JP7099563B2 - Photosensitive coloring composition, coloring spacer and image display device - Google Patents

Description

The present invention relates to a photosensitive coloring composition, a black matrix, a coloring spacer and an image display device. More specifically, the present invention relates to a photosensitive coloring composition having excellent shielding properties and plate-making properties, and its use.

The black matrix for a liquid crystal display element is used in the liquid crystal display element to prevent light from leaking from between the drive electrodes. Generally, a black matrix is a pattern of a striped or lattice-shaped light-shielding material formed by a photolithography method on a transparent substrate such as glass or a plastic sheet paired with a TFT (Thin Film Transistor) element substrate. be.
Recently, in order to support higher definition and higher brightness of color liquid crystal display elements, in active matrix type liquid crystal displays, a color filter on array method (COA method) in which a color filter is provided on the TFT element substrate side has been used. A black matrix-on-array method (BOA method) in which only the black matrix is provided on the TFT element substrate side has been proposed. According to this method, it is not necessary to take an alignment margin with the active element side as compared with the case of forming a black matrix on the color filter side, so that the aperture ratio can be increased, and as a result, the brightness is increased. Can be planned.

However, when such a structure is adopted, the black matrix has a volume resistivity of a certain level or more and a relative permittivity of a certain level or less so as not to cause a short circuit of an electric circuit even if it is mounted directly on a TFT element. Is required.
As such a black matrix, a black matrix using a plurality of kinds of organic coloring pigments and carbon black as pigments has been proposed (see, for example, Patent Document 1).

Further, a photosensitive composition for a black matrix using an organic black pigment as a pigment is also known, and specifically, aniline black (see, for example, Patent Document 2) or perylene black (see, for example, Patent Document 3) is used. The photosensitive composition that has been used is known.
On the other hand, as an organic pigment, a bis-oxodihydro-indolilen-benzofuran colorant is known (see, for example, Patent Document 4). It is described in this document that the pigment is used to form a red layer, a blue layer and a green layer of a color filter. It is also known that the pigment is also used as an organic black pigment for an electrophoretic display (see, for example, Patent Document 5).

Japanese Patent Application Laid-Open No. 2009-75446 Japanese Patent Application Laid-Open No. 8-44049 Japanese Patent Application Laid-Open No. 2006-235153 Japan Special Table 2002-528448 Japan Special Table 2012-515240 Gazette

As a result of diligent studies by the present inventors, the photosensitive composition described in Patent Document 1 has a low shielding rate (optical density) of the organic coloring pigment, and the film thickness is thick in order to obtain a sufficient optical density. I found that I needed to.
Further, the aniline black and perylene black described in Patent Documents 2 and 3 have poor dispersibility, and it is necessary to use a large amount of dispersant in order to disperse the aniline black and perylene black, which may cause problems in plate-making property and the like. It turned out that there was. In addition, it was found that the shielding rate (optical density) was not sufficient.

Further, there is no description or suggestion in Patent Documents 4 and 5 that the bis-oxodihydro-indolilen-benzofuran colorant is used as a shielding agent used in an image display device, and when it is used as a shielding agent used in an image display device. The characteristics such as optical density, dispersibility and plate-making property of the above are also unknown.
INDUSTRIAL APPLICABILITY The present invention has been made in view of the above-mentioned conventional circumstances, and provides a photosensitive coloring composition having excellent light-shielding property, excellent dispersibility and plate-making property, and exhibiting a sufficiently low relative permittivity. With the goal.

As a result of diligent studies to solve the above problems, the present inventors use an organic black pigment having a specific structure and a specific dispersant as the coloring material in the photosensitive coloring composition. Therefore, they have found that the above problems can be solved, and have reached the present invention.
That is, the present invention has the following configurations [1] to [17].
[1] A photosensitive coloring composition containing at least (A) a coloring material, (B) a dispersant, (C) an alkali-soluble resin, and (D) a photopolymerization initiator, wherein the (A) coloring material is (A-1) The compound represented by the following general formula (1), a geometric isomer thereof, a salt thereof, or an organic black pigment which is a salt of the geometric isomer thereof is contained, and the dispersant (B) is 4 A photosensitive coloring composition containing a polymer dispersant having a primary ammonium base as a functional group.

[In formula (1), R ¹ and R ⁶ are independent hydrogen atoms, CH ₃ , CF ₃ , fluorine atoms or chlorine atoms; R ² , R ³ , R ⁴ , R ⁵ , R ⁷ , R. ⁸ , R ⁹ and R ¹⁰ are independent of each other from hydrogen atom, 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 ; , 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 at least one combination selected from the group consisting of R ⁹ and R ¹⁰ together. They can be directly bonded or bonded to each other by an oxygen atom, a sulfur atom, an NH or NR ¹¹ bridge; R ¹¹ and R ¹² are independent of each other and have an alkyl group having 1 to 12 carbon atoms and 3 to 12 carbon atoms. It is a cycloalkyl group, an alkenyl group having 2 to 12 carbon atoms, a cycloalkenyl group having 3 to 12 carbon atoms, or an alkynyl group having 2 to 12 carbon atoms. ]

[2] In the general formula (1),
In the formula, R ² , R ⁴ , R ⁵ , R ⁷ , R ⁹ and R ¹⁰ are independent hydrogen atoms, fluorine atoms or chlorine atoms, and R ³ and R ⁸ are independent hydrogen atoms, NO. ₂ , OCH ₃ , OC ₂ H ₅ , bromine atom, hydrogen 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 identical to R ⁶ , R ² is identical to R ⁷ , and R ³ is identical to R ⁸ . The photosensitive coloring composition according to [1], wherein R ⁴ is the same as R ⁹ and R ⁵ is the same as R ¹⁰ .
[3] The photosensitive coloring composition according to [1] or [2], wherein the polymer dispersant further has a tertiary amine as a functional group.

[4] The photosensitive resin according to any one of [1] to [3], wherein the (C) alkali-soluble resin contains at least one of the following alkali-soluble resin (c1) and the following alkali-soluble resin (c2). Sexual coloring composition.
<Alkali-soluble resin (c1)>
It was 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 polybasic acid and / or its anhydride. Alkaline-soluble resin.
<Alkali-soluble resin (c2)>
An α, β-unsaturated monocarboxylic acid or an α, β-unsaturated monocarboxylic acid ester having a carboxyl group is added to the epoxy resin, and further reacted with a polyhydric alcohol and a polybasic acid and / or an anhydride thereof. The resulting alkali-soluble resin.

[5] The photosensitive coloring composition according to any one of [1] to [4], wherein the coloring material (A) further contains (A-2) an organic coloring pigment.
[6] The photosensitive coloring composition according to [5], wherein the organic coloring pigment contains at least one of the following pigments.
Blue: Color Index Pigment Blue 60 or 15: 6
Red: Color Index Pigment Red 177, 254, or 272
Purple: Color Index Pigment Violet 23 or 29
Orange: Color Index Pigment Orange 43, 64, or 72
[7] The content of the (A-1) organic black pigment is 30 to 90% by mass, and the content of the (A-2) organic coloring pigment is 10 to 70% by mass with respect to 100% by mass of the (A) coloring material. The photosensitive coloring composition according to [5] or [6].
[8] The photosensitive coloring composition according to any one of [1] to [7], wherein the coloring material (A) further contains (A-3) carbon black.
[9] The content ratio of the (A-1) organic black pigment is 50 to 90% by mass, and the content ratio of the (A-3) carbon black is 10 to 50% by mass with respect to 100% by mass of the (A) coloring material. , [8]. The photosensitive coloring composition.

[10] The photosensitive coloring composition according to any one of [1] to [9], wherein the (D) photopolymerization initiator is an oxime ester initiator and / or a ketooxime 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 including the black matrix according to [12] or the coloring spacer according to [13].
[15] A pigment dispersion containing (A) a colorant and (B) a dispersant, wherein the (A) colorant is (A-1) a compound represented by the following general formula (1). A pigment dispersion containing an organic black pigment which is a geometric isomer, a salt thereof, or a salt thereof, and the dispersant (B) containing a polymer dispersant having a quaternary ammonium base as a functional group.

[In the equation, R ¹ and R ⁶ are independent of each other 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 independent of each other from hydrogen atom, 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} , NO2, NH ₂ , NHR ¹¹ , NR ¹¹ R ¹² , ^{NHCOR 12} , NR ¹¹ COR ¹² , N _{= CH 2 ,} N = CHR ¹¹ , N = CR ¹¹ R ¹² , SH, SR ¹¹ , SOR ¹¹ , SO ₂ R ¹¹ , SO ₃ R ¹¹ , SO ₃ H, SO _3- ^, SO ₂ NH ₂ , SO ₂ NHR ¹¹ or SO ₂ NR ¹¹ R ¹² ; and 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 at least one combination selected from the group consisting of R ⁹ and R ¹⁰ bind directly to each other. , Or an oxygen atom, a sulfur atom, an NH or NR ¹¹ bridge, which can be bonded to each other; R ¹¹ and R ¹² are independent of each other and have an alkyl group having 1 to 12 carbon atoms and a cycloalkyl group having 3 to 12 carbon atoms. , An alkenyl group having 2 to 12 carbon atoms, a cycloalkenyl group having 3 to 12 carbon atoms, or an alkynyl group having 2 to 12 carbon atoms. ]

[16] In the general formula (1),
In the formula, R ² , R ⁴ , R ⁵ , R ⁷ , R ⁹ and R ¹⁰ are independent hydrogen atoms, fluorine atoms, or chlorine atoms, and R ³ and R ⁸ are independent hydrogen atoms. NO ₂ , OCH ₃ , OC ₂ H ₅ , bromine atom, hydrogen 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 identical to R ⁶ , R ² is identical to R ⁷ , and R ³ is identical to R ⁸ . , R ⁴ is the same as R ⁹ , and R ⁵ is the same as R ^10. The pigment dispersion according to [15].
[17] The pigment dispersion liquid according to [15] or [16], wherein the polymer dispersant further has a tertiary amine as a functional group.

Since the photosensitive coloring composition of the present invention contains an organic black pigment having a specific structure, the amount of the dispersant can be reduced at the time of producing the pigment dispersion, so that it exhibits excellent plate-making characteristics and has excellent dispersibility. Is also excellent. Therefore, 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 a malfunction even if they are formed on the TFT element substrate. The image display device having the black matrix of the present invention has no problems such as TFT failure and disturbance of liquid crystal drive, and is excellent in reliability.

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

Hereinafter, embodiments of the present invention will be specifically described, but the present invention is not limited to the following embodiments, and can be variously modified and implemented within the scope of the gist thereof.
In the present invention, "(meth) acrylic" means "acrylic and / or methacrylic", and the same applies to "(meth) acrylate" and "(meth) acryloyl".

The "(co) polymer" means that both a monopolymer (homopolymer) and a copolymer (copolymer) are contained, and "acid (anhydrous)" and "(anhydrous) ... acid" are used. , Means to contain both acids and their anhydrides. Further, in the present invention, the "acrylic resin" means a (co) polymer containing (meth) acrylic acid and a (co) polymer containing a (meth) acrylic acid ester having a carboxyl group.

Further, in the present invention, "monomer" is a term opposite to a so-called polymer substance (polymer), and means that a dimer, a trimer, an oligomer, etc. are included in addition to a monomer (monomer) in a narrow sense. Is.
In the present invention, the "total solid content" means all the components other than the solvent contained in the photosensitive coloring composition or the ink described later.
In the present invention, the weight average molecular weight refers to the polystyrene-equivalent weight average molecular weight (Mw) by GPC (gel permeation chromatography).
Further, in the present invention, the "amine value" represents an amine value in terms of effective solid content, and is a value represented by the amount of base per 1 g of solid content of the dispersant and the equivalent mass of KOH, unless otherwise specified. Is. The measurement method will be described later. On the other hand, the "acid value" represents an acid value in terms of effective solid content unless otherwise specified, and is calculated by neutralization titration.

Further, in the present specification, the percentage or part represented by "mass" is synonymous with the percentage or part represented by "weight".

[Photosensitive coloring composition]
The photosensitive coloring composition of the present invention (hereinafter, may be referred to as "photosensitive coloring composition" or "colored resin composition") is
(A) Coloring material (B) Dispersant (C) Alkaline-soluble resin (D) Photopolymerization initiator is contained as an essential component, and if necessary, an adhesion improver such as an organic solvent or a silane coupling agent is applied. It contains other compounding ingredients such as property improver, development improver, ultraviolet absorber, antioxidant, surfactant, pigment derivative, etc., and usually each compounding component is dissolved or dispersed in an organic solvent. used.

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

[In formula (1), R ¹ and R ⁶ are independent hydrogen atoms, CH ₃ , CF ₃ , fluorine atoms or chlorine atoms; R ² , R ³ , R ⁴ , R ⁵ , R ⁷ , R. ⁸ , R ⁹ and R ¹⁰ are independent of each other from hydrogen atom, 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 ; , 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 at least one combination selected from the group consisting of R ⁹ and R ¹⁰ together. They can be directly bonded or bonded to each other by an oxygen atom, a sulfur atom, an NH or NR ¹¹ bridge; R ¹¹ and R ¹² are independent of each other and have an alkyl group having 1 to 12 carbon atoms and 3 to 12 carbon atoms. It is a cycloalkyl group, an alkenyl group having 2 to 12 carbon atoms, a cycloalkenyl group having 3 to 12 carbon atoms, or an alkynyl group having 2 to 12 carbon atoms. ]
The geometric isomer of the compound represented by the general formula (1) has the following core structure (however, the substituent in the structural formula is omitted), and the trans-trans isomer is probably the most stable. ..

When the compound represented by the general formula (1) is anionic, its charge is charged to any known suitable cation such as metal, organic, inorganic or metallic organic cation, specifically alkali metal or alkaline earth metal. , Transitional metals, tertiary ammonium such as primary ammonium, secondary ammonium, trialkylammonium, quaternary ammonium such as tetraalkylammonium, or salts supplemented with organic metal complexes are preferred. When the geometric isomer of the compound represented by the general formula (1) is anionic, it is preferably a similar salt.

In the substituents of the general formula (1) and their definitions, the shielding rate tends to be high, so the following is preferable. This is because the following substituents are considered to be non-absorbent and do not affect the hue of the pigment.
R ² , R ⁴ , R ⁵ , R ⁷ , R ⁹ and R ¹⁰ are independent of each other, preferably a hydrogen atom, a fluorine atom, or a chlorine atom, and more preferably a hydrogen atom.
R ³ and R ⁸ are independent of each other, preferably hydrogen atom, NO ₂ , OCH ₃ , OC ₂ H ₅ , bromine atom, chlorine atom, CH ₃ , C ₂ H ₅ , N (CH ₃ ) ₂ , N (CH). ₃ ) (C ₂ H ₅ ), N (C ₂ H ₅ ) ₂ , α-naphthyl, β-naphthyl, SO ₃ H or SO _3- ^, more preferably a hydrogen atom or SO ₃ H.

R ¹ and R ⁶ are independent of each other, preferably a hydrogen atom, CH ₃ or CF ₃ , and 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. 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 . It is the same.

The alkyl group having 1 to 12 carbon atoms is, for example, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, an isobutyl group, a tert-butyl group, a 2-methylbutyl group, or 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-ethylhexyl Group, nonyl group, decyl group, undecyl group or 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 tudyl group, a norbornyl group, a boronyl group, or a norcaryl group. , Caryl group, mentyl group, norpinyl group, pinyl group, 1-adamantyl group or 2-adamantyl group.

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

The cycloalkenyl group having 3 to 12 carbon atoms is, for example, 2-cyclobutene-1-yl group, 2-cyclopentene-1-yl group, 2-cyclohexene-1-yl group, 3-cyclohexene-1-yl group, 2 , 4-Cyclohexadiene-1-yl group, 1-p-menten-8-yl group, 4 (10) -thujene-10-yl group, 2-norbornen-1-yl group, 2,5-norbornadiene-1 -Il group, 7,7-dimethyl-2,4-norcaladiene-3-yl group or canphenyl group.

The alkynyl group having 2 to 12 carbon atoms is, for example, 1-propin-3-yl group, 1-butin-4-yl group, 1-pentin-5-yl group, 2-methyl-3-butin-2-yl. Group, 1,4-pentaziin-3-yl group, 1,3-pentadiin-5-yl group, 1-hexin-6-yl group, cis-3-methyl-2-penten-4-in-1-yl Group, trans-3-methyl-2-penten-4-in-1-yl group, 1,3-hexadiin-5-yl group, 1-octin-8-yl group, 1-nonin-9-yl group, It is a 1-decine-10-yl group or a 1-dodecine-12-yl group.

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

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

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

The photosensitive coloring composition of the present invention may contain a coloring material other than (A-1) as the (A) coloring material. As the coloring material, a dye pigment can be used, but the pigment is preferable from the viewpoint of heat resistance, light resistance and the like. In particular, (A-2) organic color pigments and / or (A-3) carbon black are preferably used. In the present specification, the organic coloring pigment is a powder containing an organic compound used for coloring as a component, and means a powder unnecessary for water or oil.

(A-2) Various colors of organic coloring pigments such as blue pigments, green pigments, red pigments, yellow pigments, purple pigments, orange pigments, brown pigments, and black pigments other than (A-1) and (A-3). Organic pigments can be used. Further, as the structure, various inorganic pigments and the like can be used in addition to organic pigments such as azo type, phthalocyanine type, quinacridone type, benzimidazolone type, isoindolenone type, dioxazine type and indanthrone type. In the present specification, the color of the pigment means a color exhibited when a photosensitive coloring composition is formed by using the pigment alone as a coloring material, unless otherwise specified. That is, for example, a black pigment means a pigment whose color is black when a photosensitive coloring composition is formed by using the pigment alone as a coloring material.

