JP2021135506A - Photosensitive coloring composition, cured product, image display device, and pigment dispersion for image display device - Google Patents

Abstract

To provide a photosensitive coloring composition excellent in electrical reliability after ultraviolet irradiation.SOLUTION: The photosensitive coloring composition contains (a) a colorant, (b) an alkali-soluble resin, (c) a photopolymerization initiator, (d) an ethylenically unsaturated compound, (e) a solvent, and (f) a dispersant. A cured coating film of the photosensitive coloring composition has an optical density per 1 μm film thickness of 0.5 or more. The dispersant (f) contains a dispersant which has a specific repeating unit having an ammonium salt structure in a resin side chain.SELECTED DRAWING: None

Description

The present invention relates to a photosensitive coloring composition and the like. More specifically, the present invention relates to a photosensitive coloring composition preferably used for forming a coloring spacer or the like in an image display device such as a liquid crystal display, a cured product obtained by curing the photosensitive coloring composition, an image display device containing the cured product, or the like. ..

A liquid crystal display (LCD) utilizes the property that the arrangement of liquid crystal molecules is switched by turning the voltage on and off the liquid crystal. On the other hand, each member constituting the LCD cell is often formed by a method using a photosensitive composition represented by a photolithography method.
The scope of application of this photosensitive composition tends to be further expanded in the future because it is easy to form a fine structure and it is easy to process a substrate for a large screen.

However, in the LCD manufactured by using the photosensitive composition, the voltage applied to the liquid crystal is not maintained due to the electric characteristics of the photosensitive composition itself and the influence of impurities contained in the photosensitive composition, which causes the display to display. Problems such as display unevenness may occur. In particular, a member closer to the liquid crystal layer in a color liquid crystal display, for example, a so-called columnar spacer, a photo spacer, or the like used for keeping the distance between two substrates constant in a liquid crystal panel has a great influence.

Conventionally, when a spacer having no light-shielding property is used for a TFT type LCD, the TFT as a switching element may malfunction due to the light transmitted through the spacer. In order to prevent this, a method using a spacer having a light-shielding property (colored spacer) is being studied.

In recent years, with changes in the structure of panels, a method of collectively forming colored spacers by a photolithography method has been proposed. For example, in Patent Document 1, by using an organic pigment having a specific structure and a specific dispersant having a quaternary ammonium group in combination, excellent light-shielding property, excellent dispersibility and plate-making property, and a sufficiently low relative permittivity can be obtained. It is disclosed that the photosensitive coloring composition shown is obtained.

International Publication No. 2015/046178

With changes in the panel structure in recent years, a method of irradiating ultraviolet rays after creating a liquid crystal cell has become widespread in order to improve the orientation of the liquid crystal display. When ultraviolet irradiation is performed, a part of the pigment contained in the colored spacer or the like tends to be decomposed to generate impurities, and even in that case, it is required to maintain sufficient electrical reliability.

When the present inventor examined a photosensitive coloring composition containing a dispersant described in Patent Document 1, it was difficult to secure electrical reliability after irradiation with ultraviolet rays.

Therefore, the present invention has been made in view of the above circumstances, and an object of the present invention is to provide a photosensitive coloring composition having excellent electrical reliability after irradiation with ultraviolet rays.

As a result of diligent studies by the present inventor, it has been found that the above problems can be solved by using a specific dispersant, and the present invention has been completed.
That is, the gist of the present invention is as follows.

[1] Photosensitive coloring containing (a) a colorant, (b) an alkali-soluble resin, (c) a photopolymerization initiator, (d) an ethylenically unsaturated compound, (e) a solvent, and (f) a dispersant. It ’s a composition,
The optical density per 1 μm of the cured coating film is 0.5 or more.
The dispersant (f1) has a repeating unit represented by the following general formula (1).
) Is contained in the photosensitive coloring composition.

(In the formula (1), R ¹ and R ² are each independently an alkyl group which may have a substituent or an aryl group which may have a substituent, and R ¹ and R ² are They may be combined with each other to form an annular structure.
R ³ is an alkylene group.
R ⁴ is a polycyclic aromatic hydrocarbon group which may have a substituent.
R ⁵ is a hydrogen atom or a methyl group.
X is a divalent linking group.
Y is a halogen atom. )

[2] The photosensitive coloring composition according to [1], wherein the polycyclic aromatic hydrocarbon group in ^{R 4} in the formula (1) has two or more aromatic rings.
[3] The colorant (a) includes 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, [1] or [2]. ] The photosensitive coloring composition according to.
[4] The photosensitive coloring composition according to any one of [1] to [3], wherein the colorant (a) contains a black pigment.
[5] The content ratio of the colorant (a) is 10% by mass or more in the total solid content, [1] to
The photosensitive coloring composition according to any one of [4].
[6] The amine value of the dispersant (f1) is 30 mgKOH / g or more, [1] to [
5] The photosensitive coloring composition according to any one of.

[7] The photosensitive coloring composition according to any one of [1] to [6], which is used for forming a coloring spacer.
[8] A cured product obtained by curing the photosensitive coloring composition according to any one of [1] to [7].
[9] An image display device containing the cured product according to [8].

[10] A pigment dispersion liquid for an image display device containing (a) a colorant, (e) a solvent, and (f) a dispersant.
The colorant (a) contains a black pigment and contains
The dispersant (f1) has a repeating unit represented by the following general formula (1).
) Is contained in a pigment dispersion liquid for an image display device.

(In the formula (1), R ¹ and R ² are each independently an alkyl group which may have a substituent or an aryl group which may have a substituent, and R ¹ and R ² are They may be combined with each other to form an annular structure.
R ³ is an alkylene group.
R ⁴ is a polycyclic aromatic hydrocarbon group which may have a substituent.
R ⁵ is a hydrogen atom or a methyl group.
X is a divalent linking group.
Y is a halogen atom. )

[11] The pigment dispersion for an image display device according to [10], wherein the polycyclic aromatic hydrocarbon group in ^{R 4} in the formula (1) has two or more aromatic rings.
[12] The amine value of the dispersant (f1) is 30 mgKOH / g or more, [10]
Alternatively, the pigment dispersion liquid for the image display device according to [11].

According to the present invention, it is possible to provide a photosensitive coloring composition having excellent electrical reliability after irradiation with ultraviolet rays.

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

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

Further, in the present invention, "monomer" is a term relative to a so-called polymer substance (polymer), and means that a dimer, a trimer, an oligomer, etc. are included in addition to a monomer (monomer) in a narrow sense. Is.
In the present invention, the "total solid content" is contained in the photosensitive coloring composition or the pigment dispersion liquid.
It shall mean all components except solvent. Even if the components other than the solvent are liquid at room temperature, the components are not included in the solvent but are included in the total solid content.
In the present invention, the "weight average molecular weight" refers to the polystyrene-equivalent weight average molecular weight (Mw) obtained by GPC (gel permeation chromatography).
Further, in the present invention, the "amine value" represents an amine value in terms of effective solid content unless otherwise specified, and is a value represented by the amount of base per 1 g of solid content of the dispersant and the equivalent mass of KOH. Is. The measurement method will be described later. On the other hand, the "acid value" represents the acid value in terms of effective solid content unless otherwise specified, and is calculated by neutralization titration.

Regarding pigments, "CI" means a color index.

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

[Photosensitive coloring composition]
The photosensitive coloring composition of the present invention is
(A) Colorant (b) Alkaline-soluble resin (c) Photopolymerization initiator (d) Ethylene unsaturated compound (e) Solvent (f) Dispersant is contained as an essential component, and if necessary, a silane cup is further added. It contains other compounding components such as adhesion improver such as ring agent, surfactant, pigment derivative, photoacid generator, cross-linking agent, mercapto compound, polymerization inhibitor, etc., and each compounding component is usually used as a solvent. It is used in a dissolved or dispersed state.

<(A) Colorant>
The photosensitive coloring composition of the present invention contains (a) a coloring agent. (A) By containing a colorant, it is possible to obtain an appropriate light absorption property, particularly an appropriate light shielding property when used for forming a light shielding member such as a colored spacer.
Further, the photosensitive coloring composition of the present invention has an optical density per 1 μm of a cured coating film (hereinafter, may be referred to as “OD per unit film thickness”) of 0.5 or more. By containing (a) the colorant and setting the OD per unit film thickness to the lower limit value or more in this way, the light-shielding property of the obtained cured product, particularly the colored spacer, is enhanced.

