JP2023057606A - Photosensitive coloring composition, cured product, and image display device - Google Patents

Abstract

To provide a photosensitive coloring composition that gives a cured product having excellent solvent resistance even when calcined at low temperature.SOLUTION: A photosensitive coloring composition comprises (A) a colorant, (B) an alkali-soluble resin and (C) a photopolymerization initiator. The (B) alkali-soluble resin comprises an acryl copolymer resin (B1) comprising a constitutional unit (b1) derived from a compound represented by the general formula (1) and a constitutional unit (b2) derived from a compound having a carboxy group and an ethylenically unsaturated bond.SELECTED DRAWING: None

Description

TECHNICAL FIELD The present invention relates to a photosensitive coloring composition, a cured product, and an image display device. Specifically, for example, a photosensitive coloring composition used for forming pixels of each color, a black matrix, and a partition wall material in an image display device such as a liquid crystal display or an organic electroluminescent device (OLED), and curing the photosensitive coloring composition. and an image display device containing the cured product.

As a method for producing a color filter using a coloring composition, after applying a pigment-dispersed coloring composition on a substrate and drying, the coating film is irradiated with radiation through a mask pattern (
A method of obtaining pixels of each color by exposing, developing, and baking is known. A liquid crystal display device having the obtained color filter is also known.

Further, in recent years, a display device having a color filter on an OLED display panel has become popular. For example, Patent Literature 1 describes an OLED display device that includes a plurality of insulating layers and metal layers on an OLED display panel, and a black matrix and a color resist thereon.
When manufacturing such an OLED display panel, it is necessary to lower the baking temperature of the black matrix, the color resist, etc., because the OLED element has low heat resistance.

A black matrix baked at a low temperature using a conventional coloring composition tends to be inferior in heat resistance and solvent resistance. Therefore, the curability has been improved by using a resin containing a blocked isocyanate compound.
For example, in Patent Literature 1, when a resin having a unit that forms a crosslinked structure with a block group eliminated by heating to generate a highly reactive isocyanate group is used, and the firing temperature is set at 180° C., the chemical resistance is improved. Are listed.
Further, Patent Document 2 describes that substrate adhesion is improved by using a resin containing blocked isocyanate.

Japanese Patent No. 5636918 Japanese Patent No. 5357570

With the recent diversification of display panel structures and supporting substrates, there is a demand for lowering the firing temperature to produce panels. In particular, when a color filter is formed on the OLED layer, it is required to maintain the same solvent resistance as before even when baked at a temperature below 100°C.
On the other hand, when the inventor of the present invention examined a resin similar to the resin described in Patent Document 1, it was confirmed that when the baking temperature was 100° C., the solvent resistance was insufficient.

The present invention has been made in view of the above circumstances, and provides a photosensitive colored composition that gives a cured product with good solvent resistance even when baked at a low temperature, a black matrix with high solvent resistance,
An object of the present invention is to provide a partition material and to provide a highly reliable organic light-emitting device and an image display device.

As a result of diligent studies, the inventors have found that the above problems can be solved by using a specific acrylic copolymer resin, and have completed the present invention.
That is, the gist of the present invention is as follows.

[1] (A) a coloring agent, (B) an alkali-soluble resin and (C) a photopolymerization initiator,
(B) The alkali-soluble resin has a structural unit (b1) derived from a compound represented by the following general formula (1), and a structural unit (b2) derived from a compound having a carboxy group and an ethylenically unsaturated bond. A photosensitive coloring composition comprising an acrylic copolymer resin (B1).

(In Formula (1), R ¹ represents a hydrogen atom or a methyl group, and R ² and R ³ each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.)

[2] The acrylic copolymer resin (B1) according to [1], wherein the structural unit (b3) is derived from a monomer having a cyclic ether group having 2 to 4 carbon atoms and an ethylenically unsaturated bond. Photosensitive coloring composition.
[3] The photosensitive coloring composition according to [1] or [2], wherein the acrylic copolymer resin (B1) has a structural unit (b4) derived from a monomer having a hydroxyl group and an ethylenically unsaturated bond. thing.
[4] The photosensitive coloring composition according to any one of [1] to [3], wherein (A) the coloring agent contains a pigment.
[5] The (A) colorant contains at least one selected from the group consisting of red pigments and orange pigments and at least one selected from the group consisting of blue pigments and purple pigments, [4]
The photosensitive coloring composition according to .
[6] The photosensitive coloring composition of [4] or [5], wherein the (A) colorant contains an organic black pigment.
[7] The photosensitive coloring composition according to any one of [1] to [6], for use at a baking temperature of 100°C or less.
[8] A cured product obtained by curing the photosensitive coloring composition according to any one of [1] to [7].
[9] An image display device comprising the cured product of [8].
[10] A method for forming a cured product, comprising using the photosensitive coloring composition according to any one of [1] to [6] and performing at least the following steps (1) to (4).
Step (1): A step of forming a coating film on a substrate.
Step (2): A step of exposing at least part of the coating film formed in step (1).
Step (3): A step of developing the coating film exposed in step (2).
Step (4): A step of baking the coating film developed in step (3).
[11] The method for forming a cured product according to [10], wherein the baking temperature in step (4) is 100°C or lower.

ADVANTAGE OF THE INVENTION According to this invention, the photosensitive coloring composition from which a hardened|cured material with favorable solvent resistance is obtained can be provided.

Embodiments of the present invention will be specifically described below, but the present invention is not limited to the following embodiments, and can be carried out with various modifications within the scope of the gist thereof.
In the present invention, "(meth)acryl" means "acryl and/or methacryl", and the same applies to "(meth)acrylate" and "(meth)acryloyl".

"(Co)polymer" means including both a single polymer (homopolymer) and a copolymer (copolymer), and "acid (anhydride)", "(anhydride) ... acid" , is meant to include both acids and their anhydrides.
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 carboxy group.

In the present invention, the term "monomer" is a term corresponding to so-called high-molecular substances (polymers), and includes dimers, trimers, and oligomers in addition to monomers in the narrow sense.
In the present invention, the "total solid content" is contained in the photosensitive coloring composition or in the pigment dispersion,
It means all ingredients except solvent.
In the present invention, "weight average molecular weight" means the weight average molecular weight (Mw) in terms of polystyrene by GPC (gel permeation chromatography).
In the present invention, the "amine value" represents the amine value in terms of effective solid content, unless otherwise specified, and is a value represented by the mass of KOH equivalent to the amount of base per 1 g of solid content of the dispersant. .
In addition, the measuring method will be described later. Unless otherwise specified, the term "acid value" represents an acid value in terms of effective solid content and is calculated by neutralization titration.

With respect to pigments, "C.I." means Color Index.

In this specification, percentages and parts represented by "mass" are synonymous with percentages and parts represented by "weight".
As used herein, "baking" means heating until the surface hardness required for a cured film for a display element such as a black matrix or partition wall is obtained.

[Photosensitive coloring composition]
The photosensitive coloring composition of the present invention is
(A) a colorant (B) an alkali-soluble resin (C) a photopolymerization initiator as an essential component, and if necessary, an ethylenically unsaturated compound, a dispersant, an adhesion improver such as a silane coupling agent, It contains other compounding ingredients such as surfactants, pigment derivatives, photoacid generators, cross-linking agents, mercapto compounds, polymerization inhibitors, etc. Usually, each compounding ingredient is
Used in a state of being dissolved or dispersed in a solvent.

<(A) Colorant>
The photosensitive coloring composition of the present invention contains (A) a coloring agent. By containing (A) the coloring agent, it is possible to obtain moderate light absorbency, particularly when used for forming a light-shielding member such as a black matrix, moderate light-shielding property.

The type of coloring agent (A) that can be used in the photosensitive coloring composition of the present invention is not particularly limited, and may be a pigment or a dye. Among these, pigments are preferably used from the viewpoint of durability.

(A) The pigments contained in the colorant may be of one type alone, or may be of two or more types. In particular, from the viewpoint of achieving both uniform light blocking in the visible region and OD per unit film thickness, it is preferable to use two or more kinds.
(A) The type of pigment that can be used as the colorant is not particularly limited, but examples thereof include organic coloring pigments and black pigments. Here, the organic coloring pigment means an organic pigment exhibiting a color other than black, and examples thereof include red pigment, orange pigment, blue pigment, purple pigment, green pigment, and yellow pigment.

Among the pigments, it is preferable to use an organic coloring pigment from the viewpoint of suppressing the absorption of ultraviolet rays and making it easier to control the shape and level difference of the cured product. From the viewpoint of light shielding properties, it is preferable to use a black pigment.

The organic coloring pigments may be used singly or in combination of two or more. especially,
From the viewpoint of increasing the OD per unit film thickness, it is more preferable to use a combination of organic coloring pigments having different colors, and it is even more preferable to use a combination of organic coloring pigments exhibiting a color close to black.

Although the chemical structure of these organic color pigments is not particularly limited, examples thereof include azo-based, phthalocyanine-based, quinacridone-based, benzimidazolone-based, isoindolinone-based, dioxazine-based, indanthrene-based, and perylene-based pigments. Specific examples of pigments that can be used are shown below by pigment numbers. "C.I. Pigment Red 2" etc. listed below
. ” means the color index.

As a 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, 4
7, 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, 5
7:2, 58:4, 60, 63, 63:1, 63:2, 64, 64:1, 68, 69, 8
1, 81:1, 81:2, 81:3, 81:4, 83, 88, 90:1, 101, 101
: 1, 104, 108, 108: 1, 109, 112, 113, 114, 122, 123
, 144, 146, 147, 149, 151, 166, 168, 169, 170, 172
, 173, 174, 175, 176, 177, 178, 179, 181, 184, 185
, 187, 188, 190, 193, 194, 200, 202, 206, 207, 208
, 209, 210, 214, 216, 220, 221, 224, 230, 231, 232
, 233, 235, 236, 237, 238, 239, 242, 243, 245, 247
, 249, 250, 251, 253, 254, 255, 256, 257, 258, 259
, 260, 262, 263, 264, 265, 266, 267, 268, 269, 270
, 271, 272, 273, 274, 275, 276. Among these, C.I. I. Pigment Red 48:1, 122, 1
49, 168, 177, 179, 194, 202, 206, 207, 209, 224, 2
42, 254, more preferably C.I. I. Pigment Red 177, 209, 224, 25
4 can be mentioned. In terms of dispersibility and light-shielding properties, C.I. I. pigment red 17
7, 254, and 272 are preferably used, and when the photosensitive coloring composition is cured with ultraviolet rays, it is preferable to use a red pigment having a low ultraviolet absorption rate. I. Pigment Red 254, 272 is more preferably used.

As an orange pigment, 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, 7
4, 75, 77, 78, 79 can be mentioned. Among these, C.I. I. Pigment Orange 13, 43, 64, 72 is preferably used, and when the photosensitive coloring composition is cured with ultraviolet rays, it is preferable to use an orange pigment having a low ultraviolet absorption rate. C. I. pigment orange 64, 72
is more preferred.

As a 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, 2
9, 33, 35, 36, 56, 56:1, 60, 61, 61:1, 62, 63, 66, 6
7, 68, 71, 72, 73, 74, 75, 76, 78, 79 can be mentioned. Among these, C.I. I. Pigment Blue 15, 15:1, 1
5:2, 15:3, 15:4, 15:6, 60, more preferably C.I. I. Pigment Blue 15:6 may be mentioned.
In terms of dispersibility and light-shielding properties, C.I. I. Pigment Blue 15:6, 16, 60 is preferably used, and when the photosensitive coloring composition is cured with ultraviolet rays, it is preferable to use a blue pigment having a low ultraviolet absorption rate. C. I. Pigment Blue 60 is more preferably used.

As a 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
From the viewpoint of light-shielding properties, C.I. I. Pigment Violet 19, 23, 29, more preferably C.I. I. Pigment Violet 23 may be mentioned.
In terms of dispersibility and light-shielding properties, C.I. I. Pigment Violet 23, 29 is preferably used, and when the photosensitive coloring composition is cured with ultraviolet rays, it is preferable to use a violet pigment having a low ultraviolet absorption rate. I. Pigment Violet 29 is more preferably used.

As a green pigment, C.I. I. Pigment Green 1, 2, 4, 7, 8, 10, 13, 1
4, 15, 17, 18, 19, 26, 36, 45, 48, 50, 51, 54, 55, 58
, 59 can be mentioned. Among these, C.I. I. pigment green 7,
36 can be mentioned.
As a 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, 3
6, 36:1, 37, 37:1, 40, 41, 42, 43, 48, 53, 55, 61, 6
2, 62: 1, 63, 65, 73, 74, 75, 81, 83, 87, 93, 94, 95,
97, 100, 101, 104, 105, 108, 109, 110, 111, 116, 1
17, 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, 2
00, 202, 203, 204, 205, 206, 207, 208 can be mentioned.
Among these, 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.

Among these, it is preferable to use at least one selected from the group consisting of red pigments, orange pigments, blue pigments and violet pigments from the viewpoint of the light shielding property of the cured product and the control of the shape and level difference.

Among these, at least one of the following pigments is preferably contained from the viewpoint of the light shielding properties of the cured product and the control of the shape and level difference.
Red pigment: C.I. I. Pigment Red 177, 254, 272
Orange pigment: C.I. I. Pigment Orange 43, 64, 72
Blue pigment: C.I. I. pigment blue 15:6,60
Purple pigment: C.I. I. Pigment Violet 23, 29

In addition, when two or more organic coloring pigments are used in combination, the combination of the organic coloring pigments is not particularly limited, but from the viewpoint of light-shielding properties, at least one selected from the group consisting of red pigments and orange pigments and a blue pigment. and a purple pigment.
Although the combination of colors is not particularly limited, from the viewpoint of light blocking properties, for example,
A combination of a red pigment and a blue pigment, a combination of a blue pigment and an orange pigment, and a combination of a blue pigment, an orange pigment and a violet pigment can be mentioned.

Black pigments include organic black pigments and inorganic black pigments. Among them, it is preferable to use an organic black pigment from the viewpoint of suppressing the absorption of ultraviolet rays and making it easier to control the shape and level difference of the cured product.
Among organic black pigments, a compound represented by the following general formula (1A) is preferred from the viewpoint of suppressing a decrease in the voltage holding ratio of liquid crystals and suppressing the absorption of ultraviolet rays to make it easier to control the shape and steps. (hereinafter sometimes referred to as "compound (1A)"), geometric isomers of compound (1A), salts of compound (1A), and salts of geometric isomers of compound (1A). It is preferable to use an organic black pigment containing at least one (hereinafter sometimes referred to as "an organic black pigment represented by formula (1A)").

In formula (1A), R ¹¹ and R ¹⁶ each independently represent a hydrogen atom, CH ₃ , CF ₃ , a fluorine atom or a chlorine atom;
R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁷ , R ¹⁸ , R ¹⁹ and R ²⁰ are each independently hydrogen atom, halogen atom, R ²¹ , COOH, COOR ²¹ , COO ⁻ , CONH ₂ , CONHR ²¹ , ^CONR21R
22 , CN ^, OH, ^OR21 , ^COCR21 , _OOCNH2 , ^OOCNHR21 , ^OOCNR21R2
2 , _NO2 , _NH2 , ^{NHR21 , NR21R22} , ^{NHCOR22, NR21COR22 , N} = _CH2 ,
N ₌ ^CHR21 , N= ^CR21R22 , SH ^{, SR21} , ^SOR21 , ^SO2R21 _, ^SO3R21 , SO
represents ₃ H, SO ₃ ⁻ , SO ₂ NH ₂ , SO ₂ NHR ²¹ or SO ₂ NR ²¹ R ²² ;
at least one combination selected from the group consisting of R ¹² and R ¹³ , R ¹³ and R ¹⁴ , R ¹⁴ and R ¹⁵ , R ¹⁷ and R ¹⁸ , R ¹⁸ and R ¹⁹ , and R ¹⁹ and R ²⁰ are directly linked or linked to each other by an oxygen atom, sulfur atom, NH or NR ²¹ bridges;
R ²¹ and R ²² each independently represents an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms, an alkenyl group having 2 to 12 carbon atoms, a cycloalkenyl group having 3 to 12 carbon atoms, or a cycloalkenyl group having 3 to 12 carbon atoms. It represents an alkynyl group of 2-12.

Compound (1A) and geometric isomers of compound (1A) have the following core structures (provided that
Substituents in structural formulas are omitted), the trans-trans isomer is probably the most stable.

When compound (1A) is anionic, its charge can be transferred to any known suitable cation such as metallic, organic, inorganic or metal-organic cations, particularly alkali metals, alkaline earth metals, transition metals, primary ammonium , secondary ammonium, tertiary ammonium such as trialkylammonium, quaternary ammonium such as tetraalkylammonium, or a salt compensated by an organometallic complex. Moreover, when the geometric isomer of compound (1A) is anionic, it is preferably a similar salt.

Among the substituents of the general formula (1A) and their definitions, the following are preferred because they tend to increase the shielding rate. This is because the following substituents have no absorption and are considered not to affect the hue of the pigment.
R ¹² , R ¹⁴ , R ¹⁵ , R ¹⁷ , R ¹⁹ and R ²⁰ are each independently preferably hydrogen, fluorine or chlorine, more preferably hydrogen.
R ¹³ and R ¹⁸ are each independently 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 ) _{( C2H5} ), N _{( C2H5} ) ₂
, α-naphthyl, β-naphthyl, SO ₃ H or SO ₃ ^- , more preferably a hydrogen atom or SO ₃ H, particularly preferably a hydrogen atom.

R ¹¹ and R ¹⁶ are each independently preferably a hydrogen atom, CH ₃ or CF ₃ , more preferably a hydrogen atom.
Preferably, at least one combination selected from the group consisting of R ¹¹ and R ¹⁶ , R ¹² and R ¹⁷ , R ¹³ and R ¹⁸ , R ¹⁴ and R ¹⁹ , and R ¹⁵ and R ²⁰ is the same, more preferably is the same as R ¹⁶ , R ¹² is the same as R ¹⁷ , R ¹³ is the same as R ¹⁸ , R ¹⁴ is the same as R ¹⁹ , and R ^{15 is} the same as R ²⁰ are identical.

Alkyl groups having 1 to 12 carbon atoms are, for example, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, isobutyl group, tert-butyl group, 2-
methylbutyl group, n-pentyl group, 2-pentyl group, 3-pentyl group, 2,2-dimethylpropyl group, n-hexyl group, n-heptyl group, n-octyl group, 1,1,3,3-tetra methylbutyl group, 2-ethylhexyl group, nonyl group, decyl group, undecyl group or dodecyl group.