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

As the blue pigment, C.I. I. Pigment Blue 1, 1: 2, 9, 14, 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, 16, 17, 19, 25, 27, 28, 29, 33, 35, 36, 56, 56: 1, 60, 61, 61: 1, 62, 63, 66, 67, 68, 71, 72, 73, 74, 75, 76, 78, 79 can be mentioned. Among these, preferably C.I. I. Pigment Blue 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, more preferably C.I. I. Pigment Blue 15: 6 can be mentioned. In terms of dispersibility and light-shielding property, C.I. I. Pigment Blue 15: 6, 16, 60 is preferably used, and when the photosensitive coloring composition of the present invention is cured with ultraviolet rays, it is preferable to use a blue pigment having a low ultraviolet absorption rate. From the point of view, C.I. I. It is more preferable to use Pigment Blue 60.

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

Examples of the orange pigment include C.I. I. Pigment Orange 1, 2, 5, 13, 16, 17, 19, 20, 21, 22, 23, 24, 34, 36, 38, 39, 43, 46, 48, 49, 61, 62, 64, 65, 67, 68, 69, 70, 71, 72, 73, 74, 75, 77, 78, 79 can be mentioned. Among these, preferably, C.I. I. Pigment Oranges 38 and 71 can be mentioned. In terms of dispersibility and light-shielding property, C.I. I. Pigment Orange 43, 64, 72 is preferably used, and when the photosensitive coloring composition of the present invention is cured with ultraviolet rays, it is preferable to use an orange pigment having a low ultraviolet absorption rate, and from this viewpoint. Is C.I. I. It is more preferable to use Pigment Orange 64,72.

As the purple pigment, C.I. 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 can be mentioned. Among these, preferably C.I. I. Pigment Violet 19, 23, more preferably C.I. I. Pigment Violet 23 can be mentioned. In terms of dispersibility and light-shielding property, C.I. I. Pigment Violet 23, 29 is preferably used, and when the photosensitive coloring composition of the present invention is cured with ultraviolet rays, it is preferable to use a purple pigment having a low ultraviolet absorption rate, and from this viewpoint, C .. I. It is more preferable to use Pigment Violet 29.

Among these, it is preferable that the 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
When different color pigments are used in combination, the color combination is not particularly limited, but from the viewpoint of light-shielding property, for example, a combination of a red pigment and a blue pigment, or a combination of a blue pigment, an orange pigment, and a purple pigment. And so on.

Further, a dye may be used in place of the (A-2) organic coloring pigment, and a dye may be used in addition to the (A-2) organic coloring pigment. Examples of dyes that can be used as coloring materials include azo dyes, anthraquinone dyes, phthalocyanine dyes, quinone imine dyes, quinoline dyes, nitro dyes, carbonyl dyes, and methine dyes.
Examples of the azo dye include C.I. I. Acid Yellow 11, C.I. I. Acid Orange 7, C.I. I. Acid Red 37, C.I. I. Acid Red 180, C.I. I. Acid Blue 29, C.I. I. Direct Red 28, C.I. I. Direct Red 83, C.I. I. Direct Yellow 12, C.I. I. Direct Orange 26, C.I. I. Direct Green 28, C.I. I. Direct Green 59, C.I. I. Reactive Yellow 2, C.I. I. Reactive Red 17, C.I. I. Reactive Red 120, C.I. I. Reactive Black 5, C.I. I. Disperse Orange 5, C.I. I. Disperse thread 58, C.I. I. Disperse Blue 165, C.I. I. Basic Blue 41, C.I. I. Basic Red 18, C.I. I. Moldant Red 7, C.I. I. Moldant Yellow 5, C.I. I. Examples include Moldant Black 7.

Examples of the anthraquinone dye include C.I. I. Bat Blue 4, C.I. I. Acid Blue 40, C.I. I. Acid Green 25, C.I. I. Reactive Blue 19, C.I. I. Reactive Blue 49, C.I. I. Disperse thread 60, C.I. I. Disperse Blue 56, C.I. I. Disperse blue 60 and the like can be mentioned.
In addition, as a phthalocyanine dye, for example, C.I. I. Pad Blue 5 and the like can be used as quinoneimine dyes, for example, C.I. I. Basic Blue 3, C.I. I. Basic Blue 9 and the like are used as quinoline dyes, for example, C.I. I. Solvent Yellow 33, C.I. I. Acid Yellow 3, C.I. I. Disperse Yellow 64 and the like can be used as nitro dyes, for example, C.I. I. Acid Yellow 1, C.I. I. Acid Orange 3, C.I. I. Disperse Yellow 42 and the like can be mentioned.

Further, a black pigment other than (A-1) can also be used in the photosensitive coloring composition of the present invention. The black pigment other than (A-1) may be used alone or may be a mixture of red, green, blue and the like. Further, these coloring materials can be appropriately selected from inorganic or organic pigments and dyes.
Coloring materials that can be mixed and used to prepare black coloring materials include Victoria Pure Blue (42595), Auramine O (41000), Cachilon Brilliant Flavin (Basic 13), Rhodamine 6GCP (45160), Rhodamine B (45170). , Safranin OK70: 100 (50240), Eriograusin X (42080), No. 120 / Lionol Yellow (21090), Lionol Yellow GRO (21090), Simler First Yellow 8GF (21105), Benzidine Yellow 4T-564D (21095), Simler First Red 4015 (12355), Lionol Red 7B4401 (15850), Firstgen Blue TGR-L (74160), Lionor Blue SM (26150), Lionor Blue ES (Pigment Blue 15: 6), Lionor Gen Red GD (Pigment Red 168), Lionor Green 2YS (Pigment Green 36), etc. (Note that the numbers in () above mean the color index (CI)).

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

Examples of the black color material that can be used alone include acetylene black, lamp black, bone black, graphite, iron black, aniline black, cyanine black, titanium black, and perylene black.
Further, as a coloring material other than (A-1) organic black pigment, (A-3) carbon black is preferably used from the viewpoint of light shielding rate and image characteristics. Examples of carbon black include the following carbon blacks.

Made by Mitsubishi Chemical Corporation: MA7, MA8, MA11, MA77, MA100, MA100R, MA100S, MA220, MA230, MA600, MCF88, # 5, # 10, # 20, # 25, # 30, # 32, # 33, # 40 , # 44, # 45, # 47, # 50, # 52, # 55, # 650, # 750, # 850, # 900, # 950, # 960, # 970, # 980, # 990, # 1000, # 2200, # 2300, # 2350, # 2400, # 2600, # 2650, # 3030, # 3050, # 3150, # 3250, # 3400, # 3600, # 3750, # 3950, # 4000, # 4010, OIL7B, OIL9B , OIL11B, OIL30B, OIL31B
Made by Degusa: Printex (registered trademark; the same applies hereinafter) 3, Printex3OP, Printex30, Printex30OP, Printex40, Printex45, Printex55, Printex60, Printex75, Printex80, Printex85, Printex90, PrintexA, PrintexA. Ｕ、Ｐｒｉｎｔｅｘ Ｖ、ＰｒｉｎｔｅｘＧ、ＳｐｅｃｉａｌＢｌａｃｋ５５０、ＳｐｅｃｉａｌＢｌａｃｋ３５０、ＳｐｅｃｉａｌＢｌａｃｋ２５０、ＳｐｅｃｉａｌＢｌａｃｋ１００、ＳｐｅｃｉａｌＢｌａｃｋ６、ＳｐｅｃｉａｌＢｌａｃｋ５、ＳｐｅｃｉａｌＢｌａｃｋ４、Ｃｏｌｏｒ Ｂｌａｃｋ ＦＷ１、Ｃｏｌｏｒ Ｂｌａｃｋ ＦＷ２、Ｃｏｌｏｒ Ｂｌａｃｋ ＦＷ２Ｖ、Ｃｏｌｏｒ Ｂｌａｃｋ ＦＷ１８、Ｃｏｌｏｒ Ｂｌａｃｋ ＦＷ１８、Ｃｏｌｏｒ Ｂｌａｃｋ ＦＷ２００、Ｃｏｌｏｒ Ｂｌａｃｋ Ｓ１６０、Ｃｏｌｏｒ Black S170
Manufactured by Cabot Corporation: Monarch (registered trademark; the same applies hereinafter) 120, Monarch280, Monarch460, Monarch800, Monarch880, Monarch900, Monarch1000, Monarch1100, Monarch1300, Monarch1400, Monarch4630, REGAL (registered trademark. REGAL415R, REGAL250, REGAL250R, REGAL330, REGAL400R, REGAL55R0, REGAL660R, BLACK PEARLS480, PEARLS130, VULCAN (registered trademark. Same below) XC72R, ELFTEX (registered trademark) -8. ) 11, RAVEN14, RAVEN15, RAVEN16, RAVEN22RAVEN30, RAVEN35, RAVEN40, RAVEN410, RAVEN420, RAVEN450, RAVEN500, RAVEN780, RAVEN850, RAVEN890H, RAVEN1000, RAVEN1020, RAVEN10 , RAVEN3500, RAVEN5000, RAVEN5250, RAVEN5750, RAVEN7000 Carbon black may be coated with a resin. The use of carbon black coated with resin has the effect of improving the adhesion to the glass substrate and the volume resistance value. As the carbon black coated with the resin, for example, the carbon black described in Japanese Patent Application Laid-Open No. 09-71733 can be preferably used.

The carbon black to be subjected to the coating treatment with the resin preferably has a total content of Na and Ca of 100 ppm or less. Carbon black is usually raw material oil or combustion oil (or gas) at the time of production, reaction stop water or granulation water, Na mixed from the furnace material of the reactor, Ca, K, Mg, Al, Fe. Etc. are contained in the order of percent. Of these, Na and Ca are generally contained in an amount of several hundred ppm or more, respectively, but if they are present in large amounts, they permeate the transparent electrode (ITO) and other electrodes, causing an electrical short circuit. This is because it may become.

As a method for reducing the content of ash containing Na and Ca, carefully selected raw material oil, fuel oil (or gas) and reaction stop water for producing carbon black, which have as little content as possible. This is possible by reducing the amount of alkaline substances added to adjust the structure as much as possible. As another method, there is a method of washing the carbon black produced from the furnace with water, hydrochloric acid or the like to dissolve and remove Na and Ca.

Specifically, when carbon black is mixed and dispersed in water, hydrochloric acid, or hydrogen peroxide solution, and then a sparingly soluble solvent is added to water, the carbon black moves to the solvent side and completely separates from water. Most of the Na and Ca present in the carbon black are dissolved and removed in water and acid. In order to reduce the total amount of Na and Ca to 100 ppm or less, it may be possible to use the carbon black manufacturing process alone, which is a carefully selected raw material, or the water or acid dissolution method alone, but by using both methods together, it is possible to further reduce the total amount. The total amount of Na and Ca can be easily set to 100 ppm or less.

The resin-coated carbon black is preferably so-called acidic carbon black having a pH of 6 or less. Since the dispersion diameter (aggregate diameter) in water becomes small, it is possible to cover up to fine units, which is suitable. Further, it is preferable that the particle size is 40 nm or less and the absorption amount of dibutyl phthalate (DBP) is 140 ml / 100 g or less. When the particle size is larger than 40 nm and the DBP absorption amount is larger than 140 ml / 100 g, the dispersibility when made into a paste is excellent, but the density of the coating film may not be sufficient, and when the film thickness is about 1 to 2 μm, the light is shielded. This is because there is a risk of becoming poor in sex.

The method for preparing the carbon black coated with the resin is not particularly limited. For example, after appropriately adjusting the blending amounts of the carbon black and the resin, 1. A resin solution obtained by mixing a resin with a solvent such as cyclohexanone, toluene, and xylene and being heated and dissolved and a suspension containing carbon black and water are mixed and stirred to separate carbon black and water. 2. A method in which water is removed, the composition is heated and kneaded, the obtained composition is formed into a sheet, crushed, and then dried; A method of mixing and stirring a resin solution and a suspension prepared in the same manner as described above to granulate carbon black and resin, and then separating and heating the obtained granules to remove residual solvent and water; 3. 3. Carboxylic acids such as maleic acid and fumaric acid are dissolved in the above-exemplified solvent, carbon black is added, mixed and dried, the solvent is removed to obtain carboxylic acid-impregnated carbon black, and then a resin is added thereto. Dry blending method; 4. A suspension is prepared by stirring the reactive group-containing monomer component constituting the resin to be coated and water at high speed, and after polymerization, the suspension is cooled to obtain a reactive group-containing resin from the polymer suspension, and then carbon is added thereto. A method of adding black, kneading, reacting carbon black with a reactive group (grafting carbon black), cooling and pulverizing can be adopted.

The type of resin to be coated is not particularly limited, but synthetic resin is common, and a resin having a benzene nucleus in its structure has a stronger function as an amphoteric surfactant. It is preferable from the viewpoint of dispersibility and dispersion stability.
Specific synthetic resins include thermosetting resins such as phenolic resin, melamine resin, xylene resin, diallylphthalate resin, glyptal resin, epoxy resin and alkylbenzene resin, polystyrene, polycarbonate, polyethylene terephthalate, polybutylene terephthalate and modified polyphenylene. Thermoplastic resins such as oxide, polysulphon, polyparaphenylene terephthalamide, polyamideimide, polyimide, polyaminobismaleimide, polyether sulfopolyphenylensulphon, polyarylate, and polyether ether ketone can be used. The coating amount of the resin on the carbon black is preferably 1 to 30% by mass with respect to the total amount of the carbon black and the resin, and if the amount is less than 1% by mass, only the same dispersibility and dispersion stability as the untreated carbon black can be obtained. It may not be possible. On the other hand, if it exceeds 30% by mass, the adhesiveness between the resins is strong and the resin becomes a dumpling-like mass, which may prevent the dispersion from proceeding.

The carbon black coated with the resin in this way can be used as a light-shielding material for a black matrix according to a conventional method, and a color filter having this black matrix as a component can be produced by a conventional method. When such carbon black is used, a black matrix having a high shading rate, a low surface reflectance, and a small film thickness can be achieved at low cost. It is presumed that this is because the dispersibility and dispersion stability of carbon black have been significantly improved with respect to the resins and solvents that make up the black matrix liquid. It is also presumed that by coating the surface of the carbon black with a resin, Ca and Na may be contained in the carbon black.

Further, as the pigment, barium sulfate, lead sulfate, titanium oxide, yellow lead, red iron oxide, chromium oxide and the like can also be used.
A plurality of these various pigments can be used in combination. For example, a green pigment and a yellow pigment can be used in combination, or a blue pigment and a purple pigment can be used in combination for adjusting the chromaticity.
Among these various pigments, C.I. I. Pigment Blue 60, C.I. I. Pigment Blue 15: 6, C.I. I. Pigment Red 177, C.I. I. Pigment Red 242, C.I. I. Pigment Blue 254, C.I. I. Pigment Violet 23, C.I. I. Pigment Violet 29, C.I. I. Pigment Orange 49, C.I. I. Pigment Orange 64, C.I. I. Pigment Orange 79. (A-2) When the organic coloring pigment is contained, it is preferable to contain at least one of the above pigments, and it is more preferable to contain two or more of them.

Further, as the (A-3) carbon black, a resin-coated carbon black is preferably used in terms of volume resistance and dielectric constant.
These pigments are preferably dispersed and used so that the average particle size is usually 1 μm or less, preferably 0.5 μm or less, and more preferably 0.25 μm or less. Here, the standard of the average particle size is the number of pigment particles.
In the present invention, the average particle size of the pigment is a value obtained from the pigment particle size measured by dynamic light scattering (DLS). The particle size is measured by a sufficiently diluted colored resin composition (usually diluted to prepare a pigment concentration of about 0.005 to 0.2% by mass. However, if there is a concentration recommended by the measuring device, the concentration is adjusted. Follow the procedure) and measure at 25 ° C.

<(B) Dispersant>
The photosensitive coloring composition of the present invention contains (B) a dispersant because (A) finely dispersing the coloring material and stabilizing the dispersed state are important for ensuring quality stability. In particular, (A-1) contains a polymer dispersant having a quaternary ammonium base as a functional group from the viewpoint of dispersibility of the organic black pigment.
In terms of dispersion stability, the polymer dispersant further comprises a carboxyl group; a phosphate group; a sulfonic acid group; or these groups; a primary, secondary or tertiary amino group; a nitrogen-containing hetero such as pyridine, pyrimidine, and pyrazine. It may further have a functional group such as a ring-derived group. Among them, in particular, a small amount of a polymer dispersant having a basic functional group such as a primary, secondary or tertiary amino group; a group derived from a nitrogen-containing heterocycle such as pyridine, pyrimidine, or pyrazine, etc., is used to disperse the pigment. It is preferable from the viewpoint that it can be dispersed with a dispersant.
Among these, a quaternary ammonium base from the viewpoint of dispersibility of (A-1) organic black pigment and from the viewpoint of dispersibility of (A-2) organic coloring pigment and / or (A-3) carbon black. And a polymer dispersant having a tertiary amino group as a functional group is preferable.

Examples of the polymer dispersant include urethane-based dispersants, acrylic-based dispersants, polyethyleneimine-based dispersants, polyallylamine-based dispersants, dispersants consisting of monomers having amino groups and macromonomers, and polyoxyethylene alkyl ethers. Examples thereof include system dispersants, polyoxyethylene diester dispersants, polyether phosphate dispersants, polyester phosphate dispersants, sorbitan aliphatic ester dispersants, and aliphatic modified polyester dispersants.

Specific examples of such dispersants include EFKA (registered trademark, manufactured by BASF), DISPERBYK (registered trademark, manufactured by Big Chemie), Disparon (registered trademark, manufactured by Kusumoto Kasei Co., Ltd.), and SOLSERSE under the trade names. (Registered trademark, manufactured by Lubrizol), KP (manufactured by Shinetsu Chemical Industry Co., Ltd.), Polyflow (manufactured by Kyoeisha Chemical Co., Ltd.), Azisper (registered trademark, manufactured by Ajinomoto Co., Ltd.) and the like can be mentioned.
These polymer dispersants may be used alone or in combination of two or more.