The OD per unit film thickness can be calculated by measuring the optical density and the film thickness of the coating film obtained by curing the photosensitive coloring composition and dividing the optical density by the film thickness. The conditions for producing the coating film are not particularly limited, but for example, the conditions described in Examples described later can be adopted.
In order to make the OD per unit film thickness equal to or higher than the lower limit, for example, (a) the type of colorant and the content ratio in the total solid content may be appropriately adjusted.

The type of (a) colorant that can be used in the photosensitive coloring composition of the present invention is not particularly limited, and a pigment or a dye may be used. Among these, it is preferable to use a pigment from the viewpoint of durability.

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

One type of organic coloring pigment may be used alone, or two or more types may be used in combination. In particular, from the viewpoint of setting the OD per unit film thickness to 0.5 or more, it is more preferable to use a combination of organic coloring pigments having different colors, and it is preferable to use a combination of organic coloring pigments having a color close to black. More preferred.

The chemical structure of these organic coloring pigments is not particularly limited, but azo-based, phthalocyanine-based, and so on.
Examples thereof include quinacridone, benzimidazolone, isoindolinone, dioxazine, indanthrone, and perylene. Hereinafter, specific examples of pigments that can be used are shown by pigment numbers. Terms such as "CI Pigment Red 2" listed below mean the Color Index (CI).

Examples of the red pigment include 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, 255, 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 property, C.I. I. Pigment Red 17
7, 254, 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, and from this viewpoint, C.I. I. It is more preferable to use Pigment Red 254 and 272.

Examples of the orange pigment include C.I. I. Pigment Orange 1, 2, 5, 13, 16
, 17, 19, 20, 21, 22, 23, 24, 34, 36, 38, 39, 43, 46,
48, 49, 61, 62, 64, 65, 67, 68, 69, 70, 71, 72, 73, 7
4, 75, 77, 78, 79 can be mentioned. Among these, from the viewpoint of dispersibility and light-shielding property, C.I. I. Pigment Orange 13, 43, 64, 72 are 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, and from this viewpoint, it is preferable to use. C. I. Pigment Orange 64, 72
Is more preferable to use.

Examples of the blue pigment include 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, from the viewpoint of light-shielding property, 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 can be mentioned.
In terms of dispersibility and light-shielding property, C.I. I. Pigment Blue 15: 6, 16, 60 is preferably used, and when the photosensitive coloring composition is cured with ultraviolet rays, it is preferable to use a blue pigment having a low ultraviolet absorption rate, and from this viewpoint, it is preferable to use. C. I. It is more preferable to use Pigment Blue 60.

As the purple pigment, C.I. I. Pigment Violet 1, 1: 1, 2, 2: 2, 3, 3
1, 3: 3, 5, 5: 1, 14, 15, 16, 19, 23, 25, 27, 29, 31,
32, 37, 39, 42, 44, 47, 49, 50 can be mentioned. Among these,
From the viewpoint of light-shielding property, C.I. I. Pigment Violet 19, 23, 29, more preferably C.I. I. Pigment Violet 23 can be mentioned.
In terms of dispersibility and light-shielding property, C.I. I. Pigment Violet 23 and 29 are preferably used, and when the photosensitive coloring composition is cured with ultraviolet rays, it is preferable to use a purple pigment having a low ultraviolet absorption rate, and from this viewpoint, C.I. I. It is more preferable to use Pigment Violet 29.

Examples of the green pigment include 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, preferably C.I. I. Pigment Green 7,
36 can be mentioned.
Examples of the yellow pigment include 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, preferably C.I. I. Pigment Yellow 83, 117, 129, 138,
139, 150, 154, 155, 180, 185, more preferably C.I. I. Pigment Yellow 83, 138, 139, 150, 180 can be mentioned.

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

Among these, from the viewpoint of light-shielding property and shape control, it is preferable to contain at least one of the following pigments.
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

Further, when two or more kinds of organic coloring pigments are used in combination, the combination of organic coloring pigments is not particularly limited, but from the viewpoint of light-shielding property, at least one kind selected from the group consisting of red pigments and orange pigments and blue pigments. And at least one selected from the group consisting of purple pigments.
The color combination is not particularly limited, but from the viewpoint of light-shielding property, for example, a combination of a red pigment and a blue pigment, a combination of a blue pigment and an orange pigment, a combination of a blue pigment and an orange pigment and a purple pigment, and the like can be mentioned. ..

Examples of the black pigment include an organic black pigment and an inorganic black pigment. Of these, 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 steps.
Among organic black pigments, a compound represented by the following general formula (1) from the viewpoint of suppressing a decrease in the voltage retention rate of a liquid crystal and suppressing absorption of ultraviolet rays to facilitate control of shape and step. (Hereinafter, it may be referred to as "Compound (1)"), an organic containing at least one selected from the group consisting of a geometric isomer of the compound, a salt of the compound, and a salt of the geometric isomer of the compound. Black pigment (hereinafter, may be referred to as "organic black pigment represented by the general formula (1)".
) Is preferably used.

In formula (1), R ¹¹ and R ¹⁶ 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 each independently represent a hydrogen atom, a halogen ^{atom, R 21, COOH, COOR 21} , COO -, CONH 2, CONHR 21 , CONR ²¹ R
²² , CN, OH, OR ²¹ , COCR ²¹ , OOCNH ₂ , OOCNHR ²¹ , OOCNR ²¹ R ^2
2 , NO ₂ , NH ₂ , NHR ²¹ , NR ²¹ R ²² , NHCOR ²² , NR ²¹ COR ²² , N = CH ₂ ,
N = CHR ²¹ , N = CR ²¹ R ²² , SH, SR ²¹ , SOR ²¹ , SO ₂ R ²¹ , SO ₃ R ²¹ , SO
₃ H, SO ₃ ^-, represents _{SO 2 NH 2, SO 2 NHR} 21 or _{^{SO 2 NR 21 R 22; R}} 12 and R ^13, R ^1
At least one combination selected from the group consisting of 3 and R ¹⁴ , R ¹⁴ and R ¹⁵ , R ¹⁷ and R ¹⁸ , R ¹⁸ and R ¹⁹ , and R ¹⁹ and R ²⁰ may or may be directly coupled to each other. They may be bonded to each other by an oxygen atom, a sulfur atom, an NH or NR ^{21 bridge; R 21} and R ²² are independently alkyl groups having 1 to 12 carbon atoms, cycloalkyl groups having 3 to 12 carbon atoms, and carbon atoms. 2-12
Represents an alkenyl group, a cycloalkenyl group having 3 to 12 carbon atoms, or an alkynyl group having 2 to 12 carbon atoms.

The geometric isomers of compound (1) and compound (1) have the following core structure (however, the substituents in the structural formula are omitted), and the trans-trans isomer is probably the most stable.

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

In the substituents of the general formula (1) and their definitions, the following are preferable because the shielding rate tends to be high. This is because the following substituents are not absorbed and are not considered to affect the hue of the pigment.
R ¹² , R ¹⁴ , R ¹⁵ , R ¹⁷ , R ¹⁹ and R ²⁰ are each independently, preferably a hydrogen atom, a fluorine atom, or a chlorine atom, and more preferably a hydrogen atom.
R ¹³ and R ¹⁸ are independent of each other, preferably hydrogen atom, NO ₂ , OCH ₃ , OC ₂ H ₅ , bromine atom, chlorine atom, CH ₃ , C ₂ H ₅ , N (CH _{3 ) 2} , N (CH). ₃ ) (C ₂ H ₅ ), N (C ₂ H ₅ ) ₂
, Alpha-naphthyl, beta-naphthyl, SO ₃ H or SO ₃ ^- and, still more preferably a hydrogen atom or SO ₃ H, and particularly preferably a hydrogen atom.

R ¹¹ and R ¹⁶ are each independently, preferably a hydrogen atom, CH ₃ or CF ₃ , and more preferably a hydrogen atom.
Preferably, at least one combination selected from the group consisting of ^{R 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.} R ¹¹ 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 . It is the same.

Alkyl groups having 1 to 12 carbon atoms include, 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 It is a methylbutyl group, a 2-ethylhexyl group, a nonyl group, a decyl group, an undecyl group or a dodecyl group.