Cycloalkyl groups having 3 to 12 carbon atoms are, for example, cyclopropyl, cyclopropylmethyl, cyclobutyl, cyclopentyl, cyclohexyl, methylcyclohexyl, trimethylcyclohexyl, thuzyl, norbornyl, bornyl and norcalyl groups. , a karyl group, a menthyl group, a norpinyl group, a pinyl group, an adamantan-1-yl group or an adamantan-2-yl group.

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

Cycloalkenyl groups having 3 to 12 carbon atoms are, for example, 2-cyclobuten-1-yl group, 2
- cyclopenten-1-yl group, 2-cyclohexen-1-yl group, 3-cyclohexen-1-yl group, 2,4-cyclohexadien-1-yl group, 1-p-menthen-8-yl group, 4 (10) -thugen-10-yl group, 2-norbornen-1-yl group, 2,5-norbornadien-1-yl group, 7,7-dimethyl-2,4-norcaradien-3-yl group or camphenyl is the base.

Alkynyl groups having 2 to 12 carbon atoms are, for example, 1-propyn-3-yl group, 1-butyne-
4-yl group, 1-pentyn-5-yl group, 2-methyl-3-butyn-2-yl group, 1,4
- pentadiyn-3-yl group, 1,3-pentadiyn-5-yl group, 1-hexyne-6-
yl group, cis-3-methyl-2-penten-4-yn-1-yl group, trans-3-methyl-2-penten-4-yn-1-yl group, 1,3-hexadiyn-5-yl 1-octin-8-yl group, 1-nonin-9-yl group, 1-decyn-10-yl group or 1-dodecyn-12-yl group.

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

The organic black pigment represented by the general formula (1A) is preferably a compound represented by the following general formula (2A) (hereinafter also referred to as "compound (2A)"), and geometric isomerism of compound (2A) organic black pigment containing at least one selected from the group consisting of

As such an organic black pigment, for example, the trade name Irgaphor (registered trademark)
Black S 0100 CF (manufactured by BASF) can be mentioned.
This organic black pigment is preferably used by dispersing it with a dispersant, solvent, and method, which will be described later. In addition, when a sulfonic acid derivative of compound (1A), particularly a sulfonic acid derivative of compound (2A) is present during dispersion, dispersibility and storage stability may be improved. is preferably included.

Examples of organic black pigments other than the organic black pigment represented by the general formula (1A) include aniline black and perylene black.

On the other hand, it is preferable to use an inorganic black pigment from the viewpoint of light shielding properties.
Examples of inorganic black pigments include carbon black, acetylene black, lamp black, bone black, graphite, iron black, cyanine black, and titanium black.
Among these, carbon black can be preferably used from the viewpoint of light shielding properties and image characteristics. Examples of carbon black include the following carbon blacks.

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, #97
0, #980, #990, #1000, #2200, #2300, #2350, #240
0, #2600, #2650, #3030, #3050, #3150, #3250, #3
400, #3600, #3750, #3950, #4000, #4010, OIL7B,
OIL9B, OIL11B, OIL30B, OIL31B
Manufactured by Degussa: Printex (registered trademark, hereinafter the same) 3, Printex 3OP, P
Printex30, Printex30OP, Printex40, Printex45
, Printex55, Printex60, Printex75, Printex80
, Printex 85, Printex 90, Printex A, Printex L
, Printex G, Printex P, Printex U, Printex V
, Printex G, Special Black 550, Special Black 35
0, Special Black 250, Special Black 100, Special
lBlack6, Special Black5, Special Black4, Colo
r Black FW1, Color Black FW2, Color Black
FW2V, Color Black FW18, Color Black FW18, C
Color Black FW200, Color Black S160, Color
Black S170
Cabot Corporation: Monarch (registered trademark, hereinafter the same) 120, Monarch2
80, Monarch460, Monarch800, Monarch880, Mona
rch900, Monarch1000, Monarch1100, Monarch13
00, Monarch1400, Monarch4630, REGAL (registered trademark, hereinafter the same) 99, REGAL99R, REGAL415, REGAL415R, REGAL
250, REGAL250R, REGAL330, REGAL400R, REGAL55
R0, REGAL660R, BLACK PEARLS480, PEARLS130, V
ULCAN (registered trademark, hereinafter the same) XC72R, ELFTEX (registered trademark)-8
Birler: RAVEN (registered trademark, hereinafter the same) 11, RAVEN 14, RAVE
N15, RAVEN16, RAVEN22, RAVEN30, RAVEN35, RAVE
N40, RAVEN410, RAVEN420, RAVEN450, RAVEN500,
RAVEN780, RAVEN850, RAVEN890H, RAVEN1000, RA
VEN1020, RAVEN1040, RAVEN1060U, RAVEN1080U,
RAVEN1170, RAVEN1190U, RAVEN1250, RAVEN1500
, RAVEN2000, RAVEN2500U, RAVEN3500, RAVEN500
0, RAVEN5250, RAVEN5750, RAVEN7000

Carbon black that is coated with a resin may be used. The use of resin-coated carbon black has the effect of improving the adhesion to the glass substrate and the volume resistivity. Examples of resin-coated carbon black include, for example, Japanese Patent Laid-Open No. 09-7173
Carbon black described in JP-A No. 3 can be preferably used. Resin-coated carbon black is preferably used in terms of volume resistance and dielectric constant.

In addition to the organic coloring pigments and black pigments described above, dyes may also be used. Dyes that can be used as coloring materials include, for example, azo dyes, anthraquinone dyes, phthalocyanine dyes, quinoneimine dyes, quinoline dyes, nitro dyes, carbonyl dyes, and methine dyes.

<(B) Alkali-soluble resin>
In the composition of the present invention, (B) as an alkali-soluble resin, a structural unit (b1) derived from a compound represented by the following general formula (1), a carboxy group, and a compound having an ethylenically unsaturated bond Derived structural unit (b2)
Contains an acrylic copolymer resin (B1) having

(In Formula (1), R ¹ represents a hydrogen atom or a methyl group, and R ² and R ³ each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.)

<Constituent unit (b1)>
The structural unit (b1) derived from the compound represented by the general formula (1) has a blocked isocyanate group, and has a structure derived from an active methylene compound as a blocking agent. Here, the active methylene compound is R ² —O—(CO)—CH ₂ —(CO)—OR
means ³ .
It is presumed that a blocked isocyanate group having a structure derived from an active methylene compound as a blocking agent is dealcoholized by heating to form a ketene group and an ester bond.
Therefore, a blocked isocyanate group derived from an active methylene compound can be cured at a lower temperature than a blocked isocyanate group that regenerates and cures when heated, such as a blocked isocyanate group having a urethane bond or a urea bond. It is characterized in that it is possible to react and that it becomes easy to react even at a low temperature of 100° C. or less.
Therefore, the acrylic copolymer resin (B1) is suitably used as a photosensitive composition material for producing a cured product at a baking temperature of 100° C. or less.

< ^R2 , ^R3 >
Specific examples of the alkyl group having 1 to 4 carbon atoms represented by R ² and R ³ include methyl group, ethyl group, propyl group, isopropyl group, butyl group and isobutyl group. Among these, from the viewpoint of solvent resistance, a methyl group and an ethyl group are preferable, and an ethyl group is more preferable.

Specific examples of commercially available products of the compound represented by the general formula (1) include, for example, malonic acid-2-[[[[2-[1-oxo-2-propenyl]oxy]ethyl]amino] carbonyl]
-1,3-diethyl ester (AOI-DEM manufactured by Showa Denko), malonic acid-2-[[[[
2-[-2methyl-1-oxo-2-propenyl]oxy]ethyl]amino]carbonyl]-
1,3-diethyl ester (MOI-DEM manufactured by Showa Denko KK) can be mentioned.

<Constituent unit (b2)>
A structural unit (b2) derived from a compound having a carboxy group and an ethylenically unsaturated bond
Developability is improved, and there is a tendency that residues in non-image areas can be reduced.

A compound having a carboxy group and an ethylenically unsaturated bond may be any compound having a carboxy group and an ethylenically unsaturated bond. For example, (meth)acrylic acid, α-bromo(meth)acrylic acid, β-furyl(meth)acrylic acid, crotonic acid, propiolic acid, cinnamic acid, α-cyanocinnamic acid, maleic acid, maleic anhydride, maleic acid Unsaturated carboxylic acids such as monomethyl acid, monoethyl maleate, monoisopropyl maleate, fumaric acid, itaconic acid, itaconic anhydride, citraconic acid, citraconic anhydride and the like, and anhydrides thereof. Among these, (meth)acrylic acid is preferred. These monomers may be used alone or in combination of two or more.

The acrylic copolymer resin (B1) of the present application has, in addition to the structural unit (b1) and the structural unit (b2),
It preferably contains structural units (b3) to (b4) derived from other monomers.

<Constituent unit (b3)>
A structural unit (b3) derived from a monomer having a cyclic ether group having 2 to 4 carbon atoms and an ethylenically unsaturated bond.
Having the structural unit (b3) is preferable in that it promotes the reaction with the structure derived from the active methylene in the blocked isocyanate group in the structural unit (b1) and improves the solvent resistance. In the monomer for forming the structural unit (b3), the cyclic ether group having 2 to 4 carbon atoms is
Examples include epoxy group, oxetanyl group, and tetrahydrofuryl group.

Examples of monomers having an epoxy group and an ethylenically unsaturated bond include glycidyl (
meth)acrylate, 2-methylglycidyl (meth)acrylate, 2-ethylglycidyl (meth)acrylate, 3,4-epoxybutyl (meth)acrylate, 6,7-epoxyheptyl (meth)acrylate, 3,4-epoxycyclohexyl (Meth)acrylate, 3,4-epoxycyclohexylmethyl (meth)acrylate, glycidyl vinyl ether, 1,2-epoxy-4-vinylcyclohexane, 2-vinylbenzyl glycidyl ether, 3-vinylbenzyl glycidyl ether, 4-vinylbenzyl glycidyl ether, α-methyl-2-vinylbenzyl glycidyl ether, α-methyl-3-vinylbenzyl glycidyl ether, α-methyl-4-vinylbenzyl glycidyl ether, 2
,3-bis(glycidyloxymethyl)styrene, 2,4-bis(glycidyloxymethyl)styrene, 2,5-bis(glycidyloxymethyl)styrene, 2,6-bis(glycidyloxymethyl)styrene, 2,3 ,4-tris(glycidyloxymethyl)styrene, 2,3,5-tris(glycidyloxymethyl)styrene, 2,3,6-tris(glycidyloxymethyl)styrene, 3,4,5-tris(glycidyloxymethyl) ) styrene and 2,4,6-tris(glycidyloxymethyl)styrene.

Examples of monomers having an oxetanyl group and an ethylenically unsaturated bond include 3-methyl-3-(meth)acryloyloxymethyloxetane, 3-ethyl-3-(meth)acryloyloxymethyloxetane, 3-methyl- 3-(meth)acryloyloxyethyloxetane and 3-ethyl-3-(meth)acryloyloxyethyloxetane.

Monomers having a tetrahydrofuryl group and an ethylenically unsaturated bond include, for example, tetrahydrofurfuryl (meth)acrylate, 2-methacryloyloxy-propionic acid tetrahydrofurfuryl ester, (meth)acrylic acid tetrahydrofuran-3-yl ester is mentioned.

Among these, monomers having an epoxy group and an ethylenically unsaturated bond are preferred from the viewpoint of curability during low-temperature baking, and glycidyl (meth)acrylate, 2-methylglycidyl (
meth)acrylate, 3,4-epoxycyclohexyl (meth)acrylate, 3,4-
Epoxycyclohexylmethyl (meth)acrylate is more preferred, and glycidyl (meth)acrylate is even more preferred.
The structural unit (b3) derived from these monomers may be used alone or in combination of two or more.

<Constituent unit (b4)>
A structural unit (b4) derived from a monomer having a hydroxyl group and an ethylenically unsaturated bond
Having the structural unit (b4) is preferable in that it promotes the reaction with the structure derived from the active methylene in the blocked isocyanate group in the structural unit (b1) and improves the solvent resistance. The monomer for forming the structural unit (b4) may have one, two or more hydroxyl groups. Specifically, for example, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-
Hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 3-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 6-hydroxyhexyl (meth)acrylate, 8-hydroxyoctyl (meth)acrylate
acrylates, 10-hydroxydecyl (meth) acrylate, 12-hydroxylauryl (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, glycerol (meth) acrylate, or cyclohexanedimethanol mono (meth) acrylate, etc. Hydroxyalkyl (meth)acrylates; ethyl-α-(hydroxymethyl)acrylate, p-hydroxyphenylethyl (meth)acrylate. These may be used alone or in combination of two or more.
Among these monomers, 2-hydroxypropyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (
Meth)acrylates are preferred, and 2-hydroxyethyl (meth)acrylate is more preferred.

<Other structural units>
In addition to the structural units (b1) to (b4), it may have structural units derived from the following monomers.
Specific examples of other monomers include styrene, α-methylstyrene, o-vinyltoluene, m-vinyltoluene, p-vinyltoluene, o-chlorostyrene, m-chlorostyrene, p-chlorostyrene, o- aromatic vinyl compounds such as methoxystyrene, m-methoxystyrene, p-methoxystyrene, p-nitrostyrene, p-cyanostyrene, p-acetylaminostyrene;

methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, iso-propyl (meth) acrylate, n-butyl (meth) acrylate, sec-butyl (meth) acrylate, iso-butyl ( meth) acrylate, ter
t-butyl (meth)acrylate, pentyl (meth)acrylate, neopentyl (
meth)acrylate, benzyl (meth)acrylate, isoamyl (meth)acrylate, hexyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, cyclopentyl (meth)acrylate, cyclohexyl (meth)acrylate, methylcyclohexyl (meth)acrylate, ethyl Cyclohexyl (meth)acrylate, norbornyl (meth)acrylate, 5-methylnorbornyl (meth)acrylate, 5-ethylnorbornyl (meth)acrylate, dicyclopentenyl (meth)acrylate, dicyclopentanyl (meth)acrylate , dicyclopentenyloxyethyl acrylate-isobornyl (meth)acrylate, adamantyl (meth)acrylate and other (meth)acrylate monomers;

(Meth) acrylic acid amide, (meth) acrylic acid N,N-dimethylamide, (meth) acrylic acid N,N-diethylamide, (meth) acrylic acid N,N-dipropylamide, (
(meth)acrylic acid amides such as meth)acrylic acid N,N-di-isopropylamide, (meth)acrylic acid anthracenylamide; (meth)acrylic acid anilide, (meth)acrylonitrile, acrolein, vinyl chloride, chloride Vinyl compounds such as vinylidene, vinyl fluoride, vinylidene fluoride, N-vinylpyrrolidone, vinylpyridine, vinyl acetate, vinyltoluene; Unsaturated dicarboxylic acid diesters such as diethyl citraconate, diethyl maleate, diethyl fumarate, diethyl itaconate ; N-phenylmaleimide, N-
monomaleimides such as cyclohexylmaleimide, N-laurylmaleimide, N-(4-hydroxyphenyl)maleimide; and the like. These can be used individually or in combination of 2 or more types.

Among these, aromatic vinyl compounds and (meth)acrylate monomers are preferably used.

Although the weight average molecular weight of the acrylic copolymer resin (B1) is not particularly limited, it is preferably 1000 or more, more preferably 3000 or more, further preferably 5000 or more.
0 or less is preferable, 20000 or less is more preferable, and 15000 or less is even more preferable.
Adhesion to the substrate tends to be improved by making it equal to or higher than the lower limit. The solubility tends to be good when the content is equal to or less than the above upper limit.

The acid value of the acrylic copolymer resin (B1) is not particularly limited, but is preferably 10 mgKOH/g or more, more preferably 20 mgKOH/g or more, still more preferably 30 mgKOH/g or more, and preferably 200 mgKOH/g or less, and 150 mgKOH/g. g or less is more preferable, and 100 mgKOH/g or less is even more preferable. When the content is at least the above lower limit, there is a tendency that appropriate development solubility can be obtained. When the amount is equal to or less than the above upper limit, there is a tendency to suppress the dissolution of the film due to excessive progress of development.

The content of the structural unit (b1) in the acrylic copolymer resin (B1) is not particularly limited, but is usually 5 mol% or more, preferably 10 mol% or more, more preferably 15 mol%.
Above, more preferably 20 mol % or more. Also, it is usually 50 mol % or less, preferably 40 mol % or less, more preferably 30 mol % or less, still more preferably 25 mol % or less.
By making it more than the said lower limit, there exists a tendency for solvent resistance to become favorable. The stability tends to be good when the content is equal to or less than the above upper limit.

The content of the structural unit (b2) in the acrylic copolymer resin (B1) is not particularly limited, but is usually 5 mol% or more, preferably 10 mol% or more, more preferably 15 mol%.
That's it. Also, it is usually 50 mol % or less, preferably 40 mol % or less, more preferably 30 mol % or less.
When the content is at least the above lower limit, there is a tendency that appropriate development solubility can be obtained. When the amount is equal to or less than the above upper limit, there is a tendency that the dissolution of the film due to excessive progress of development can be suppressed.

When the acrylic copolymer resin (B1) has a structural unit (b3), the acrylic copolymer resin (
The content of the structural unit (b3) in B1) is not particularly limited, but is usually 5 mol% or more, preferably 10 mol% or more, more preferably 15 mol% or more. Also, it is usually 40 mol % or less, preferably 30 mol % or less, more preferably 25 mol % or less.
By making it more than the said lower limit, there exists a tendency for solvent resistance to become favorable. Storage stability tends to be improved by making it equal to or less than the above upper limit.

When the acrylic copolymer resin (B1) has a structural unit (b4), the acrylic copolymer resin (
The content of the structural unit (b4) in B1) is not particularly limited, but is usually 5 mol% or more, preferably 10 mol% or more, more preferably 15 mol% or more. Moreover, it is usually 50 mol % or less, preferably 40 mol % or less, and more preferably 30 mol % or less. When the amount is not more than the above upper limit, there is a tendency to suppress the dissolution of the film due to excessive development.

The acrylic copolymer resin (B1) in the present invention can be produced by a known method. For example, it can be produced by the method disclosed in WO 2014/141731.

<Other alkali-soluble resins>
The composition of the present invention may contain an alkali-soluble resin other than the acrylic copolymer resin (B1) as the (B) alkali-soluble resin.
The alkali-soluble resin other than the acrylic copolymer resin (B1) is not particularly limited as long as it contains a carboxy group or a hydroxyl group. Examples include epoxy (meth)acrylate resins, acrylic resins, carboxy group-containing epoxy resins, Carboxy group-containing urethane resins, novolak-based resins, and polyvinylphenol-based resins can be used. Among them,
(B2) Epoxy (meth)acrylate resin (B3) Acrylic copolymer resin is preferably used from the viewpoint of excellent plate-making properties. These can be used individually by 1 type or in mixture of multiple types.