The weight average molecular weight (Mw) of the polymer dispersant is usually 700 or more, preferably 1000 or more, and usually 100,000 or less, preferably 50,000 or less.
Among these, from the viewpoint of adhesion and linearity, the dispersant (B) preferably contains a urethane-based polymer dispersant having a functional group and / or an acrylic polymer dispersant, and the acrylic polymer dispersant. Is particularly preferable.
Further, from the viewpoint of dispersibility and storage stability, a polymer 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 DISPERBYK 160 to 166, 182 series (all urethane-based), DISPERBYK2000, 2001, LPN21116 and the like (all acrylic-based) (all manufactured by Big Chemie).
To specifically exemplify a preferable chemical structure as a urethane-based polymer dispersant, for example, it is the same as a polyisocyanate compound and a compound having one or two hydroxyl groups in the molecule and having a number average molecular weight of 300 to 10,000. Examples thereof include a dispersed resin having a weight average molecular weight of 1,000 to 200,000, which is obtained by reacting an active hydrogen with a compound having a tertiary amino group in the molecule. By treating these with a quaternary agent such as benzyl chloride, all or part of the tertiary amino group can be converted into a quaternary ammonium base.

Examples of the above polyisocyanate compounds include paraphenylene diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, naphthalene-1,5-diisocyanate, trizine diisocyanate and the like. Aromatic diisocyanate, hexamethylene diisocyanate, lysine methyl ester diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, aliphatic diisocyanate such as dimerate diisocyanate, isophorone diisocyanate, 4,4'-methylenebis (cyclohexylisocyanate), ω, ω Alicyclic diisocyanate such as ′-diisocinatedimethylcyclohexane, aliphatic diisocyanate having aromatic ring such as xylylene diisocyanate, α, α, α ′, α ′-tetramethylxylylene diisocyanate, lysine ester triisocyanate, 1, 6,11-Undecantriisocyanate, 1,8-diisocyanate-4-isocyanatemethyloctane, 1,3,6-hexamethylenetriisocyanate, bicycloheptantriisocyanate, tris (isocyanatephenylmethane), tris (isocyanatephenyl) thiophosphate Such as triisocyanates, trimerics thereof, water adducts, and polyol adducts thereof. The polyisocyanate is preferably a trimer of organic diisocyanate, and most preferably a trimer of tolylene diisocyanate and a trimer of isophorone diisocyanate. These may be used alone or in combination of two or more.

As a method for producing an isocyanate trimeric, the polyisocyanate is subjected to an isocyanate group moiety using an appropriate trimerization catalyst, for example, tertiary amines, phosphins, alkoxides, metal oxides, carboxylates and the like. A method of obtaining a desired isocyanurate group-containing polyisocyanate by subjecting it to a specific quantification, stopping the quantification by adding a catalytic poison, and then removing the unreacted polyisocyanate by solvent extraction and thin film distillation.

As a compound having one or two hydroxyl groups in the same molecule and having an average molecular weight of 300 to 10,000, polyether glycol, polyester glycol, polycarbonate glycol, polyolefin glycol and the like, and one terminal hydroxyl group of these compounds have the number of carbon atoms. Examples thereof include those analkylated with 1 to 25 alkyl groups and mixtures of two or more of these.
Examples of the polyether glycol include a polyether diol, a polyether ester diol, and a mixture of two or more of these. Polyether diols are obtained by using alkylene oxide alone or in copolymerization, for example, polyethylene glycol, polypropylene glycol, polyethylene-propylene glycol, polyoxytetramethylene glycol, polyoxyhexamethylene glycol, polyoxyoctamethylene glycol and them. A mixture of two or more of the above can be mentioned.

Polyester ester diols are obtained by reacting ether group-containing diols or mixtures with other glycols with dicarboxylic acids or their anhydrides, or by reacting polyester glycols with alkylene oxides, such as poly (poly). Oxytetramethylene) adipate and the like. The most preferable polyether glycol is polyethylene glycol, polypropylene glycol, polyoxytetramethylene glycol, or a compound in which one terminal hydroxyl group of these compounds is alkoxylated with an alkyl group having 1 to 25 carbon atoms.

Examples of polyester glycols include 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, etc.). Dipropylene glycol, tripropylene glycol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, 3-methyl-1,5-pentanediol, neopentyl glycol , 2-Methyl-1,3-propanediol, 2-methyl-2-propyl-1,3-propanediol, 2-butyl-2-ethyl-1,3-propanediol, 1,5-pentanediol, 1 , 6-Glycoldiol, 2-Methyl-2,4-Pentanediol, 2,2,4-trimethyl-1,3-Pentanediol, 2-Ethyl-1,3-Hexanediol, 2,5-dimethyl-2 , 5-Hexanediol, 1,8-octamethylene glycol, 2-methyl-1,8-octamethylene glycol, 1,9-nonanediol and other aliphatic glycols, bishydroxymethylcyclohexane and other alicyclic glycols, xyl It is obtained by polycondensing with aromatic glycol such as len glycol, bishydroxyethoxybenzene, N-alkyldialkanolamine such as N-methyldiethanolamine), for example, polyethylene adipate, polybutylene adipate, polyhexamethylene adipate. Polylactone diols or polylactone monools obtained by using the above diols or monovalent alcohols having 1 to 25 carbon atoms as an initiator, such as polyethylene / propylene adipate, for example, polycaprolactone glycols, polymethylvalerolactones and the like. Examples include a mixture of two or more. The most preferable polyester glycol is polycaprolactone glycol or polycaprolactone using an alcohol having 1 to 25 carbon atoms as an initiator.

Polyolefin glycols include poly (1,6-hexylene) carbonate and poly (3-methyl-1,5-pentylene) carbonates, and polyolefin glycols include polybutadiene glycols, hydrogenated polybutadiene glycols and hydrogenated polyisoprene glycols. Can be mentioned.
These may be used alone or in combination of two or more.

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.

A compound having an active hydrogen and a tertiary amino group in the same molecule used in the present invention will be described.
Examples of active hydrogen, that is, a hydrogen atom directly bonded to an oxygen atom, a nitrogen atom or a sulfur atom, include hydrogen atoms in functional groups such as hydroxyl groups, amino groups and thiol groups, and among them, amino groups, particularly first-class. The hydrogen atom of the amino group of is preferable.

The tertiary amino group is not particularly limited, and examples thereof include an amino group having an alkyl group having 1 to 4 carbon atoms, a heterocyclic structure, and more specifically, an imidazole ring or a triazole ring.
To exemplify such a compound having an active hydrogen and a tertiary amino group in the same molecule, N, N-dimethyl-1,3-propanediamine, N, N-diethyl-1,3-propanediamine, N , N-dipropyl-1,3-propanediamine, N, N-dibutyl-1,3-propanediamine, N, N-dimethylethylenediamine, N, N-diethylethylenediamine, N, N-dipropylethylenediamine, N, N -Dibutylethylenediamine, N, N-dimethyl-1,4-butanediamine, N, N-diethyl-1,4-butanediamine, N, N-dipropyl-1,4-butanediamine, N, N-dibutyl-1 , 4-Butanediamine and the like.

When the tertiary amino group has a nitrogen-containing heterocyclic structure, the nitrogen-containing heterocycle includes a pyrazole ring, an imidazole ring, a triazole ring, a tetrazole ring, an indole ring, a carbazole ring, an indazole ring, a benzimidazole ring, and a benzo. Nitrogen-containing hetero 5-membered ring such as triazole ring, benzoxazole ring, benzothiazole ring, benzothiazol ring, pyridine ring, pyridazine ring, pyrimidine ring, triazine ring, quinoline ring, aclysine ring, isoquinoline ring and the like. Ring is mentioned. Of these nitrogen-containing heterocycles, the imidazole ring or the triazole ring is preferable.

Specific examples of these compounds having an imidazole ring and an amino group include 1- (3-aminopropyl) imidazole, histidine, 2-aminoimidazole, 1- (2-aminoethyl) imidazole and the like. Specific examples of the compound having a triazole ring and an amino group include 3-amino-1,2,4-triazole and 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 and the like. Among them, N, N-dimethyl-1,3-propanediamine, N, N-diethyl-1,3-propanediamine, 1- (3-aminopropyl) imidazole, 3-amino-1,2,4-triazole preferable.
These may be used alone or in combination of two or more.

The preferred blending ratio of the raw materials for producing a urethane-based polymer dispersant is 10 compounds 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. Up to 200 parts by mass, 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, a compound having an active hydrogen and a tertiary amino group in the same molecule. ~ 24 parts by mass.

The urethane-based polymer dispersant is produced according to a known method for producing a polyurethane resin. 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, toluene, xylene and hexane are used. Hydrocarbons such as, diacetone alcohol, isopropanol, second butanol, some alcohols such as tertiary butanol, chlorides such as methylene chloride and chloroform, ethers such as tetrahydrofuran and diethyl ether, dimethylformamide, N-methyl. An aprotonic polar solvent such as pyrrolidone or dimethylsulfoxide is used. These may be used alone or in combination of two or more.

In the above production, a urethanization reaction catalyst is usually used. Examples of this catalyst include tin-based catalysts such as dibutyltin dilaurate, dioctyltin dilaurate, dibutyltin dioctoate, and stanas octoate, iron-based catalysts such as iron acetylacetonate and ferric chloride, triethylamine, and triethylenediamine. Examples include grade amines. These may be used alone or in combination of two or more.

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

When the isocyanate group remains in the polymer dispersant by the above reaction, it is preferable to crush the isocyanate group with an alcohol or an amino compound because the stability of the product with time is improved.
The weight average molecular weight (Mw) of the urethane-based polymer dispersant is usually in the range of 1,000 to 200,000, preferably 2,000 to 100,000, and more preferably 3,000 to 50,000. If the molecular weight is less than 1,000, the dispersibility and dispersion stability are poor, and if it exceeds 200,000, the solubility is lowered and the dispersibility is poor, and at the same time, it becomes difficult to control the reaction.

The acrylic polymer dispersant includes an unsaturated group-containing monomer having a functional group (the functional group referred to here is the above-mentioned functional group as the functional group contained in the polymer dispersant). It is preferable to use a random copolymer, a graft copolymer, or a block copolymer with an unsaturated group-containing monomer having no functional group. These copolymers can be produced by known methods.

Examples of the unsaturated group-containing monomer having a functional group include (meth) acrylic acid, 2- (meth) acryloyloxyethyl succinic acid, 2- (meth) acryloyloxyethyl phthalic acid, and 2- (meth) acrylic acid. Unsaturated monomers having a carboxyl group such as leuroxyethyl hexahydrophthalic acid and acrylic acid dimer, tertiary amino groups such as dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate and quaternized products thereof, Specific examples include unsaturated monomers having a quaternary ammonium base. These may be used alone or in combination of two or more.

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, and isobutyl ( Meta) 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 -N-substituted maleimides such as benzylmaleimide, acrylonitrile, vinyl acetate and polymethyl (meth) acrylate macromonomers, polystyrene macromonomers, poly2-hydroxyethyl (meth) acrylate macromonomers, polyethylene glycol macromonomers, polypropylene glycol macromonomers, poly Examples thereof include macromonomers such as caprolactone macromonomers. These may be used alone or in combination of two or more.

The acrylic polymer dispersant is particularly preferably an AB or BAB block copolymer composed of an A block having a functional group and a B block having no functional group. In this case, A. In addition to the partial structure derived from the unsaturated group-containing monomer containing the functional group, the block may contain a partial structure derived from the unsaturated group-containing monomer not containing the functional group. May be contained in the A block in any aspect of random copolymerization or block copolymerization. The content of the partial structure containing no functional group in the A block 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 the unsaturated group-containing monomer that does not contain the functional group, but one B block contains a partial structure derived from two or more kinds of monomers. Also, these may be contained in the B block in any mode of random copolymerization or block copolymerization.
The AB or BAB block copolymer is prepared, for example, by the living polymerization method shown below.
The living polymerization method includes an anion living polymerization method, a cationic living polymerization method, and a radical living polymerization method. Among them, in the anion living polymerization method, the polymerization active species is an anion, and is represented by, for example, the following scheme.

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 integers of 1 or more, respectively.

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

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

In synthesizing this acrylic polymer dispersant, Japanese Patent Application Laid-Open No. 9-62002 and P.I. Lutz, P.M. Masson et al, Polym. Bull. 12, 79 (1984), B.I. C. Anderson, G.M. D. Andrews et al, Macromolecules, 14, 1601 (1981), K. et al. Hatada, K.K. Ute, et al, Polym. J. 17, 977 (1985), 18, 1037 (1986), Koichi Right Hand, Koichi Hatada, Polymer Processing, 36, 366 (1987), Toshinobu Higashimura, Mitsuo Sawamoto, Journal of Polymer Papers, 46, 189 (1989), M. Kuroki, T.K. Aida, J.M. Am. Chem. Sic, 109, 4737 (1987), Takuzo Aida, Shohei Inoue, Synthetic Organic Chemistry, 43, 300 (1985), D.I. Y. Sogoh, W. R. A known method described in Hertler et al, Macromolecules, 20, 1473 (1987) and the like can be adopted.

The acrylic polymer dispersant that can be used in the present invention may be an AB block copolymer or a BAB block copolymer, and the A block constituting the copolymer may be used. The / B block ratio is preferably 1/99 to 80/20, particularly 5/95 to 60/40 (mass ratio), and outside this range, good heat resistance and dispersibility cannot be achieved. There is.
Further, the amount of the quaternary ammonium base in 1 g of the AB block copolymer and the BAB block copolymer that can be used in the present invention is usually preferably 0.1 to 10 mmol, and this is preferable. Outside the range, it may not be possible to combine good heat resistance and dispersibility.

In addition, such a block copolymer may usually contain an amino group generated in the production process, but its amine value is about 1 to 100 mgKOH / g, and from the viewpoint of dispersibility, it is considered. It is preferably 10 mgKOH / g or more, more preferably 30 mgKOH / g or more, still more preferably 50 mgKOH / g or more, 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 the dispersant such as these block copolymers is expressed by the amount of base per 1 g of solid content excluding the solvent in the dispersant sample and the equivalent amount of KOH, and is measured by the following method.
Weigh 0.5-1.5 g of the dispersant sample into a 100 mL beaker and dissolve in 50 mL of acetic acid. This solution is neutralized and titrated with 0.1 mol / L _HClO4 acetic acid solution using an automatic titrator equipped with a pH electrode. The amine value is calculated by the following formula with the inflection point of the titration pH curve as the titration end point.

Amine value [mgKOH / g] = (561 × V) / (W × S)
[However, W: Dispersant sample weighing amount [g], V: Titration determination at the end point of titration [mL], S: Solid content concentration [mass%] of the dispersant sample. ]
The acid value of this block copolymer depends on the presence or absence and type of an acidic group that is the source of the acid value, but is generally preferably low, 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, the dispersion stability tends to decrease, and when it exceeds 100,000, the developability and the resolution tend to decrease.

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

In the above formula (i), R ³¹ to R ³³ each independently have a hydrogen atom, an alkyl group which may have a substituent, an aryl group which may have a substituent, or a substituent. It is an aralkyl group which may be present, and two or more of R ³¹ to R ³³ 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 of the alkyl group which may have a substituent in R ³¹ to R ³³ of the above formula (i) is not particularly limited, but is usually 1 or more, preferably 10 or less, and 6 The following is more preferable. 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 and a butyl group. It is preferably a group, a pentyl group, or a hexyl group, and more preferably a methyl group, an ethyl group, a propyl group, or a butyl group. Further, it may be linear or branched. Further, it may contain a cyclic structure such as a cyclohexyl group or a cyclohexylmethyl group.

The number of carbon atoms of the aryl group which may have a substituent in R ³¹ to R ³³ of the above formula (i) is not particularly limited, but is usually 6 or more, preferably 16 or less, and 12 The following is more preferable. 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 anthrasenyl group and the like, and among these, a phenyl group, a methylphenyl group and an ethylphenyl group. , Dimethylphenyl group, or diethylphenyl group, more preferably phenyl group, methylphenyl group, or ethylphenyl group.

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

Among these, from the viewpoint of dispersibility, it is preferable that R ³¹ to R ³³ are independently alkyl groups or aralkyl groups, and specifically, R ³¹ and R ³³ are independently methyl groups or ethyls, respectively. It is preferable that R ³² is a phenylmethylene group or a phenylethylene group, R ³¹ and R ³³ are methyl groups, and R ³² is a phenylmethylene group.

When the polymer dispersant has a tertiary amine as a functional group, it may be referred to as a repeating unit represented by the following formula (ii) (hereinafter referred to as “repeating unit (ii)” from the viewpoint of dispersibility. It is preferable to have.).

In the above formula (ii), R ³⁵ and R ³⁶ each independently have a hydrogen atom, an alkyl group which may have a substituent, an aryl group which may have a substituent, or a substituent. It is an aralkyl group which may be present, and R ³⁵ and R ³⁶ 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.

Further, as the alkyl group which may have a substituent in R ³⁵ and R ³⁶ of the above formula (ii), those exemplified as R ³¹ to R ³³ of the above formula (i) are preferably adopted. can.
Similarly, as the aryl group which may have a substituent in R ³⁵ and R ³⁶ of the above formula (ii), those exemplified as R ³¹ to R ³³ of the above formula (i) are preferably adopted. Can be done. Further, as the aralkyl group which may have a substituent in R ³⁵ and R ³⁶ of the above formula (ii), those exemplified as R ³¹ to R ³³ of the above formula (i) are preferably adopted. can.

