaya Adachi, and Hideyuki Murata). An organic EL display can be produced.

In addition, the black matrix of the present invention can be applied to both a passive driving type organic EL display and an active driving type organic EL display.

Example

Next, the present invention will be described in more detail by way of synthetic examples, examples and comparative examples, but the present invention is not limited to the following examples unless the gist thereof is exceeded.

Components of the photosensitive coloring composition used in the following Examples and Comparative Examples are as follows.

<(A-1) organic black pigment>

Irgaphor (registered trademark) Black S 0100 CF manufactured by BASF (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>

145 parts by mass of propylene glycol monomethyl ether acetate was stirred while substituting with nitrogen, and the temperature was raised to 120°C. To this, 10 parts by mass of styrene, 85.2 parts by mass of glycidyl methacrylate, and 66 parts by mass of monoacrylate (FA-513M manufactured by Hitachi Chemical Co., Ltd.) having a tricyclodecane skeleton were added dropwise thereto, and 2,2'-azobis- 8.47 parts by mass of 2-methylbutyronitrile was added dropwise over 3 hours, and stirring was continued at 90°C for 2 hours. Next, the inside of the reaction vessel was replaced with air substitution, 0.7 mass part of trisdimethylaminomethylphenol and 0.12 mass part of hydroquinone were introduced to 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 part of triethylamine were added, and it was made to react at 100 degreeC for 3.5 hours. The weight average molecular weight Mw of alkali-soluble resin-I obtained in this way measured by GPC was about 8400, and the acid value was 80 mgKOH/g.

<Alkali Soluble Resin-II>

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

<Alkali-soluble resin-III>

[Formula 31]

50 g of the above structured epoxy compound (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 added to a flask equipped with a thermometer, stirrer and cooling tube. , and reacted at 90°C while stirring until the acid value became 5 mgKOH/g or less. The reaction required 12 hours to obtain an epoxy acrylate solution.

25 parts by mass of the 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 as to have a solid content of 50% by mass, acid value 131 mgKOH / g, polystyrene conversion weight average molecular weight (Mw) of 4000 carboxyl group-containing epoxy 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 Big Chemie Co., Ltd. (an acrylic A-B block copolymer consisting of 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. Amine value: 70 mg KOH/g. The acid value is 1 mgKOH/g or less.)

The content ratios of the repeating units of the following formulas (1a), (2a), and (3a) in all the 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 Big Chemie Co., Ltd. (acrylic A-B block copolymer consisting of an A block having a quaternary ammonium base group in the side chain and a B block having no quaternary ammonium base group)

<Dispersant-III>

"EFKA-4300" manufactured by EFKA (an acrylic polymer dispersant having a tertiary amino group and a butyl group in the side chain. It does not have a quaternary ammonium base group in the side chain.)

＜Pigment derivatives＞

"Solsperse12000" made 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-necked flask under a nitrogen atmosphere. After cooling this at 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 added little by little to ice water (400 ml). 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 an evaporator to obtain compound 2 (2.13 g, crude yield: 100%). This was used for the next reaction without purification.

[Formula 34]

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

The organic layer was washed with a saturated aqueous sodium hydrogencarbonate solution and a saturated aqueous sodium chloride solution in that order, and dried over anhydrous magnesium sulfate. After filtering anhydrous magnesium sulfate, the solvent was distilled off with an evaporator to obtain compound 3 (1.72 g, crude yield 78%). This was used for the next reaction without purification.

[Formula 35]

Compound 3 (1.00 g, 2.26 mmol) and methylene chloride (10 mL) were put in a 50 mL three-necked flask under a nitrogen atmosphere, and cooled at 10°C. 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 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 pale yellow solid (0.88 g) was obtained. This was recrystallized and purified with toluene (3.5 ml) to obtain compound 4 (0.45 g, 42% yield).