The cycloalkyl group having 3 to 12 carbon atoms includes, for example, a cyclopropyl group, a cyclopropylmethyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cyclohexylmethyl group, a trimethylcyclohexyl group, a tudyl group, a norbornyl group, a bornyl group and a norcaryl group. , Caryl group, mentyl group, norpinyl group, pinyl group, adamantan-1-yl group or adamantan-2-yl group.

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

The cycloalkenyl group having 3 to 12 carbon atoms is, for example, 2-cyclobutene-1-yl group, 2
-Cyclopentene-1-yl group, 2-cyclohexene-1-yl group, 3-cyclohexene-1-yl group, 2,4-cyclohexadiene-1-yl group, 1-p-mentene-8-yl group, 4 (10) -Thujene-10-yl group, 2-norbornene-1-yl group, 2,5-norbornadiene-1-yl group, 7,7-dimethyl-2,4-norcaladien-3-yl group or phenyl It is a group.

The alkynyl group having 2 to 12 carbon atoms is, for example, 1-propyne-3-yl group, 1-butyne-.
4-yl group, 1-pentyne-5-yl group, 2-methyl-3-butin-2-yl group, 1,4
−Pentaziin-3-yl group, 1,3-pentadiin-5-yl group, 1-hexyne-6-
Il group, cis-3-methyl-2-pentene-4-in-1-yl group, trans-3-methyl-2-pentene-4-in-1-yl group, 1,3-hexadiine-5-yl group Group, 1-octyne-8-yl group, 1-nonyne-9-yl group, 1-decyne-10-yl group or 1-dodecyne-12-yl group.

The 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 (1) is preferably a compound represented by the following general formula (2) (hereinafter, also referred to as “compound (2)”) and a geometric isomer of the compound (2). It is an organic black pigment containing at least one selected from the group consisting of isomers.

As a specific example of such an organic black pigment, the trade name is Irgaphor (registered trademark).
Black S 0100 CF (manufactured by BASF) can be mentioned.
This organic black pigment is preferably dispersed and used by a dispersant, a solvent, or a method described later. Further, if the sulfonic acid derivative of the compound (1), particularly the sulfonic acid derivative of the compound (2) is present at the time of dispersion, the dispersibility and storage stability may be improved. Therefore, the organic black pigment is a sulfonic acid derivative of these. Is preferably included.

Examples of the organic black pigment other than the organic black pigment represented by the general formula (1) 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 property.
Examples of the inorganic black pigment include carbon black, acetylene black, lamp black, bone black, graphite, iron black, cyanine black, titanium black and the like. Among these, carbon black can be preferably used from the viewpoint of light-shielding property and image characteristics. Examples of carbon black include the following carbon blacks.

Made by Mitsubishi Chemical Corporation: MA7, MA8, MA11, MA77, MA100, MA100R
, MA100S, MA220, MA230, MA600, MCF88, # 5, # 10, #
20, # 25, # 30, # 32, # 33, # 40, # 44, # 45, # 47, # 50, #
52, # 55, # 650, # 750, # 850, # 900, # 950, # 960, # 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
Made by Degusa: Printex (registered trademark, the same shall apply hereinafter) 3, Printex3OP, P
Printex30, Printex30OP, Printex40, Printex45
, Printex55, Printex60, Printex75, Printex80
, Printex85, Printex90, Printex A, Printex L
, Printex G, Printex P, Printex U, Printex V
, PrintexG, SpecialBlack550, SpecialBlack35
0, SpecialBlack250, SpecialBlack100, Special
lBlack6, SpecialBlack5, SpecialBlack4, Color
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
Made by Cabot: Monarch (registered trademark, the same shall apply hereinafter) 120, Monarch2
80, Monarch 460, Monarch 800, Monarch 880, Mona
rch900, Monarch1000, Monarch1100, Monarch13
00, Monarch1400, Monarch4630, REGAL (registered trademark, the same shall apply hereinafter) 99, REGAL99R, REGAL415, REGAL415R, REGAL
250, REGAL250R, REGAL330, REGAL400R, REGAL55
R0, REGAL660R, BLACK PEARLS480, PEARLS130, V
ULCAN (registered trademark, the same shall apply hereinafter) XC72R, ELFTEX (registered trademark) -8
Made by Biller: RAVE (registered trademark, the same shall apply hereinafter) 11, RAVE14, RAVE
N15, RAVEN16, RAVEN22 RAVEN30, RAVEN35, RAVEN
40, RAVEN410, RAVEN420, RAVEN450, RAVEN500, R
AVEN780, RAVEN850, RAVEN890H, RAVEN1000, RAV
EN1020, RAVEN1040, RAVEN1060U, RAVEN1080U, R
AVEN1170, RAVEN1190U, RAVEN1250, RAVEN1500,
RAVEN2000, RAVEN2500U, RAVEN3500, RAVEN5000
, RAVEN5250, RAVEN5750, RAVEN7000

As the carbon black, one coated with a resin may be used. The use of carbon black coated with resin has the effect of improving the adhesion to the glass substrate and the volume resistance value. As the carbon black coated with the resin, for example, the carbon black described in JP-A-09-71733 can be preferably used. In terms of volume resistance and permittivity
Resin-coated carbon black is preferably used.

The total content of Na and Ca is 1 for carbon black to be coated with resin.
It is preferably 00 ppm or less. Carbon black is usually raw material oil or combustion oil (or gas) at the time of production, reaction stop water or granulation water, or Na or C mixed from the reactor material of the reactor.
Ash containing a, K, Mg, Al, Fe and the like is contained on the order of percentage. Of these, Na and Ca are generally contained in an amount of several hundred ppm or more, respectively, but by reducing these, permeation into the transparent electrode (ITO) and other electrodes is suppressed, and electricity is obtained. There is a tendency to prevent short circuits.

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

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

The resin-coated carbon black is preferably so-called acidic carbon black having a pH of 6 or less. Since the dispersion diameter (aggregate diameter) in water becomes small, it is possible to cover even fine units, which is suitable. Further, it is preferable that the average particle size is 40 nm or less and the absorption amount of dibutyl phthalate (DBP) is 140 ml / 100 g or less. Within the above range, a coating film having a good light-shielding property tends to be obtained. The average particle size means a number average particle size, and particle image analysis in which photographs taken at tens of thousands of times by electron microscope observation are taken in several fields and about 2000 to 3000 particles of these photographs are measured by an image processing device. Means the equivalent circle diameter obtained by.

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

The type of resin to be coated is not particularly limited, but synthetic resin is generally used.
Further, a resin having a benzene ring in its structure is preferable from the viewpoint of dispersibility and dispersion stability because it has a stronger action as an amphoteric surfactant.
Specific synthetic resins include thermosetting resins such as phenol resin, melamine resin, xylene resin, diallyl phthalate resin, glyptal resin, epoxy resin and alkylbenzene resin, polystyrene, polycarbonate, polyethylene terephthalate, polybutylene terephthalate and modified polyphenylene. Thermoplastic resins such as oxide, polysulphon, polyparaphenylene terephthalamide, polyamideimide, polyimide, polyaminobismaleimide, polyether sulfopolyphenylensulfon, polyarylate, and polyether ether ketone can be used. The coating amount of the resin on the carbon black is preferably 1 to 30% by mass with respect to the total amount of the carbon black and the resin, and the coating tends to be sufficient by setting the coating amount to the lower limit value or more. On the other hand, by setting it below the above upper limit value,
There is a tendency that the resins can be prevented from adhering to each other and the dispersibility can be improved.

The carbon black coated with the resin in this way can be used as a light-shielding material for the colored spacer according to a conventional method, and a color filter having the colored spacer as a component can be produced by a conventional method. When such carbon black is used, a colored spacer having a high shading rate and a low surface reflectance tends to be achieved at low cost. again,
By coating the surface of the carbon black with a resin, it is presumed that it also has a function of confining Ca and Na in the carbon black.

These pigments are preferably dispersed and used so that the average particle size is usually 1 μm or less, preferably 0.5 μm or less, and more preferably 0.25 μm or less. Here, the standard of the average particle size is the number of pigment particles.
In the photosensitive coloring composition of the present invention, the average particle size of the pigment is dynamic light scattering (DLS).
) Is a value obtained from the pigment particle size. The particle size is measured by a sufficiently diluted photosensitive coloring composition (usually diluted to prepare a pigment concentration of about 0.005 to 0.2% by mass. However, if there is a concentration recommended by the measuring device, the concentration thereof is adjusted. (According to the concentration), and measure at 25 ° C.