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

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

In the above formulas (i) and (ii), the divalent linking groups X and Z include, for example, an alkylene group having 1 to 10 carbon atoms, an arylene group having 6 to 12 carbon atoms, and -CONH-R ^43- group. -COOR ⁴⁴ -group [However, R ⁴³ and R ⁴⁴ are a single bond, an alkylene group having 1 to 10 carbon atoms, or an ether group having 2 to 10 carbon atoms (alkyloxyalkyl group)] and the like are preferable. Is a -COO-R ⁴⁴ -group.
Further, in the above formula (i), examples of the counter anion Y ⁻ include Cl ⁻ , Br ⁻ , I ⁻ , ClO _4- , BF _4- ^, CH ₃ COO ⁻ , PF ₆ ^{− and} the like.

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

The content ratio of the repeating unit represented by the above formula (i) to all the repeating units of the polymer dispersant is not particularly limited, but is preferably 1 mol% or more, preferably 5 mol, from the viewpoint of dispersibility. % Or more, more preferably 10 mol% or more, further preferably 50 mol% or less, more preferably 30 mol% or less, and 20 mol% or less. Is more preferable, and 15 mol% or less is particularly preferable.

The content ratio of the repeating unit represented by the above formula (ii) in the total repeating units of the polymer dispersant is not particularly limited, but is preferably 5 mol% or more, preferably 10 mol, from the viewpoint of dispersibility. % Or more, more preferably 15 mol% or more, particularly preferably 20 mol% or more, and preferably 60 mol% or less, preferably 40 mol% or less. Is more preferable, 30 mol% or less is further preferable, and 25 mol% or less is particularly preferable.

Further, the polymer dispersant is a repeating unit represented by the following formula (iii) (hereinafter, “repeating unit (iii)” from the viewpoint of increasing the compatibility with the binder component such as a solvent and improving the dispersion stability. It is preferable to have).

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

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

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

Further, the content ratio of the repeating unit represented by the above formula (iii) to all the repeating units of the polymer dispersant is not particularly limited, but is preferably 1 mol% or more, and preferably 2 mol% or more. It is more preferably 4 mol% or more, further preferably 30 mol% or less, still more preferably 20 mol% or less, still more preferably 10 mol% or less. Within the above range, it tends to be possible to achieve both compatibility with a binder component such as a solvent and dispersion stability.

Further, the polymer dispersant is a repeating unit represented by the following formula (iv) from the viewpoint of increasing the compatibility of the dispersant with a binder component such as a solvent and improving the dispersion stability (hereinafter, “repeating unit (iv”). ) ”.).

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 of the alkyl group which may have a substituent in R ³⁸ of the above formula (iv) is not particularly limited, but is usually 1 or more, preferably 2 or more, and preferably 4 or more. More preferably, it is preferably 10 or less, and 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 and a butyl group. It is preferably a group, a pentyl group, or a hexyl group, and more preferably a methyl group, an ethyl group, a propyl group, or a butyl group. Further, it may be linear or branched. Further, it may contain a cyclic structure such as a cyclohexyl group or a cyclohexylmethyl group.

The carbon number of the aryl group which may have a substituent in R ³⁸ of the above formula (iv) is not particularly limited, but is usually 6 or more, preferably 16 or less, and preferably 12 or less. It is more preferable, and it is further preferable that it is 8 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 anthrasenyl group and the like, and among these, a phenyl group, a methylphenyl group and an ethylphenyl group. , Dimethylphenyl group, or diethylphenyl group, more preferably phenyl group, methylphenyl group, or ethylphenyl group.

The carbon number of the aralkyl group which may have a substituent in R ³⁸ of the above formula (iv) is not particularly limited, but is usually 7 or more, preferably 16 or less, and preferably 12 or less. More preferably, it is more preferably 10 or less. Specific examples of the aralkyl group include a phenylmethylene group, a phenylethylene group, a phenylpropylene group, a phenylbutylene group, a phenylisopropylene group and the like, and among these, a phenylmethylene group, a phenylethylene group, a phenylpropylene group, or It is preferably a phenylbutylene group, 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.
Examples of the substituent that the alkyl group may have in R ³⁸ include a halogen atom and an alkoxy group. Examples of the substituent that the aryl group or the aralkyl group may have include a chain-like alkyl group, a halogen atom, an alkoxy group and the like. Further, the chain-like alkyl group represented by R ³⁸ includes both a linear chain and a branched chain.

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

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

From the viewpoint of further enhancing the dispersibility, the polymer dispersant has an A block having a repeating unit (i) and a repeating unit (ii) and a B block having no repeating unit (i) and a repeating unit (ii). It is preferably a block copolymer having and. The block copolymer is preferably an AB block copolymer or a BAB block copolymer. Surprisingly, by introducing not only a quaternary ammonium base but also a tertiary amino group into the A block, the dispersion ability of the dispersant tends to be significantly improved. Further, it is preferable that the B block has a repeating unit (iii), and it is more preferable that the B block has a repeating unit (iv).

In the A block, the repeating unit (i) and the repeating unit (ii) may be contained in any aspect of random copolymerization and block copolymerization. Further, two or more kinds of the repeating unit (i) and the repeating unit (ii) may be contained in one A block, and in that case, each repeating unit is randomly copolymerized in the A block. It may be contained in any aspect of block copolymerization.

Further, a repeating unit other than the repeating unit (i) and the repeating unit (ii) may be contained in the A block, and as an example of such a repeating unit, the above-mentioned (meth) acrylic acid ester-based simple unit may be contained. Examples include repeating units derived from a quantity. The content of the repeating unit (i) and the repeating unit other than the repeating unit (ii) in the A block is preferably 0 to 50 mol%, more preferably 0 to 20 mol%, and the repeating unit is A. Most preferably, it is not contained in the block.

Repeating units other than the repeating units (iii) and (iv) may be contained in the B block, and examples of such repeating units include styrene-based monomers such as styrene and α-methylstyrene; (Meta) acrylate-based monomers such as (meth) acrylic acid chloride; (meth) acrylamide-based monomers such as (meth) acrylamide and N-methylol acrylamide; vinyl acetate; acrylonitrile; allylglycidyl ether, glycidyl crotonate. Ether; repeat units derived from monomers such as N-methacryloylmorpholine. The content of the repeating unit other than the repeating unit (iii) and the repeating unit (iv) in the B block is preferably 0 to 50 mol%, more preferably 0 to 20 mol%, and the repeating unit is B. Most preferably, it is not contained in the block.

Further, from the viewpoint of improving dispersion stability, the dispersant (B) 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 is, for example, an epoxy (meth) acrylate resin, an acrylic resin, a carboxyl group-containing epoxy resin, or a carboxyl group-containing resin. Examples thereof include urethane resin, novolak resin, polyvinylphenol resin and the like, and among them, epoxy (meth) acrylate resin and acrylic resin are preferable. These can be used alone or in admixture of a plurality of types.

As the alkali-soluble resin used in the present invention, the following alkali-soluble resin (c1) and / or alkali-soluble resin (c2) (hereinafter, may be referred to as "carboxyl group-containing epoxy (meth) acrylate resin") are particularly excellent. It is preferably used from the viewpoint of plate-making property.
<Alkali-soluble resin (c1)>
It was 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 polybasic acid and / or its anhydride. Alkaline-soluble resin.
<Alkali-soluble resin (c2)>
An α, β-unsaturated monocarboxylic acid or an α, β-unsaturated monocarboxylic acid ester having a carboxyl group is added to the epoxy resin, and further reacted with a polyhydric alcohol and a polybasic acid and / or an anhydride thereof. The resulting alkali-soluble resin.

Examples of the epoxy resin as a raw material include bisphenol A type epoxy resin (for example, "Epicoat (registered trademark; the same applies hereinafter) 828", "Epicoat 1001", "Epicoat 1002", "Epicoat 1004" manufactured by Mitsubishi Chemical Corporation, etc. ), Epoxy obtained by the reaction of the alcoholic hydroxyl group of the bisphenol A type epoxy resin with epichlorohydrin (for example, "NER-1302" (epoxy equivalent 323, softening point 76 ° C.) manufactured by Nippon Kayaku Co., Ltd.), bisphenol F type resin ( For example, "Epicoat 807", "EP-4001", "EP-4002", "EP-4004", etc. manufactured by Mitsubishi Chemical Corporation), an epoxy resin obtained by the reaction of an alcoholic hydroxyl group of a bisphenol F type epoxy resin with epichlorohydrin. (For example, "NER-7406" manufactured by Nippon Kayaku Co., Ltd. (epoxy equivalent 350, softening point 66 ° C.)), bisphenol S type epoxy resin, biphenyl glycidyl ether (for example, "YX-4000" manufactured by Mitsubishi Chemical Corporation), Phenol novolak type epoxy resin (for example, "EPPN-201" manufactured by Nippon Kayaku Co., Ltd., "EP-152", "EP-154" manufactured by Mitsubishi Chemical Corporation, "DEN-438" manufactured by Dow Chemical Corporation), ( o, m, p-) Cresol novolac type epoxy resin (for example, "EOCN (registered trademark; the same shall apply hereinafter) -102S", "EOCN-1020", "EOCN-104S") manufactured by Nippon Kayaku Co., Ltd., triglycidyl Isocyanurate (for example, "TEPIC (registered trademark)" manufactured by Nissan Chemical Corporation), Trisphenol methane type epoxy resin (for example, "EPPN (registered trademark; the same applies hereinafter) -501" manufactured by Nippon Kayaku Co., Ltd., "EPN". -502 "," EPPN-503 "), alicyclic epoxy resin ("Selokiside 2021P "manufactured by Daicel Chemical Industries, Ltd.," Selokiside (registered trademark; the same shall apply hereinafter) EHPE "), due to the reaction of dicyclopentadiene and phenol. Epoxy resin obtained by glycidylizing a phenol resin (for example, "EXA-7200" manufactured by DIC, "NC-7300" manufactured by Nippon Kayaku Co., Ltd.), epoxy resin represented by the following general formulas (C1) to (C4). , Etc. can be preferably used. Specifically, "XD-1000" manufactured by Nippon Kayaku Co., Ltd. is used as the epoxy resin represented by the following general formula (C1), and "XD-1000" manufactured by Nippon Kayaku Co., Ltd. is used as the epoxy resin represented by the following general formula (C2). Examples of the epoxy resin represented by the following general formula (C4) include "NC-3000" and "ESF-300" manufactured by Nippon Steel Chemical Co., Ltd.

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

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

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

In the above general formulas (C3-1) and (C3-2), R ¹³¹ to R ¹³⁴ and R ¹³⁵ to R ¹³⁷ independently have an adamantyl group, a hydrogen atom, and a substituent which may have a substituent. Indicates an alkyl group having 1 to 12 carbon atoms which may have a substituent, or a phenyl group which may have a substituent. * Indicates a bond.

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

Among these, it is preferable to use an epoxy resin represented by any of the general 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). ) Monocarboxylic acids such as α-position haloalkyl, alkoxyl, halogen, nitro, cyano-substituted acrylic acid, 2- (meth) acryloyloxyethyl succinic acid, 2- (meth) acryloyloxyethyl adipic acid, 2- ( Meta) acryloyloxyethyl phthalic acid, 2- (meth) acryloyloxyethyl hexahydrophthalic acid, 2- (meth) acryloyloxyethyl maleic acid, 2- (meth) acryloyloxypropyl succinic acid, 2- ( Meta) acryloyloxypropyl adipic acid, 2- (meth) acryloyloxypropyltetrahydrophthalic acid, 2- (meth) acryloyloxypropyl phthalic acid, 2- (meth) acryloyloxypropyl maleic acid, 2- (meth) ) Acryloyloxybutyl succinic acid, 2- (meth) acryloyloxybutyl adipic acid, 2- (meth) acryloyloxybutylhydrophthalic acid, 2- (meth) acryloyloxybutylphthalic acid, 2- (meth) Acryloyloxybutylmaleic acid (meth), a monomer obtained by adding lactones such as ε-caprolactone, β-propiolactone, γ-butyrolactone, and δ-valerolactone to acrylic acid, or hydroxyalkyl ( A monomer obtained by adding an acid (anhydrous) such as (anhydrous) succinic acid, (anhydrous) phthalic acid, and (anhydrous) maleic acid to meta) acrylate and pentaerythritol tri (meth) acrylate, (meth) acrylic acid dimer. And so on.
Of these, (meth) acrylic acid is particularly preferable from the viewpoint of sensitivity.

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

As the epoxy resin, α, β-unsaturated monocarboxylic acid, α, β-unsaturated monocarboxylic acid ester having a carboxyl group, and the esterification catalyst, one type may be used alone or two types may be used. The above may be used together.
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 with respect to 1 equivalent of the epoxy group of the epoxy resin. , More preferably in the range of 0.7 to 1.1 equivalents. If the amount of α, β-unsaturated monocarboxylic acid or α, β-unsaturated monocarboxylic acid ester having a carboxyl group used is small, the amount of unsaturated group introduced will be insufficient, and the subsequent polybasic acid and / or its anhydride will be insufficient. The reaction with is also 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 product. In either case, the curing characteristics tend to deteriorate.

Examples of the polybasic acid and / or its anhydride include maleic acid, succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, pyromellitic acid, trimellitic acid, benzophenone tetracarboxylic acid and methylhexahydrophthalic acid. Examples thereof include one or more selected from acids, endomethylenetetrahydrophthalic acid, chlorendic acid, methyltetrahydrophthalic acid, biphenyltetracarboxylic acid, and anhydrides thereof.

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

A known method can also be used for the addition reaction of a polybasic acid and / or its anhydride, and an α, β-unsaturated monocarboxylic acid or an α, β-unsaturated monocarboxylic acid having a carboxyl group to an epoxy resin can be used. The desired product can be obtained by a continuous reaction under the same conditions as the addition reaction of the ester. 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 further 20 It is preferably in the range of ~ 140 mgKOH / g. If the acid value of the carboxyl group-containing epoxy (meth) acrylate resin is less than the above range, the alkali developability tends to be poor, and if it exceeds the above range, the curing performance tends to be inferior.

A polyfunctional alcohol such as trimethylolpropane, pentaerythritol, or dipentaerythritol may be added during the addition reaction of the polybasic acid and / or its anhydride to introduce a multi-branched structure.
A carboxyl group-containing epoxy (meth) acrylate resin is usually a reaction product of an epoxy resin and an α, β-unsaturated monocarboxylic acid or an α, β-unsaturated monocarboxylic acid ester having a carboxyl group, and a polybasic acid and a polybasic acid. / Or after mixing the anhydride thereof, or after mixing the epoxy resin with α, β-unsaturated monocarboxylic acid or α, β-unsaturated monocarboxylic acid ester having a carboxyl group, polybasic acid and / or Alternatively, it can be obtained by mixing the anhydride thereof and the polyfunctional alcohol and then heating the mixture. In this case, the mixing order of the polybasic acid and / or its anhydride and the polyfunctional alcohol is not particularly limited. Any hydroxyl group present in the mixture of the reaction product of the epoxy resin and the α, β-unsaturated monocarboxylic acid or the α, β-unsaturated monocarboxylic acid ester having a carboxyl group and the polyfunctional alcohol by heating. Polycarboxylic acid and / or its anhydride undergoes an addition reaction with respect to.

The polystyrene-equivalent weight average molecular weight (Mw) of the carboxyl group-containing epoxy (meth) acrylate resin measured by gel permeation chromatography (GPC) is usually 1000 or more, preferably 1500 or more, usually 10,000 or less, preferably 8000. Below, it is more preferably 6000 or less. If the weight average molecular weight is small, the solubility in a developing solution is high, and if it is too large, the solubility in a developing solution is low.

As the carboxyl group-containing epoxy (meth) acrylate resin, one type may be used alone, or two or more types of resins may be mixed and used.
Further, in the alkali-soluble resin (C) used in the present invention, a part of the above-mentioned carboxyl group-containing epoxy (meth) acrylate resin may be replaced with another binder resin as long as the performance of the present invention is not impaired. That is, a carboxyl group-containing epoxy (meth) acrylate resin may be used in combination with another binder resin. In this case, the proportion of the carboxyl group-containing epoxy (meth) acrylate resin in the alkali-soluble resin (C) alkali-soluble resin is preferably 50% by mass or more, particularly 80% by mass or more.

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

In addition, each of the other binder resins may be used alone or in combination of two or more.

<(D) Photopolymerization Initiator>
(D) The photopolymerization initiator is a component having a function of directly absorbing light, causing a decomposition reaction or a hydrogen abstraction reaction, and generating a polymerization active radical. If necessary, an additive such as a polymerization accelerator (chain transfer agent) or a sensitizing dye may be added and used.
As the photopolymerization initiator, for example, a metallocene compound containing a titanosen compound described in JP-A-59-152396 and JP-A-61-151197 of Japan; Japanese Patent Application Laid-Open No. 2000-56118. Hexaaryl-biimidazole derivative according to Japanese Patent Application Laid-Open No. 10-39503, halomethylated oxadiazole derivative, halomethyl-s-triazine derivative, N-aryl-α-amino acids such as N-phenylglycine, N. -Radical activators such as aryl-α-amino acid salts, N-aryl-α-amino acid esters, α-aminoalkylphenone derivatives; Japanese Patent Laid-Open No. 2000-80068, Japanese Patent Application Laid-Open No. 2006-36750, etc. Examples thereof include the oxime ester derivative described in 1.

Specifically, for example, as titanosen derivatives, dicyclopentadienyl titanium dichloride, dicyclopentadienyl titanium bisphenyl, dicyclopentadienyl titanium bis (2,3,4,5,6-pentafluoro) Pheni-1-yl), Dicyclopentadienyl Titanium Bis (2,3,5,6-Tetrafluoropheni-1-yl), Dicyclopentadienyl Titanium Bis (2,4,6-Trifluorophenyl) 1-yl), Dicyclopentadienyl Titanium Di (2,6-difluoropheni-1-yl), Dicyclopentadienyl Titanium Di (2,4-difluoropheni-1-yl), Di (Methylcyclopenta) Dienyl) Titanium Bis (2,3,4,5,6-pentafluoropheni-1-yl), Di (Methylcyclopentadienyl) Titanium Bis (2,6-difluoropheni-1-yl), Dicyclo Examples thereof include pentadienyl titanium [2,6-di-fluoro-3- (pyro-1-yl) -pheni-1-yl].