<(B2) Epoxy (meth)acrylate resin>
(B2) Epoxy (meth)acrylate resin is an epoxy compound (epoxy resin) and an α,β-unsaturated monocarboxylic acid and/or an α,β-
It is a resin obtained by reacting a hydroxyl group generated by a reaction with an unsaturated monocarboxylic acid ester with a compound having two or more substituents capable of reacting with a hydroxyl group such as a polybasic acid and/or its anhydride.
Further, before reacting the polybasic acid and/or its anhydride with a hydroxyl group, after reacting a compound having two or more substituents capable of reacting with a hydroxyl group, the polybasic acid and/or its anhydride is reacted. The resin obtained by the reaction is also included in the (B2) epoxy (meth)acrylate resin.

The epoxy (meth)acrylate resin (B2) also includes a resin obtained by reacting the carboxy group of the resin obtained by the above reaction with a compound having a reactive functional group.
Thus, the epoxy (meth)acrylate resin has substantially no epoxy group due to its chemical structure, and is not limited to "(meth)acrylate", but an epoxy compound (epoxy resin) is a raw material. and "(meth)acrylate" is a typical example, so it is named in this way according to common practice.

The (B2) epoxy (meth)acrylate resin used in the present invention is particularly the following epoxy (meth)acrylate resin (B2-1) and/or epoxy (meth)acrylate resin (B2-2) (hereinafter “carboxy group-containing epoxy (meth)acrylate resin") is preferably used from the viewpoint of developability and reliability.

<Epoxy (meth)acrylate resin (B2-1)>
Obtained by adding an α,β-unsaturated monocarboxylic acid or an α,β-unsaturated monocarboxylic acid ester having a carboxy group to an epoxy resin, and further reacting a polybasic acid and / or its anhydride. Alkali-soluble resin.
<Epoxy (meth)acrylate resin (B2-2)>
An α,β-unsaturated monocarboxylic acid or an α,β-unsaturated monocarboxylic acid ester having a carboxy group is added to an epoxy resin, and further reacted with a polyhydric alcohol and a polybasic acid and/or its anhydride. Alkali-soluble resin obtained by

Here, the epoxy resin includes a raw material compound before forming a resin by thermosetting, and the epoxy resin can be appropriately selected and used from known epoxy resins. As the epoxy resin, a compound obtained by reacting a phenolic compound and epihalohydrin can be used. The phenolic compound is preferably a compound having a divalent or more divalent phenolic hydroxyl group, and may be a monomer or a polymer.
Examples of types of epoxy resins used as raw materials include cresol novolak type epoxy resin, phenol novolak type epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin, trisphenolmethane type epoxy resin, biphenyl novolak type epoxy resin, and naphthalene. A novolak type epoxy resin, an epoxy resin which is a reaction product of a polyaddition reaction product of dicyclopentadiene and phenol or cresol and epihalohydrin, an adamantyl group-containing epoxy resin, and a fluorene type epoxy resin can be preferably used. Among them, those having an aromatic ring in the main chain can be used more preferably.

Examples of epoxy resins include bisphenol A type epoxy resins (e.g., Mitsubishi Chemical Corporation's "jER (registered trademark, hereinafter the same) 828", "jER1001", "
jER1002", "jER1004", etc.), epoxy resin obtained by reaction of alcoholic hydroxyl group of bisphenol A type epoxy resin and epichlorohydrin (for example, Nippon Kayaku Co., Ltd. "NER-1302" (epoxy equivalent 323, softening point 76 ° C. )), bisphenol F type resin (e.g., "jER807", "EP-4001", "E
P-4002”, “EP-4004”, etc.), epoxy resin obtained by reaction of alcoholic hydroxyl group of bisphenol F type epoxy resin and 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”), phenolic novolac type epoxy resin (for example, Nippon Kayaku Co., Ltd. “EP
PN-201", Mitsubishi Chemical's "EP-152", "EP-154", Dow Chemical Co.'s "DEN-438"), (o, m, p-) cresol novolac type epoxy resin (for example, Nippon Kayaku Co., Ltd. "EOCN (registered trademark, hereinafter the same.) -102S", "EOC
N-1020", "EOCN-104S"), triglycidyl isocyanurate (e.g., "TEPIC (registered trademark)" manufactured by Nissan Chemical Industries, Ltd.), trisphenolmethane-type epoxy resin (e.g., "EPPN" manufactured by Nippon Kayaku Co., Ltd. (Registered trademark, hereinafter the same.)-501”, “EPP
N-502", "EPPN-503"), alicyclic epoxy resins ("Celoxide (registered trademark, hereinafter the same) 2021P" and "Celoxide EHPE" manufactured by Daicel), phenol by the reaction of dicyclopentadiene and phenol Epoxy resins obtained by glycidylating resins (for example, "EXA-7200" manufactured by DIC Corporation, "NC-7300" manufactured by Nippon Kayaku Co., Ltd.),
Epoxy resins represented by the following general formulas (B1) to (B4) can be preferably used.
Specifically, for example, "XD-1000" manufactured by Nippon Kayaku Co., Ltd. as an epoxy resin represented by the following general formula (B1), and Nippon Kayaku Co., Ltd. as an epoxy resin represented by the following general formula (B2) "NC-3000", "E-201" manufactured by Osaka Organic Chemical Industry Co., Ltd. as an epoxy resin represented by the following general formula (B3), and Nippon Steel & Sumikin Chemical Co., Ltd. as an epoxy resin represented by the following general formula (B4) "ESF-300" manufactured by

In the above general formula (B1), a is an average value and represents a number of 0 to 10, and R ¹¹¹ is each independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 8 carbon atoms, a represents a cycloalkyl group, a phenyl group, a naphthyl group, or a biphenyl group; Plural R ¹¹¹ in one molecule may be the same or different.

In the general formula (B2), b1 and b2 are each independently an average value and represent a number of 0 to 10, R ¹²¹ is each independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 8 carbon atoms, a carbon It represents a cycloalkyl group, phenyl group, naphthyl group or biphenyl group of numbers 3 to 10. Plural R ¹²¹ in one molecule may be the same or different.

In general formula (B3) above, X represents a linking group represented by general formula (B3-1) or (B3-2) below. However, it contains one or more adamantane structures in its molecular structure. c is 2 or 3
represents

In the above general formulas (B3-1) and (B3-2), R ¹³¹ to R ¹³⁴ and R ¹³⁵ to R ¹³⁷ are each independently an optionally substituted adamantyl group, a hydrogen atom, a substituent or an optionally substituted phenyl group, and * represents a bond.

In the general formula (B4), p and q each independently represent an integer of 0 to 4, R ¹⁴¹ and R ¹⁴² each independently represent an alkyl group having 1 to 4 carbon atoms or a halogen atom, and R ¹⁴³ and R ¹⁴⁴
each independently represents an alkylene group having 1 to 4 carbon atoms, and x and y each independently represents an integer of 0 or more.

Among these, epoxy resins represented by any one of general formulas (B1) to (B4) are preferably used.

Examples of α,β-unsaturated monocarboxylic acids or α,β-unsaturated monocarboxylic acid esters having a carboxy group include (meth)acrylic acid, crotonic acid, o-, m- or p-vinylbenzoic acid, (meth) ) Monocarboxylic acids such as α-position haloalkyl, alkoxyl, halogen, nitro, and cyano-substituted acrylic acid, 2-(meth) acryloyloxyethyl succinic acid, 2-(meth) acryloyloxyethyl adipic acid, 2-( meth) acryloyloxyethyl phthalate, 2-(meth) acryloyloxyethyl hexahydrophthalate, 2-(meth) acryloyloxyethyl maleate, 2-(meth) acryloyloxypropyl succinate, 2-( meth) acryloyloxypropyl adipate, 2-(meth) acryloyloxypropyl tetrahydrophthalate, 2-(meth) acryloyloxypropyl phthalate, 2-(meth) acryloyloxypropyl maleate, 2-(meth) ) acryloyloxybutyl succinate, 2-(
meth) acryloyloxybutyl adipate, 2-(meth) acryloyloxybutyl hydrophthalate, 2-(meth) acryloyloxybutyl phthalate, 2-(meth) acryloyloxybutyl maleate (meth), acrylic Monomers obtained by adding lactones such as ε-caprolactone, β-propiolactone, γ-butyrolactone and δ-valerolactone to acids, or hydroxyalkyl (meth)acrylates and pentaerythritol tri(meth)acrylates monomers obtained by adding acids (anhydrides) such as (anhydride) succinic acid, (anhydride) phthalic acid, and (anhydride) maleic acid, and (meth)acrylic acid dimers.
Among these, (meth)acrylic acid is particularly preferable from the viewpoint of sensitivity.

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

In addition, epoxy resin, α,β-unsaturated monocarboxylic acid or α,β having a carboxy group
- Unsaturated monocarboxylic acid ester and each component of the esterification catalyst may be used by selecting one of each component, or two or more of them may be used in combination.
The amount of the α,β-unsaturated monocarboxylic acid or the α,β-unsaturated monocarboxylic acid ester having a carboxy group is preferably in the range of 0.5 to 1.2 equivalents per equivalent of the epoxy group of the epoxy resin. , more preferably in the range of 0.7 to 1.1 equivalents. By setting the amount of the α,β-unsaturated monocarboxylic acid or the α,β-unsaturated monocarboxylic acid ester having a carboxyl group to the above lower limit or more, the shortage of the amount of the unsaturated group to be introduced can be suppressed, and the continuous increase in the amount of the unsaturated group can be suppressed. Reaction with basic acids and/or their anhydrides also tends to be sufficient. On the other hand, by adjusting the amount to the above upper limit or less, the remaining unreacted matter of the α,β-unsaturated monocarboxylic acid or the α,β-unsaturated monocarboxylic acid ester having a carboxy group can be suppressed, and the curing property is good. There is a tendency that it is easy to

Examples of polybasic acids and/or anhydrides thereof include maleic acid, succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, pyromellitic acid, trimellitic acid, benzophenonetetracarboxylic acid, methylhexacarboxylic acid, Hydrophthalic acid, endomethylenetetrahydrophthalic acid, chlorendic acid, methyltetrahydrophthalic acid, biphenyltetracarboxylic acid, and anhydrides thereof.

preferably 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, and biphenyltetracarboxylic dianhydride.

The addition reaction of the polybasic acid and/or its anhydride can be performed using a known technique, and an α,β-unsaturated monocarboxylic acid or an α,β-unsaturated monocarboxylic acid having a carboxy group to the epoxy resin. The desired product can be obtained by continuing the reaction under the same conditions as the addition reaction of the carboxylic acid ester. The amount of polybasic acid and/or its anhydride component to be added is preferably such that the acid value of the resulting carboxy group-containing epoxy (meth)acrylate resin is in the range of 10 to 150 mgKOH/g, and further It is preferred to be in the range of 20 to 140 mgKOH/g. Alkali developability tends to be improved by setting the amount to the above lower limit or more, and curing performance tends to be improved by setting the amount to the above upper limit or less.

Polyfunctional alcohols such as trimethylolpropane, ditrimethylolpropane, pentaerythritol, dipentaerythritol, trimethylolethane, 1,2,3-propanetriol (polyhydric alcohol ) to introduce a multi-branched structure. In this case, the order of mixing the polybasic acid and/or its anhydride and the polyfunctional alcohol is not particularly limited. By heating, epoxy resin and α, β-
Polybasic acid and/or its anhydride for any hydroxyl group present in a mixture of unsaturated monocarboxylic acid or α,β-unsaturated monocarboxylic acid ester having carboxyl group and polyfunctional alcohol substances undergo an addition reaction.

The use of a polyhydric alcohol tends to increase the molecular weight of the (B2) epoxy (meth)acrylate resin, introduce branches into the molecule, and balance the molecular weight and viscosity. In addition, the rate of introduction of acid groups into the molecule can be increased, and there is a tendency to easily balance sensitivity, adhesion, and the like.

As the carboxy group-containing epoxy (meth)acrylate resin, in addition to the above,
Examples thereof include those described in Korean Patent Publication No. 10-2013-0022955.

The weight-average molecular weight (Mw) of the carboxy group-containing epoxy (meth)acrylate resin measured by gel permeation chromatography (GPC) in terms of polystyrene is usually 1000 or more, preferably 1500 or more, more preferably 2000 or more, more preferably 2000 or more. is 3,000 or more, more preferably 4,000 or more, particularly preferably 5,000 or more, and usually 10,000 or less, preferably 8,000 or less, more preferably 7,000 or less. For example, 1000 to 10000 is preferable, 1500 to 10000 is more preferable, 1500
~ 8000 is more preferable, 2000 to 8000 is even more preferable, 2000 to 7
000 is particularly preferred. When the content is at least the above lower limit, there is a tendency that the solubility in the developer can be suppressed from becoming too high. By setting the content to the above upper limit or less, there is a tendency that the solubility in the developer tends to be good.

Although the acid value of the carboxy group-containing epoxy (meth)acrylate resin is not particularly limited,
10 mg KOH / g or more is preferable, 20 mg KOH / g or more is more preferable, 40 mg
More preferably 50 mgKOH/g or more, more preferably 200 mgKOH/g or less, more preferably 150 mgKOH/g or less, 1
20 mgKOH/g or less is more preferable, and 100 mgKOH/g or less is particularly preferable.
For example, 10 mgKOH / g ~ 200mgKOH / g is preferable, 20mgKOH / g ~
150 mg KOH/g is more preferred, 40 mg KOH/g to 120 mg KOH/g is even more preferred, and 50 mg KOH/g to 100 mg KOH/g is even more preferred. When the content is at least the above lower limit, there is a tendency that appropriate development solubility can be obtained. When the amount is equal to or less than the above upper limit, there is a tendency to suppress the dissolution of the film due to excessive progress of development.

Carboxy group-containing epoxy (meth) acrylate resin, even if one type is used alone, two
More than one kind of resin may be mixed and used.

(B3) Acrylic copolymer resin In addition, as (B) alkali-soluble resin, from the viewpoint of compatibility with pigments, dispersants, etc., (B
3) It is preferable to use an acrylic copolymer resin, and those described in Japanese Patent Application Laid-Open No. 2014-137466 can be preferably used.

(B3) The acrylic copolymer resin includes, for example, an ethylenically unsaturated monomer having one or more carboxyl groups (hereinafter referred to as "unsaturated monomer (B3-1)") and other copolymers. A copolymer with a possible ethylenically unsaturated monomer (hereinafter referred to as “unsaturated monomer (B3-2)”) can be mentioned.
Examples of the unsaturated monomer (B3-1) include (meth)acrylic acid, crotonic acid, α-
Unsaturated monocarboxylic acids such as chloroacrylic acid and cinnamic acid; maleic acid, maleic anhydride,
Unsaturated dicarboxylic acids such as fumaric acid, citraconic acid, citraconic anhydride, and mesaconic acid or their anhydrides; succinic acid mono[2-(meth)acryloyloxyethyl], phthalic acid mono[2-
(Meth)acryloyloxyethyl] mono[(meth)acryloyloxyalkyl] ester of polyvalent carboxylic acid with a valence of 2 or more; and p-vinylbenzoic acid.
These unsaturated monomers (B3-1) can be used alone or in combination of two or more.

Examples of the unsaturated monomer (B3-2) include N-substituted maleimides such as N-phenylmaleimide and N-cyclohexylmaleimide;
aromatic vinyl compounds such as styrene, α-methylstyrene, p-hydroxystyrene, p-hydroxy-α-methylstyrene, p-vinylbenzyl glycidyl ether, acenaphthylene;

Methyl (meth) acrylate, n-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, allyl (meth) acrylate, benzyl (meth) acrylate, polyethylene glycol (degree of polymerization 2 ~10
) Methyl ether (meth) acrylate, polypropylene glycol (degree of polymerization 2-10)
methyl ether (meth) acrylate, polyethylene glycol (degree of polymerization 2 to 10) mono (meth) acrylate, polypropylene glycol (degree of polymerization 2 to 10) mono (meth) acrylate, cyclohexyl (meth) acrylate, isobornyl (meth) acrylate,
Tricyclo[5.2.1.0 ^2,6 ]decane-8-yl (meth)acrylate, dicyclopentenyl (meth)acrylate, glycerol mono (meth)acrylate, 4-hydroxyphenyl (meth)acrylate, paracumylphenol Ethylene oxide-modified (meth)acrylate, glycidyl (meth)acrylate, 3,4-epoxycyclohexylmethyl (meth)acrylate, 3-[(meth)acryloyloxymethyl]oxetane,
(meth)acrylic acid esters such as 3-[(meth)acryloyloxymethyl]-3-ethyloxetane;

cyclohexyl vinyl ether, isobornyl vinyl ether, tricyclo [5.2.
1.0 ^2,6 ]vinyl ethers such as decan-8-yl vinyl ether, pentacyclopentadecanyl vinyl ether, 3-(vinyloxymethyl)-3-ethyloxetane;
Macromonomers having a mono(meth)acryloyl group at the end of a polymer molecular chain such as polystyrene, polymethyl(meth)acrylate, poly-n-butyl(meth)acrylate and polysiloxane can be mentioned.
These unsaturated monomers (B3-2) can be used alone or in combination of two or more.

In the copolymer of the unsaturated monomer (B3-1) and the unsaturated monomer (B3-2), the copolymerization ratio of the unsaturated monomer (B3-1) is preferably 5 to 50% by mass. , more preferably 10 to 4
It is 0% by mass. By copolymerizing the unsaturated monomer (B3-1) in such a range, there is a tendency that a photosensitive coloring composition having excellent alkali developability and storage stability can be obtained.

As the copolymer of the unsaturated monomer (B3-1) and the unsaturated monomer (B3-2), for example,
Japanese Unexamined Patent Publication No. 7-140654, Japanese Unexamined Patent Publication No. 8-259876, Japanese Unexamined Patent Publication No. 10-31308, Japanese Unexamined Patent Publication No. 10-300922, Japanese Unexamined Patent Publication No. 1
1-174224, Japanese Unexamined Patent Publication No. 11-258415, Japanese Unexamined Patent Publication 2000
-56118 and Japanese Patent Application Laid-Open No. 2004-101728.
A copolymer of the unsaturated monomer (B3-1) and the unsaturated monomer (B3-2) can be produced by a known method. The structure, Mw, and Mw/Mn can also be controlled by the methods disclosed in Japanese Patent Application Laid-Open No. 2006-259680 and International Publication No. 2007/029871.

In addition, International Publication No. 2016/194619, International Publication No. 2017/154439
You may use the resin as described in No.

<(C) Photoinitiator>
(C) The photopolymerization initiator is a component that has the function of directly absorbing light, causing a decomposition reaction or a hydrogen abstraction reaction, and generating polymerization active radicals. Additives such as polymerization accelerators (chain transfer agents) and sensitizing dyes may be added as necessary.
(C) Photopolymerization initiators include, for example, metallocene compounds including titanocene compounds described in JP-A-59-152396 and JP-A-61-151197;
Hexaarylbiimidazole derivatives described in JP-A-2000-56118; halomethylated oxadiazole derivatives described in JP-A-10-39503;
halomethyl-s-triazine derivatives; α-aminoalkylphenone derivatives; and oxime ester compounds described in JP-A-2000-80068 and JP-A-2006-36750.