Further, in the photosensitive coloring composition of the present invention, a coloring agent such as an organic coloring pigment or a black pigment is used.
The types may be used alone, or two or more types may be used in combination. Of these, it is preferable to use the organic black pigment and the organic coloring pigment together from the viewpoint of making it easy to control the shape and the step, and on the other hand, it is preferable to use the carbon black and the organic coloring pigment together from the viewpoint of light-shielding property.

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

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

<(B) Alkali-soluble resin>
The alkali-soluble resin used in the present invention is not particularly limited as long as it is a resin containing a carboxy group or a hydroxyl group, and is, for example, an epoxy (meth) acrylate resin, an acrylic resin, a carboxy group-containing epoxy resin, or a carboxy group-containing resin. Examples thereof include urethane resin, novolak resin, polyvinylphenol resin and the like. Among them, (b1) epoxy (meth) acrylate resin (b2) acrylic copolymer resin is preferably used from the viewpoint of excellent plate-making property. These can be used alone or in admixture of a plurality of types.

<(B1) Epoxy (meth) acrylate resin>
(B1) The epoxy (meth) acrylate-based resin is an epoxy compound (epoxy resin) and α, β-unsaturated monocarboxylic acid and / or α, β- having a carboxy group at the ester moiety.
Obtained by reacting a reaction product with an unsaturated monocarboxylic acid ester with a compound having two or more substituents capable of reacting the hydroxyl group generated by the reaction with a hydroxyl group such as a polybasic acid and / or an anhydride thereof. Resin to be used.
Further, before reacting the above-mentioned polybasic acid and / or its anhydride with a hydroxyl group, after reacting a compound having two or more substituents capable of reacting with the hydroxyl group, the polybasic acid and / or its anhydride is added. The resin obtained by reacting an object is also included in the (b1) epoxy (meth) acrylate-based resin described above.

Further, the resin obtained by reacting the carboxy group of the resin obtained by the above reaction with a compound having a functional group capable of further reacting is also included in the (b1) epoxy (meth) acrylate-based resin.
As described above, the epoxy (meth) acrylate-based resin has substantially no epoxy group in terms of chemical structure and is not limited to "(meth) acrylate", but the epoxy compound (epoxy resin) is used as a raw material. And since "(meth) acrylate" is a typical example, it is named in this way according to the convention.

Examples of the (b1) epoxy (meth) acrylate-based resin used in the present invention include the following epoxy (meth) acrylate-based resin (b1-1) and / or epoxy (meth) acrylate-based resin (b1-2) (hereinafter, “carboxy”). A group-containing epoxy (meth) acrylate-based resin ”may be referred to as“ group-containing epoxy (meth) acrylate resin ”), which is preferably used from the viewpoint of developability and reliability.
Further, as the (b1) epoxy (meth) acrylate-based resin, one having an aromatic ring in the main chain can be more preferably used from the viewpoint of outgassing.

<Epoxy (meth) acrylate resin (b1-1)>
It was 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 with a polybasic acid and / or its anhydride. Alkaline-soluble resin.
<Epoxy (meth) acrylate resin (b1-2)>
An α, β-unsaturated monocarboxylic acid or an α, β-unsaturated monocarboxylic acid ester having a carboxy group is added to the epoxy resin, and the epoxy resin is further reacted with a polyhydric alcohol and a polybasic acid and / or its anhydride. Alcohol-soluble resin obtained by.

Here, the epoxy resin includes a raw material compound before forming the resin by thermosetting, and the epoxy resin can be appropriately selected from known epoxy resins and used. Further, as the epoxy resin, a compound obtained by reacting a phenolic compound with epihalohydrin can be used. The phenolic compound is preferably a compound having a divalent or divalent or higher phenolic hydroxyl group, and may be a monomer or a polymer.
The types of epoxy resins used as raw materials include cresol novolac type epoxy resin, phenol novolac type epoxy resin, bisphenol A type epoxy resin, and bisphenol F.
Type epoxy resin, trisphenol methane type epoxy resin, biphenyl novolac type epoxy resin, naphthalene novolac type epoxy resin, epoxy resin which is a reaction product of dicyclopentadiene and phenol or cresol and epihalohydrin, adamantyl group A containing epoxy resin, a fluorene type epoxy resin, or the like can be preferably used, and those having an aromatic ring in the main chain as described above can be preferably used.

Specific examples of the epoxy resin include, for example, bisphenol A type epoxy resin (for example, "jER (registered trademark, the same applies hereinafter) 828" and "jER100" manufactured by Mitsubishi Chemical Corporation.
1 ”,“ jER1002 ”,“ jER1004 ”, etc.), an epoxy resin obtained by the reaction of epichlorohydrin with the alcoholic hydroxyl group of bisphenol A type epoxy resin (for example,“ NER-1302 ”(epoxy equivalent 323) manufactured by Nippon Kayaku Co., Ltd. Softening point 76 ° C)), bisphenol F type resin (for example, "jER807" manufactured by Mitsubishi Chemical Co., Ltd., "EP-4001"
, "EP-4002", "EP-4004", etc.), an epoxy resin obtained by the reaction of epichlorohydrin with an alcoholic hydroxyl group of a bisphenol F type epoxy resin (for example,
"NER-7406" manufactured by Nippon Kayaku Co., Ltd. (epoxy equivalent 350, softening point 66 ° C), bisphenol S type epoxy resin, biphenyl glycidyl ether (for example, "YX-4000" manufactured by Mitsubishi Chemical Co., Ltd.), phenol novolac type Epoxy resins (for example, "EPPN-201" manufactured by Nippon Kayaku Co., Ltd., "EP-152" and "EP-154" manufactured by Mitsubishi Chemical Co., Ltd., "DEN-438" manufactured by Dow Chemical Co., Ltd.), (o, m , P-) Cresol novolac type epoxy resin (for example, "EOCN (registered trademark, the same shall apply hereinafter) -102S" manufactured by Nippon Kayaku Co., Ltd.,
"EOCN-1020", "EOCN-104S"), triglycidyl isocyanurate (for example, "TEPIC (registered trademark)" manufactured by Nissan Chemical Industries, Ltd.), trisphenol methane type epoxy resin (for example, "EOCN-1020" manufactured by Nippon Kayaku Co., Ltd.) EPPN (registered trademark, the same shall apply hereinafter) -501 ",
"EPPN-502", "EPPN-503"), alicyclic epoxy resin (Daicel's "Celoxide (registered trademark, the same shall apply hereinafter) 2021P", "Celoxide EHPE"),
Epoxy resin made by glycidylating a phenol resin produced by the reaction of dicyclopentadiene and phenol (for example, "EXA-7200" manufactured by DIC Corporation and "NC-730" manufactured by Nippon Kayaku Co., Ltd.
0 ”), epoxy resins represented by the following general formulas (B1) to (B4), and the like can be preferably used. Specifically, "XD-1000" manufactured by Nippon Kayaku Co., Ltd. is used as the epoxy resin represented by the following general formula (B1), and "XD-1000" manufactured by Nippon Kayaku Co., Ltd. is used as the 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 & Sumitomo Metal Chemical Co., Ltd. as an epoxy resin represented by the following general formula (B4). Examples thereof include "ESF-300".

In the above general formula (B1), a is an average value and represents a number from 0 to 10, and R ¹¹¹ is independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 8 carbon atoms, and 3 to 10 carbon atoms, respectively. Represents a cycloalkyl group, a phenyl group, a naphthyl group, or a biphenyl group. The plurality of R ^111s present in one molecule may be the same or different.

In the above general formula (B2), b1 and b2 are independently average values and represent numbers 0 to 10, and R ¹²¹ is independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 8 carbon atoms, and carbon. Represents a cycloalkyl group, a phenyl group, a naphthyl group, or a biphenyl group having a number of 3 to 10. The plurality of R ^121s present in one molecule may be the same or different.