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

Examples of halomethylated oxadiazole derivatives include 2-trichloromethyl-5- (2'-benzofuryl) -1,3,4-oxadiazole and 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 and the like can be mentioned.

Examples of halomethyl-s-triazine derivatives include 2- (4-methoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine and 2- (4-methoxynaphthyl) -4,6-bis ( Trichloromethyl) -s-triazine, 2- (4-ethoxynaphthyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4-ethoxycarbonylnaphthyl) -4,6-bis (trichloromethyl) -S-Triazine and the like can be mentioned.

Examples of α-aminoalkylphenone derivatives include 2-methyl-1 [4- (methylthio) phenyl] -2-morpholinopropane-1-one and 2-benzyl-2-dimethylamino-1- (4-). Morphorinophenyl) -butanone-1, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butane-1-one, 4-dimethylaminoethylbenzoate, 4-dimethylaminoisoamylbenzoe -To, 4-diethylaminoacetophenone, 4-dimethylaminopropiophenone, 2-ethylhexyl-1,4-dimethylaminobenzoate, 2,5-bis (4-diethylaminobenzal) cyclohexanone, 7-diethylamino-3- (4) -Diethylaminobenzoyl) coumarin, 4- (diethylamino) chalcone and the like can be mentioned.

As the photopolymerization initiator, oxime derivatives (oxime-based and keto-oxime-based compounds) are particularly effective in terms of sensitivity and plate-making property, and when an alkali-soluble resin containing a phenolic hydroxyl group is used, in terms of sensitivity, etc. Oxime derivatives (oxime esters and keto-oxime ester compounds) having such excellent sensitivity are particularly useful because they are disadvantageous.
Examples of the oxime-based compound include a compound containing a structural portion represented by the following general formula (3), and preferably an oxime ester-based compound represented by the following general formula (3a).

In formula (3), R ²² may be substituted with an alkanoyl group having 2 to 12 carbon atoms, a heteroaryl alkanoyl group having 1 to 20 carbon atoms, an alkenoyl group having 3 to 25 carbon atoms, and 3 carbon atoms. Cyclo alkanoyl group of 8 to 8, alkoxycarbonyl alkanoyl group of 3 to 20 carbon atoms, phenoxycarbonyl alkanoyl group of 8 to 20 carbon atoms, heteroallyloxycarbonyl alkanoyl group of 3 to 20 carbon atoms, amino of 2 to 10 carbon atoms. An alkylcarbonyl group, an allylloyl group having 7 to 20 carbon atoms, a heteroallyloyl group having 1 to 20 carbon atoms, an alkoxycarbonyl group having 2 to 10 carbon atoms, or an aryloxycarbonyl group having 7 to 20 carbon atoms is shown.

In formula (3a), R ^21a is a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 25 carbon atoms, and a heteroarylalkyl group having 1 to 20 carbon atoms, which may be substituted with each other. , An alkoxycarbonylalkyl group having 3 to 20 carbon atoms, a phenoxycarbonylalkyl group having 8 to 20 carbon atoms, a heteroaryloxycarbonylalkyl group or a heteroarylthioalkyl group having 1 to 20 carbon atoms, and an aminoalkyl group having 1 to 20 carbon atoms. Group, alkanoyl group having 2 to 12 carbon atoms, alkenoyl group having 3 to 25 carbon atoms, cycloalkanoyl group having 3 to 8 carbon atoms, allylloyl group having 7 to 20 carbon atoms, heteroallyloyl group having 1 to 20 carbon atoms, An alkoxycarbonyl group having 2 to 10 carbon atoms, an aryloxycarbonyl group having 7 to 20 carbon atoms, or a cycloalkylalkyl group having 1 to 10 carbon atoms is shown. R ^21b represents any substituent, including aromatic or heteroaromatic rings.
In addition, R ^21a may form a ring together with R ^21b , and the linking group thereof may be an alkylene group having 1 to 10 carbon atoms and a polyethylene group (-(CH = CH) _r , which may have a substituent, respectively. -), Polyethynylene group (-(C≡C) _r- ) or a group composed of a combination thereof can be mentioned (where r is an integer of 0 to 3).

In formula (3a), R ^22a may be substituted with an alkanoyl group having 2 to 12 carbon atoms, a heteroaryl alkanoyl group having 1 to 20 carbon atoms, an alkenoyl group having 3 to 25 carbon atoms, and 3 carbon atoms. Cyclo alkanoyl group to 8 to 8, alkoxycarbonyl alkanoyl group having 3 to 20 carbon atoms, phenoxycarbonyl alkanoyl group having 8 to 20 carbon atoms, heteroallyloxycarbonyl alkanoyl group having 3 to 20 carbon atoms, amino having 2 to 10 carbon atoms. A carbonyl group, an allylloyl group having 7 to 20 carbon atoms, a heteroallyloyl group having 1 to 20 carbon atoms, an alkoxycarbonyl group having 2 to 10 carbon atoms or an aryloxycarbonyl group having 7 to 20 carbon atoms is shown.

The R ²² in the general formula (3) and the R ^22a in the general formula (3a) are preferably an alkanoyl group having 2 to 12 carbon atoms, a heteroaryl alkanoyl group having 1 to 20 carbon atoms, and 3 to 8 carbon atoms. Cycloalkanoyl group of.
The R ^21a in the general formula (3a) preferably includes an unsubstituted methyl group, an ethyl group, a propyl group, and a propyl group substituted with an N-acetyl-N-acetoxyamino group.
Further, examples of R ^21b in the above general formula (3a) include a carbazoyl group which may be substituted, a thioxanthonyl group which may be substituted, and a phenylsulfide group which may be substituted.

In addition, examples of the optional substituents in the general formulas (3) and (3a) include 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 and the like. Be done.
Specific examples of the oxime ester compound suitable for the present invention include, but are not limited to, the compounds exemplified below.

An oxime ester initiator having a carbazole group having a nitro group is also effective.
Examples of the keto-oxime-based compound include a compound containing a structural portion represented by the following general formula (4), and preferably an oxime ester-based compound represented by the following general formula (5).

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

In the above general formula (5), R ^23a may be substituted with a phenyl group, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 25 carbon atoms, and a heteroarylalkyl group having 1 to 20 carbon atoms. Group, alkoxycarbonylalkyl group with 3 to 20 carbon atoms, phenoxycarbonylalkyl group with 8 to 20 carbon atoms, alkylthioalkyl group with 2 to 20 carbon atoms, heteroaryloxycarbonylalkyl group with 1 to 20 carbon atoms or heteroarylthio Alkyl group, aminoalkyl group with 1 to 20 carbon atoms, alkanoyl group with 2 to 12 carbon atoms, alkenoyl group with 3 to 25 carbon atoms, cycloalkanoyl group with 3 to 8 carbon atoms, allylloyl group with 7 to 20 carbon atoms, A heteroallyloyl group having 1 to 20 carbon atoms, an alkoxycarbonyl group having 2 to 10 carbon atoms, an aryloxycarbonyl group having 7 to 20 carbon atoms, or a cycloalkylalkyl group having 1 to 10 carbon atoms is shown.
R ^23b represents any substituent, including aromatic or heteroaromatic rings.
In addition, R ^23a may form a ring together with R ^23b , and the linking group thereof may be an alkylene group having 1 to 10 carbon atoms and a polyethylene group (-(CH = CH) _r , respectively, which may have a substituent. -), Polyethynylene group (-(C≡C) _r- ) or a group composed of a combination thereof can be mentioned (where r is an integer of 0 to 3).

In the general formula (5), R ^24a may be substituted with an alkanoyl group having 2 to 12 carbon atoms, an alkenoyl group having 3 to 25 carbon atoms, a cycloalkanoyl group having 4 to 8 carbon atoms, and 7 carbon atoms. ~ 20 benzoyl group, 3 ~ 20 carbon heteroallyloyl group, 2 ~ 10 carbon alkoxycarbonyl group, 7 ~ 20 carbon aryloxycarbonyl group, 2 ~ 20 carbon heteroaryl group, or carbon Represents an alkylaminocarbonyl group of number 2-20.

The R ²⁴ in the general formula (4) and the R ^24a in the general formula (5) are preferably an alkanoyl group having 2 to 12 carbon atoms, a heteroaryl alkanoyl group having 1 to 20 carbon atoms, and 3 to 8 carbon atoms. Cycloalkanoyl group and allyloyl group having 7 to 20 carbon atoms can be mentioned.
The R ^23a in the above general formula (5) preferably includes an unsubstituted ethyl group, a propyl group, a butyl group, and an ethyl group or a propyl group substituted with a methoxycarbonyl group.
Further, examples of the R ^23b in the above general formula (5) include a carbazoyl group which may be substituted, and a phenylsulfide group which may be substituted.

In addition, examples of the optional substituents in the above general formulas (4) and (5) include 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 and the like. Be done.
Specific examples of the ketooxime ester-based compound suitable for the present invention include, but are not limited to, the compounds exemplified below.

These oxime and ketooxyester compounds are known compounds themselves, and are, for example, a series of compounds described in Japanese Patent Laid-Open No. 2000-80068 and Japanese Patent Application Laid-Open No. 2006-36750. It is a kind. In the present invention, the (D) photopolymerization initiator is preferably an oxime ester initiator and / or a ketooxime ester initiator.
The above photopolymerization initiator may be used alone or in combination of two or more.

The ratio of the photopolymerization initiator in the photosensitive coloring composition of the present invention is usually 0.4 to 15% by mass, preferably 0.5 to 10% by mass, based on the total solid content. If the proportion of the photopolymerization initiator is too large in this range, the developability tends to deteriorate, while if it is too small, a preferable shape of the colored cured product and the formation of steps may not be possible.
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. Classes; benzophenone derivatives such as benzophenone, Michler's ketone, 2-methylbenzophenone, 3-methylbenzophenone, 4-methylbenzophenone, 2-chlorobenzophenone, 4-bromobenzophenone, 2-carboxybenzophenone; 2,2-dimethoxy-2-phenyl Acetphenone, 2,2-diethoxyacetophenone, 1-hydroxycyclohexylphenyl ketone, α-hydroxy-2-methylphenylpropanol, 1-hydroxy-1-methylethyl- (p-isopropylphenyl) ketone, 1-hydroxy Acetphenone such as -1- (p-dodecylphenyl) ketone, 2-methyl- (4'-methylthiophenyl) -2-morpholino-1-propanone, 1,1,1-trichloromethyl- (p-butylphenyl) ketone Derivatives; Thioxanthone derivatives such as thioxanthone, 2-ethylthioxanthone, 2-isopropylthioxanthone, 2-chlorothioxanthone, 2,4-dimethylthioxanthone, 2,4-diisopropylthioxanthone, 2,4-diisopropylthioxanthone; p-dimethylamino An benzoate ester derivatives such as ethyl benzoate and ethyl p-diethylaminobenzoate; aclysine derivatives such as 9-phenylaclysine and 9- (p-methoxyphenyl) acridin; phenazine derivatives such as 9,10-dimethylbenzphenazine. ; Anthron derivatives such as Benz anthron can also be mentioned.

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

Here, R ^23a and R ^24a have the same meaning as the general formula (5).
R ^25a and R ^25b 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 having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, or an arylalkyl group having 7 to 30 carbon atoms. The hydrogen atom of the substituent represented by R ^25c may be further substituted 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. R ^25d represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, or an arylalkyl group having 7 to 30 carbon atoms. The alkyl moiety of the substituent represented by R ^25c may have a branched side chain and 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.

In formula (5-2), R ^26a represents —O—, —S—, —OCO— or —COO—.
R ^26b represents an alkylene group having 1 to 20 carbon atoms, an arylene group having 6 to 30 carbon atoms, or an arylene alkylene group having 7 to 30 carbon atoms.
The alkylene moiety of the substituent represented by R ^26b may be interrupted 1 to 5 times by —O—, —S—, —COO— or —OCO—. The alkylene moiety of the substituent represented by R ^26b may have a branched side chain or may be cyclohexylene.
R ^26c represents OH or COOH, and i represents an integer of 1 to 3.
* Indicates a bond.

The photopolymerization initiator may be used alone or in combination of two or more.
If necessary, the photopolymerization initiator may be blended with a sensitizing dye and a polymerization accelerator according to the wavelength of the image exposure light source for the purpose of increasing the sensitivity. Examples of the sensitizing dye are described in Japanese Patent Application Laid-Open No. 4-221958, Japanese Patent Application Laid-Open No. 4-219756, Japanese Patent Application Laid-Open No. 3-239703, and Japanese Patent Application Laid-Open No. 5-289335. Cmarin dye having a heterocyclic ring, 3-ketocoumarin compound described in Japanese Patent Application Laid-Open No. 3-239703, Japanese Patent Application Laid-Open No. 5-289335, pyrromethene dye described in Japanese Patent Application Laid-Open No. 6-19240, and others. Japanese Patent Application Laid-Open No. 47-2528, Japanese Patent Application Laid-Open No. 54-155292, Japanese Patent Application Laid-Open No. 45-373777, Japanese Patent Application Laid-Open No. 48-84183, Japanese Patent Application Laid-Open No. 52-112681, Japan Japanese Patent Application Laid-Open No. 58-15503, Japanese Patent Application Laid-Open No. 60-88805, Japanese Patent Application Laid-Open No. 59-56403, Japanese Patent Application Laid-Open No. 2-69, Japanese Patent Application Laid-Open No. 57-168888, Japan Examples thereof include dyes having a dialkylaminobenzene skeleton described in JP-A-5-107761, Japanese Patent Laid-Open No. 5-210240, and Japanese Patent Application Laid-Open No. 4-288818.

Of these sensitizers, preferred are amino group-containing sensitizers, and more preferred are compounds having an amino group and a phenyl group in the same molecule. Particularly preferred are, for example, 4,4'-dimethylaminobenzophenone, 4,4'-diethylaminobenzophenone, 2-aminobenzophenone, 4-aminobenzophenone, 4,4'-diaminobenzophenone, 3,3'-diaminobenzophenone. , 3,4-Diaminobenzophenone and other benzophenone compounds; 2- (p-dimethylaminophenyl) benzoxazole, 2- (p-diethylaminophenyl) benzoxazole, 2- (p-dimethylaminophenyl) benzo [4,5 ] Benzoxazole, 2- (p-dimethylaminophenyl) benzo [6,7] benzoxazole, 2,5-bis (p-diethylaminophenyl) -1,3,4-oxazole, 2- (p-dimethylaminophenyl) ) Benzothiazole, 2- (p-diethylaminophenyl) benzothiazole, 2- (p-dimethylaminophenyl) benzimidazole, 2- (p-diethylaminophenyl) benzimidazole, 2,5-bis (p-diethylaminophenyl)- 1,3,4-Thiadiazol, (p-dimethylaminophenyl) pyridine, (p-diethylaminophenyl) pyridine, (p-dimethylaminophenyl) quinoline, (p-diethylaminophenyl) quinoline, (p-dimethylaminophenyl) pyrimidine , (P-diethylaminophenyl) P-dialkylaminophenyl group-containing compound such as pyrimidin. The most preferable of these is 4,4'-dialkylaminobenzophenone.
The sensitizing dye may also be used alone or in combination of two or more.

As the polymerization accelerator, for example, aromatic amines such as ethyl p-dimethylaminobenzoate and 2-dimethylaminoethyl benzoate, aliphatic amines such as n-butylamine and N-methyldiethanolamine, and mercapto compounds described later are used. Be done. The polymerization accelerator may be used alone or in combination of two or more.

<Photopolymerizable monomer>
In the photosensitive coloring composition of the present invention, it is preferable to further contain a photopolymerizable monomer (photopolymerizable compound) in terms of sensitivity and the like.
Examples of the photopolymerizable monomer used in the present invention include compounds having at least one ethylenically unsaturated group in the molecule (hereinafter, may be referred to as “ethylenic monomer”). Specifically, for example, (meth) acrylic acid, (meth) acrylic acid alkyl ester, acrylonitrile, styrene, a carboxylic acid having one ethylenically unsaturated bond, and a monoester of polyvalent or monovalent alcohol, etc. Can be mentioned.

In the present invention, it is particularly desirable to use a polyfunctional ethylenic monomer having two or more ethylenically unsaturated groups in one 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; aliphatic polyhydroxy compounds, aromatics. Examples thereof include an ester obtained by an esterification reaction between a polyvalent hydroxy compound such as a polyhydroxy compound and an unsaturated carboxylic acid and a polybasic carboxylic acid.

Examples of the ester of the aliphatic polyhydroxy compound and the unsaturated carboxylic acid include ethylene glycol diacrylate, triethylene glycol diacrylate, trimethylol propanetriacrylate, trimethylol ethanetriacrylate, pentaerythritol diacrylate, and pentaerythritol triacrylate. Acrylic acid esters of aliphatic polyhydroxy compounds such as pentaerythritol tetraacrylate, dipentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, and glycerol acrylate, and methacrylic acid esters in which the acrylates of these exemplary compounds are replaced with methacrylates. Similarly, an itaconic acid ester replaced with itaconate, a crotonic acid ester replaced with clonate, a maleic acid ester replaced with maleate, and the like can be mentioned.

Examples of the ester of the aromatic polyhydroxy compound and the unsaturated carboxylic acid include acrylic acid esters and methacrylic acid esters of aromatic polyhydroxy compounds such as hydroquinone diacrylate, hydroquinone dimethacrylate, resorcindiacrylate, resorcindimethacrylate, and pyrogalloltriacrylate. And so on.
The ester obtained by the esterification reaction of a polybasic carboxylic acid and an unsaturated carboxylic acid with a polyvalent hydroxy compound is not necessarily a single substance, but typical specific examples include acrylic acid, phthalic acid, and Examples thereof include a condensate of ethylene glycol, a condensate of acrylic acid, maleic acid and diethylene glycol, a condensate of methacrylic acid, terephthalic acid and pentaerythritol, a condensate of acrylic acid, adipic acid, butanediol and glycerin.