Examples of metallocene compounds include dicyclopentadienyl titanium dichloride,
Dicyclopentadienyl titanium bisphenyl, dicyclopentadienyl titanium bis(2,3,4,5,6-pentafluorophenyl-1-yl), dicyclopentadienyl titanium bis(2,3,5, 6-tetrafluorophenyl-1-yl), dicyclopentadienyl titanium bis(2,4,6-trifluorophenyl-1-yl), dicyclopentadienyl titanium di(2,6-difluorophenyl-1 -yl), dicyclopentadienyl titanium di(2,4-difluorophenyl-1-yl), di(methylcyclopentadienyl) titanium bis(2,3,4,5,6-pentafluorophenyl-1 -yl), di(methylcyclopentadienyl) titanium bis(2,6-difluorophenyl-1-yl), dicyclopentadienyl titanium [2,6-di-fluoro-3-(pyro-1-yl )-phenyl-1-yl].

Examples of hexaarylbiimidazole derivatives include 2-(2′-chlorophenyl)-4,5-diphenylimidazole dimer, 2-(2′-chlorophenyl)-4,5
-bis(3'-methoxyphenyl)imidazole dimer, 2-(2'-fluorophenyl)-4,5-diphenylimidazole dimer, 2-(2'-methoxyphenyl)-4,5
-diphenylimidazole dimer, (4'-methoxyphenyl)-4,5-diphenylimidazole dimer.

Examples of halomethylated oxadiazole derivatives include 2-trichloromethyl-5
-(2'-benzofuryl)-1,3,4-oxadiazole, 2-trichloromethyl-5
-[β-(2′-benzofuryl)vinyl]-1,3,4-oxadiazole, 2-trichloromethyl-5-[β-(2′-(6″-benzofuryl)vinyl)]-1, 3,4-oxadiazole, 2-trichloromethyl-5-furyl-1,3,4-oxadiazole.

Examples of halomethyl-s-triazine derivatives include 2-(4-methoxyphenyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(4-methoxynaphthyl)-4,6-bis( trichloromethyl)-s-triazine, 2-(4-ethoxynaphthyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(4-ethoxycarbonylnaphthyl)-4,6-bis(trichloromethyl) -s-triazines.

Examples of α-aminoalkylphenone derivatives include 2-methyl-1[4-(methylthio)phenyl]-2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1-(4- morpholinophenyl)butan-1-one, 2-dimethylamino-
2-(4-methylbenzyl)-1-(4-morpholinophenyl)butan-1-one, 3,
and 6-bis(2-methyl-2-morpholinopropionyl)-9-octylcarbazole.

As the photopolymerization initiator (C), oxime ester compounds are particularly effective in terms of sensitivity and plate-making properties. For example, when using an alkali-soluble resin containing a phenolic hydroxyl group, such sensitivity is particularly excellent. oxime ester compounds are useful. The oxime ester compound has a high quantum yield in photoreaction and high activity of the radicals generated, so even a small amount of the oxime ester compound has high sensitivity, is stable against thermal reaction, and is highly sensitive in a small amount. It is possible to obtain compositions.

Examples of oxime ester compounds include compounds represented by the following general formula (IV).

In formula (IV) above, R ^21a represents a hydrogen atom, an optionally substituted alkyl group, or an optionally substituted aromatic ring group.
R ^21b represents any substituent containing an aromatic ring.
R ^22a represents an optionally substituted alkanoyl group or an optionally substituted aryloyl group.
n represents an integer of 0 or 1;

Although the number of carbon atoms in the alkyl group in R ^21a is not particularly limited, it is usually 1 or more, preferably 2 or more, and usually 20 or less, preferably 15 or less, more preferably 10 or less, from the viewpoint of solvent solubility and sensitivity. is. For example, specific examples of alkyl groups include methyl, ethyl, propyl, butyl, pentyl, hexyl, cyclopentylmethyl, cyclopentylethyl, cyclohexylmethyl, and cyclohexylethyl groups.
Examples of substituents that the alkyl group may have include an aromatic ring group, a hydroxyl group, a carboxy group, a halogen atom, an amino group, an amide group, 4-(2-methoxy-1-methyl)ethoxy-2- Examples thereof include a methylphenyl group and an N-acetyl-N-acetoxyamino group, and unsubstituted groups are preferred from the viewpoint of ease of synthesis.

The aromatic ring group for R ^21a includes aromatic hydrocarbon ring groups and aromatic heterocyclic groups. Although the number of carbon atoms in the aromatic ring group is not particularly limited, it is preferably 5 or more from the viewpoint of solubility in the photosensitive coloring composition. From the viewpoint of developability, it is preferably 30 or less, more preferably 20 or less, and even more preferably 12 or less.

Examples of the aromatic ring group include a phenyl group, a naphthyl group, a pyridyl group, and a furyl group. Among these, from the viewpoint of developability, a phenyl group or a naphthyl group is preferable, and a phenyl group is more preferable.
Examples of the substituent that the aromatic ring group may have include a hydroxyl group, a carboxy group, a halogen atom, an amino group, an amide group, an alkyl group, an alkoxy group, and groups in which these substituents are linked. From the viewpoint of developability, an alkyl group, an alkoxy group, or a group in which these are linked is preferable, and a linked alkoxy group is more preferable.
Among these, from the viewpoint of developability, R ^21a is preferably an optionally substituted aromatic ring group, more preferably an aromatic ring group having a linked alkoxy group as a substituent. preferable.

R ^21b is an optionally substituted carbazolyl group, an optionally substituted thioxanthonyl group, an optionally substituted diphenyl sulfide group, an optionally substituted fluorenyl group, or an optionally substituted An indolyl group can be mentioned. Among these, an optionally substituted carbazolyl group is preferable from the viewpoint of sensitivity. From the viewpoint of electrical reliability, an optionally substituted diphenyl sulfide group is preferred.

The number of carbon atoms in the alkanoyl group in R ^22a is not particularly limited, but from the viewpoint of solubility in solvents and sensitivity, it is usually 2 or more, and usually 20 or less, preferably 15 or less, more preferably 10 or less, more preferably 10 or less. is 5 or less. For example, alkanoyl groups include acetyl, propanoyl and butanoyl groups.
Examples of substituents that the alkanoyl group may have include aromatic ring groups, hydroxyl groups, carboxy groups, halogen atoms, amino groups, and amide groups.
It is preferably unsubstituted.

Although the number of carbon atoms in the aryloyl group in R ^22a is not particularly limited, it is usually 7 or more and usually 20 or less, preferably 15 or less, more preferably 10 or less, from the viewpoint of solvent solubility and sensitivity. The aryloyl group includes a benzoyl group and a naphthoyl group.
Substituents that the aryloyl group may have include, for example, a hydroxyl group, a carboxy group,
halogen atoms, amino groups, amido groups, and alkyl groups; from the viewpoint of ease of synthesis,
It is preferably unsubstituted.
Among these, from the viewpoint of sensitivity, R ^22a is preferably an optionally substituted alkanoyl group, more preferably an unsubstituted alkanoyl group, and still more preferably an acetyl group.

For example, Japanese Patent No. 4454067, International Publication No. 2002/100903, International Publication No. 2012/45736, International Publication No. 2015/36910, International Publication No. 20
06/18973, International Publication No. 2008/78678, Japanese Patent 4818458
Publications, WO2005/80338, WO2008/75564,
WO2009/131189, WO2009/131189, WO2010/133077, WO2010/102502, WO201
2/68879 and Japanese Patent Application Laid-Open No. 2016-133574, and the like can be used.

(C) A photoinitiator may be used individually by 1 type, or may be used in combination of 2 or more types.
The photopolymerization initiator (C) may optionally be blended with a sensitizing dye and a polymerization accelerator corresponding to the wavelength of the image exposure light source for the purpose of increasing sensitivity. Examples of sensitizing dyes include the xanthene dyes described in JP-A-4-221958 and JP-A-4-219756, JP-A-3-239703 and JP-A-5-289335.
JP-A-3-239703, 3-ketocoumarin compound described in JP-A-5-289335, JP-A-6-
Pyromethene dyes described in JP-A-19240, JP-A-47-2528, JP-A-54-155292, JP-B-45-37377, JP-A-48-84183 Publications, Japanese Patent Laid-Open No. 52-112681, Japanese Patent Laid-Open No. 58-
15503, Japanese Patent Laid-Open No. 60-88005, Japanese Patent Laid-Open No. 59-5640
No. 3, Japanese Patent Laid-Open Publication No. 2-69, Japanese Patent Laid-Open Publication No. 57-168088, Japanese Patent Laid-Open Publication No. 5-107761, Japanese Patent Laid-Open Publication No. 5-210240, Japanese Patent Laid-Open Publication No. 4 A dye having a dialkylaminobenzene skeleton described in JP-A-288818 can be mentioned.

Among these sensitizing dyes, amino group-containing sensitizing dyes are preferred, and compounds having an amino group and a phenyl group in the same molecule are more preferred. For example, 4,4′-dimethylaminobenzophenone, 4,4′-diethylaminobenzophenone, 2-aminobenzophenone, 4-
Benzophenone compounds such as aminobenzophenone, 4,4'-diaminobenzophenone, 3,3'-diaminobenzophenone, 3,4-diaminobenzophenone; 2-(p-dimethylaminophenyl)benzoxazole, 2-(p-diethylaminophenyl) ) benzoxazole, 2-(p-dimethylaminophenyl)benzo[4,5]benzoxazole, 2-(p-dimethylaminophenyl)benzo[6,7]benzoxazole, 2,
5-bis(p-diethylaminophenyl)-1,3,4-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-thiadiazole, (p-dimethylaminophenyl)pyridine, (p-diethylaminophenyl)pyridine, (p-dimethylaminophenyl)quinoline, (p-diethylaminophenyl)quinoline, (p-dimethylaminophenyl) P-dialkylaminophenyl group-containing compounds such as pyrimidine and (p-diethylaminophenyl)pyrimidine are preferred, and 4,4'-dialkylaminobenzophenone is particularly preferred.
The sensitizing dyes may be used singly or in combination of two or more.

Examples of polymerization accelerators include aromatic amines such as ethyl 4-dimethylaminobenzoate, 2-ethylhexyl 4-dimethylaminobenzoate, 4-dimethylaminoacetophenone, and 4-dimethylaminopropiophenone, and n-butylamine. , N-methyldiethanolamine, and 2-dimethylaminoethyl benzoate can be used. The polymerization accelerator may be used alone or in combination of two or more.

<Ethylenically unsaturated compound>
The photosensitive coloring composition of the present invention may optionally contain an ethylenically unsaturated compound. Sensitivity is improved by including an ethylenically unsaturated compound.
The ethylenically unsaturated compound used in the present invention is a compound having at least one ethylenically unsaturated group in its molecule. Specific examples thereof include (meth)acrylic acid, (meth)acrylic acid alkyl esters, acrylonitrile, styrene, carboxylic acids having one ethylenically unsaturated bond, and monoesters of polyhydric or monohydric alcohols.

In the present invention, it is particularly desirable to use polyfunctional ethylenic monomers having two or more ethylenically unsaturated groups in one molecule. The number of ethylenically unsaturated groups possessed by the polyfunctional ethylenic monomer is not particularly limited, but is usually 2 or more, preferably 4 or more, more preferably 5 or more, and preferably It is 8 or less, more preferably 7 or less. For example, 2 to 8 are preferred, 2 to 7 are more preferred, 4 to 7 are even more preferred, and 5 to 7 are particularly preferred. By making it more than the said lower limit, there exists a tendency which becomes high sensitivity. Solubility in a solvent tends to be improved by adjusting the content to be equal to or less than the above upper limit.
Examples of polyfunctional ethylenic monomers include esters of aliphatic polyhydroxy compounds and unsaturated carboxylic acids; esters of aromatic polyhydroxy compounds and unsaturated carboxylic acids; aliphatic polyhydroxy compounds, aromatic Esters obtained by an esterification reaction between a polyhydric hydroxy compound such as a polyhydroxy compound and an unsaturated carboxylic acid or a polybasic carboxylic acid can be mentioned.

Esters of aliphatic polyhydroxy compounds and unsaturated carboxylic acids include, for example, ethylene glycol diacrylate, triethylene glycol diacrylate, trimethylolpropane triacrylate, trimethylolethane triacrylate, pentaerythritol diacrylate, and pentaerythritol triacrylate. , pentaerythritol tetraacrylate, dipentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, acrylic acid esters of aliphatic polyhydroxy compounds such as glycerol acrylate, methacrylic acid esters obtained by replacing these acrylates with methacrylates, itaconates Itaconate in place of , crotonate in place of clonate, and maleate in place of maleate.

Esters of aromatic polyhydroxy compounds and unsaturated carboxylic acids include acrylic acid esters and methacryl esters of aromatic polyhydroxy compounds such as hydroquinone diacrylate, hydroquinone dimethacrylate, resorcin diacrylate, resorcin dimethacrylate, and pyrogallol triacrylate. acid esters.

The ester obtained by the esterification reaction of polybasic carboxylic acid and unsaturated carboxylic acid and polyvalent hydroxy compound is not necessarily a single substance, but for example, acrylic acid, phthalic acid, and condensate of ethylene glycol, Condensates of acrylic acid, maleic acid and diethylene glycol, condensates of methacrylic acid, terephthalic acid and pentaerythritol, condensates of acrylic acid, adipic acid, butanediol and glycerol.

In addition, as the polyfunctional ethylenic monomer used in the present invention, for example, a polyisocyanate compound and a hydroxyl group-containing (meth)acrylic acid ester or a polyisocyanate compound, a polyol and a hydroxyl group-containing (meth)acrylic acid ester are reacted. urethane (meth)acrylates such as those obtained; epoxy acrylates such as addition reaction products of polyepoxy compounds and hydroxy (meth) acrylate or (meth) acrylic acid; acrylamides such as ethylenebisacrylamide; diallyl phthalate and vinyl group-containing compounds such as divinyl phthalate are useful.

Urethane (meth)acrylates include, for example, DPHA-40H, UX-500
0, UX-5002D-P20, UX-5003D, UX-5005 (manufactured by Nippon Kayaku Co., Ltd.),
U-2PPA, U-6LPA, U-10PA, U-33H, UA-53H, UA-32P
, UA-1100H (manufactured by Shin-Nakamura Chemical Co., Ltd.), UA-306H, UA-510H, UF-
8001G (manufactured by Kyoeisha Chemical Co., Ltd.), UV-1700B, UV-7600B, UV-7605
B, UV-7630B, and UV7640B (manufactured by Nippon Synthetic Chemical Industry Co., Ltd.).

Among these, it is preferable to use (meth)acrylic acid alkyl ester as the ethylenically unsaturated compound from the viewpoint of curability, and it is more preferable to use dipentaerythritol hexaacrylate.
These may be used individually by 1 type, and may use 2 or more types together.

<Solvent>
The photosensitive coloring composition of the present invention may contain a solvent, if necessary. By containing a solvent, (A) the colorant can be dispersed or dissolved in the solvent, and coating is facilitated.
The photosensitive coloring composition of the present invention preferably contains (A) a coloring agent, (B) an alkali-soluble resin,
In addition to (C) a photopolymerization initiator, an ethylenically unsaturated compound, a dispersant, and other various materials used are used in a state of being dissolved or dispersed in a solvent. Among the solvents, organic solvents are preferred from the viewpoint of dispersibility and coatability.

Among organic solvents, those having a boiling point of 100 to 300° C., more preferably 120 to 280° C., are preferred from the viewpoint of coating properties. In addition, the boiling point here is the pressure 101
It means the boiling point at 3.25 hPa, the same applies hereinafter for all boiling points.

Examples of such organic solvents include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, and 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-methoxybutanol, 3-methyl-3-methoxybutanol, triethylene glycol monomethyl ether, Glycol monoalkyl ethers such as triethylene glycol monoethyl ether, tripropylene glycol methyl ether;
glycol dialkyl ethers such as ethylene glycol dimethyl ether, ethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, 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 glycol alkyl ether acetates such as ether acetate, 3-methyl-3-methoxybutyl acetate;
Ethylene glycol diacetate, 1,3-butylene glycol diacetate, 1,6
- glycol diacetates such as hexanol diacetate;
Alkyl acetates such as cyclohexanol acetate;
amyl ether, diethyl ether, dipropyl ether, diisopropyl ether,
Ethers such as dibutyl ether, diamyl ether, ethyl isobutyl ether, dihexyl ether;

Acetone, methyl ethyl ketone, methyl amyl ketone, methyl isopropyl ketone, methyl isoamyl ketone, diisopropyl ketone, diisobutyl ketone, methyl isobutyl ketone, cyclohexanone, ethyl amyl ketone, methyl butyl ketone, methylhexyl ketone, methyl nonyl ketone, methoxymethyl pentanone 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;
Amyl formate, ethyl formate, ethyl acetate, butyl acetate, propyl acetate, amyl acetate, methyl isobutyrate, ethylene glycol acetate, ethyl propionate, propyl propionate, butyl butyrate, isobutyl butyrate, methyl isobutyrate, ethyl Caprylate, butyl stearate, ethyl benzoate, 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 and 3-ethoxypropionic acid;
Halogenated hydrocarbons such as butyl chloride, amyl chloride;
ether ketones such as methoxymethylpentanone;
nitriles such as acetonitrile and benzonitrile;

Examples of commercially available organic solvents include Mineral Spirit, Valsol #2, and Apco #18.
Solvent, Apco Thinner, Socal Solvent No. 1 and no. 2, Solvesso #
150, Shell TS28 Solvent, Carbitol, Ethyl Carbitol, Butyl Carbitol, Methyl Cellosolve ("Cellosolve" is a registered trademark. The same shall apply hereinafter.), Ethyl Cellosolve, Ethyl Cellosolve Acetate, Methyl Cellosolve Acetate, Diglyme (all trade names) can be used.
These organic solvents may be used alone or in combination of two or more.

When the black matrix is formed by photolithography, the organic solvent preferably has a boiling point of 100 to 200°C, more preferably 120 to 170°C.

Among the above organic solvents, glycol alkyl ether acetates are preferable because they have a good balance of applicability, surface tension, etc., and relatively high solubility of the components in the composition.
Also, the glycol alkyl ether acetates may be used alone, or may be used in combination with other organic solvents. Glycol monoalkyl ethers are particularly preferred as organic solvents to be used in combination. Among them, propylene glycol monomethyl ether is particularly preferred because of the solubility of the constituents in the composition. Glycol monoalkyl ethers have a high polarity, and if the amount added is too large, the pigment tends to aggregate, and the viscosity of the photosensitive coloring composition obtained later tends to decrease, resulting in a decrease in storage stability. , the ratio of the glycol monoalkyl ether in the solvent is preferably 5% by mass to 30% by mass, more preferably 5% by mass to 20% by mass.