[Formula 36]

Compound 4 (3.50 g, 7.44 mmol) and methylene chloride (35 mL) were put in a 50 mL three-necked flask under nitrogen atmosphere, and cooled at 4°C. To this was added triethylamine (1.50 g, 14.9 mmol). 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, washed with a saturated aqueous sodium hydrogencarbonate solution and a saturated aqueous sodium chloride solution in that order, and dried over anhydrous magnesium sulfate. After filtering anhydrous magnesium sulfate, the solvent was distilled off with the evaporator, and the yellow oily substance (3.65g) was obtained. This was purified by column chromatography (ethyl acetate/hexane = 1/1) to obtain compound 5 (3.12 g, yield 82%, photopolymerization initiator-I). The chemical shift of compound 5 is shown below.

<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>

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

<Surfactant-I>

Mega Pack F-559 manufactured by DIC Co., Ltd.

<Preparation of Pigment Dispersion-1 to 7>

The pigments, dispersants, dispersing aids, alkali-soluble resins, and solvents shown in Table 1 were mixed in a mass ratio shown in Table 1. This solution was subjected to dispersion treatment in the range of 25 to 45°C for 3 hours with a paint shaker. As beads, 0.5 mmφ zirconia beads were used, and 2.5 times the mass of the dispersion liquid was added. After completion of the dispersion, the beads and the dispersion were separated by a filter to prepare Pigment Dispersions-1 to 7.

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

<Coated carbon black dispersion>

Carbon black was manufactured by a conventional oil furnace method. However, ethylene bottom oil with a small amount of Na, Ca, and S was used as raw material oil, 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 at 5,000 to 6,000 rpm for 30 minutes using a homomixer together with 14500 g of pure water to obtain a slurry. This slurry was transferred to a vessel with a screw-type stirrer, and 600 g of toluene in which 60 g of epoxy resin "Epicoat 828" (manufactured by Mitsubishi Chemical Corporation) was dissolved was added in small portions while mixing at about 1,000 rpm. In about 15 minutes, the total amount of carbon black dispersed in water migrated to the toluene side and became about 1 mm grains.

Next, after draining water with a 60-mesh wire mesh, it was placed in a vacuum dryer and dried at 70°C for 7 hours to completely remove toluene and water.

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

This was thoroughly stirred with a stirrer, and premixing was performed. Next, dispersion treatment was performed in the range of 25 to 45°C for 6 hours with a paint shaker. As beads, the same mass as the dispersion liquid was added using 0.5 mmφ zirconia beads. After completion of the dispersion, the beads and the dispersion were separated by a filter and prepared.

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

Using the above-prepared pigment dispersion and coated carbon black dispersion, each component was added so that the proportion in the solid content was the blending ratio shown in Table 2, and PGMEA was further added so that the solid content was 17% by mass, stirred and dissolved, and photosensitivity was obtained. A coloring composition was prepared. In Examples 1 to 8 and Comparative Examples 1, 2 and 4, the pigment concentration in the solid content was 40% by mass, and in Comparative Example 3, the pigment concentration in the solid content was 30% by mass. In addition, in all the photosensitive coloring compositions, the mass ratio of the alkali-soluble resin (including the resin in the dispersion) to the photopolymerizable monomer is 3, the photopolymerization initiator is 4% by mass in the solid content, the additive is 0.5% by mass, Surfactant was made into 0.1 mass %. Evaluation was performed by the method mentioned later using the obtained photosensitive coloring composition.

[Measurement of Optical Density (OD) per 1 μm]

The prepared photosensitive coloring composition was applied to a glass substrate with a spin coater to a final film thickness of 2 µm, dried under reduced pressure for 1 minute, and then dried at 100°C for 90 seconds with a hot plate. By heating at 230°C for 30 minutes, a resist-coated 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 VertScan(R) 2.0 non-contact surface/layer cross-sectional shape measurement system manufactured by Yoka Systems Co., Ltd. Table 3 shows the optical density (OD) per 1 μm of film thickness.