In addition, as an example of the polyfunctional ethylenic monomer used in the present invention, a polyisocyanate compound is reacted with a hydroxyl group-containing (meth) acrylic acid ester or a polyisocyanate compound is reacted with a polyol and a hydroxyl group-containing (meth) acrylic acid ester. Urethane (meth) acrylates as obtained; epoxy acrylates such as an addition reaction product of a polyvalent epoxy compound and hydroxy (meth) acrylate or (meth) acrylic acid; acrylamides such as ethylenebisacrylamide; diallyl phthalate. Allyl esters such as; vinyl group-containing compounds such as divinylphthalate 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 (manufactured by Nippon Kayaku Kagaku Co., Ltd.) and the like.
These may be used alone or in combination of two or more.

<Other ingredients of the photosensitive coloring composition>
In addition to the above-mentioned components, the photosensitive coloring composition of the present invention includes an adhesion improver such as an organic solvent and a silane coupling agent, a coatability improver, a development improver, an ultraviolet absorber, an antioxidant, and a surfactant. , Pigment derivatives and the like can be appropriately blended.

(1) Organic Solvent The photosensitive coloring composition of the present invention is usually used as (A) a coloring material, (B) a dispersant, (C) an alkali-soluble resin, (D) a photopolymerization initiator, and if necessary. The photopolymerizable monomer and other various materials are used in a state of being dissolved or dispersed in an organic solvent.
As the organic solvent, it is preferable to select a solvent having a boiling point in the range of 100 to 300 ° C. More preferably, it is a solvent having a boiling point of 120 to 280 ° C.

Examples of such an organic solvent include the following.
Ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-n-butyl ether, propylene glycol-t-butyl ether, diethylene glycol monomethyl Ether, diethylene glycol monoethyl ether, diethylene glycol mono-n-butyl ether, methoxymethylpentanol, dipropylene glycol monoethyl ether, dipropylene glycol monomethyl ether, 3-methyl-3-methoxybutanol, triethylene glycol monomethyl ether, triethylene glycol Glycol monoalkyl ethers such as monoethyl ether, tripropylene glycol methyl ether;
Glycoldialkyl 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, 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 monomethyl ether acetate, triethylene glycol monomethyl ether acetate, triethylene glycol monoethyl Glycolalkyl ether acetates such as ether acetate, 3-methyl-3-methoxybutyl acetate;
Glycol diacetates such as ethylene glycol diacetate, 1,3-butylene glycol diacetate, 1,6-hexanol diacetate;
Alkyl acetates such as cyclohexanol acetate;
Ethers such as amyl ether, diethyl ether, dipropyl ether, diisopropyl ether, dibutyl ether, diamil ether, ethylisobutyl ether, dihexyl ether;

Like acetone, methyl ethyl ketone, methyl amyl ketone, methyl isopropyl ketone, methyl isoamyl ketone, diisopropyl ketone, diisobutyl ketone, methyl isobutyl ketone, cyclohexanone, ethyl amyl ketone, methyl butyl ketone, methylhexyl ketone, methylnonyl ketone, methoxymethylpentanone. Ketones;
Monohydric or polyhydric alcohols such as ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, propylene glycol, butanediol, diethylene glycol, dipropylene glycol, triethylene glycol, methoxymethylpentanol, glycerin, benzyl alcohol;
Aliphatic hydrocarbons such as n-pentane, n-octane, diisobutylene, n-hexane, hexene, isoprene, dipentene, dodecane;
Alicyclic hydrocarbons such as cyclohexane, methylcyclohexane, methylcyclohexene, bicyclohexyl;

Aromatic hydrocarbons such as benzene, toluene, xylene, cumene;
Amilformate, ethylformate, ethyl acetate, butyl acetate, propyl acetate, amyl acetate, methylisobutyrate, ethylene glycol acetate, ethylpropionate, propylpropionate, butyl butyrate, isobutyl butyrate, methyl isobutyrate, ethyl Caprilate, butyl stearate, ethyl benzoate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, propyl 3-methoxypropionate, 3-methoxypropionic acid Chain or cyclic esters such as butyl, γ-butyrolactone;
Alkoxycarboxylic acids such as 3-methoxypropionic acid, 3-ethoxypropionic acid;
Halogenated hydrocarbons such as butyl chloride and amilkloride;
Etheretones such as methoxymethylpentanone;
Nitriles such as acetonitrile and benzonitrile.

Examples of commercially available solvents corresponding to the above include Mineral Spirit, Barsol # 2, Apco # 18 Solvent, Apco Thinner, and Sokal Solvent No. 1 and No. 2. Solvento # 150, Shell TS28 Solvent, Calbitol, Ethylcarbitol, Butylcarbitol, Methylcellosolve (“Cellosolve” is a registered trademark; the same shall apply hereinafter), Ethylcellosolve, Ethylcellosolve acetate, Methylcellosolve acetate, Diglime (any of them). Also the product name) and so on.
These organic solvents may be used alone or in combination of two or more.

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

Among the above organic solvents, glycol alkyl ether acetates are preferable because they have a good balance of coatability, surface tension and the like, and the solubility of the constituent components in the composition is relatively high.
Further, the glycol alkyl ether acetates may be used alone or in combination with other organic solvents. Glycol monoalkyl ethers are particularly preferable as the organic solvent to be used in combination. Of these, propylene glycol monomethyl ether is particularly preferable because of the solubility of the constituents in the composition. Glycol monoalkyl ethers have high polarity, and if the amount added is too large, the pigment tends to aggregate, and the storage stability of the colored resin composition obtained later tends to increase and the storage stability tends to decrease. The proportion of glycol monoalkyl ethers in the solvent is preferably 5% by mass to 30% by mass, more preferably 5% by mass to 20% by mass.

It is also preferable to use an organic solvent having a boiling point of 150 ° C. or higher (hereinafter, may be referred to as “high boiling point solvent”) in combination. By using such a high boiling point solvent in combination, the colored resin composition becomes difficult to dry, but there is an effect of preventing the uniformly dispersed state of the pigment in the composition from being destroyed by rapid drying. That is, for example, there is an effect of preventing the generation of foreign matter defects due to precipitation and solidification of coloring materials and the like at the tip of the slit nozzle. Among the above-mentioned various solvents, diethylene glycol mono-n-butyl ether, diethylene glycol mono-n-butyl ether acetate, and diethylene glycol monoethyl ether acetate are particularly preferable because of such a high effect.

The content of the high boiling point solvent in the organic solvent is preferably 3% by mass to 50% by mass, more preferably 5% by mass to 40% by mass, and particularly preferably 5% by mass to 30% by mass. If the amount of the high boiling point solvent is too small, for example, coloring material may precipitate and solidify at the tip of the slit nozzle to cause foreign matter defects, and if it is too large, the drying temperature of the composition becomes slow, and black described later In the matrix manufacturing process, there is a concern that it may cause problems such as poor tact in the vacuum drying process and pin marks of prebake.

The high boiling point solvent having a boiling point of 150 ° C. or higher may be glycol alkyl ether acetates or glycol alkyl ethers. In this case, a high boiling point solvent having a boiling point of 150 ° C. or higher is separately contained. It doesn't have to be.
As a preferable high boiling solvent, for example, among the above-mentioned various solvents, diethylene glycol mono-n-butyl ether acetate, diethylene glycol monoethyl ether acetate, dipropylene glycol methyl ether acetate, 1,3-butylene glycol diacetate, 1,6-hexanoldi Examples include acetate and triacetin.

(2) Adhesion Improver The photosensitive coloring composition of the present invention may contain an adhesion improver in order to improve the adhesion to the substrate. As the adhesion improver, a silane coupling agent, a phosphoric acid group-containing compound and the like are preferable.
As the type of silane coupling agent, various types such as epoxy type, (meth) acrylic type, and amino type can be used alone or in combination of two or more.

Preferred silane coupling agents include (meth) acryloxysilanes such as 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, and 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane. , Epoxysilanes such as 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, ureidosilanes such as 3-ureidopropyltriethoxysilane, Examples thereof include isocyanate silanes such as 3-isocyanate propyltriethoxysilane, and a silane coupling agent for epoxy silanes is particularly preferable.
As the phosphoric acid group-containing compound, (meth) acryloyl group-containing phosphates are preferable, and those represented by the following general formulas (g1), (g2) or (g3) are preferable.

In the above 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 be used alone or in combination of two or more.

(3) Surfactant The photosensitive coloring composition of the present invention may contain a surfactant in order to improve coatability.

As the surfactant, for example, various agents such as anionic type, cationic type, nonionic type and amphoteric surfactant can be used. Of these, nonionic surfactants are preferable because they are less likely to adversely affect various properties, and fluorine-based and silicon-based surfactants are particularly effective in terms of coatability.
Examples of such a surfactant include TSF4460 (manufactured by GE Toshiba Silicone Co., Ltd.), DFX-18 (manufactured by Neos Co., Ltd.), BYK-300, BYK-325, BYK-330 (manufactured by BIC Chemie Co., Ltd.), and KP340 (Shinetsu Silicone Co., Ltd.). F-470, F-475, F-478, F-559 (DIC), SH7PA (Torre Silicone), DS-401 (Daikin), L-77 (Nippon Unicar) ), FC4430 (manufactured by Sumitomo 3M) and the like.
As the surfactant, one type may be used, or two or more types may be used in combination in any combination and ratio.

(4) Pigment Derivative The photosensitive coloring composition of the present invention may contain a pigment derivative as a dispersion aid in order to improve dispersibility and storage stability.
Pigment derivatives include azo-based, phthalocyanine-based, quinacridone-based, benzimidazolone-based, quinophthalone-based, isoindoleinone-based, dioxazine-based, anthraquinone-based, indanslen-based, perylene-based, perinone-based, diketopyrrolopyrrole-based, and dioxazine. Derivatives such as those of the system can be mentioned, but among them, phthalocyanine-based and quinophthalone-based derivatives are preferable.
As the substituent of the pigment derivative, a sulfonic acid group, a sulfonamide group and a quaternary salt thereof, a phthalimidemethyl group, a dialkylaminoalkyl group, a hydroxyl group, a carboxyl group, an amide group and the like are directly on the pigment skeleton or an alkyl group, an aryl group or a complex. Examples thereof include those bonded via a ring group or the like, and a sulfonic acid group is preferable. Further, a plurality of these substituents may be substituted into one pigment skeleton.

Specific examples of the pigment derivative include phthalocyanine sulfonic acid derivative, quinophthalone sulfonic acid derivative, anthraquinone sulfonic acid derivative, quinacridone sulfonic acid derivative, diketopyrrolopyrrole sulfonic acid derivative, dioxazine sulfonic acid derivative and the like. These may be used alone or in combination of two or more.

(5) Photoacid generator A photoacid generator is a compound that can generate an acid by ultraviolet rays, and there is a cross-linking agent such as a melamine compound due to the action of the acid generated during exposure. The cross-linking reaction will proceed. Among the photoacid generators, those having high solubility in a solvent, particularly those having high solubility in a solvent used in a photosensitive coloring composition are preferable, and for example, diphenyliodonium, ditriliodonium, and phenyl (p-anisyl) are preferable. Iodium, bis (m-nitrophenyl) iodonium, bis (p-tert-butylphenyl) iodonium, bis (p-chlorophenyl) iodonium, bis (n-dodecyl) iodonium, p-isobutylphenyl (p-tolyl) iodonium, p -Diaryliodonium such as isopropylphenyl (p-tolyl) iodonium, or chloride, bromide, or borofluoride salt, hexafluorophosphate salt, hexafluoroarsenate salt, aromatic sulfonate salt of triarylsulfonium such as triphenylsulfonium. , Tetrakiss (pentafluorophenyl) borate salt and the like, sulfonium organic boron complexes such as diphenylphenacil sulfonium (n-butyl) triphenyl borate, or 2-methyl-4,6-bistrichloromethyltriazine, 2- ( Examples include, but are not limited to, triazine compounds such as 4-methoxyphenyl) -4,6-bistrichloromethyltriazine.

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

In formula (6), R ⁶¹ represents -NR ⁶⁶ R ⁶⁷ groups or an aryl group having 6 to 12 carbon atoms, and when R ⁶¹ is -NR ⁶⁶ R ⁶⁷ groups, R ⁶² , R ⁶³ , R ⁶⁴ , R ⁶⁵ . , R ⁶⁶ and one of R ⁶⁷ , and when R ⁶¹ is an aryl group having 6 to 12 carbon atoms, one of R ⁶² , R ⁶³ , R ⁶⁴ and R ⁶⁵ represents a -CH ₂ OR ⁶⁸ group, and R ⁶² . , R ⁶³ , R ⁶⁴ , R ⁶⁵ , R ⁶⁶ and R ⁶⁷ independently represent hydrogen or -CH ₂ OR ⁶⁸ groups, where R ⁶⁸ is a hydrogen atom or an alkyl group with 1-4 carbon atoms. show.
Here, the aryl group having 6 to 12 carbon atoms is typically a phenyl group, a 1-naphthyl group or a 2-naphthyl group, and these phenyl groups and naphthyl groups include an alkyl group, an alkoxy group, a halogen atom and the like. Substituents may be attached. The alkyl group and the alkoxy group can each 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.

The melamine-based compound corresponding to the general formula (6), that is, the compound of the following general formula (6-1) includes hexamethylol melamine, pentamethylol melamine, tetramethylol melamine, hexamethoxymethyl melamine, pentamethoxymethyl melamine, and tetramethoxy. Includes methyl melamine, hexaethoxymethyl melamine and the like.

In formula (6-1), if 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 . The rest of R ⁶² , R ⁶³ , R ⁶⁴ , R ⁶⁵ , R ⁶⁶ and R ⁶⁷ represent hydrogen atoms or -CH ₂ OR ⁶⁸ groups independently of each ^{other, where R 68 is} a hydrogen atom or Represents an alkyl group.

Further, the guanamine compound corresponding to the general formula (6), that is, the compound in which R ⁶¹ is aryl in the general formula (6) includes tetramethylolbenzoguanamine, tetramethoxymethylbenzoguanamine, trimethoxymethylbenzoguanamine, and tetraethoxymethylbenzoguanamine. Etc. are included.

Further, a cross-linking agent having a methylol group or a methylol alkyl ether group can also be used. An example is given below.
2,6-bis (hydroxymethyl) -4-methylphenol, 4-tert-butyl-2,6-bis (hydroxymethyl) phenol, 5-ethyl-1,3-bis (hydroxymethyl) perhydro-1,3 , 5-Triazine-2-one (commonly known as N-ethyldimethyloltriazone) or its dimethyl ether form, Dimethylol trimethyleneurea or its dimethyl ether form, 3,5-bis (hydroxymethyl) perhydro-1,3,5- Oxaziazine-4-one (commonly known as dimethylolurone) or a dimethyl ether form thereof, tetramethylol glioxaldiurein or a tetramethyl ether form thereof.

It should be noted that these cross-linking agents may be used alone or in combination of two or more. The amount of the cross-linking agent used is preferably 0.1 to 15% by mass, particularly preferably 0.5 to 10% by mass, based on the total solid content of the photosensitive coloring composition.

(7) Mercapto compound It is also possible to add a mercapto compound as a polymerization accelerator and in order to improve the adhesion to the substrate.

Types of mercapto compounds include 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, 2-mercaptobenzoimidazole, hexanedithiol, decandithiol, 1,4-dimethylmercaptobenzene, butanediol bisthiopropionate, butanediol bis. Thioglycolate, Ethylene Glycol Bisthioglycolate, Trimethylol Propantristhioglycolate, Butanediol Bisthiopropionate, Trimethylol Propanistristhiopropionate, Trimethylol Propanistristhioglycolate, Pentaerythritol Tetrakissthiopropio Nate, pentaerythritol tetrakisthioglycolate, trishydroxyethyltristhiopropionate, ethylene glycol bis (3-mercaptobutyrate), butanediol bis (3-mercaptobutyrate), 1,4-bis (3-mercaptobutyrate) Liloxy) butane, trimethylol propanthris (3-mercaptobutyrate), pentaerythritol tetrakis (3-mercaptobutyrate), pentaerythritol tris (3-mercaptobutyrate), ethylene glycol bis (3-mercaptoisobutyrate) , Butanediol bis (3-mercaptoisobutyrate), trimethylpropanthris (3-mercaptoisobutyrate), 1,3,5-tris (3-mercaptobutyloxyethyl) -1,3,5-triazine- Examples thereof include mercapto compounds having a heterocycle such as 2,4,6 (1H, 3H, 5H) -trione, or aliphatic polyfunctional mercapto compounds. These can be used alone or in admixture of two or more.

<Amount of ingredients in the photosensitive coloring composition>
In the photosensitive coloring composition of the present invention, the content of the coloring material (A) is usually preferably 10% by mass or more and 20% by mass or more with respect to the total solid content in the photosensitive coloring composition. , Usually 50% by mass or less. If the content of the (A) coloring material is too small, a sufficient optical density (OD) may not be obtained, and conversely, if the content of the (A) coloring material is too large, sufficient image forming property is obtained. May not be obtained. The content ratio of the (A-1) organic black pigment to 100% by mass of the (A) coloring material is usually 10% by mass or more, preferably 30% by mass or more, and usually 100% by mass or less. If the content of the (A-1) organic black pigment in the (A) coloring material is too small, a sufficient optical density (OD) may not be obtained.