In addition, an organic solvent with a boiling point of 150°C or higher (hereinafter sometimes referred to as a "high boiling point solvent")
It is also preferable to use together. By using such a high boiling point solvent in combination, the photosensitive coloring composition becomes difficult to dry, but has the effect of preventing the uniformly dispersed state of the pigment in the composition from being destroyed by rapid drying. That is, for example, at the tip of the slit nozzle,
It has the effect of preventing the occurrence of defects due to precipitation and solidification of coloring agents and the like. Among the various solvents described above, diethylene glycol mono-n-butyl ether, diethylene glycol mono-n-butyl ether acetate, and diethylene glycol monoethyl ether acetate are particularly preferred because of their high effect.

When a high-boiling solvent is used in combination, the content of the high-boiling solvent in the organic solvent is preferably 3% to 50% by mass, more preferably 5% to 40% by mass, particularly 5% to 30% by mass. preferable. By making it equal to or higher than the above lower limit, for example, it tends to be possible to suppress the deposition and solidification of the coloring material and the like at the tip of the slit nozzle to cause foreign matter defects. It tends to suppress problems such as poor tact in the vacuum drying process and pin marks in the pre-bake process.

The high-boiling solvent having a boiling point of 150° C. or higher may be glycol alkyl ether acetates or glycol alkyl ethers. In this case, boiling point 1
It is not necessary to separately contain a high boiling point solvent of 50° C. or higher.
Preferred high-boiling solvents include diethylene glycol mono-n-butyl ether acetate, diethylene glycol monoethyl ether acetate, dipropylene glycol methyl ether acetate, 1,3-butylene glycol diacetate, 1,6- Hexanol diacetate, triacetin.

<Dispersant>
When the photosensitive resin composition of the present invention contains (A) a colorant, it preferably contains a dispersant in order to finely disperse the (A) colorant and stabilize the dispersion state.
As the dispersant, a polymer dispersant having a functional group is preferable, and from the viewpoint of dispersion stability, a carboxy group; a phosphoric acid group; a sulfonic acid group; or a base thereof; a primary, secondary or tertiary amino group; Polymeric dispersants having functional groups such as quaternary ammonium bases; groups derived from nitrogen-containing heterocycles such as pyridine, pyrimidine and pyrazine are preferred. Above all, polymeric dispersants having basic functional groups such as primary, secondary or tertiary amino groups; quaternary ammonium bases; groups derived from nitrogen-containing heterocycles such as pyridine, pyrimidine and pyrazine disperse pigments. It is particularly preferable from the viewpoint that it can be dispersed with a small amount of dispersant.

Examples of polymer dispersants include urethane-based dispersants, acrylic dispersants, polyethyleneimine-based dispersants, polyallylamine-based dispersants, dispersants composed of a monomer having an amino group and a macromonomer, polyoxyethylene alkyl Ether dispersants, polyoxyethylene diester dispersants, polyether phosphate dispersants, polyester phosphate dispersants,
Sorbitan aliphatic ester-based dispersants and aliphatic modified polyester-based dispersants can be mentioned.

Specific examples of such a dispersant include EFKA (registered trademark, BAS) under the trade name.
Made by F company. ), DISPERBYK (registered trademark, manufactured by BYK-Chemie), Disparon (registered trademark, manufactured by Kusumoto Kasei Co., Ltd.), SOLSPERSE (registered trademark, manufactured by Lubrizol),
KP (manufactured by Shin-Etsu Chemical Co., Ltd.), Polyflow (manufactured by Kyoeisha Chemical Co., Ltd.), and Ajisper (registered trademark, manufactured by Ajinomoto Co., Inc.) can be mentioned.
Polymer dispersants may be used alone or in combination of two or more.

The weight average molecular weight (Mw) of the polymeric dispersant is preferably 700 or more, more preferably 10
00 or more, preferably 100,000 or less, more preferably 50,000 or less. For example, the weight average molecular weight (Mw) of the polymeric dispersant is preferably 700-100,000, more preferably 1,000-50,000.
Among these, from the viewpoint of pigment dispersibility, the dispersant (F) preferably contains either or both of a functional group-containing urethane polymer dispersant and an acrylic polymer dispersant. It is particularly preferred to include a molecular dispersant.
From the viewpoint of dispersibility and storage stability, a polymer dispersant having a basic functional group and either or both of a polyester bond and a polyether bond is preferred.

Examples of urethane-based and acrylic-based polymer dispersants include DISPERBYK-16
0-167, 182 series (all urethane), DISPERBYK-2000,
2001, and BYK-LPN21116 (both acrylic) (all manufactured by BYK-Chemie).

As the acrylic polymer dispersant, an unsaturated group-containing monomer having a functional group (the functional group here is the functional group described above as the functional group contained in the polymer dispersant), It is preferable to use random copolymers, graft copolymers and block copolymers with unsaturated group-containing monomers having no functional groups. These copolymers can be produced by known methods.

Examples of unsaturated group-containing monomers having functional groups include (meth) acrylic acid, 2-(meth) acryloyloxyethyl succinic acid, 2-(meth) acryloyloxyethyl phthalate,
2-(meth)acryloyloxyethylhexahydrophthalic acid, unsaturated monomers having a carboxyl group such as acrylic acid dimer, dimethylaminoethyl (meth)acrylate, diethylaminoethyl (meth)acrylate and quaternized products thereof, etc. and unsaturated monomers having a tertiary amino group and a quaternary ammonium base.
These may be used individually by 1 type, and may use 2 or more types together.

Examples of unsaturated group-containing monomers having no functional group include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth)
Acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, t
- butyl (meth)acrylate, benzyl (meth)acrylate, phenyl (meth)acrylate, cyclohexyl (meth)acrylate, phenoxyethyl (meth)acrylate, phenoxymethyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, isobornyl (meth)acrylate ) 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, poly 2-hydroxyethyl (meth)acrylate macromonomers, polyethylene glycol macromonomers, polypropylene glycol macromonomers, poly Examples include macromonomers such as caprolactone macromonomers.
These may be used individually by 1 type, and may use 2 or more types together.

The acrylic polymer dispersant is particularly preferably an AB or BAB block copolymer consisting of an A block having a functional group and a B block having no functional group.
In addition to the partial structure derived from the unsaturated group-containing monomer containing the functional group, the A block may contain a partial structure derived from the unsaturated group-containing monomer that does not contain the functional group. These may be contained in the A block in any form of random copolymerization or block copolymerization.
The content of the partial structure containing no functional group in the A block is preferably 80% by mass or less, more preferably 50% by mass or less, and even more preferably 30% by mass or less.

The B block consists of a partial structure derived from an unsaturated group-containing monomer that does not contain the above functional group, but one B block contains partial structures derived from two or more monomers. These may be contained in the B block in any form of random copolymerization or block copolymerization.
The AB or BAB block copolymer is prepared, for example, by the following living polymerization method.
The living polymerization method includes an anion living polymerization method, a cationic living polymerization method, and a radical living polymerization method.

When synthesizing this acrylic polymer dispersant, for example, Japanese Patent Laid-Open No. 9-620
02, P.S. Lutz, P.; Masson et al, Polym. Bull. 1
2, 79 (1984), B.P. C. Anderson, G.; D. Andrews et a
1, Macromolecules, 14, 1601 (1981), K.I. Hatada,
K. Ute, et al, Polym. J. 17, 977 (1985), 18, 1037
(1986), Kouichi Ugi, Koichi Hatada, Kobunshi Kako, 36, 366 (1987), Toshinobu Higashimura, Mitsuo Sawamoto, Kobunshi Ronbunshu, 46, 189 (1989), M.M. Kuroki, T.; aid
a, J. Am. Chem. Sic, 109, 4737 (1987), Takuzo Aida, Shohei Inoue, Synthetic Organic Chemistry, 43, 300 (1985), D. Y. Sogoh, W.; R. Hertl
er et al, Macromolecules, 20, 1473 (1987) can be employed.

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 /B block ratio is preferably 1/99 to 80/20 (mass ratio), particularly 5/95 to 60/4
0 (mass ratio) is more preferred. By setting the amount within the above range, there is a tendency that a balance between dispersibility and storage stability can be ensured.
AB block copolymer that can be used in the present invention, BAB block copolymer 1
The amount of quaternary ammonium base in g is preferably 0.1 to 10 mmol. By setting the amount within the above range, there is a tendency that good dispersibility can be ensured.

When such a block copolymer contains an amino group generated during the production process, the amine value is preferably 1 to 100 mgKOH/g, and from the viewpoint of dispersibility, preferably 10 m
gKOH/g or more, more preferably 30 mgKOH/g or more, more preferably 50 mg
KOH/g or more, preferably 90 mgKOH/g or less, more preferably 80 mgK
OH/g or less, more preferably 75 mgKOH/g or less. For example, 1-100m
gKOH/g is preferred, 10 to 90 mgKOH/g is more preferred, and 30 to 80 mgK
OH/g is more preferred, and 50-75 mg KOH/g is particularly preferred.
The amine value of a dispersant such as a block copolymer is expressed by the mass of KOH equivalent to the amount of base per 1 g of solid content excluding the solvent in the dispersant sample, and is measured by the following method.
Accurately weigh 0.5 to 1.5 g of a dispersant sample in a 100 mL beaker and dissolve it in 50 mL of acetic acid. This solution was diluted with 0.1 mol/L HCl using an automatic titrator equipped with a pH electrode.
Neutralization titration is carried out with O ₄ acetic acid solution. The inflection point of the titration pH curve is defined as the end point of the titration, and the amine value is obtained by the following formula.

Amine value [mgKOH / g] = (561 × V) / (W × S) [W: dispersant sample weighed amount [g], V: titration amount at the end point of titration [mL], S: dispersant Solid content concentration of sample [mass%]
represents ]
The acid value of the block copolymer is preferably as low as possible, preferably 10 mgKOH/g or less, although it depends on the presence and type of acidic groups that are the source of the acid value.
The weight average molecular weight (Mw) of the block copolymer is preferably in the range of 1,000 to 100,000. Within the above range, there is a tendency to ensure good dispersibility.

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

(In formula (ri), each of R ³¹ to R ³³ independently represents a hydrogen atom, an optionally substituted alkyl group, an optionally substituted aryl group, or a substituent represents an aralkyl group which may have;
two or more of R ³¹ to R ³³ may bond together to form a cyclic structure;
R ³⁴ is a hydrogen atom or a methyl group;
X is a divalent linking group;
Y ⁻ is a counter anion. )

The number of carbon atoms in the optionally substituted alkyl group in R ³¹ to R ³³ of formula (ri) is not particularly limited, but is preferably 1 or more and 10 or less, and 6 or less. more preferred. Specific examples of alkyl groups include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, and octyl groups, and among these, methyl, ethyl, propyl, A butyl group, a pentyl group and a hexyl group are preferable, and a methyl group, an ethyl group, a propyl group and a butyl group are more preferable. Also, it may be linear or branched. Moreover, a cyclic structure such as a cyclohexyl group or a cyclohexylmethyl group may be included.

The number of carbon atoms in the optionally substituted aryl group in R ³¹ to R ³³ of formula (ri) is not particularly limited, but is preferably 6 or more, preferably 16 or less, and 12 or less. is more preferred. Specific examples of the aryl group include, for example, a phenyl group, a methylphenyl group,
ethylphenyl group, dimethylphenyl group, diethylphenyl group, naphthyl group, anthracenyl group, among these, phenyl group, methylphenyl group, ethylphenyl group,
A dimethylphenyl group and a diethylphenyl group are preferred, and a phenyl group, a methylphenyl group,
An ethylphenyl group is more preferred.

The number of carbon atoms in the optionally substituted aralkyl group in R ³¹ to R ³³ of formula (ri) is not particularly limited, but is preferably 7 or more, preferably 16 or less, and 12 or less. is more preferred. Specific examples of the aralkyl group include, for example, a phenylmethyl group (benzyl group), a phenylethyl group (phenethyl group), a phenylpropyl group, a phenylbutyl group and a phenylisopropyl group. An ethyl group, a phenylpropyl group and a phenylbutyl group are preferable, and a phenylmethyl group and a phenylethyl group are more preferable.

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

The counter anion Y ⁻ in formula (ri) is not particularly limited, but examples include Cl ⁻ , Br ⁻
, I ⁻ , ClO ⁴⁻ , BF ⁴⁻ , CH ₃ COO−, PF ⁶⁻ , CH ₃ SO ⁴⁻ .

When the polymer dispersant has a tertiary amine as a functional group, from the viewpoint of dispersibility, the following formula (
It preferably has a repeating unit represented by r-ii) (hereinafter sometimes referred to as "repeating unit (r-ii)").

(In formula (r-ii), R ³⁵ and R ³⁶ each independently represent a hydrogen atom, an optionally substituted alkyl group, an optionally substituted aryl group, or a substituent an aralkyl group which may have;
R ³⁵ and R ³⁶ may be linked together to form a cyclic structure;
R ³⁷ is a hydrogen atom or a methyl group;
Z is a divalent linking group. )

As the optionally substituted alkyl group for R ³⁵ and R ³⁶ in formula (rii), those exemplified as R ³¹ to R ³³ in formula (ri) can be preferably employed. can.
As the optionally substituted aryl group for R ³⁵ and R ³⁶ in formula (rii), those exemplified as R ³¹ to R ³³ in formula (ri) can be preferably employed. can.
As the optionally substituted aralkyl group for R ³⁵ and R ³⁶ in formula (rii), those exemplified as R ³¹ to R ³³ in formula (ri) can be preferably employed. can.

Among these, R ³⁵ and R ³⁶ are each independently preferably an optionally substituted alkyl group, more preferably a methyl group or an ethyl group.

Substituents that the alkyl group, aralkyl group or aryl group in R ³¹ to R ³³ of formula (ri) and R ³⁵ and R ³⁶ of formula (r-ii) may have include, for example, a halogen atom ,
An alkoxy group, a benzoyl group, and a hydroxyl group can be mentioned.

In the formulas (ri) and (r-ii), the divalent linking groups X and Z are, for example,
Alkylene group having 1 to 10 carbon atoms, arylene group having 6 to 12 carbon atoms, -CONH-R ⁴³ - group, -COOR ⁴⁴ - group (provided that R ⁴³ and R ⁴⁴ are single bonds, alkylene groups having 1 to 10 carbon atoms, or an ether group (alkyloxyalkyl group) having 2 to 10 carbon atoms), preferably -COO-R ⁴⁴ - group.

The content ratio of the repeating unit represented by the formula (ri) is not particularly limited, but from the viewpoint of dispersibility, the content ratio of the repeating unit represented by the formula (ri) and the formula (rii) 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, relative to the total content of repeating units represented. 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. For example, 5 to 60 mol% is preferred, 10 to 50 mol% is more preferred, 20 to 40 mol% is even more preferred, and 30 to 35 mol% is particularly preferred.

The content ratio of the repeating unit represented by the formula (ri) in the total repeating units of the polymer dispersant is not particularly limited, but from the viewpoint of dispersibility, it is preferably 1 mol% or more, and 5 mol% or more. It is more preferably 10 mol % or more, more preferably 50 mol % or less, more preferably 30 mol % or less, even more preferably 20 mol % or less, and particularly preferably 15 mol % or less. For example, 1 to 50 mol% is preferable, 1 to 30 mol% is more preferable, 5
~20 mol% is more preferred, and 10 to 15 mol% is particularly preferred.

The content ratio of the repeating unit represented by the formula (r-ii) in the total repeating units of the polymer dispersant is not particularly limited, but from the viewpoint of dispersibility, it is preferably 5 mol% or more, and 10 mol. % or more, more preferably 15 mol% or more, particularly preferably 20 mol% or more, and preferably 60 mol% or less, and 40 mol% or less. is more preferably 30 mol % or less, and particularly preferably 25 mol % or less. For example, 5 to 60 mol % is preferred, 10 to 40 mol % is more preferred, 15 to 30 mol % is even more preferred, and 20 to 25 mol % is particularly preferred.

Polymeric dispersants are repeating units represented by the following formula (r-iii) (hereinafter referred to as “repeating units (r -iii)”.) is preferred.

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

The number of carbon atoms in the optionally substituted alkyl group in R ⁴¹ of formula (r-iii) is not particularly limited, but is 1 or more, preferably 2 or more, and 10 or less. It is preferably 6 or less, more preferably 6 or less. Specific examples of alkyl groups include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, and octyl groups, and among these, methyl, ethyl, propyl, A butyl group, a pentyl group, or a hexyl group is preferable, and a methyl group, an ethyl group, a propyl group, or a butyl group is more preferable. Also, it may be linear or branched. Moreover, a cyclic structure such as a cyclohexyl group or a cyclohexylmethyl group may be included. For example, the number of carbon atoms in the alkyl group is preferably 1-10, more preferably 2-6.

n in the formula (r-iii) is 1 or more, preferably 2 or more, and preferably 10 or less, and 5 or less, from the viewpoint of compatibility and dispersibility in solvents and alkali-soluble resins. is more preferable. For example, 1 to 10 are preferred, 1 to 5 are more preferred, and 2 to 5 are even more preferred.

In addition, the content ratio of the repeating unit represented by the formula (r-iii) in the total repeating units of the polymer dispersant is not particularly limited, but is preferably 1 mol% or more, more preferably 2 mol% or more. mol % or more is more preferable, 30 mol % or less is preferable, 20 mol % or less is more preferable, and 10 mol % or less is even more preferable. Within the above range, compatibility with solvents and alkali-soluble resins and dispersion stability tend to be compatible. For example, the content of the repeating unit represented by the formula (r-iii) in the total repeating units of the polymer dispersant is preferably 1 to 30 mol%, more preferably 2 to 20 mol%, and 4 to 10 mol. % is more preferred.

In addition, the polymeric dispersant is a repeating unit represented by the following formula (r-iv) (hereinafter referred to as "repeating It is sometimes referred to as a unit (r-iv).).

(In formula (r-iv), R ³⁸ is an optionally substituted alkyl group, an optionally substituted aryl group, or an optionally substituted aralkyl group; ;
^R39 is a hydrogen atom or a methyl group. )

The number of carbon atoms in the optionally substituted alkyl group in R ³⁸ of formula (r-iv) is not particularly limited, but is 1 or more, preferably 2 or more, more preferably 4 or more, and 1
0 or less is preferable, and 8 or less is more preferable. Specific examples of alkyl groups include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, and octyl groups, and among these, methyl, ethyl, propyl, A butyl group, a pentyl group and a hexyl group are preferable, and a methyl group, an ethyl group, a propyl group and a butyl group are more preferable. Also, it may be linear or branched. Moreover, a cyclic structure such as a cyclohexyl group or a cyclohexylmethyl group may be included. For example, the number of carbon atoms in the alkyl group is preferably 1-10, more preferably 2-8, even more preferably 4-8.