In the above general formula (B3), X represents a linking group represented by the following general formula (B3-1) or (B3-2). However, the molecular structure contains one or more adamantane structures. 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 each independently may have a substituent, an adamantyl group, a hydrogen atom, and a substituent. Represents an alkyl group having 1 to 12 carbon atoms which may have, or a phenyl group which may have a substituent, and * represents a bond.

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

Among these, it is preferable to use an epoxy resin represented by any of the general formulas (B1) to (B4).

Examples of the α, β-unsaturated monocarboxylic acid or α, β-unsaturated monocarboxylic acid ester having a carboxy group include (meth) acrylic acid, crotonic acid, o-, m- or p-vinylbenzoic acid, and (meth). ) Monocarboxylic acids such as α-position haloalkyl, alkoxyl, halogen, nitro, and cyano-substituted acrylic acids, 2- (meth) acryloyloxyethyl succinic acid, 2-(
Meta) acryloyloxyethyl adipic acid, 2- (meth) acryloyloxyethyl phthalic acid, 2- (meth) acryloyloxyethyl hexahydrophthalic acid, 2- (meth) acryloyloxyethyl maleic acid, 2- ( Meta) acryloyloxypropyl succinic acid, 2- (meth) acryloyloxypropyl adipic acid, 2- (meth) acryloyloxypropyl tetrahydrophthalic acid, 2- (meth) acryloyloxypropyl phthalic acid, 2- (meth) ) Acryloyloxypropyl maleic acid, 2- (meth) acryloyloxybutyl succinic acid, 2-
(Meta) acryloyloxybutyl adipate, 2- (meth) acryloyloxybutylhydrophthalic acid, 2- (meth) acryloyloxybutylphthalic acid, 2- (meth) acryloyloxybutylmaleic acid (meth), Acrylic acid to which lactones such as ε-caprolactone, β-propiolactone, γ-butyrolactone, and δ-valerolactone are added, or hydroxyalkyl (meth) acrylate, pentaerythritol tri (meth). Examples thereof include a monomer obtained by adding an acid (anhydride) such as (anhydrous) succinic acid, (anhydrous) phthalic acid, and (anhydrous) maleic acid to acrylate, and (meth) acrylic acid dimer.
Of these, (meth) acrylic acid is particularly preferable from the viewpoint of sensitivity.

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

Epoxy resin, α, β-unsaturated monocarboxylic acid or α, β having a carboxy group
-For each component of the unsaturated monocarboxylic acid ester and the esterification catalyst, one type of each component may be selected and used, or two or more types may be used in combination.
The amount of α, β-unsaturated monocarboxylic acid or α, β-unsaturated monocarboxylic acid ester having a carboxy group is preferably in the range of 0.5 to 1.2 equivalents with respect to 1 equivalent of the epoxy group of the epoxy resin. , More preferably in the range of 0.7 to 1.1 equivalents. By setting the amount of α, β-unsaturated monocarboxylic acid or α, β-unsaturated monocarboxylic acid ester having a carboxy group to be equal to or higher than the above lower limit, the shortage of the amount of unsaturated group introduced can be suppressed, and the amount of introduction of the unsaturated group can be suppressed. The reaction with the basic acid and / or its anhydride also tends to be sufficient. On the other hand, when the value is not more than the above upper limit, the residual unreacted product of α, β-unsaturated monocarboxylic acid or α, β-unsaturated monocarboxylic acid ester having a carboxy group can be suppressed, and the curing characteristics are good. There is a tendency for it to be easy to do.

Examples of polybasic acid and / or its anhydride include maleic acid, succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, pyromellitic acid, trimellitic acid,
One or more selected from benzophenone tetracarboxylic acid, methyl hexahydrophthalic acid, endomethylene tetrahydrophthalic acid, chlorendic acid, methyl tetrahydrophthalic acid, biphenyl tetracarboxylic acid, and anhydrides thereof can be mentioned. ..

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, or biphenyltetracarboxylic dianhydride.

Known methods can also be used for the addition reaction of polybasic acids and / or anhydrides thereof.
The desired product can be obtained by a continuous reaction under the same conditions as the addition reaction of an α, β-unsaturated monocarboxylic acid or an α, β-unsaturated monocarboxylic acid ester having a carboxy group to an epoxy resin. The amount of the polybasic acid and / or its anhydride component added is preferably such that the acid value of the carboxy group-containing epoxy (meth) acrylate-based resin to be produced is in the range of 10 to 150 mgKOH / g. It is preferably in the range of 20 to 140 mgKOH / g. When it is at least the above lower limit value, the alkali developability tends to be good, and when it is at least the above upper limit value, the curing performance tends to be good.

During the addition reaction of this polybasic acid and / or its anhydride, trimethylolpropane,
A polyfunctional alcohol (polyhydric alcohol) such as ditrimethylolpropane, pentaerythritol, dipentaerythritol, trimethylolethane, 1,2,3-propanetriol may be added to introduce a multi-branched structure.

In this case, the mixing order of the polybasic acid and / or its anhydride and the polyfunctional alcohol is not particularly limited. By heating, any hydroxyl group present in the mixture of the reaction product of the epoxy resin with the α, β-unsaturated monocarboxylic acid or the α, β-unsaturated monocarboxylic acid ester having a carboxy group and the polyfunctional alcohol. Polycarboxylic acid and / or its anhydride undergoes an addition reaction with respect to.

By using a polyhydric alcohol, the molecular weight of the (b1) epoxy (meth) acrylate resin can be increased, branching can be introduced into the molecule, and the molecular weight and viscosity tend to be balanced. In addition, the introduction rate of acid groups into the molecule can be increased, and there is a tendency for the sensitivity, adhesion, and the like to be easily balanced.

Examples of the carboxy group-containing epoxy (meth) acrylate resin include those mentioned above.
Examples thereof include those described in Korean Publication No. 10-2013-0022955.

The polystyrene-equivalent weight average molecular weight (Mw) of the carboxy group-containing epoxy (meth) acrylate resin measured by gel permeation chromatography (GPC) is usually 1000 or more, preferably 1500 or more, more preferably 2000 or more, and more preferably. Is 3000 or more, more preferably 4000 or more, particularly preferably 5000 or more, and usually 10000 or less, preferably 8000 or less, and more preferably 7000 or less. When it is set to the lower limit value or more, the solubility in the developing solution tends to be suppressed from becoming too high, and when it is set to the upper limit value or less, the solubility in the developing solution tends to be good.

The acid value of the carboxy group-containing epoxy (meth) acrylate resin is not particularly limited, but
10 mgKOH / g or more is preferable, 20 mgKOH / g or more is more preferable, and 40 mg
KOH / g or more is further preferable, 50 mgKOH / g or more is further preferable, 200 mgKOH / g or less is preferable, and 150 mgKOH / g or less is more preferable.
20 mgKOH / g or less is more preferable, and 100 mgKOH / g or less is particularly preferable.
When it is set to the lower limit value or more, appropriate development solubility tends to be obtained, and when it is set to the upper limit value or less, development tends to proceed too much and film dissolution tends to be suppressed.

The chemical structure of the epoxy (meth) acrylate-based resin is not particularly limited, but from the viewpoint of developability and reliability, an epoxy (meth) acrylate-based resin having a partial structure represented by the following general formula (b1-I) (hereinafter, , "(B1-I) Epoxy (meth) acrylate-based resin") and / or an epoxy (meth) acrylate-based resin having a partial structure represented by the following general formula (b1-II). Hereinafter, it may be abbreviated as "(b1-II) epoxy (meth) acrylate-based resin").

In formula (b1-I), R ¹¹ represents a hydrogen atom or a methyl group, R ¹² represents a divalent hydrocarbon group which may have a substituent, k represents 1 or 2, and * represents 1 or 2. Represents a bond. Equation (b1-I)
The benzene ring inside may be further substituted with any substituent.

In formula (b1-II), R ¹³ independently represents a hydrogen atom or a methyl group, R ¹⁴ represents a divalent hydrocarbon group having a cyclic hydrocarbon group as a side chain, and R ¹⁵ and R ¹⁶ Each independently represents a divalent aliphatic group which may have a substituent, m and n each independently represent an integer of 0 to 2, and * represents a bond.

<(B1-I) Epoxy (meth) acrylate resin>
First, an epoxy (meth) acrylate-based resin having a partial structure represented by the general formula (b1-I) will be described in detail.