In the photosensitive coloring composition of the present invention, the (A) coloring material may contain (A-2) an organic coloring pigment together with (A-1) an organic black pigment. At that time, the content ratio of the (A-1) organic black pigment to 100% by mass of the (A) coloring material is usually 10% by mass or more, preferably 20% by mass or more, more preferably 30% by mass or more, and usually 90% by mass. Hereinafter, it is preferably 80% by mass or less, more preferably 60% by mass or less. The content of the (A-2) organic coloring 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. Below, it is more preferably 70% by mass or less. (A-2) If the content of the organic coloring pigment is too large, a sufficient optical density may not be obtained. The content ratio of the (A-1) organic black pigment to 100 parts by mass of the (A-2) organic coloring pigment is usually 15 parts by mass or more, preferably 20 parts by mass or more, usually 900 parts by mass or less, preferably 800 parts by mass. Parts 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-1) carbon black may be contained in the (A) coloring material together with (A-1) organic black pigment. At that time, the content ratio of the (A-1) organic black pigment to 100% by mass of the (A) coloring material is usually 50% by mass or more, preferably 60% by mass or more, and usually 95% by mass or less, preferably 90% by mass. It is as follows. The content of (A-3) carbon black 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) If the content of carbon black is too large, the volume resistance value may decrease or the relative permittivity may increase. The content ratio of the (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, usually 2000 parts by mass or less, preferably 1000 parts by mass. It is as follows.

Further, in the photosensitive coloring composition of the present invention, the (A) coloring material may contain (A-2) an organic coloring pigment and (A-3) carbon black together with (A-1) an organic black pigment. be. At that time, the content ratio of the (A-1) organic black pigment to 100% by mass of the (A) coloring material is usually 10% by mass or more, preferably 20% by mass or more, and usually 80% by mass or less, preferably 70% by mass or less. Is. The content of the (A-2) organic coloring pigment is usually 10% by mass or more, preferably 20% by mass or more, and usually 60% by mass or less, preferably 50% by mass or less.
Further, the content ratio of (A-3) carbon black 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 (A-1) organic black pigment to 100 parts by mass of the (A-2) organic coloring pigment is usually 15 parts by mass or more, preferably 20 parts by mass or more, usually 800 parts by mass or less, preferably 700. It is less than the mass part. The content ratio of the (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, usually 1000 parts by mass or less, preferably 900 parts by mass. It is as follows.

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

The content of the alkali-soluble resin (C) is usually 5% by mass or more, preferably 10% by mass or more, and usually 85% by mass or less, preferably preferably 85% by mass, based on the total solid content of the photosensitive coloring composition of the present invention. It is 80% by mass or less. (C) When the content of the alkali-soluble resin is extremely low, the solubility of the unexposed portion in the developing solution is lowered, and development defects are likely to be induced. On the contrary, if the content of the (C) alkali-soluble resin is too large, the permeability of the developing solution to the exposed portion tends to be high, and the sharpness and adhesion of the pixels may be deteriorated.

The content of the photopolymerization initiator (D) is usually 0.1% by mass or more, preferably 0.5% by mass or more, more preferably 1% by mass, based on the total solid content of the photosensitive coloring composition of the present invention. % Or more, usually 15% by mass or less, preferably 10% by mass or less. (D) If the content of the photopolymerization initiator is too small, the sensitivity may decrease, and if it is too large, the solubility of the unexposed portion in the developing solution decreases, and development defects are likely to be induced.

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

(D) If the blending ratio of the photopolymerization initiator-based component consisting of the photopolymerization initiator and the polymerization accelerator is extremely low, it may cause the sensitivity to the exposed light to decrease, and conversely, if it is extremely high, the unexposed portion Solubility in the developer may decrease, leading to poor development.
Further, the proportion 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 15% by mass or less, based on the total solid content in the photosensitive coloring composition from the viewpoint of sensitivity. It is preferably 10% by mass or less.

When a photopolymerizable monomer is used, its content is usually 30% by mass or less, preferably 20% by mass or less, based on the total solid content of the photosensitive coloring composition. If the content of the photopolymerizable monomer is too large, the permeability of the developing solution to the exposed portion becomes high, and it may be difficult to obtain a good image. The lower limit of the content of the photopolymerizable monomer is usually 1% by mass or more, preferably 5% by mass or more.

When the adhesion improver is used, the content thereof is usually 0.1 to 5% by mass, preferably 0.2 to 3% by mass, and more preferably 0.4 with respect to the total solid content in the photosensitive coloring composition. ~ 2% by mass. If the content of the adhesion improver is less than the above range, the effect of improving the adhesion may not be sufficiently obtained, and if it is too large, the sensitivity may be lowered or a residue may remain after development and become a defect. ..

When a surfactant is used, its content is usually 0.001 to 10% by mass, preferably 0.005 to 1% by mass, more preferably 0, based on the total solid content in the photosensitive coloring composition. It is 0.01 to 0.5% by mass, most preferably 0.03 to 0.3% by mass. If the content of the surfactant is less than the above range, the smoothness and uniformity of the coating film may not be exhibited, and if it is too large, the smoothness and uniformity of the coating film may not be exhibited and other properties may be deteriorated. In some cases.
The photosensitive coloring composition of the present invention is prepared by using the above-mentioned organic solvent so that the solid content concentration is usually 5 to 50% by mass, preferably 10 to 30% by mass.

<Physical characteristics of the photosensitive coloring composition>
The photosensitive coloring composition of the present invention can be suitably used for forming a black matrix, and from such a viewpoint, it is preferably black, and the optical density (OD) per 1 μm of the coating film thereof is high. It is preferably 1.0 or more.

<Manufacturing method of photosensitive coloring composition>
The photosensitive coloring composition of the present invention (hereinafter, may be referred to as "resist") is produced according to a conventional method.
Usually, it is preferable that the coloring material (A) is dispersed in advance using a paint conditioner, a sand grinder, a ball mill, a roll mill, a stone mill, a jet mill, a homogenizer or the like. Since the (A) coloring material is made into fine particles by the dispersion treatment, the coating characteristics of the resist are improved.

The dispersion treatment is usually preferably carried out in a system in which (A) a coloring material, an organic solvent, and (B) a dispersant, and (C) a part or all of an alkali-soluble resin are used in combination (hereinafter, for the dispersion treatment). The mixture to be provided and the composition obtained by the treatment may be referred to as "ink" or "pigment dispersion"). In particular, it is preferable to use a polymer dispersant as the dispersant (B) because the thickening of the obtained ink and resist over time is suppressed (excellent in dispersion stability).
As described above, in the step of producing the resist, it is preferable to produce a pigment dispersion liquid containing at least (A) a coloring material, an organic solvent, and (B) a dispersant. As the (A) coloring material, the organic solvent, and the (B) dispersant that can be used in the pigment dispersion liquid, those described as being usable in the photosensitive coloring composition can be preferably adopted.

When the liquid containing all the components to be blended in the colored resin composition is subjected to the dispersion treatment, the highly reactive component may be denatured due to the heat generated during the dispersion treatment. Therefore, it is preferable to perform the dispersion treatment in a system containing a polymer dispersant.
When the (A) coloring material is dispersed by a sand grinder, glass beads or zirconia beads having a diameter of about 0.1 to 8 mm are preferably used. The dispersion treatment conditions are such that the temperature is usually 0 ° C to 100 ° C, preferably in the range of room temperature to 80 ° C. The dispersion time varies depending on the composition of the liquid, the size of the dispersion treatment device, etc., and is appropriately adjusted. The guideline for dispersion is to control the gloss of the ink so that the 20-degree mirror gloss (JIS Z8741) of the resist is in the range of 50 to 300. When the glossiness of the resist is low, the dispersion treatment is not sufficient and rough pigment (coloring material) particles often remain, which may result in insufficient developability, adhesion, resolution, etc. .. Further, 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 that the dispersion stability tends to be impaired.

The dispersed 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 above dispersion treatment and the above other components contained in the resist are mixed to obtain a uniform solution. In the resist manufacturing process, fine dust is often mixed in the liquid, so it is desirable to filter the obtained resist with a filter or the like.

[Cursed product]
A cured product can be obtained by curing the photosensitive coloring composition of the present invention. The cured product obtained by curing the photosensitive coloring composition can be suitably used as a black matrix or a coloring spacer.

[Black Matrix]
Next, the black matrix using the photosensitive coloring composition of the present invention will be described according to the production method thereof.

(1) Support The material of the support for forming the black matrix is not particularly limited as long as it has an appropriate strength. A transparent substrate is mainly used, and as the material, for example, polyester resin such as polyethylene terephthalate, polyolefin resin such as polypropylene and polyethylene, thermoplastic resin sheet such as polycarbonate, polymethylmethacrylate and polysulphon, and epoxy resin. , A heat-curable resin sheet such as an unsaturated polyester resin or a poly (meth) acrylic resin, or various types of glass. Among these, glass and heat-resistant resin are preferable from the viewpoint of heat resistance. Further, a transparent electrode such as ITO or IZO may be formed on the surface of the substrate. Other than the transparent substrate, it can be formed on the 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, and the like, if necessary, in order to improve surface physical properties such as adhesiveness. ..
The thickness of the transparent substrate is usually in the range of 0.05 to 10 mm, preferably 0.1 to 7 mm. When the thin film forming treatment of various resins is performed, 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 by the above-mentioned photosensitive coloring composition of the present invention, the photosensitive coloring composition of the present invention is applied on a transparent substrate, dried, and then the photosensitive coloring composition is dried. A photomask is placed on the sex coloring composition, and a black matrix is formed by image exposure, development, and heat curing or photocuring as necessary through the photomask.
Although the black matrix of the present invention is effective for forming on the TFT element substrate, its configuration is not particularly limited in each of the COA and BOA methods, and various configurations can be supported. ..

(3) Formation of Black Matrix (3-1) Application of Photosensitive Coloring Composition The application of the photosensitive coloring composition for black matrix onto a transparent substrate is performed by a spinner method, a wire bar method, a flow coating method, or a die coating method. , The roll coating method, the spray coating method, or the like. Above all, according to the die coating method, the amount of coating liquid used is significantly reduced, and there is no influence of mist or the like adhering when the spin coating method is used, and the generation of foreign substances is suppressed. It is preferable from.

If the thickness of the coating film is too thick, it may be difficult to develop the pattern and it may be difficult to adjust the gap in the liquid crystal cell formation step. May be impossible. The thickness of the coating film is usually preferably in the range of 0.2 to 10 μm, more preferably in the range of 0.5 to 6 μm, and further preferably in the range of 1 to 4 μm as the film thickness after drying. be.

(3-2) Drying of coating film It is preferable to dry the coating film after applying the photosensitive coloring composition to the substrate by a drying method using a hot plate, an IR oven, or a convection oven. The drying conditions can be appropriately selected according to the type of the solvent component, the performance of the dryer used, and the like. The drying time is usually selected in the range of 15 seconds to 5 minutes at a temperature of 40 to 200 ° C., preferably at a temperature of 50 to 130 ° C., depending on the type of solvent component, the performance of the dryer used, and the like. It is selected in the range of 30 seconds to 3 minutes.
The higher the drying temperature, the better the adhesiveness of the coating film to the transparent substrate, but if it is too high, the (C) alkali-soluble resin may be decomposed to induce thermal polymerization and cause development defects. The step of drying the coating film may be a vacuum drying method in which the coating film is dried in a reduced pressure chamber without raising the temperature.

(3-3) Exposure Image exposure is performed by superimposing a negative mask pattern on a coating film of a photosensitive coloring composition and irradiating a light source of ultraviolet rays or visible light through the mask pattern. At this time, if necessary, in order to prevent the sensitivity of the photopolymerizable layer from being lowered by oxygen, exposure may be performed after forming an oxygen blocking layer such as a polyvinyl alcohol layer on the photopolymerizable coating film. The light source used for the above image exposure is not particularly limited. Examples of the light source include a lamp light source such as a xenon lamp, a halogen lamp, a tungsten lamp, a high pressure mercury lamp, an ultrahigh pressure mercury lamp, a metal halide lamp, a medium pressure mercury lamp, a low pressure mercury lamp, a carbon arc, and a fluorescent lamp, an argon ion laser, and a YAG laser. Examples thereof include laser light sources such as an excima laser, a nitrogen laser, a helium cadmium laser, and a semiconductor laser. An optical filter can also be used when irradiating light of a specific wavelength for use.

(3-4) Development The black matrix according to the present invention is an aqueous solution containing an organic solvent or a surfactant and an alkaline compound after image exposure of a coating film made of a photosensitive coloring composition with the above-mentioned light source. An image can be formed and produced on a substrate by development using. The aqueous solution may further contain an organic solvent, a buffer, a complexing agent, a dye or a pigment.

Examples of alkaline compounds include sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium carbonate, potassium carbonate, sodium hydrogencarbonate, potassium hydrogencarbonate, sodium silicate, potassium silicate, sodium metasilicate, sodium phosphate, and potassium phosphate. , Inorganic alkaline compounds such as sodium hydrogen phosphate, potassium hydrogen phosphate, sodium dihydrogen phosphate, potassium dihydrogen phosphate, ammonium hydroxide, mono-di or triethanolamine, mono-di or trimethylamine. , Mono-di- or triethylamine, mono- or diisopropylamine, n-butylamine, mono-di- or triisopropanolamine, ethyleneimine, ethylenediimine, tetramethylammonium hydroxide (TMAH), organic alkaline such as choline. Examples include compounds. These alkaline compounds may be a mixture of two or more kinds.

Examples of the surfactant include nonionic surfactants such as polyoxyethylene alkyl ethers, polyoxyethylene alkylaryl ethers, polyoxyethylene alkyl esters, sorbitan alkyl esters, and monoglyceride alkyl esters, and alkylbenzene sulfonic acids. Examples thereof include anionic surfactants such as salts, alkylnaphthalene sulfonates, alkyl sulfates, alkyl sulfonates and sulfosuccinic acid ester salts, and amphoteric surfactants such as alkylbetaines and amino acids.

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

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

(3-5) Thermosetting Treatment The substrate after development is subjected to a thermosetting treatment or a photocuring treatment, preferably a thermosetting treatment. The thermosetting treatment conditions at this time are selected in the range of 100 to 280 ° C., preferably 150 to 250 ° C., and the time is selected in the range of 5 to 60 minutes.
The line width of the black matrix formed as 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. 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, usually 2 or more.
Further, 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 a method described later.

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

[Image display device]
The image display device of the present invention is not particularly limited as long as it is a device for displaying an image or a moving image, and examples thereof include a liquid crystal display device and an organic EL (Electro Luminesence) display described later.

[Liquid crystal display device]
The liquid crystal display device of the present invention is manufactured by using the above-mentioned black matrix of the present invention, and is not particularly limited in terms of the formation order and formation position of the color pixels and the black matrix.
For example, the black matrix of the present invention is provided on the TFT element substrate, red, green, and blue pixels are formed, and if necessary, an overcoat layer is formed. Etc. are formed and used as a part of parts such as color displays and liquid crystal displays. Further, in some applications such as a plane alignment type drive system (IPS mode), a transparent electrode may not be formed.

In a liquid crystal display device, usually, an alignment film is formed on a color filter, a spacer is sprayed on the alignment film, a photo spacer is formed, and then the liquid crystal cell is formed by bonding with a facing substrate. The liquid crystal is injected into the cell and connected to the counter electrode to complete the process. As the alignment film, a resin film such as polyimide is suitable. A gravure printing method and / or a flexographic printing method is usually adopted for forming the alignment film, and the thickness of the alignment film is several tens of nm. After the alignment film is cured by heat firing, it is surface-treated by irradiation with ultraviolet rays or treatment with a rubbing cloth to obtain a surface state in which the inclination of the liquid crystal can be adjusted.

If the black matrix of the present invention is used, there are no particular restrictions on the formation order and formation position of the color pixels and the black matrix.
As the spacer, a spacer having a size corresponding to a gap (gap) with the facing substrate is used, and a spacer having a size of 2 to 8 μm is usually preferable. A photospacer (PS) of a transparent resin film can be formed on a color filter substrate by a photolithography method, and this can be used instead of the spacer.

The gap for bonding to the facing substrate varies depending on the application of the liquid crystal display device, but is usually selected in the range of 2 to 8 μm. After bonding to the facing substrate, the parts other than the liquid crystal injection port are sealed with a sealing material such as epoxy resin. The sealing material is cured by UV irradiation and / or heating, and the periphery of the liquid crystal cell is sealed.
The liquid crystal cell whose periphery is sealed is cut into panel units, then depressurized in a vacuum chamber, the liquid crystal injection port is immersed in the liquid crystal, and then the inside of the chamber leaks to inject the liquid crystal into the liquid crystal cell. .. The degree of decompression in the liquid crystal cell is usually 1 × 10 ^-2-1 × 10 ^-7 Pa, but preferably 1 × 10 ^-3 to 1 × 10 ^-6 Pa. Further, it is preferable to heat the liquid crystal cell at the time of depressurization, and the heating temperature is usually 30 to 100 ° C, more preferably 50 to 90 ° C. The warming retention at the time of depressurization is usually in the range of 10 to 60 minutes, and then immersed in the liquid crystal display. A liquid crystal display device (panel) is completed by sealing the liquid crystal cell into which the liquid crystal is injected with a UV curable resin in which the liquid crystal injection port is cured.