Although the number of carbon atoms in the optionally substituted aryl group in R ³⁸ of formula (r-iv) is not particularly limited, it is preferably 6 or more, preferably 16 or less, and more preferably 12 or less. , 8 or less are more preferred. Specific examples of aryl groups include phenyl, methylphenyl, ethylphenyl, dimethylphenyl, diethylphenyl, naphthyl, and anthracenyl groups. A phenyl group, a dimethylphenyl group and a diethylphenyl group are preferred, and a phenyl group, a methylphenyl group and an ethylphenyl group are more preferred. For example, the aryl group preferably has 6 to 16 carbon atoms, more preferably 6 to 12 carbon atoms, and even more preferably 8 to 12 carbon atoms.

Although the number of carbon atoms in the optionally substituted aralkyl group in R ³⁸ of formula (r-iv) is not particularly limited, it is preferably 7 or more, preferably 16 or less, and more preferably 12 or less. , 10 or less is more preferable. Specific examples of the aralkyl group include, for example, a phenylmethyl group (benzyl group), a phenylethyl group (phenethyl group), a phenylpropyl group, a phenylbutyl group, and a phenylisopropyl group. An ethyl group, a phenylpropyl group and a phenylbutyl group are preferable, and a phenylmethyl group and a phenylethyl group are more preferable. For example, the number of carbon atoms in the aralkyl group is 7 to
16 is preferred, 7 to 12 are more preferred, and 7 to 10 are even more preferred.

Among these, from the viewpoint of solvent compatibility and dispersion stability, R ³⁸ is preferably an alkyl group or an aralkyl group, more preferably a methyl group, an ethyl group, or a phenylmethyl group.
Examples of the substituent that the alkyl group in R ³⁸ may have include a halogen atom and an alkoxy group. Examples of the substituent that the aryl group or aralkyl group in R ³⁸ may have include a chain alkyl group, a halogen atom, and an alkoxy group. The chain alkyl group represented by R ³⁸ includes both straight chain and branched chain alkyl groups.

From the viewpoint of dispersibility, the content of the repeating unit represented by the formula (r-iv) in the total repeating units of the polymer dispersant is preferably 30 mol% or more, more preferably 40 mol% or more, and 50 mol% or more is more preferable, and 80 mol% or less is preferable, and 70 mol%
The following are more preferred. For example, 30 to 80 mol% is preferred, 40 to 80 mol% is more preferred, and 50 to 70 mol% is even more preferred.

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

From the viewpoint of further increasing dispersibility, the polymer dispersant includes an A block having a repeating unit (ri) and a repeating unit (r-ii), a repeating unit (ri) and a repeating unit (r- It is preferably a block copolymer having a B block that does not have ii). Preferably, the block copolymer is an AB block copolymer or a BAB block copolymer. Introducing not only a quaternary ammonium base but also a tertiary amino group into the A block unexpectedly tends to significantly improve the dispersing ability of the dispersant. In addition, it is preferable that the B block has a repeating unit (r-iii), and the repeating unit (r-i
It is more preferred to have v).

In the A block, the repeating unit (ri) and the repeating unit (rii) may be contained in any form of random copolymerization or block copolymerization. repeating unit (
ri) and the repeating unit (r-ii) may be contained in one A block each one or two or more, in which case each repeating unit is random copolymerized in the A block , may be contained in any mode of block copolymerization.

A repeating unit other than the repeating unit (ri) and the repeating unit (r-ii) may be contained in the A block. Examples of such repeating units include the above-mentioned (meth)acrylic A repeating unit derived from an acid ester-based monomer is included. repeating unit (
The content of repeating units other than ri) and repeating units (r-ii) in the A block is preferably 0 to 50 mol%, more preferably 0 to 20 mol%, and 0 mol% is particularly preferable.

Repeating units other than the repeating units (r-iii) and (r-iv) may be contained in the B block. Examples of such repeating units include styrene units such as styrene and α-methylstyrene. (Meth)acrylate-based monomers such as (meth)acrylic acid chloride; (meth)acrylamide-based monomers such as (meth)acrylamide and N-methylolacrylamide; vinyl acetate; acrylonitrile; allyl glycidyl ether , crotonic acid glycidyl ether; and repeating units derived from N-methacryloylmorpholine. of repeating units other than repeating units (r-iii) and repeating units (r-iv),
The content in the B block is preferably 0 to 50 mol %, more preferably 0 to 20 mol %, particularly preferably 0 mol %.

<Other ingredients of the photosensitive coloring composition>
In addition to the components described above, the photosensitive coloring composition of the present invention contains adhesion improvers such as silane coupling agents, surfactants, pigment derivatives, photoacid generators, cross-linking agents, mercapto compounds, polymerization inhibitors, and the like. Additives can be appropriately blended.

(1) Adhesion Improver The photosensitive coloring composition of the present invention may contain an adhesion improver in order to improve adhesion to a substrate. Preferred adhesion improvers are silane coupling agents and phosphoric acid group-containing compounds.
As for the types of silane coupling agents, epoxy, (meth)acrylic, amino, and the like can be used singly or in combination of two or more.

Examples of silane coupling agents include (meth)acryloxysilanes such as 3-methacryloxypropylmethyldimethoxysilane and 3-methacryloxypropyltrimethoxysilane, and 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane. , epoxysilanes such as 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, ureidosilanes such as 3-ureidopropyltriethoxysilane, Examples include isocyanate silanes such as 3-isocyanatopropyltriethoxysilane. Silane coupling agents of the epoxysilane class are particularly preferred.
As the phosphoric acid group-containing compound, (meth)acryloyl group-containing phosphates are preferred,
Those represented by the following general formulas (g1), (g2) or (g3) are preferred.

In general formulas (g1), (g2) and (g3) above, 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 singly or in combination of two or more.

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

Various surfactants such as anionic surfactants, cationic surfactants, nonionic surfactants and amphoteric surfactants can be used as surfactants. Among them, nonionic surfactants are preferred because they are less likely to adversely affect various properties. Among them, fluorine-based and silicon-based surfactants are effective in terms of coating properties.
Examples of such surfactants include TSF4460 (manufactured by Momentive Performance Materials), DFX-18 (manufactured by Neos), BYK-300 and BYK-3.
25, BYK-330 (manufactured by BYK-Chemie), KP340 (manufactured by Shin-Etsu Silicone Co., Ltd.), F-
470, F-475, F-478, F-554, F-559 (manufactured by DIC), SH7PA
(manufactured by Dow Corning Toray), DS-401 (manufactured by Daikin), L-77 (manufactured by Nihon Unicar), and FC4430 (manufactured by 3M).
One type of surfactant may be used, or two or more types may be used together in any combination and ratio.

(3) Pigment Derivative The photosensitive coloring composition of the present invention may contain a pigment derivative as a dispersing aid in order to improve dispersibility and storage stability.
Examples of pigment derivatives include azo-based, phthalocyanine-based, quinacridone-based, benzimidazolone-based, quinophthalone-based, isoindolinone-based, dioxazine-based, anthraquinone-based, indanthrene-based, perylene-based, perinone-based, and diketopyrrolopyrroles. and dioxazine-based derivatives, among which phthalocyanine-based and quinophthalone-based derivatives are preferred.
Substituents of pigment derivatives include, for example, sulfonic acid groups, sulfonamide groups and their quaternary salts, phthalimidomethyl groups, dialkylaminoalkyl groups, hydroxyl groups, carboxyl groups, amide groups, etc., directly on the pigment skeleton or alkyl groups, aryl groups, etc. groups, heterocyclic groups, etc., preferably sulfonic acid groups. A single pigment skeleton may be substituted with a plurality of these substituents.

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

(4) Mercapto compound A mercapto compound can be added as a polymerization accelerator and for improving adhesion to the substrate.

Mercapto compounds include, for example, 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, 2-mercaptobenzimidazole, hexanedithiol, decanedithiol, 1,4-dimethylmercaptobenzene, butanediol bisthiopropionate, butanediol bis Thioglycolate, ethylene glycol bisthioglycolate, trimethylolpropane tristhioglycolate, butanediol bisthiopropionate, trimethylolpropane tristhiopropionate, trimethylolpropane tristhioglycolate, pentaerythritol tetrakisthiopropio pentaerythritol tetrakisthioglycolate, trishydroxyethyl tristhiopropionate, ethylene glycol bis(3-mercaptobutyrate), butanediol bis(
3-mercaptobutyrate), 1,4-bis(3-mercaptobutyryloxy)butane,
Trimethylolpropane tris (3-mercaptobutyrate), pentaerythritol tetrakis (3-mercaptobutyrate), pentaerythritol tris (3-mercaptobutyrate), ethylene glycol bis (3-mercaptoisobutyrate), butanediol bis ( 3-mercaptoisobutyrate), trimethylolpropane tris(3-mercaptoisobutyrate), 1,3,5-tris(3-mercaptobutyloxyethyl)-
Mercapto compounds having a heterocyclic ring such as 1,3,5-triazine-2,4,6(1H,3H,5H)-trione, and aliphatic polyfunctional mercapto compounds can be mentioned. These various things can be used individually by 1 type, or in mixture of 2 or more types.

(5) Polymerization Inhibitor The photosensitive coloring composition of the present invention may contain a polymerization inhibitor from the viewpoint of controlling the shape of the cured product. It is thought that the taper angle (the angle between the support and the cured product in the cross section of the cured product) can be controlled because the polymerization inhibitor inhibits the radical polymerization of the lower layer of the coating film.
Examples of polymerization inhibitors include hydroquinone, hydroquinone monomethyl ether,
Methylhydroquinone, methoxyphenol, 2,6-di-tert-butyl-4-cresol (BHT). Among these, from the viewpoint of shape control, 2,6-di-ter
t-butyl-4-cresol is preferred. Moreover, hydroquinone monomethyl ether and methylhydroquinone are preferable from the viewpoint of being particularly excellent in safety to the human body.
A polymerization inhibitor can be used individually by 1 type or in mixture of 2 or more types.
(b) When producing an alkali-soluble resin, the resin may contain a polymerization inhibitor, which may be used as the polymerization inhibitor of the present invention. The same or different polymerization inhibitor may be added during the production of the photosensitive coloring composition.

<Content ratio of each component in the photosensitive coloring composition>
The content of the coloring agent (A) in the photosensitive coloring composition of the present invention is not particularly limited, but is preferably 5% by mass or more, more preferably 10% by mass or more, and even more preferably 20% by mass or more in the total solid content. , More preferably 25% by mass or more, particularly preferably 30% by mass or more, preferably 70% by mass or less, more preferably 60% by mass or less, further preferably 50% by mass or less, and particularly preferably 40% by mass or less . For example, 5% by mass to 70% by mass is preferable, 10% by mass to 70% by mass is more preferable, 20% by mass to 60% by mass is more preferable, 20% by mass to 50% by mass is even more preferable, and 20% by mass to 45% by weight is particularly preferred. By making it equal to or higher than the above lower limit, there is a tendency that the light-shielding property can be ensured. When the content is equal to or less than the above upper limit, there is a tendency that the solvent resistance is improved.

When the photosensitive coloring composition contains an organic coloring pigment, the content is not particularly limited,
The total solid content of the photosensitive coloring composition is preferably 5% by mass or more, more preferably 20% by mass or more, still more preferably 30% by mass or more, particularly preferably 35% by mass or more, and preferably 70% by mass or less. , 60% by mass or less is more preferable, and 50% by mass or less is particularly preferable. For example, 5% by mass to 70% by mass is preferable, 20% by mass to 70% by mass is more preferable, and 20
% to 60% by mass is more preferred, and 20% to 50% by mass is particularly preferred. When the content is at least the above lower limit, there is a tendency for the light-shielding property to be enhanced while suppressing the loss of ultraviolet light necessary for curing. When the content is equal to or less than the above upper limit, there is a tendency that the solvent resistance is improved.

(A) When the colorant contains a red pigment and/or an orange pigment, the total content of the red pigment and the orange pigment is not particularly limited, but is preferably 5% by mass or more, and 8% by mass in the colorant (A).
10% by mass or more is more preferable, 12% by mass or more is particularly preferable, 40% by mass or less is preferable, 30% by mass or less is more preferable, and 20% by mass or less is particularly preferable. For example, it is preferably 5% to 40% by mass, more preferably 8% to 40% by mass, even more preferably 10% to 30% by mass, and particularly preferably 12% to 20% by mass. When the content is equal to or higher than the lower limit, there is a tendency that a color tone close to black can be obtained. When the content is equal to or less than the upper limit, there is a tendency for the sensitivity to be high.

(A) When the colorant contains a blue pigment and/or a purple pigment, the total content of the blue pigment and the purple pigment is not particularly limited, but is preferably 30% by mass or more, and 50% by mass in the colorant (A). 70% by mass or more is more preferable, 80% by mass or more is particularly preferable, 95% by mass or less is preferable, 92% by mass or less is more preferable, and 90% by mass or less is particularly preferable. For example, 30% by mass to 95% by mass is preferable, 50% by mass to 95% by mass is more preferable, 70% by mass to 92% by mass is more preferable, and 80% by mass to 90% by mass is preferable.
is particularly preferred. By making it more than the said lower limit, there exists a tendency for light-shielding property to be high and to become high sensitivity.
By making it equal to or less than the above upper limit, there is a tendency that a color tone close to black can be obtained.

When the photosensitive coloring composition contains a black pigment, the content is not particularly limited, but preferably 2% by mass or more, more preferably 3% by mass or more, in the total solid content of the photosensitive coloring composition, 5% by mass 10% by mass or more is more preferable, 20% by mass or more is particularly preferable, 60% by mass or less is preferable, 50% by mass or less is more preferable, and 40% by mass or less is particularly preferable. For example, it is preferably 2% to 60% by mass, more preferably 5% to 60% by mass, even more preferably 10% to 50% by mass, and particularly preferably 20% to 40% by mass. When the content is equal to or higher than the lower limit, the light-shielding property tends to be enhanced. When the content is equal to or less than the above upper limit, there is a tendency that the solvent resistance is improved.

Further, when the photosensitive coloring composition contains an organic black pigment, the content is not particularly limited, but preferably 2% by mass or more, more preferably 3% by mass or more, in the total solid content of the photosensitive coloring composition, 5% by mass or more is more preferable, 10% by mass or more is still more preferable, 20% by mass or more is particularly preferable, 60% by mass or less is preferable, 50% by mass or less is more preferable, and 40% by mass or less is particularly preferable. For example, 2% by mass to 60% by mass is preferable, 5% by mass to 60% by mass is more preferable, 10% by mass to 50% by mass is more preferable, and 20% by mass
~40% by weight is particularly preferred. When the content is equal to or higher than the lower limit, the light-shielding property tends to be enhanced. When the content is equal to or less than the above upper limit, there is a tendency that the solvent resistance is improved.

(A) When the colorant contains an organic black pigment, the content is not particularly limited, but (A)
5% by mass or more in the colorant is preferable, 30% by mass or more is more preferable, 50% by mass or more is even more preferable, 80% by mass or more is particularly preferable, and 100% by mass or less is preferable;
95% by mass or less is more preferable, and 90% by mass or less is particularly preferable. For example, 5% by mass to 1
00% by mass is preferred, 10% by mass to 100% by mass is more preferred, 15% by mass to 80% by mass is even more preferred, and 20% by mass to 70% by mass is particularly preferred. When the content is equal to or higher than the lower limit, the light-shielding property tends to be enhanced. The solvent resistance tends to be improved by making it equal to or less than the above upper limit.

Further, when the photosensitive coloring composition contains carbon black as an inorganic black pigment, the content is not particularly limited, but is preferably 1% by mass or more, more preferably 5% by mass or more, in (A) the coloring agent. % by mass or more is more preferable, and 60% by mass or less is preferable.
0% by mass or less is more preferable, and 40% by mass or less is particularly preferable. For example, 1 mass% to 60
% by mass is preferable, 5% to 50% by mass is more preferable, and 10% to 40% by mass is even more preferable. When the content is equal to or higher than the lower limit, the light-shielding property tends to be enhanced. When the content is equal to or less than the above upper limit, there is a tendency that the solvent resistance is improved.

In addition, when the (A) colorant contains an organic coloring pigment and a black pigment, the total content is not particularly limited, but is preferably 5% by mass or more, more preferably 10% by mass or more, in the (A) colorant. , more preferably 15% by mass or more, preferably 100% by mass or less, more preferably 70% by mass or less, and particularly preferably 50% by mass or less. For example, 5% by mass to 100% by mass is preferable, 10% by mass to 70% by mass is more preferable, and 15% by mass to 50% by mass is even more preferable. When the content is equal to or higher than the lower limit, the light-shielding property tends to be enhanced. When the content is equal to or less than the above upper limit, there is a tendency that the solvent resistance is improved.

(B) The content of the alkali-soluble resin is not particularly limited, but usually 5% by mass or more, preferably 10% by mass or more, more preferably 20% by mass or more in the total solid content of the photosensitive coloring composition of the present invention, More preferably 30% by mass or more, particularly preferably 35% by mass or more, usually 85% by mass or less, preferably 80% by mass or less, more preferably 70% by mass or less, still more preferably 60% by mass or less, and even more preferably is 50% by mass or less, particularly preferably 45
% by mass or less. For example, 5% by mass to 85% by mass is preferable, 5% by mass to 80% by mass is more preferable, 10% by mass to 70% by mass is more preferable, 20% by mass to 60% by mass is even more preferable, and 30% by mass to 50% by weight is particularly preferred, and 35% to 45% by weight is particularly preferred. When the amount is at least the above lower limit, there is a tendency that the deterioration of the solubility of the unexposed portion in the developing solution can be suppressed, and the poor development can be suppressed. By adjusting the amount to the above upper limit or less, there is a tendency that appropriate sensitivity can be maintained, dissolution of the exposed portion by the developer can be suppressed, and deterioration of the sharpness and adhesion of the pattern can be suppressed.

The content of the acrylic copolymer resin (B1) in the photosensitive coloring composition of the present invention is not particularly limited, but usually 5% by mass or more in the total solid content of the photosensitive coloring composition, preferably 10% by mass
Above, more preferably 20% by mass or more, more preferably 30% by mass or more, particularly preferably 35% by mass or more, usually 85% by mass or less, preferably 80% by mass or less, more preferably 70% by mass or less, and further It is preferably 60% by mass or less, more preferably 50% by mass or less, and particularly preferably 45% by mass or less. For example, 5% by mass to 85% by mass is preferable, 5% by mass to 80% by mass is more preferable, and 10% by mass to 70% by mass is even more preferable.
20% by mass to 60% by mass is more preferable, 30% by mass to 50% by mass is particularly preferable, and 35% by mass to 45% by mass is particularly preferable. By making it more than the said lower limit, there exists a tendency for solvent resistance to improve. By making it below the said upper limit, there exists a tendency which can maintain appropriate sensitivity and can suppress the deterioration of the sharpness of a pattern, and adhesiveness.