In formula (b1-I), R ¹¹ represents a hydrogen atom or a methyl group, R ¹² represents a divalent hydrocarbon group which may have a substituent, k represents 1 or 2, and * represents 1 or 2. Represents a bond. Equation (b1-I)
The benzene ring inside may be further substituted with any substituent.

(R ¹² )
In the formula (b1-I), R ¹² represents a divalent hydrocarbon group which may have a substituent.
As the divalent hydrocarbon group, a divalent aliphatic group, a divalent aromatic ring group, a group in which a divalent aliphatic group of 1 or more and a divalent aromatic ring group of 1 or more are linked is used. Can be mentioned.

Examples of the divalent aliphatic group include linear, branched and cyclic groups. Among these, linear ones are preferable from the viewpoint of development solubility. On the other hand, from the viewpoint of reducing the penetration of the developing solution into the exposed portion, a ring-shaped one is preferable. The carbon number is usually 1 or more, preferably 20 or less, more preferably 15 or less, still more preferably 10 or less. When it is set to the above lower limit value or more, a strong film is easily obtained, surface roughness is less likely to occur, and the adhesion to the substrate tends to be good. It is easy to suppress the film loss at the time, and the resolution tends to be improved.

Specific examples of the divalent linear aliphatic group include a methylene group, an ethylene group, an n-propylene group, an n-butylene group, an n-pentylene group, an n-hexylene group, an n-heptylene group and the like. .. Among these, a methylene group is preferable from the viewpoint of skeletal rigidity.
The divalent branched aliphatic group includes the above-mentioned divalent linear aliphatic group, and the side chains include a methyl group, an ethyl group, an n-propyl group, an iso-propyl group, and an n-butyl group. , Iso-butyl group, sec-butyl group, tert-butyl group and the like.
The number of rings contained in the divalent cyclic aliphatic group is not particularly limited, but is usually 1 or more, preferably 2 or more, and usually 12 or less, preferably 10 or less. When the value is equal to or higher than the lower limit, the film tends to be strong and the adhesion to the substrate tends to be improved. When the value is equal to or higher than the upper limit, deterioration of sensitivity and film loss during development can be easily suppressed, and resolution The sex tends to improve. 2
Specific examples of the cyclic aliphatic group of valence include a cyclohexane ring, a cycloheptane ring, a cyclodecane ring, a cyclododecane ring, a norbornane ring, an isobornane ring, an adamantane ring, a cyclododecane ring, a dicyclopentadiene, a dicyclopentane, and the like. A group obtained by removing two hydrogen atoms from the above can be mentioned. Among these, from the viewpoint of skeletal rigidity, a group obtained by removing two hydrogen atoms from a dicyclopentadiene ring, a dicyclopentane ring, and an adamantane ring is preferable.

Examples of the substituent that the divalent aliphatic group may have include an alkoxy group having 1 to 5 carbon atoms such as a methoxy group and an ethoxy group; a hydroxyl group; a nitro group; a cyano group; and a carboxy group.
Among these, from the viewpoint of easiness of synthesis, it is preferably unsubstituted.

Examples of the divalent aromatic ring group include a divalent aromatic hydrocarbon ring group and a divalent aromatic heterocyclic group. The carbon number is usually 4 or more, preferably 5 or more, more preferably 6 or more, preferably 20 or less, more preferably 15 or less, still more preferably 10 or less. When it is set to the above lower limit value or more, a strong film is easily obtained, surface roughness is less likely to occur, and the adhesion to the substrate tends to be good. It is easy to suppress the film loss at the time, and the resolution tends to be improved.

The aromatic hydrocarbon ring in the divalent aromatic hydrocarbon ring group may be a monocyclic ring or a condensed ring. Examples of the aromatic hydrocarbon ring group include a benzene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring, a perylene ring, a tetracene ring, a pyrene ring, a benzpyrene ring, a chrysene ring, and a triphenylene ring, which have two free valences. Examples include groups such as acenaphthene ring, fluoranthene ring, and fluorene ring.
Further, the aromatic heterocycle in the aromatic heterocyclic group may be a monocyclic ring or a condensed ring. Examples of the aromatic heterocyclic group include a furan ring, a benzofuran ring, a thiophene ring, a benzothiophene ring, a pyrazole ring, a pyrazole ring, an imidazole ring, an oxadiazole ring, an indol ring, and a carbazole ring having two free atomic valences. Ring, pyrroloidazole ring,
Pyrrolopyrazole ring, pyrrolopyrrole ring, thienopyrrole ring, thienothiophene ring, flopyrol ring, flofuran ring, thienoflan ring, benzoisooxazole ring, benzoisothiazole ring, benzimidazole ring, pyridine ring, pyrazine ring, pyridazine ring, pyrimidine ring, Examples thereof include groups such as a triazine ring, a quinoline ring, an isoquinoline ring, a synolin ring, a quinoxaline ring, a phenanthridine ring, a benzimidazole ring, a perimidine ring, a quinazoline ring, a quinazolinone ring, and an azulene ring.
Among these, from the viewpoint of patterning characteristics, a benzene ring or a naphthalene ring having two free valences is preferable, and a benzene ring having two free valences is more preferable.

Examples of the substituent that the divalent aromatic ring group may have include a hydroxy group, a methyl group, a methoxy group, an ethyl group, an ethoxy group, a propyl group, a propoxy group and the like. Of these, no substitution is preferable from the viewpoint of development solubility.

Further, as a group in which one or more divalent aliphatic groups and one or more divalent aromatic ring groups are linked,
Examples thereof include a group in which one or more of the above-mentioned divalent aliphatic groups and one or more of the above-mentioned divalent aromatic ring groups are linked.
The number of divalent aliphatic groups is not particularly limited, but is usually 1 or more, preferably 2 or more, usually 10 or less, preferably 5 or less, and more preferably 3 or less. When it is set to the above lower limit value or more, a strong film is easily obtained, surface roughness is less likely to occur, and the adhesion to the substrate tends to be good. It is easy to suppress the film loss at the time, and the resolution tends to be improved.
The number of divalent aromatic ring groups is not particularly limited, but is usually 1 or more, preferably 2 or more.
It is usually 10 or less, preferably 5 or less, and more preferably 3 or less. When it is set to the above lower limit value or more, a strong film is easily obtained, surface roughness is less likely to occur, and the adhesion to the substrate tends to be good. It is easy to suppress the film loss at the time, and the resolution tends to be improved.

Specific examples of a group in which one or more divalent aliphatic groups and one or more divalent aromatic ring groups are linked are represented by the following formulas (b1-IA) to (b1-IF). Examples include the groups to be used. Among these, the group represented by the following formula (b1-IA) is preferable from the viewpoint of skeletal rigidity and film hydrophobization.

k represents 1 or 2. From the viewpoint of adhesion and patterning property, k is preferably 1, and from the viewpoint of NMP resistance, which will be described later, k is preferably 2. Further, the (b1-I) epoxy (meth) acrylate may contain both a partial structure having a k of 1 and a partial structure having a k of 2.

As described above, the benzene ring in the formula (b1-I) may be further substituted with an arbitrary substituent. Examples of the substituent include a hydroxy group, a methyl group, a methoxy group, an ethyl group, an ethoxy group, a propyl group, a propoxy group and the like. The number of substituents is not particularly limited, and may be one or two or more.
Among these, it is preferable that it is not substituted from the viewpoint of patterning characteristics.

Further, the partial structure represented by the above formula (b1-I) has the following formula (from the viewpoint of simplicity of synthesis).
It is preferably a partial structure represented by b1-I-1).

In formula (b1-I-1), R ¹¹ R ¹² and k are synonymous with those in formula (b1-I).
R ^X represents a hydrogen atom or a polybasic acid residue, * represents a bond. The benzene ring in the formula (b1-I-1) may be further substituted with any substituent.

The polybasic acid residue means a monovalent group obtained by subtracting one OH group from the polybasic acid or its anhydride. Polybasic acids include maleic acid, succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, pyromellitic acid, trimellitic acid, benzophenone tetracarboxylic acid, methylhexahydrophthalic acid, endomethylenetetrahydrophthalic acid. Selected from acid, chlorendic acid, methyltetrahydrophthalic acid, biphenyltetracarboxylic acid 1
Species or two or more species may be mentioned.
Among these, from the viewpoint of patterning properties, maleic acid, succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, pyromellitic acid,
It is a trimellitic acid or a biphenyltetracarboxylic acid, more preferably a tetrahydrophthalic acid, a biphenyltetracarboxylic acid or a biphenyltetracarboxylic acid.