[Measurement of relative permittivity]

A substrate (substrate-2) was fabricated in the same manner as in the method for producing substrate-1, except that a glass substrate having a chromium-deposited film was used instead of the glass substrate. Using the chromium film of this sample as a main electrode, a gold counter electrode was formed on the resist coating film by vapor deposition. In addition, the relative permittivity at 1 kHz·1 V was measured using "LCR Meter 4284A" manufactured by HP (now Agilent). A result is shown in Table 3.

[Plate Characteristics]

Drying with a hot plate was performed in the same manner as for Substrate-1. This sample was image-exposed with a high-pressure mercury-vapor lamp through a negative-type mask having a straight-line pattern with 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 200 µm. Then, spray development was carried out at a temperature of 25°C using a developing solution having a KOH concentration of 0.05% by mass. The development time was 1.5 times the dissolution time of the unexposed part. The result of the line width of the obtained linear pattern is shown in Table 3. However, when the resists of Comparative Examples 1 and 2 were used, no pattern was obtained even after developing for 10 minutes.

From the comparison between Example 1 and Comparative Examples 1, 2 and 4, it was confirmed that the OD of the substrate obtained from the photosensitive coloring composition of the present invention was higher and the shielding property was higher when the pigment concentration was the same. In Comparative Examples 1 and 2, even if developed for 10 minutes, a linear pattern was not obtained. This is because Comparative Examples 1 and 2 contain perylene black as a pigment, but when dispersing perylene black, it is necessary to use a large amount of dispersant, and it is considered that this adversely affects the plate-making properties. In addition, the larger the value of the line width, the higher the sensitivity. However, by using the organic black pigment (A-1) and the organic color pigment (A-2) in combination, the sensitivity can be increased without significantly lowering the OD. Example 4 and 5.

In Comparative Example 3, the pigment was only coated carbon black and showed a high OD, but it was found that the relative dielectric constant was high. It was confirmed from Examples 6 and 7 that the organic black pigment (A-1) used in the present invention and the carbon black (A-3) can be used together to keep the OD high and the dielectric constant low.

[Dispersity evaluation]

<Preparation of Pigment Dispersion-8 to 11>

The pigments, dispersants, dispersing aids, alkali-soluble resins, and solvents shown in Table 4 were mixed in a mass ratio shown in Table 4. This solution was subjected to dispersion treatment in the range of 25 to 45°C for 3 hours with a paint shaker. As beads, 0.5 mmφ zirconia beads were used, and 2.5 times the mass of the dispersion liquid was added. After completion of the dispersion, the beads and the dispersion were separated by a filter to prepare Pigment Dispersions-8 to 11.

[Example 9 and Comparative Examples 5 to 7]

Using the above-prepared pigment dispersion, each component was added so that the proportion in the solid content was the blending ratio shown in Table 5, and further, PGMEA was added so that the solid content was 17% by mass, stirred and dissolved to prepare a photosensitive coloring composition. .

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

In general, in order to disperse an organic pigment in a photosensitive coloring composition, a basic polymer dispersing agent having a quaternary ammonium salt group and a basic polymer dispersing agent having no quaternary ammonium salt group are treated equally, and it is known that they exhibit equivalent dispersibility. In fact, in Comparative Examples 6 and 7 of Table 5, perylene black, which is an organic black pigment, has no significant difference in viscosity of the photosensitive coloring composition whether dispersant I or dispersant III is used.

Surprisingly, in the photosensitive coloring composition containing the organic black pigment (A-1), from the comparison between Example 9 and Comparative Example 5 in Table 5, by using a polymeric dispersant (dispersant I) having a quaternary ammonium base as a functional group, 4 Compared to the case where a polymeric dispersant (dispersant III) having no quaternary ammonium salt group as a functional group was used, the viscosity of the photosensitive coloring composition was about half, and (A-1) the organic black pigment was uniformly dispersed.