(B) The acrylic copolymer resin contained in the alkali-soluble resin (the content of B1 is not particularly limited, but is usually 20% by mass or more, preferably 30% by mass or more, more preferably 40% by mass or more, and is usually 90% by mass or more. % by mass or less, preferably 85% by mass or less, more preferably 80% by mass or less
% by mass or less. For example, 20% by mass to 90% by mass is preferable, 30% by mass to 85% by mass is more preferable, and 40% by mass to 80% by mass is even more preferable. By making it more than the said lower limit, there exists a tendency for solvent resistance to improve. By making it below the said upper limit, there exists a tendency which can maintain appropriate sensitivity and can suppress the deterioration of the sharpness of a pattern, and adhesiveness.

(C) The content of the photopolymerization initiator is not particularly limited, but usually 0.1% by mass or more, preferably 0.5% by mass or more, more preferably 0.5% by mass or more in the total solid content of the photosensitive coloring composition of the present invention 1% by mass or more, more preferably 2% by mass or more, still more preferably 3% by mass or more, usually 15% by mass or less, preferably 10% by mass or less, more preferably 8% by mass or less, and further preferably 6% by mass % or less. For example, 0.1% by mass to 15% by mass is preferable, 0.5% by mass to 15% by mass is more preferable, 1% by mass to 10% by mass is more preferable, and 2% by mass to
8% by mass is even more preferred, and 3% to 6% by mass is particularly preferred. By making it equal to or higher than the above lower limit, there is a tendency that a decrease in sensitivity can be suppressed. When the amount is equal to or less than the above upper limit, there is a tendency that the deterioration of the solubility in the developing solution of the unexposed portion can be suppressed, and the poor development can be suppressed.

(C) when using a polymerization accelerator together with the photopolymerization initiator, the content of the polymerization accelerator is not particularly limited, preferably 0.05 wt% or more in the total solid content of the photosensitive coloring composition of the present invention,
It is usually 10% by mass or less, preferably 5% by mass or less. The polymerization accelerator is preferably used in a proportion of usually 0.1 to 50 parts by weight, particularly 0.1 to 20 parts by weight, per 100 parts by weight of the photopolymerization initiator (C). By making the content of the polymerization accelerator equal to or higher than the above lower limit, there is a tendency that the decrease in sensitivity to exposure light can be suppressed. When the amount is equal to or less than the above upper limit, there is a tendency that deterioration of the solubility in the developing solution of the unexposed portion can be suppressed, and poor development can be suppressed.
Further, (C) when using a sensitizing dye together with the photopolymerization initiator, the content is not particularly limited, but from the viewpoint of sensitivity usually 20 wt% or less in the total solid content in the photosensitive coloring composition, preferably It is 15% by mass or less, more preferably 10% by mass or less.

When the photosensitive resin composition of the present invention contains an ethylenically unsaturated compound, the content of the ethylenically unsaturated compound is not particularly limited, but usually 1 mass in the total solid content of the photosensitive coloring composition of the present invention % or more, preferably 5 mass % or more, more preferably 10 mass % or more, and usually 30 mass % or less, preferably 20 mass % or less, more preferably 15 mass % or less. For example, preferably 1% by mass to 30% by mass, more preferably 5% by mass to 20% by mass,
10% by mass to 15% by mass is more preferable. When the amount is at least the above lower limit, it tends to be possible to maintain an appropriate sensitivity, suppress dissolution of the exposed portion by the developer, and suppress deterioration of the sharpness and adhesion of the pattern. By making it equal to or less than the above upper limit, there is a tendency that it becomes easy to obtain a good image by suppressing an increase in the permeability of the developer to the exposed area.

When the photosensitive resin composition of the present invention contains a solvent, by using the solvent, the content of the total solid content is usually 5% by mass or more, preferably 10% by mass or more, more preferably 15% by mass or more, In addition, it is prepared so that the concentration is usually 50% by mass or less, preferably 30% by mass or less, more preferably 25% by mass or less. For example, 5% to 50% by mass, preferably 10% to 3% by mass
The solution is prepared so as to be 0% by mass, more preferably 15% to 25% by mass.

When the photosensitive resin composition of the present invention contains a dispersant, the content of the dispersant is not particularly limited, but usually 1% by mass or more in the total solid content of the photosensitive coloring composition, 3% by mass or more , more preferably 5% by mass or more, and usually 30% by mass or less, preferably 20% by mass or less, more preferably 15% by mass or less, and even more preferably 10% by mass or less. For example, it is preferably 1% to 30% by mass, more preferably 1% to 20% by mass, even more preferably 3% to 15% by mass, and particularly preferably 5% to 10% by mass. By making it more than the said lower limit, there exists a tendency which is easy to obtain sufficient dispersibility. By setting the content to the above upper limit or less, the ratio of other components can be relatively maintained at a certain level or more, so there is a tendency to suppress deterioration in sensitivity, plate-making properties, and the like.

In addition, the content ratio of the dispersant (A) to 100 parts by mass of the colorant is usually 5 parts by mass or more, 1
More preferably 0 parts by mass or more, more preferably 15 parts by mass or more, usually 50 parts by mass or less,
In particular, it is preferably 30 parts by mass or less. For example, 5 parts by mass to 50 parts by mass is preferable,
10 parts by mass to 50 parts by mass is more preferable, and 15 parts by mass to 30 parts by mass is even more preferable. By making it more than the said lower limit, there exists a tendency which is easy to obtain sufficient dispersibility. By setting the content to the above upper limit or less, there is a tendency to suppress deterioration in sensitivity, plate-making properties, etc. due to a relative decrease in the ratio of other components.

On the other hand, the content of the (B) alkali-soluble resin with respect to 100 parts by mass of the ethylenically unsaturated compound is usually 80 parts by mass or more, preferably 100 parts by mass or more, more preferably 150 parts by mass or more, and further 200 parts by mass or more. 250 parts by mass or more is particularly preferred, and usually 700 parts by mass or less, preferably 500 parts by mass or less, more preferably 400 parts by mass or less, and even more preferably 300 parts by mass or less. For example, 80 parts by mass to 700 parts by mass is preferable, 100 parts by mass to 700 parts by mass is more preferable, 150 parts by mass to 500 parts by mass is more preferable, 200 parts by mass to 400 parts by mass is even more preferable, and 250 parts by mass to 300 parts by weight is particularly preferred. When the amount is at least the above lower limit, there is a tendency to obtain an appropriate dissolution and development state without peeling or the like. When the content is equal to or less than the above upper limit, there is a tendency that an appropriate dissolution time can be obtained in the developer.

When using an adhesion improver, the content is not particularly limited, but usually 0.1 to 5% by mass, preferably 0.2 to 3% by mass, more preferably 0 in the total solid content of the photosensitive coloring composition .
4 to 2% by mass. There is a tendency that a sufficient effect of improving adhesion can be obtained by setting the content to be at least the above lower limit. When the content is equal to or less than the upper limit, it tends to be possible to prevent the sensitivity from deteriorating and the residue remaining after development from becoming a defect.

When using a surfactant, its content is not particularly limited, usually 0.001 to 10% by weight in the total solid content of the photosensitive coloring composition, preferably 0.005 to 1% by weight, more preferably 0 0.01-0.5% by weight, most preferably 0.03-0.3% by weight. By making it more than the said lower limit, there exists a tendency for the smoothness and uniformity of a coating film to express easily. When the content is equal to or less than the above upper limit, smoothness and uniformity of the coating film are likely to be exhibited, and deterioration of other properties tends to be suppressed.

When a mercapto compound is included, its content is not particularly limited, but usually 0.1% by mass or more, preferably 0.5% by mass or more, more preferably 1% by mass or more in the total solid content of the photosensitive coloring composition and usually 5% by mass or less, preferably 3% by mass or less, more preferably 2
% by mass or less. For example, 0.1% by mass to 5% by mass is preferable, 0.5% by mass to 3% by mass is more preferable, and 0.5% by mass to 2% by mass is even more preferable. By making it more than the said lower limit, there exists a tendency which becomes high sensitivity. When the content is equal to or less than the above upper limit, there is a tendency that the storage stability of the photosensitive composition over time is improved.

When the polymerization inhibitor is included, the content is not particularly limited, but usually 0.0005 mass% or more, preferably 0.001 mass% or more, more preferably 0.01 in the total solid content of the photosensitive coloring composition % by mass or more, and usually 0.3 mass % or less, preferably 0.2 mass % or less, more preferably 0.1 mass % or less. For example, 0.0005% by mass to 0.3% by mass is preferable, 0.001% by mass to 0.2% by mass is more preferable, and 0.01% by mass to 0.01% by mass is preferable.
1% by mass is more preferred. When the content is at least the above lower limit, there is a tendency that the shape of the cured product can be controlled. By making it equal to or less than the above upper limit, there is a tendency that the required sensitivity can be maintained.

<Physical properties of photosensitive coloring composition>
In the photosensitive coloring composition of the present invention, the optical density (OD) per 1 μm of the coating film thickness is not particularly limited, but is preferably 0.5 or more, more preferably 0.7 or more, and further 1.0 or more. It is preferably 1.2 or more, more preferably 4.0 or less, more preferably 3.0 or less, and even more preferably 2.0 or less. For example, 0.5 to 4.0 is preferable, and 0
. 7 to 4.0 are more preferred, 1.0 to 3.0 are even more preferred, and 1.2 to 3.0 are even more preferred. By making it more than the said lower limit, there exists a tendency for sufficient light-shielding property to be obtained. When the content is equal to or less than the above upper limit, solvent resistance tends to be improved.
The optical density (OD) per 1 μm of the film thickness of the coating film may be measured using a coating film obtained by curing the photosensitive coloring composition of the present invention, and using a coating film cured by heating at 85 ° C. for 60 minutes. can be measured.
Optical density means that the spectral sensitivity characteristics of the light-receiving part meet ISO visu in the ISO 5-3 standard.
Refers to transmission optical density indicated by al density. Normally, the A light source defined by CIE (International Commission on Illumination) is used as the light source. As a measuring instrument that can be used for measuring the transmission optical density, for example, X-Rite manufactured by SAKATA INX ENGINEERING CO., LTD.
361T(V) can be mentioned.

<Method for producing a photosensitive coloring composition>
The photosensitive coloring composition of the present invention is produced according to a conventional method.
Generally, (A) the colorant is preferably dispersed in advance using a paint conditioner, sand grinder, ball mill, roll mill, stone mill, jet mill, homogenizer, or the like. Since the coloring agent (A) is finely divided by the dispersing treatment, the coating properties of the resist are improved.

Dispersion treatment is usually preferably carried out in a system in which (A) a coloring agent, a solvent, a dispersant, and (B) a part or all of an alkali-soluble resin are used in combination (hereinafter referred to as The composition is sometimes referred to as a "pigment dispersion"). In particular, it is preferable to use a polymer dispersant as the dispersant, because the increase in viscosity of the obtained pigment dispersion and photosensitive coloring composition over time is suppressed, that is, the dispersion stability is excellent.
Thus, in the process of producing a photosensitive coloring composition, it is preferable to produce (A) a pigment dispersion containing at least a coloring agent, a solvent and a dispersant.
As the (A) colorant, solvent, and dispersant that can be used in the pigment dispersion, those described as those that can be used in the photosensitive coloring composition can be preferably employed. Also, as the content ratio of each colorant of (A) the colorant in the pigment dispersion, the content ratio described as the content ratio in the photosensitive coloring composition can be preferably employed.

When dispersion treatment is performed on a liquid containing all the components to be blended in the photosensitive coloring composition, highly reactive components may be denatured due to heat generated during the dispersion treatment. Therefore, it is preferable to carry out the dispersion treatment in a system containing a polymer dispersant.
When dispersing (A) the colorant with a sand grinder, glass beads or zirconia beads having a particle size of about 0.1 to 8 mm are preferably used. As for the dispersion treatment conditions, the temperature is usually from 0°C to 100°C, preferably from room temperature to 80°C. The appropriate dispersion time varies depending on the composition of the liquid, the size of the dispersion treatment apparatus, etc., and is therefore adjusted as appropriate. So that the 20 degree specular glossiness (JIS Z8741) of the photosensitive coloring composition is in the range of 50 to 300,
The aim of dispersion is to control the gloss of the pigment dispersion. When the glossiness of the photosensitive coloring composition is low, the dispersion treatment is often insufficient and coarse pigment (coloring material) particles remain, resulting in poor developability,
Adhesion, resolution, etc. may become insufficient. If the dispersion treatment is carried out until the gloss value exceeds the above range, the pigment is crushed to produce a large number of ultrafine particles, which tends to impair the dispersion stability.
The dispersed particle diameter of the pigment dispersed in the pigment dispersion liquid is usually 0.03 to 0.3 μm, and can be measured by a dynamic light scattering method.

Next, the pigment dispersion liquid obtained by the dispersion treatment and the other components contained in the photosensitive coloring composition are mixed to form a uniform solution or dispersion liquid. In the manufacturing process of the photosensitive coloring composition, since fine dust may be mixed in the liquid, it is desirable to filter the obtained photosensitive coloring composition with a filter or the like.

[Cured product]
The cured product of the present invention can be obtained by curing the photosensitive coloring composition of the present invention.
The cured product of the present invention can be suitably used as a black matrix.
Moreover, a cured product obtained by curing the photosensitive coloring composition of the present invention can be suitably used as a partition wall.

[Method of forming cured product]
Next, a method for forming a cured product using the photosensitive coloring composition of the present invention will be described. In the present invention, it is preferable to form a cured product by performing at least the following steps (1) to (4).
Step (1): A step of forming a coating film on a substrate.
Step (2): A step of exposing at least part of the coating film formed in step (1).
Step (3): A step of developing the coating film exposed in step (2).
Step (4): A step of baking the coating film developed in step (3).

<Step (1): Step of forming a coating film on a substrate>
[1] Support The material of the support for forming the cured product is not particularly limited as long as it has an appropriate strength. Transparent substrates are mainly used, and materials such as polyester resins such as polyethylene terephthalate, polyolefin resins such as polypropylene and polyethylene, thermoplastic resin sheets such as polycarbonate, polymethyl methacrylate, and polysulfone, and epoxy resins are used. Thermosetting resin sheets such as resins, unsaturated polyester resins and poly(meth)acrylic resins, and various types of glass can be used. Among them, from the viewpoint of heat resistance, glass,
Heat resistant resins are preferred. In some cases, a transparent electrode such as ITO or IZO is formed on the surface of the substrate. Besides the transparent substrate, it can also be formed on a TFT array or a touch panel. For example, it is suitably used in the panel structure described in Japanese Patent Application Laid-Open No. 2021-110936.

In order to improve surface physical properties such as adhesiveness, the support may be subjected, if necessary, to, for example, corona discharge treatment, ozone treatment, and thin film formation treatment using various resins such as silane coupling agents and urethane resins. .
The thickness of the transparent substrate is usually in the range of 0.05-10 mm, preferably 0.1-7 mm. When thin films of various resins are formed, the film thickness is usually in the range of 0.01 to 10 μm, preferably 0.05 to 5 μm.

[2] Method for Supplying Photosensitive Coloring Composition to Substrate The photosensitive coloring composition of the present invention is usually supplied onto a substrate in a state of being dissolved or dispersed in a solvent. The supply method can be a conventionally known method such as a spinner method, a wire bar method, a flow coating method, a die coating method, a roll coating method, or a spray coating method. Moreover, for example, it may be supplied in a pattern by an inkjet method or a printing method. Above all, according to the die coating method, the amount of the coating liquid used is greatly reduced, and there is no effect of mist etc. that adheres when using the spin coating method, the generation of foreign matter is suppressed, etc.
It is preferable from a comprehensive point of view.

Although the coating amount varies depending on the application, the coating is applied so that the film thickness after drying is usually 0.5 μm to 10 μm, preferably 1 μm to 9 μm, particularly preferably 1 μm to 7 μm. It is important that the dry film thickness or the film thickness of the finally formed cured product be uniform over the entire substrate. If the variation is small, uneven defects occurring in the cured product can be suppressed.

When the photosensitive coloring composition of the present invention is used to collectively form cured products having different film thicknesses, the finally formed cured products have different film thicknesses.

[3] Drying method After supplying the photosensitive coloring composition onto the substrate, it is preferably dried to form a coating film. Drying is preferably by a drying method using a hot plate, IR oven or convection oven. A reduced pressure drying method, in which drying is performed in a reduced pressure chamber without raising the temperature, may be combined.

The drying conditions can be appropriately selected according to the type of solvent component, the performance of the dryer to be used, and the like. The drying time is usually 40, depending on the type of solvent component, the performance of the dryer used, etc.
C. to 100.degree. C. for 15 seconds to 5 minutes, preferably 50.degree. C. to 80.degree. C. for 30 seconds to 3 minutes.
It should be noted that it is preferable to carry out the firing within a range not exceeding the firing temperature described later.

<Step (2): Step of exposing at least part of the coating film formed in step (1)>
[4] Exposure method Exposure is carried out by overlaying a negative mask pattern on the coating film of the photosensitive coloring composition, and irradiating a light source of ultraviolet rays or visible light through this mask pattern. When performing exposure using an exposure mask, a method of bringing the exposure mask close to the coating film of the photosensitive coloring composition, or placing the exposure mask at a position away from the coating film of the photosensitive coloring composition, the exposure mask It is also possible to use a method of projecting the exposure light through. A scanning exposure method using a laser beam without using a mask pattern may also be used. If necessary, in order to prevent the sensitivity of the photopolymerizable layer from deteriorating due to oxygen, the exposure may be carried out in an oxygen-free atmosphere or after forming an oxygen blocking layer such as a polyvinyl alcohol layer on the photopolymerizable layer. good too.

When simultaneously forming cured products with different film thicknesses, for example, for a light shielding portion (light transmittance of 0%) and a plurality of openings, the opening having the highest average light transmittance (perfectly transmitting opening) An exposure mask having openings with a small average light transmittance (intermediate transmission openings) is used. By this method,
The difference in the average light transmittance between the intermediate transmission opening and the complete transmission opening, that is, the difference in the amount of exposure, causes the difference in the residual film ratio.
A method is known in which the intermediate transmission openings are formed by, for example, a matrix-shaped light shielding pattern having minute polygonal light shielding units. Also, as an absorber, for example, chromium-based,
Methods are known for controlling the light transmittance and creating films of molybdenum, tungsten, and silicon materials.