The formula (b1) contained in one molecule of the (b1-I) epoxy (meth) acrylate resin.
Partial structure represented by -I-1) may be one kind or two or more species, for example, as R ^X is a hydrogen atom and R ^X is a polybasic acid residue may be mixed ..

The number of partial structures represented by the formula (b1-I) contained in one molecule of the (b1-I) epoxy (meth) acrylate resin is not particularly limited, but 1 or more is preferable, and 3 or more is preferable. More preferably, 20 or less is preferable, and 15 or less is further preferable. By setting the value to the lower limit or higher, a strong film is likely to be obtained, surface roughness tends to be less likely to occur, and the surface is less likely to be roughened.
By setting the value to the upper limit or less, it is easy to suppress deterioration of sensitivity and film loss during development, and resolution tends to be improved.

The polystyrene-equivalent weight average molecular weight (Mw) of the (b1-I) epoxy (meth) acrylate resin measured by gel permeation chromatography (GPC) is not particularly limited, but is preferably 1000 or more, more preferably 1500 or more. , 2000 or more is even more preferable, 3000 or more is even more preferable, 4000 or more is particularly preferable, and 50 or more.
00 or more is most preferable, 30,000 or less is preferable, 20,000 or less is more preferable, 10,000 or less is further preferable, and 8,000 or less is particularly preferable. When it is at least the above lower limit value, the residual film ratio of the photosensitive coloring composition tends to be good, and when it is at least the above upper limit value, the resolution tends to be good.

The acid value of the (b1-I) epoxy (meth) acrylate resin is not particularly limited, but 1
0 mgKOH / g or more is preferable, 20 mgKOH / g or more is more preferable, and 40 mgK
OH / g or more is more preferable, 50 mgKOH / g or more is even more preferable, 80 m.
GKOH / g or more is particularly preferable, and 200 mgKOH / g or less is particularly preferable, 150.
More preferably mgKOH / g or less, even more preferably 130 mgKOH / g or less.
100 mgKOH / g or less is particularly preferable. When it is set to the lower limit value or more, the development solubility tends to be improved and the resolution tends to be good, and when it is set to the upper limit value or less, the residual film ratio of the photosensitive coloring composition tends to be good. There is.

Specific examples of the (b1-I) epoxy (meth) acrylate-based resin will be given below. Note that * in the example indicates a bond.

<(B1-II) Epoxy (meth) acrylate resin>
Next, an epoxy (meth) acrylate-based resin having a partial structure represented by the general formula (b1-II) will be described in detail.

In formula (b1-II), R ¹³ independently represents a hydrogen atom or a methyl group, R ¹⁴ represents a divalent hydrocarbon group having a cyclic hydrocarbon group as a side chain, and R ¹⁵ and R ¹⁶ Each independently represents a divalent aliphatic group which may have a substituent, m and n each independently represent an integer of 0 to 2, and * represents a bond.

(R ¹⁴ )
In the general formula (b1-II), R ¹⁴ represents a divalent hydrocarbon group having a cyclic hydrocarbon group as a side chain.
Examples of the cyclic hydrocarbon group include an aliphatic ring group and an aromatic ring group.

The number of rings contained in the aliphatic ring group is not particularly limited, but is usually 1 or more, preferably 2 or more, and usually 10 or less, preferably 5 or less, and more preferably 3 or less. When it is set to the upper limit value or more, a strong film tends to be easily obtained and surface roughness tends to be less likely to occur, and when it is set to the upper limit value or less, deterioration of sensitivity and film loss during development can be easily suppressed. The resolution tends to improve.
The carbon number of the aliphatic ring group is usually 4 or more, preferably 6 or more, more preferably 8 or more, preferably 40 or less, more preferably 30 or less, further preferably 20 or less, and particularly preferably 15 or less. preferable. When it is set to the upper limit value or more, a strong film tends to be easily obtained and surface roughness tends to be less likely to occur, and when it is set to the upper limit value or less, deterioration of sensitivity and film loss during development can be easily suppressed. The resolution tends to improve.
Specific examples of the aliphatic ring in the aliphatic ring group include a cyclohexane ring, a cycloheptane ring, and the like.
Cyclodecane ring, cyclododecane ring, norbornane ring, isobornane ring, adamantane ring, cyclododecane ring and the like can be mentioned. Among these, the adamantane ring is preferable from the viewpoint of the residual film ratio and the resolution of the photosensitive coloring composition.

On the other hand, the number of rings contained in the aromatic ring group is not particularly limited, but is usually 1 or more, preferably 2 or more, more preferably 3 or more, and usually 10 or less, preferably 5 or less, 4 or less.
The following is more preferable. When it is set to the upper limit value or more, a strong film tends to be easily obtained and surface roughness tends to be less likely to occur, and when it is set to the upper limit value or less, deterioration of sensitivity and film loss during development can be easily suppressed. The resolution tends to improve.
Examples of the aromatic ring group include an aromatic hydrocarbon ring group and an aromatic heterocyclic group. The carbon number of the aromatic ring group is usually 4 or more, preferably 6 or more, more preferably 8 or more, further preferably 10 or more, particularly preferably 12 or more, and preferably 40 or less, preferably 30 or less. More preferably, 20 or less is further preferable, and 15 or less is particularly preferable. By setting the value to the lower limit or higher, a strong film is likely to be obtained, surface roughness tends to be less likely to occur, and the surface is less likely to be roughened.
When the value is not more than the upper limit, the patterning characteristics tend to be good.
Specific examples of the aromatic ring in the aromatic ring group include a benzene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring, a perylene ring, a tetracene ring, a pyrene ring, a benzpyrene ring, a chrysene ring, a triphenylene ring, an acenaphthene ring, and a fluoranthene ring. Examples include a fluorene ring. Among these, a fluorene ring is preferable from the viewpoint of patterning characteristics.

The divalent hydrocarbon group in the divalent hydrocarbon group having a cyclic hydrocarbon group as a side chain is not particularly limited, but for example, a divalent aliphatic group, a divalent aromatic ring group, 1 or more. Examples thereof include a group in which a divalent aliphatic group of 1 or more and a divalent aromatic ring group of 1 or more are linked.

Examples of the divalent aliphatic group include linear, branched and cyclic groups. Among these, a linear one is preferable from the viewpoint of development solubility, while a cyclic one is preferable from the viewpoint of reducing the penetration of the developer into the exposed portion. The carbon number is usually 1 or more, preferably 3 or more, more preferably 6 or more, preferably 25 or less, more preferably 20 or less, still more preferably 15 or less. When it is set to the above lower limit value or more, a strong film is easily obtained, surface roughness is less likely to occur, and the adhesion to the substrate tends to be good. It is easy to suppress the film loss at the time, and the resolution tends to be improved.

Specific examples of the divalent linear aliphatic group include a methylene group, an ethylene group, an n-propylene group, an n-butylene group, an n-pentylene group, an n-hexylene group, an n-heptylene group and the like. .. Among these, a methylene group is preferable from the viewpoint of skeletal rigidity.
The divalent branched aliphatic group includes the above-mentioned divalent linear aliphatic group, and the side chains include a methyl group, an ethyl group, an n-propyl group, an iso-propyl group, and an n-butyl group. , Iso-butyl group, sec-butyl group, tert-butyl group and the like.
The number of rings contained in the divalent cyclic aliphatic group is not particularly limited, but is usually 1 or more, preferably 2 or more, and usually 10 or less, preferably 5 or less, and even more preferably 3 or less. When it is at least the above lower limit value, the film becomes strong and tends to have good substrate adhesion, and when it is at least the above upper limit value, it is easy to suppress deterioration of sensitivity and film loss during development, and resolution is achieved. The sex tends to improve.
Specific examples of the divalent cyclic aliphatic group include two hydrogen atoms removed from rings such as cyclohexane ring, cycloheptane ring, cyclodecane ring, cyclododecane ring, norbornane ring, isobornane ring, adamantane ring, and cyclododecane ring. The group that was used is mentioned. Among these, from the viewpoint of skeletal rigidity, a group obtained by removing two hydrogen atoms from the adamantane ring is preferable.