The type of liquid crystal is not particularly limited, and is a conventionally known liquid crystal such as an aromatic type, an aliphatic type, or a polycyclic compound, and may be any of a liotropic liquid crystal, a thermotropic liquid crystal, and the like. As the thermotropic liquid crystal, a nematic liquid crystal, a smestic liquid crystal, a cholesteric liquid crystal and the like are known, but 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 an organic EL display is manufactured using the black matrix of the present invention, for example, as shown in FIG. 1, a pattern formed by a colored resin composition (that is, pixels 20 and adjacent to each other) is first placed on a transparent support substrate 10. A color filter in which a black matrix (not shown) provided between the pixels 20 is formed is produced, and an organic illuminant 500 is laminated on the color filter via an organic protective layer 30 and an inorganic oxide film 40. By doing so, the organic EL element 100 can be manufactured. At least one of the pixels 20 and the black matrix was produced by using the photosensitive coloring composition of the present invention. As a method of laminating the organic illuminant 500, a method of sequentially forming a transparent anode 50, a hole injection layer 51, a hole transport layer 52, a light emitting layer 53, an electron injection layer 54, and a cathode 55 on the upper surface of a color filter, or Examples thereof include a method of bonding the organic light emitter 500 formed on another substrate onto the inorganic oxide film 40. Using the organic EL element 100 thus produced, for example, the method described in "Organic EL Display" (Ohmsha, August 20, 2004, Luminous, Shizushi Tokito, Chihaya Adachi, Hideyuki Murata), etc. , An organic EL display can be manufactured.
The black matrix of the present invention can be applied to both a passive drive type organic EL display and an active drive type organic EL display.

Next, the present invention will be described in more detail with reference to synthetic examples, examples and comparative examples, but the present invention is not limited to the following examples as long as the gist of the present invention is not exceeded.
The constituents of the photosensitive coloring composition used in the following Examples and Comparative Examples are as follows.
<(A-1) Organic black pigment>
Made by BASF, Irgaphor (registered trademark) Black S 0100 CF (having a chemical structure represented by the following formula (2))

<Organic black pigment: Perylene black>
BASF, Lumogen® Black FK4281
<Organic black pigment: Aniline black>
BASF, Pariodol® 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, and 2,2'-azobis-2-methyl. 8.47 parts by mass of butyronitrile 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, 0.7 parts by mass of trisdimethylaminomethylphenol and 0.12 parts by mass of hydroquinone were added to 43.2 parts by mass of acrylic acid, and the reaction was continued at 100 ° C. for 12 hours. Then, 56.2 parts by mass of tetrahydrophthalic anhydride (THPA) and 0.7 parts by mass of triethylamine were added, and the mixture was reacted at 100 ° C. for 3.5 hours. The weight average molecular weight Mw of the alkali-soluble resin-I thus obtained 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>

50 g of an epoxy compound (epoxy equivalent 247) having the above structure, 14.3 g of acrylic acid, 59.5 g of methoxybutyl acetate, 1.29 g of triphenylphosphine, and 0.05 g of paramethoxyphenol were attached with a thermometer, a stirrer, and a cooling tube. The mixture was placed in a flask and reacted at 90 ° C. with stirring until the acid value became 5 mgKOH / g or less. The reaction took 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 acid anhydride (BPDA), and 2.8 parts by mass of tetrahydrophthalic acid anhydride (THPA). Was placed in a flask equipped with a thermometer, a stirrer, and a cooling tube, and the temperature was slowly raised to 105 ° C. while stirring to react.
When the resin solution becomes transparent, it is diluted with methoxybutyl acetate to prepare a solid content of 50% by mass, and has an acid value of 131 mgKOH / g and a polystyrene-equivalent weight average molecular weight (Mw) of 4000 measured by GPC. The contained epoxy 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 (both acrylic AB blocks 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 an amino group). Polymer. Amine value is 70 mgKOH / g. Acid value is 1 mgKOH / g or less.)
The content ratios of the repeating units of the following formulas (1a), (2a), and (3a) in the total repeating units of the dispersant-I are 11.1 mol%, 22.2 mol%, and 6.7 mol%, respectively. be.

<Dispersant-II>
"DISPERBYK-2000" manufactured by Big Chemie (an acrylic AB block copolymer consisting of an A block having a quaternary ammonium base in the side chain and a B block having no quaternary ammonium base).
<Dispersant-III>
"EFKA-4300" manufactured by EFKA (Acrylic polymer dispersant having a tertiary amino group and a butyl group in the side chain. It does not have a quaternary ammonium base in the side chain).

<Pigment derivative>
"Solspec 12000" manufactured by Lubrizor
<Solvent-I>
PGMEA: Propylene Glycol Monomethyl Ether Acetate <Solvent-II>
MB: 3-Methoxybutanol <Photopolymerization Initiator-I>

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 to 3 ° C., o-tor oil chloride (0.77 g, 5 mmol) was added dropwise. 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, glutaric anhydride (0.68 g, 6 mmol) was added over 30 minutes, and then aluminum chloride (1.90 g, 14 mmol) was added over 30 minutes.

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

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 the mixture was heated under reflux for 3 hours. After cooling, the solvent was concentrated and water (10 mL) and ethyl acetate (30 mL) were added.
The organic layer was washed with saturated aqueous sodium hydrogen carbonate solution and saturated aqueous sodium chloride solution in this order, and anhydrous magnesium sulfate was added and dried. After filtering anhydrous magnesium sulfate, the solvent was distilled off by an evaporator to obtain Compound 3 (1.72 g, crude yield 78%). This was not purified and was used in the next reaction.

Compound 3 (1.00 g, 2.26 mmol) and methylene chloride (10 mL) were placed in a 50 mL three-necked flask under a nitrogen atmosphere and cooled to 10 ° C. To this was added a diethyl ether solution of 1N hydrogen chloride (4.68 mL). Next, amyl nitrite (0.36 g, 3.04 mmol) was added, and the reaction was carried out at 10 ° C. for 4 hours. After adding water (10 mL), the mixture was washed with saturated aqueous sodium hydrogen carbonate solution and saturated aqueous sodium chloride solution in this order, and anhydrous magnesium sulfate was added and dried. After filtering anhydrous magnesium sulfate, the solvent was distilled off by an evaporator to obtain a pale yellow solid (0.88 g). This was reconstituted and purified with toluene (3.5 mL) to obtain compound 4 (0.45 g, yield 42%).

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

^{1 1} H-NMR δ [ppm] (CDCl ₃ ) 1.49 (t, 3H), 2.29 (s, 3H), 2.36 (s, 3H), 2.73 (t, 2H), 3. 14 (t, 2H), 3.60 (s, 3H), 4.43 (q, 2H), 7.3 to r7.5 (m, 6H), 8.06 (dd, 1H), 8.29 (Dd, 1H), 8.59 (d, 1H), 8.83 (dd, 1H)

<Photopolymerization Initiator-II>

<Photopolymerizable Monomer-I>
DPHA: 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 (methacyloyl group-containing phosphate) manufactured by Nippon Kayaku Co., Ltd.
<Surfactant-I>
Megafuck F-559 manufactured by DIC Corporation

<Preparation of pigment dispersions-1 to 7>
The pigments, dispersants, dispersion aids, alkali-soluble resins, and solvents shown in Table 1 were mixed so as to have the mass ratios shown in Table 1. This solution was dispersed with a paint shaker in the range of 25 to 45 ° C. for 3 hours. As the beads, 0.5 mmφ zirconia beads were used, and a mass 2.5 times that of the dispersion was added. After the dispersion was completed, 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 liquid-1, the viscosity of perylene black increased significantly. Therefore, in order to disperse these pigments, it is necessary to greatly increase the amount of the dispersant as in the pigment dispersion liquid-6.

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

Next, after draining with a 60-mesh wire mesh, the mixture 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) was added as a dispersant, and 4.5 parts by mass of Solspirase 12000 (manufactured by Lubrizol) was added as a pigment derivative to increase the solid content concentration. Propylene glycol monomethyl ether acetate (PGMEA) was added so as to be 25% by mass.

This was sufficiently stirred with a stirrer and premixed. Next, a paint shaker was used to perform a dispersion treatment in the range of 25 to 45 ° C. for 6 hours. As the beads, 0.5 mmφ zirconia beads were used, and the same mass as that of the dispersion was added. After the dispersion was completed, the beads and the dispersion were separated and prepared by a filter.

[Examples 1 to 8 and Comparative Examples 1 to 4]
Using the pigment dispersion and the coated carbon black dispersion prepared above, add each component so that the ratio in the solid content is the blending ratio shown in Table 2, and further add PGMEA so that the solid content is 17% by mass. , Stirring and dissolving to prepare a photosensitive coloring composition. In Examples 1 to 8 and Comparative Examples 1, 2 and 4, the pigment concentration in the solid content was 40% by mass, and in Comparative Example 3, the pigment concentration in the solid content was 30% by mass. Further, in all the photosensitive coloring compositions, the mass ratio of the alkali-soluble resin (including the resin in the dispersion) to the photopolymerizable monomer was set to 3, the photopolymerization initiator was 4% by mass in the solid content, and the additive was added. The amount was 0.5% by mass and the amount of the surfactant was 0.1% by mass. The obtained photosensitive coloring composition was used for evaluation by the method described later.

[Measurement of optical density (OD) per μm]
The prepared photosensitive coloring composition was applied to a glass substrate with a spin coater so that the final film thickness was 2 μm, dried under reduced pressure for 1 minute, and then dried on a hot plate at 100 ° C. for 90 seconds. A resist-coated substrate (substrate-1) was obtained by heating at 230 ° C. for 30 minutes. The optical density (OD) of the obtained substrate is measured by the transmission densitometer Gretag Macbeth D200-II, and the film thickness is measured by the non-contact surface / layer cross-sectional shape measurement system VertScan (R) 2.0 manufactured by Ryoka System Co., Ltd. It was measured. Table 3 shows the optical density (OD) per 1 μm film thickness.

[Measurement of relative permittivity]
In the method for producing the substrate-1, the substrate (substrate-2) was produced in the same manner 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 the main electrode, a gold counter electrode was formed on the resist coating film by a vapor deposition method. In addition, the relative permittivity at 1 kHz and 1 V was measured using an "LCR meter 4284A" manufactured by HP (currently Agilent). The results are shown in Table 3.

[Plate making characteristics]
Drying with a hot plate was performed in the same manner as for the substrate-1. This sample was image-exposed with a high-pressure mercury lamp through a negative type mask having a linear pattern with an aperture of 20 μm (illuminance 30 mW / cm ² , exposure amount 20 mJ / cm ² ). At this time, the distance between the sample and the mask was set to 200 μm. Then, it was spray-developed 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 portion. Table 3 shows the results of the line width of the obtained linear pattern. However, when the resists of Comparative Examples 1 and 2 were used, no pattern was obtained even after developing for 10 minutes.

From the comparison between Example 1 and Comparative Examples 1, 2 and 4, it was confirmed that the substrate obtained from the photosensitive coloring composition of the present invention has higher OD and higher shielding property at the same pigment concentration. .. Further, in Comparative Examples 1 and 2, no linear pattern was obtained even after developing for 10 minutes. This is because Comparative Examples 1 and 2 contain perylene black as a pigment, but it is necessary to use a large amount of dispersant when dispersing perylene black, which seems to have adversely affected the plate-making characteristics. Further, the larger the line width is, the higher the sensitivity is. However, by using the (A-1) organic black pigment and the (A-2) organic coloring pigment in combination, the sensitivity can be improved without significantly lowering the OD. It was confirmed from Examples 4 and 5 that it could be raised.

In Comparative Example 3, the pigment is only coated carbon black, which shows a high OD, but it can be seen that the relative permittivity is high. From Examples 6 and 7, it is possible to keep the OD high and the relative permittivity low by using the (A-1) organic black pigment and (A-3) carbon black used in the present invention in combination. confirmed.

[Dispersity evaluation]
<Preparation of Pigment Dispersion Liquid-8-11>
The pigments, dispersants, dispersion aids, alkali-soluble resins, and solvents shown in Table 4 were mixed so as to have the mass ratios shown in Table 4. This solution was dispersed with a paint shaker in the range of 25 to 45 ° C. for 3 hours. As the beads, 0.5 mmφ zirconia beads were used, and a mass 2.5 times that of the dispersion was added. After the dispersion was completed, 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 pigment dispersion prepared above, each component was added so that the ratio in the solid content was the blending ratio shown in Table 5, and PGMEA was further added so that the solid content was 17% by mass, and the mixture was stirred and dissolved. , A photosensitive coloring composition was prepared.
The viscosity of each of the obtained photosensitive coloring compositions was measured with an RC80L type viscometer (measurement conditions: 23 ° C., 50 rpm) manufactured by Toki Sangyo Co., Ltd. The results are shown in Table 5.

Generally, in order to disperse an organic pigment in a photosensitive coloring composition, a basic polymer dispersant having a quaternary ammonium base and a basic polymer dispersant having no quaternary ammonium base are treated equally. It is known to show the same dispersibility. In fact, in Comparative Examples 6 and 7 of Table 5, there is no significant difference in the viscosity of the photosensitive coloring composition between the organic black pigment perylene black and the dispersant I and the dispersant III. ..

Surprisingly, in the photosensitive coloring composition containing (A-1) an organic black pigment, a polymer dispersant having a quaternary ammonium base as a functional group was compared with Example 9 and Comparative Example 5 in Table 5. By using (dispersant I), the viscosity of the photosensitive coloring composition is reduced to about half as compared with the case of using the polymer dispersant (dispersant III) which does not have a quaternary ammonium base as a functional group. , (A-1) The organic black pigment was uniformly dispersed.

In addition, Table 6 shows the viscosity values of the photosensitive coloring compositions of Examples 1 to 8 measured by the same method as in Example 9.

As shown in Table 6, not only Examples 1 and 2 in which (A-1) the organic black pigment was used alone as the pigment, but also (A-1) the organic black pigment and (A-2) the organic coloring pigment were used in combination. Examples 3 to 5 and 8, (A-1) Organic black pigment and (A-3) Carbon black used in combination Example 6, (A-1) Organic black pigment and (A-2) Organic coloring pigment (A-3) In each of Examples 7 in which carbon black was used in combination, the viscosity was the same as in Examples 1 and 2, and the pigment was uniformly dispersed in any of the photosensitive coloring compositions.

Although the present invention has been described in detail and with reference to specific embodiments, it will be apparent to those skilled in the art that various changes and modifications can be made without departing from the spirit and scope of the invention. This application is based on a Japanese patent application filed on September 25, 2013 (Japanese Patent Application No. 2013-198425), 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 light emitter

Claims (13)

A photosensitive coloring composition containing at least (A) a coloring material, (B) a dispersant, (C) an alkali-soluble resin, and (D) a photopolymerization initiator.
The (A) coloring material contains (A-1) a compound represented by the following general formula (1), a geometric isomer thereof, a salt thereof, or an organic black pigment which is a salt of the geometric isomer thereof.
The content of the coloring material (A) is 20% by mass or more with respect to the total solid content in the photosensitive coloring composition, and
The dispersant (B) contains a polymer dispersant having a quaternary ammonium base as a functional group.
A photosensitive coloring composition comprising the alkali-soluble resin (C) at least one of the following alkali-soluble resin (c1) and the following alkali-soluble resin (c2) .

[In formula (1), R ¹ and R ⁶ are independent hydrogen atoms, CH ₃ , CF ₃ , fluorine atoms or chlorine atoms; R ² , R ³ , R ⁴ , R ⁵ , R ⁷ , R. ⁸ , R ⁹ and R ¹⁰ are independent of each other from hydrogen atom, 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 ; , 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 at least one combination selected from the group consisting of R ⁹ and R ¹⁰ together. They can be directly bonded or bonded to each other by an oxygen atom, a sulfur atom, an NH or NR ¹¹ bridge; R ¹¹ and R ¹² are independent of each other and have an alkyl group having 1 to 12 carbon atoms and 3 to 12 carbon atoms. It is a cycloalkyl group, an alkenyl group having 2 to 12 carbon atoms, a cycloalkenyl group having 3 to 12 carbon atoms, or an alkynyl group having 2 to 12 carbon atoms. ]
<Alkali-soluble resin (c1)>
It was 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 polybasic acid and / or its anhydride. Alkaline-soluble resin.
<Alkali-soluble resin (c2)>
An α, β-unsaturated monocarboxylic acid or an α, β-unsaturated monocarboxylic acid ester having a carboxyl group is added to the epoxy resin, and further reacted with a polyhydric alcohol and a polybasic acid and / or an anhydride thereof. The resulting alkali-soluble resin. In the general formula (1),
In the formula, R ² , R ⁴ , R ⁵ , R ⁷ , R ⁹ and R ¹⁰ are independent hydrogen atoms, fluorine atoms or chlorine atoms, and R ³ and R ⁸ are independent hydrogen atoms, NO. ₂ , OCH ₃ , OC ₂ H ₅ , bromine atom, hydrogen 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 identical to R ⁶ , R ² is identical to R ⁷ , and R ³ is identical to R ⁸ . The photosensitive coloring composition according to claim 1, wherein R ⁴ is the same as R ⁹ and R ⁵ is the same as R ¹⁰ . The photosensitive according to claim 1 or 2, wherein the coloring material (A) contains an organic black pigment which is a compound represented by the following general formula (2) and a sulfonic acid derivative of the following general formula (2). Coloring composition.

The photosensitive coloring composition according to any one of claims 1 to 3, wherein the polymer dispersant further has a tertiary amine as a functional group. The photosensitive coloring composition according to any one of claims 1 to 4 , wherein the coloring material (A) further contains an organic coloring pigment (A-2). The photosensitive coloring composition according to claim 5 , wherein the organic coloring pigment (A-2) 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 The content ratio of the (A-1) organic black pigment is 30 to 90% by mass, and the content ratio of the (A-2) organic coloring pigment is 10 to 70% by mass with respect to 100% by mass of the (A) coloring material. , The photosensitive coloring composition according to claim 5 or 6 . The photosensitive coloring composition according to any one of claims 1 to 7 , wherein the (A) coloring material further contains (A-3) carbon black. The photosensitive coloring composition according to any one of claims 1 to 8 , wherein the (D) photopolymerization initiator is an oxime ester initiator and / or a ketooxime ester initiator. A cured product obtained by curing the photosensitive coloring composition according to any one of claims 1 to 9 . A black matrix formed from the cured product according to claim 10 . A colored spacer formed from the cured product according to claim 10 . An image display device comprising the black matrix according to claim 11 or the colored spacer according to claim 12 .

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