The light source used for the above exposure is not particularly limited. Examples of light sources include xenon lamps, halogen lamps, tungsten lamps, high pressure mercury lamps, ultra high pressure mercury lamps,
Lamp light sources such as metal halide lamps, medium pressure mercury lamps, low pressure mercury lamps, carbon arcs, fluorescent lamps, argon ion lasers, YAG lasers, excimer lasers, nitrogen lasers, helium cadmium lasers, blue-violet semiconductor lasers, near infrared semiconductor lasers A laser light source is mentioned. An optical filter can also be used when using it by irradiating the light of a specific wavelength.

The optical filter may be, for example, a thin film type capable of controlling the light transmittance at the exposure wavelength, and the material in that case may be, for example, a Cr compound (Cr oxide, nitride, oxynitride, fluoride, etc.). , MoSi, Si, W, and Al.

The exposure dose is usually 1 mJ/cm ² or more, preferably 5 mJ/cm ² or more, more preferably 10 mJ/cm ² or more, and usually 300 mJ/cm ² or less, preferably 200 mJ.
/cm ² or less, more preferably 150 mJ/cm ² or less.
In the case of the proximity exposure method, the distance between the exposure target and the mask pattern is usually 10 μm.
Above, it is preferably 50 μm or more, more preferably 75 μm or more, and usually 500 μm or less, preferably 400 μm or less, more preferably 300 μm or less.

<Step (3): Step of developing the coating film exposed in step (2)>
[4] Development method After the above exposure, an image pattern can be formed on the substrate by development using an aqueous solution of an alkaline compound or an organic solvent. The aqueous solution of alkaline compound may further contain, for example, surfactants, organic solvents, buffers, complexing agents, dyes or pigments.

Alkaline compounds include sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium carbonate, potassium carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, sodium silicate, potassium silicate, sodium metasilicate, sodium phosphate, potassium phosphate. , sodium hydrogen phosphate, potassium hydrogen phosphate, sodium dihydrogen phosphate, potassium dihydrogen phosphate, inorganic alkaline compounds such as 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) and organic alkaline compounds such as choline. These alkaline compounds may be a mixture of two or more.

Examples of surfactants include nonionic surfactants such as polyoxyethylene alkyl ethers, polyoxyethylene alkylaryl ethers, polyoxyethylene alkyl esters, sorbitan alkyl esters, and monoglyceride alkyl esters;
anionic surfactants such as alkylbenzenesulfonates, alkylnaphthalenesulfonates, alkylsulfates, alkylsulfonates, sulfosuccinate salts;
Examples include amphoteric surfactants such as alkylbetaines and amino acids.

Examples of organic solvents include isopropyl alcohol, benzyl alcohol, ethyl cellosolve, butyl cellosolve, phenyl cellosolve, propylene glycol, and diacetone alcohol. These organic solvents may be used in combination of two or more. Moreover, the organic solvent may be used alone or in combination with water or an aqueous solution of an alkaline compound.

The conditions for development processing are not particularly limited, and the development temperature is usually 10 to 50° C., preferably 15 to 50° C.
45°C, more preferably 20-40°C. The development method can be, for example, an immersion development method, a spray development method, a brush development method, or an ultrasonic development method.
If necessary, the substrate after the development treatment may be additionally exposed by the same method as the above exposure method.

<Step (4): Step of baking the coating film developed in step (3)>
[5] Baking method It is preferable to bake the obtained coating film.
The baking method is not particularly limited, but hot plates, IR ovens, convection ovens and the like are preferably used. The baking treatment temperature is preferably 50° C. or higher, more preferably 70° C. or higher. Also, the temperature is preferably 150° C. or lower, more preferably 100° C. or lower, still more preferably 90° C. or lower, and even more preferably 80° C. or lower. The baking time is preferably 5 to 60 minutes.

[Black Matrix]
When the photosensitive coloring composition of the present invention is used as a black matrix, the width, shape, etc. of the black matrix are appropriately adjusted according to the specifications of the color filter to which it is applied. Although the film thickness of the black matrix is not particularly limited, it is usually about 0.5 to 7 μm, preferably 1 to 5 μm, more preferably 1 to 3 μm.

[Partition wall]
When the photosensitive coloring composition of the present invention is used as partition walls, the size, shape and the like are appropriately adjusted depending on the specifications of the organic electroluminescence device to which it is applied. Although the film thickness of the partition is not particularly limited, it is usually about 0.5 to 10 μm, preferably 1 to 5 μm, more preferably 1 to 3 μm.

[Organic electroluminescent device]
The organic electroluminescence device of the present invention comprises a cured product, such as partition walls, composed of the photosensitive coloring composition described above.
For example, various organic electroluminescence devices are manufactured using a substrate provided with a partition pattern manufactured by the method described above. Although the method for forming the organic electroluminescent device is not particularly limited,
Preferably, after forming a partition pattern on the substrate by the above-described method, the functional material is sublimated in a vacuum state and adhered to the area surrounded by the partition on the substrate to form a film;
An organic electroluminescence element is manufactured by forming an organic layer such as pixels by a wet process such as a casting method, a spin coating method, or an inkjet printing method.

Types of organic electroluminescence devices include bottom emission type and top emission type.
In the bottom emission type, for example, partition walls are formed on a glass substrate laminated with transparent electrodes, and a hole transport layer, a light emitting layer, an electron transport layer, and a metal electrode layer are laminated in an opening surrounded by the partition walls. be. On the other hand, in the top emission type, for example, barrier ribs are formed on a glass substrate laminated with a metal electrode layer, and an electron transport layer, a light emitting layer, a hole transport layer, and a transparent electrode layer are stacked in an opening surrounded by the barrier ribs. created by
In addition, as the light emitting layer, Japanese Patent Laid-Open No. 2009-146691 and Japanese Patent No. 57
An organic electroluminescent layer as described in JP-A-34681 can be mentioned. Quantum dots as described in Japanese Patent No. 5653387 and Japanese Patent No. 5653101 may also be used.

The layer structure is not limited to this, and for example, each layer of the hole transport layer and the electron transport layer may have a laminate structure of two or more layers from the viewpoint of luminous efficiency. Although the thickness of each layer is not particularly limited, it is usually 1 to 500 nm from the viewpoint of luminous efficiency and brightness.

The organic electroluminescence element may be formed by separately forming each color of RGB for each opening, or may laminate two or more colors in one opening. From the viewpoint of improving reliability, the organic electroluminescence device may have a sealing layer. The sealing layer has a function of preventing moisture in the air from being adsorbed on the organic electroluminescence element and reducing the luminous efficiency. The organic electroluminescence element may be provided with a low-reflection film at the interface with air from the viewpoint of improving light extraction efficiency. By arranging the low-reflection film at the interface between the air and the device, it is expected that the refractive index gap can be reduced and the reflection at the interface can be suppressed. For such a low-reflection film, for example, a moth-eye structure or super-multilayer film technology can be applied.

When an organic electroluminescent element is used as a pixel of an image display device, it is necessary to prevent the light from the light emitting layer of one pixel from leaking to other pixels. Since it is necessary to prevent the image quality from deteriorating due to the reflection of light, it is preferable to impart a light-shielding property to the partition wall constituting the organic electroluminescence device.
Further, in the organic electroluminescence device, electrodes must be provided on the upper and lower surfaces of the partition, so from the viewpoint of insulation, the partition preferably has a high resistance and a low dielectric constant. Therefore, when a colorant is used to impart a light-shielding property to the barrier ribs, it is preferable to use the organic pigment having high resistance and low dielectric constant.

[Image display device]
The image display device of the present invention contains the cured product of the present invention.
For example, a liquid crystal driving substrate (array substrate) having a black matrix formed of the photosensitive coloring composition of the present invention, or placed on the counter electrode substrate side, these are bonded together to form a liquid crystal cell, and the formed liquid crystal cell. An image display device such as a liquid crystal display device containing the cured product of the present invention can be produced by injecting a liquid crystal into.

A color filter having a black matrix formed from the photosensitive coloring composition of the present invention can also be used for sub-pixels of an organic light-emitting display panel. The color filter layer can increase the light extraction efficiency compared to the polarizing plate, thereby extending the service life of the organic light emitting diode display. For example, it can be used in the display devices described in Japanese Patent Publication No. 2021-517333 and Japanese Patent Publication No. 2021-110936.

Examples of the image display device of the present invention include an organic EL display device having partition walls containing the cured product of the present invention and organic electroluminescence elements.
The organic EL display device is not particularly limited in terms of the type and structure of the image display device as long as it contains the above-described organic electroluminescence device. can. For example, "organic EL display" (Ohmsha,
It can be formed by a method as described in Shizu Tokito, Chihaya Adachi, and Hideyuki Murata, published on August 20, 2004. For example, an image may be displayed by combining an organic electroluminescent element that emits white light and a color filter, or an image may be displayed by combining organic electroluminescent elements emitting different colors such as RGB.

EXAMPLES Next, the present invention will be described in more detail with reference to Synthesis Examples, Examples and Comparative Examples, but the present invention is not limited to the following examples as long as the gist thereof is not exceeded.
The constituent components of the photosensitive coloring compositions used in the following examples and comparative examples are as follows.

<Alkali-soluble resin-1>
Monoacrylate having a tricyclodecane skeleton (FA-513M manufactured by Hitachi Chemical Co., Ltd.)/styrene/glycidyl methacrylate, an acrylic copolymer resin having a molar ratio of (0.3/0.1/0.6) was mixed with 0.00% of acrylic acid. Resin to which 0.39 mol of tetrahydrophthalic anhydride was added after addition of 6 mol.
Weight average molecular weight 8400, acid value 80 mgKOH/g, double bond equivalent 480 g/mol.

<Alkali-soluble resin-2>
Monoacrylate having a tricyclodecane skeleton (FA-513M manufactured by Hitachi Chemical Co., Ltd.) / glycidyl methacrylate / methacrylic acid / methyl methacrylate / malonic acid-2-[[[
[2-[1-oxo-2-propenyl]oxy]ethyl]amino]carbonyl]-1,3-diethyl ester (AOI-DEM manufactured by Showa Denko) / 2-hydroxyethyl methacrylate, molar ratio (0.10/ 0.24/0.23/0.007/0.21/0.22) acrylic copolymer resin.
Weight average molecular weight 8100, acid value 60 mgKOH/g. The alkali-soluble resin-2 corresponds to the acrylic copolymer resin (B1) of the present application.

<Alkali-soluble resin-3>
Methacrylic acid / methyl methacrylate / ethylhexyl methacrylate / 2-[(3,
5-dimethylpyrazolyl)carbonylamino]ethyl methacrylate (MOI manufactured by Showa Denko K.K.)
-BP)/2-hydroxyethyl methacrylate, molar ratio (0.22/0.10/0.2
0/0.24/0.24) acrylic copolymer resin.
Weight average molecular weight 10200, acid value 70 mgKOH/g. The alkali-soluble resin-3 does not correspond to the acrylic copolymer resin (B1) of the present application.

<Alkali-soluble resin-4>
Monoacrylate having a tricyclodecane skeleton (FA-513M manufactured by Hitachi Chemical Co., Ltd.)/glycidyl methacrylate/methacrylic acid/methyl methacrylate/2-hydroxyethyl methacrylate, molar ratio (0.10/0.19/0.21/0. 30/0.20) acrylic copolymer resin.
Weight average molecular weight 7600, acid value 78 mgKOH/g. Alkali-soluble resin-4 does not correspond to the acrylic copolymer resin (B1) of the present application.

<Pigment-1>
BASF Corporation: Irgaphor (registered trademark) Black S 0101 CF
<Dispersant-1>
BYK-Chemie: DISPERBYK-LPN21116
<Dispersing aid-1>
Manufactured by Lubrizol: Solsperse 12000

<Solvent-1>
PGMEA: propylene glycol monomethyl ether acetate <solvent-2>
Propylene glycol monoethyl ether

<Ethylenically unsaturated compound-1>
DPHA: Nippon Kayaku Co., Ltd. (mixture of dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate)
<Ethylenically unsaturated compound-2>
AOI-DEM: Showa Denko malonic acid 2-[[[[2-[1-oxo-2-propenyl]oxy]ethyl]amino]carbonyl]-1,3-diethyl ester

<Photoinitiator-1>
A compound having the following chemical structure.

<Surfactant-1>
DIC Corporation: Megafac F-559

<Preparation of pigment dispersion liquid 1>
The pigment, dispersant, dispersing aid, alkali-soluble resin, and solvent shown in Table 1 were mixed in the mass ratio shown in Table 1. This solution was subjected to dispersion treatment for 3 hours in the range of 25 to 45° C. using a paint shaker. As the beads, 0.5 mmφ zirconia beads were used, and 2.5 times the mass of the dispersion liquid was added. After the dispersion was completed, the beads and the dispersion liquid were separated by a filter to prepare a pigment dispersion liquid 1.

[Example 1 and Comparative Examples 1 and 2]
Using the pigment dispersion 1 prepared above, each component is added so that the ratio in the solid content is the mixing ratio shown in Table 2, and PGMEA is added so that the solid content is 17% by mass, and stirred and dissolved. to prepare a photosensitive coloring composition. Using the obtained photosensitive coloring composition, a pattern was prepared by the method described later and evaluated.

<PGMEA resistance evaluation Remaining film rate>
PGMEA resistance evaluation was measured by the following procedure.
First, the prepared photosensitive coloring composition was applied to a glass substrate with a spin coater so that the film thickness after heat curing was 1.5 μm, dried under reduced pressure for 1 minute, and then heated at 80 ° C. with a hot plate.
and dried for 100 seconds. The obtained coating film was exposed without using an exposure mask.
A high-pressure mercury lamp having an intensity of 45 mW/cm ² at a wavelength of 365 nm was used as the irradiation light source, and the exposure amount was 30 mJ/cm ² . Subsequently, the resist-coated substrate 1 was obtained by baking and heating in an oven at 85° C. for 60 minutes. Three-dimensional non-contact surface profile measurement system M manufactured by Ryoka Systems Co., Ltd.
The thickness was measured using icromap MM3500-M100, and the resist-coated substrate was immersed in PGMEA for 1 hour, then the film thickness was measured again, and the residual film ratio was calculated by the following formula. Residual film ratio (%) = ( Film thickness after PGMEA immersion [μm])/(Film thickness before PGMEA immersion [μm]
m]) * 100
The residual film ratio is preferably 90% or more.

<PGMEA resistance evaluation substrate observation>
After the resist-coated substrate 1 was immersed in PGMEA for 1 hour, the substrate surface was observed with a non-contact surface/layer cross-sectional shape measurement system VertScan (R) 2.0 manufactured by Ryoka Systems Co., Ltd. at 10x magnification. Confirmed that this is happening. ○ (good) when unevenness is not seen
), and the case where it was seen was evaluated as x (no good).
<Optical density (OD) per unit film thickness>
The optical density (OD) of the resist-coated substrate 1 of Example 1 before immersion in PGMEA was measured with X-Rite 361T (V) manufactured by Sakata Engineering. The optical density per 1 μm film thickness calculated by dividing the optical density value by the film thickness value before immersion in PGMEA was 1.2/μm.

In the resist-coated substrate 1 using the photosensitive coloring compositions of Comparative Examples 1 and 2, unevenness on the surface was observed by microscopic observation after immersion in PGMEA, and the residual film rate was also confirmed to be less than 90%. .
In alkali-soluble resin-2, which has a structural unit in which the blocking group is eliminated by heating to generate a highly reactive isocyanate group and form a crosslinked structure, as in Comparative Example 1, the blocking group is not sufficiently eliminated in baking at 85 ° C. It is presumed that the solvent resistance was insufficient because it was not possible to sufficiently harden it because it was not separated. Also, as in Comparative Example 2, the alkali-soluble resin-3, which does not have a blocked isocyanate group, is presumed to have poorer solvent resistance because it does not have a reactive group that reacts at low temperatures.
On the other hand, in Comparative Example 3, although surface unevenness was not observed, a residual film rate of less than 90% was confirmed. It is presumed that this is because even if the compound of the general formula (1) is contained as a monomer, the reaction between the resins does not occur, and the solvent resistance of the cured product is insufficient.
In the resist-coated substrate 1 using the photosensitive coloring composition of Example 1, even after immersion in PGMEA for 1 hour, unevenness on the surface was not observed by microscopic observation, and the residual film rate was as high as 94%. was confirmed.
This is because in the alkali-soluble resin-1 having a blocked isocyanate group having a structure derived from an active methylene compound, a ketene group that serves as a reaction site is generated even at 85°C,
Since ester bonds are formed, the reaction proceeds sufficiently, and the solvent resistance of the cured product is improved.
It is estimated to be.
From this, it can be seen that the photosensitive coloring composition of the present invention can obtain a high-quality black matrix even when used on a material with low heat resistance such as an OLED display panel.

Claims (11)

(A) a coloring agent, (B) an alkali-soluble resin and (C) a photopolymerization initiator,
(B) The alkali-soluble resin has a structural unit (b1) derived from a compound represented by the following general formula (1), and a structural unit (b2) derived from a compound having a carboxy group and an ethylenically unsaturated bond. A photosensitive coloring composition comprising an acrylic copolymer resin (B1).

(In Formula (1), R ¹ represents a hydrogen atom or a methyl group, and R ² and R ³ each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.) The acrylic copolymer resin (B1) has a structural unit (b3) derived from a monomer having a cyclic ether group and an ethylenically unsaturated bond having 2 to 4 carbon atoms, photosensitive coloring according to claim 1 Composition. The photosensitive coloring composition according to claim 1 or 2, wherein the acrylic copolymer resin (B1) has a structural unit (b4) derived from a monomer having a hydroxyl group and an ethylenically unsaturated bond. The photosensitive coloring composition according to any one of claims 1 to 3, wherein the (A) colorant comprises a pigment. The photosensitive material according to claim 4, wherein the (A) colorant contains at least one selected from the group consisting of red pigments and orange pigments and at least one selected from the group consisting of blue pigments and purple pigments. coloring composition. The photosensitive coloring composition according to claim 4 or 5, wherein the (A) colorant contains an organic black pigment. The photosensitive coloring composition according to any one of claims 1 to 6, for use at a baking temperature of 100°C or less. A cured product obtained by curing the photosensitive coloring composition according to any one of claims 1 to 7. An image display device comprising the cured product according to claim 8 . A method for forming a cured product, comprising using the photosensitive coloring composition according to any one of claims 1 to 6 and performing at least the following steps (1) to (4).
Step (1): A step of forming a coating film on a substrate.
Step (2): A step of exposing at least part of the coating film formed in step (1).
Step (3): A step of developing the coating film exposed in step (2).
Step (4): A step of baking the coating film developed in step (3). 11. The method of forming a cured product according to claim 10, wherein the baking temperature in step (4) is 100[deg.] C. or less.