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 using the organic black pigment (A-1) alone as the pigment, but also the practice using the organic black pigment (A-1) and the organic color pigment (A-2) in combination. Examples 3 to 5 and 8, Example 6 in which (A-1) organic black pigment and (A-3) carbon black were used in combination, (A-1) organic black pigment and (A-2) organic color pigment ( A-3) In any of Example 7 in which carbon black was used in combination, the viscosity was equivalent to that of Examples 1 and 2, and the pigment was uniformly dispersed in any photosensitive coloring composition.

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 Japanese Patent Application (Japanese Patent Application No. 2013-198425) filed on September 25, 2013, the contents of which are incorporated herein by reference.

10: transparent support substrate
20: pixels
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 element
500: organic luminous body

Claims (18)

A pigment dispersion containing (A) a color material and (B) a dispersant,
The (A) colorant contains (A-1) an organic black pigment that is a compound represented by the following general formula (1), a geometric isomer thereof, a salt thereof, or a salt of a geometric isomer thereof, and
The (B) dispersant includes a polymer dispersant having a quaternary ammonium base,
The polymeric dispersant is an acrylic block copolymer of AB or BAB, consisting of an A block having a quaternary ammonium base and a tertiary amino group, and a B block having no quaternary ammonium base and tertiary amino group, pigment for photosensitive coloring composition production dispersion.
[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 , They may be directly bonded to each other or bonded to each other by an oxygen atom, a sulfur atom, NH or NR ¹¹ bridge; R ¹¹ and R ¹² are each independently an alkyl group of 1 to 12 carbon atoms, a cycloalkyl group of 3 to 12 carbon atoms, an alkenyl group of 2 to 12 carbon atoms, a cycloalkenyl group of 3 to 12 carbon atoms, or an alkynyl group of 2 to 12 carbon atoms. ] According to claim 1,
In the above 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, and 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 , , R ⁵ is the same as R ¹⁰ , a pigment dispersion for photosensitive coloring composition production. According to claim 1,
The pigment dispersion liquid for producing a photosensitive coloring composition in which the said organic black pigment is a compound represented by the following general formula (2).
[Formula 2]

According to claim 1,
The pigment dispersion liquid for photosensitive coloring composition manufacture in which said (A) color material further contains (A-2) organic color pigment. According to claim 1,
The pigment dispersion liquid for photosensitive coloring composition manufacture in which said (A) color material further contains (A-3) carbon black. According to claim 1,
A pigment dispersion liquid for producing a photosensitive coloring composition, wherein the amount of the quaternary ammonium base in 1 g of the copolymer is 0.1 to 10 mmol. According to claim 1,
The pigment dispersion liquid for producing a photosensitive coloring composition whose amine value of the said copolymer is 1-100 mgKOH/g. According to claim 1,
A pigment dispersion for photosensitive coloring composition production, wherein the amount of the quaternary ammonium base in 1 g of the copolymer is 0.1 to 10 mmol and the amine value is 1 to 100 mgKOH/g. According to any one of claims 1 to 8,
A pigment dispersion liquid for producing a photosensitive coloring composition, which further contains an organic solvent. According to claim 9,
A pigment dispersion liquid for producing a photosensitive coloring composition, wherein the organic solvent contains propylene glycol monomethyl ether acetate. According to any one of claims 1 to 8,
Further (C) a pigment dispersion for photosensitive coloring composition production containing an alkali-soluble resin. A photosensitive coloring composition containing the pigment dispersion for photosensitive coloring composition production according to claim 11 and (D) a photopolymerization initiator. According to claim 12,
A photosensitive colored composition for forming a colored spacer. A cured product obtained by curing the photosensitive coloring composition according to claim 12. A black matrix formed from the cured product according to claim 14. A colored spacer formed from the cured product according to claim 14. An image display device comprising the black matrix according to claim 15. An image display device comprising the colored spacer according to claim 16.

Images