Examples of the substituent that the divalent aliphatic group may have include an alkoxy group having 1 to 5 carbon atoms such as a methoxy group and an ethoxy group; a hydroxyl group; a nitro group; a cyano group; and a carboxy group.
Among these, from the viewpoint of easiness of synthesis, it is preferably unsubstituted.

Examples of the divalent aromatic ring group include a divalent aromatic hydrocarbon ring group and a divalent aromatic heterocyclic group. The carbon number is usually 4 or more, preferably 5 or more, more preferably 6 or more, preferably 30 or less, more preferably 20 or less, still more preferably 15 or less. When it is set to the above lower limit value or more, a strong film is easily obtained, surface roughness is less likely to occur, and the adhesion to the substrate tends to be good. It is easy to suppress the film loss at the time, and the resolution tends to be improved.

The aromatic hydrocarbon ring in the divalent aromatic hydrocarbon ring group may be a monocyclic ring or a condensed ring. Examples of the aromatic hydrocarbon ring group include a benzene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring, a perylene ring, a tetracene ring, a pyrene ring, a benzpyrene ring, a chrysene ring, and a triphenylene ring, which have two free valences. Examples include groups such as acenaphthene ring, fluoranthene ring, and fluorene ring.
Further, the aromatic heterocycle in the aromatic heterocyclic group may be a monocyclic ring or a condensed ring. Examples of the aromatic heterocyclic group include a furan ring, a benzofuran ring, a thiophene ring, a benzothiophene ring, a pyrazole ring, a pyrazole ring, an imidazole ring, an oxadiazole ring, an indol ring, and a carbazole ring having two free atomic valences. Ring, pyrroloidazole ring,
Pyrrolopyrazole ring, pyrrolopyrrole ring, thienopyrrole ring, thienothiophene ring, flopyrol ring, flofuran ring, thienoflan ring, benzoisooxazole ring, benzoisothiazole ring, benzimidazole ring, pyridine ring, pyrazine ring, pyridazine ring, pyrimidine ring, Examples thereof include groups such as a triazine ring, a quinoline ring, an isoquinoline ring, a synolin ring, a quinoxaline ring, a phenanthridine ring, a benzimidazole ring, a perimidine ring, a quinazoline ring, a quinazolinone ring, and an azulene ring. Among these, from the viewpoint of patterning characteristics, a benzene ring or a naphthalene ring having two free valences is preferable, and a benzene ring having two free valences is more preferable.

Examples of the substituent that the divalent aromatic ring group may have include a hydroxy group, a methyl group, a methoxy group, an ethyl group, an ethoxy group, a propyl group, a propoxy group and the like. Of these, no substitution is preferable from the viewpoint of development solubility.

Further, as a group in which one or more divalent aliphatic groups and one or more divalent aromatic ring groups are linked,
Examples thereof include a group in which one or more of the above-mentioned divalent aliphatic groups and one or more of the above-mentioned divalent aromatic ring groups are linked.
The number of divalent aliphatic groups is not particularly limited, but is usually 1 or more, preferably 2 or more, usually 10 or less, preferably 5 or less, and more preferably 3 or less. When it is set to the above lower limit value or more, a strong film is easily obtained, surface roughness is less likely to occur, and the adhesion to the substrate tends to be good. It is easy to suppress the film loss at the time, and the resolution tends to be improved.
The number of divalent aromatic ring groups is not particularly limited, but is usually 1 or more, preferably 2 or more.
It is usually 10 or less, preferably 5 or less, and more preferably 3 or less. When it is set to the above lower limit value or more, a strong film is easily obtained, surface roughness is less likely to occur, and the adhesion to the substrate tends to be good. It is easy to suppress the film loss at the time, and the resolution tends to be improved.

Specific examples of a group in which one or more divalent aliphatic groups and one or more divalent aromatic ring groups are linked are represented by the above formulas (b1-IA) to (b1-IF). Examples include the groups to be used. Among these, the group represented by the above formula (b1-IC) is preferable from the viewpoint of skeletal rigidity and film hydrophobization.

The bonding mode of the cyclic hydrocarbon group, which is a side chain, is not particularly limited with respect to these divalent hydrocarbon groups. For example, one hydrogen atom of an aliphatic group or an aromatic ring group is substituted with the side chain. And the mode
An embodiment in which a cyclic hydrocarbon group as a side chain is formed by including one of the carbon atoms of the aliphatic group can be mentioned.

(R ¹⁵ , R ¹⁶ )
In the general formula (b1-II), R ¹⁵ and R ¹⁶ each independently represent a divalent aliphatic group which may have a substituent.

Examples of the divalent aliphatic group include linear, branched and cyclic groups. Among these, a linear one is preferable from the viewpoint of development solubility, while a cyclic one is preferable from the viewpoint of reducing the penetration of the developer into the exposed portion. The carbon number is usually 1 or more, preferably 3 or more, more preferably 6 or more, preferably 20 or less, more preferably 15 or less, still more preferably 10 or less. When it is set to the above lower limit value or more, a strong film is easily obtained, surface roughness is less likely to occur, and the adhesion to the substrate tends to be good. It is easy to suppress the film loss at the time, and the resolution tends to be improved.

Specific examples of the divalent linear aliphatic group include a methylene group, an ethylene group, an n-propylene group, an n-butylene group, an n-pentylene group, an n-hexylene group, an n-heptylene group and the like. .. Among these, a methylene group is preferable from the viewpoint of skeletal rigidity.
The divalent branched aliphatic group includes the above-mentioned divalent linear aliphatic group, and the side chains include a methyl group, an ethyl group, an n-propyl group, an iso-propyl group, and an n-butyl group. , Iso-butyl group, sec-butyl group, tert-butyl group and the like.
The number of rings contained in the divalent cyclic aliphatic group is not particularly limited, but is usually 1 or more, preferably 2 or more, and usually 12 or less, preferably 10 or less. When the value is equal to or higher than the lower limit, the film tends to be strong and the adhesion to the substrate tends to be improved. When the value is equal to or higher than the upper limit, deterioration of sensitivity and film loss during development can be easily suppressed, and resolution The sex tends to improve.
Specific examples of the divalent cyclic aliphatic group include hydrogen atoms from rings such as cyclohexane ring, cycloheptane ring, cyclodecane ring, cyclododecane ring, norbornane ring, isobornane ring, adamantane ring, cyclododecane ring, and dicyclopentadiene. Can be mentioned as a group obtained by dividing two. Among these, from the viewpoint of skeletal rigidity, a group obtained by removing two hydrogen atoms from the dicyclopentadiene ring and the adamantane ring is preferable.

Examples of the substituent that the divalent aliphatic group may have include an alkoxy group having 1 to 5 carbon atoms such as a methoxy group and an ethoxy group; a hydroxyl group; a nitro group; a cyano group; and a carboxy group.
Among these, from the viewpoint of easiness of synthesis, it is preferably unsubstituted.

(M, n)
In the general formula (b1-II), m and n each independently represent an integer of 0 to 2. When it is set to the lower limit value or more, the patterning suitability is improved and surface roughness tends to be less likely to occur, and when it is set to the upper limit value or less, the developability tends to be improved. From the viewpoint of developability, m and n are preferably 0. On the other hand, it is preferable that m and n are 1 or more from the viewpoint of patterning suitability and surface roughness.

Further, the partial structure represented by the general formula (b1-II) is from the viewpoint of adhesion to the substrate.
It is preferable that the partial structure is represented by the following general formula (b1-II-1).

In formula (b1-II-1), R ¹³ , R ¹⁵ , R ¹⁶ , m and n are synonymous with the above formula (b1-II), and R ^α is a monovalent that may have a substituent. Represents the cyclic hydrocarbon group of, p is an integer of 1 or more, and * represents the bond. The benzene ring in the formula (b1-II-1) may be further substituted with any substituent.

(R ^α )
In the general formula (b1-II-1), R ^α represents a monovalent cyclic hydrocarbon group which may have a substituent.
Examples of the cyclic hydrocarbon group include an aliphatic ring group and an aromatic ring group.

The number of rings contained in the aliphatic ring group is not particularly limited, but is usually 1 or more, preferably 2 or more, and usually 6 or less, preferably 4 or less, and more preferably 3 or less. By setting the value to the lower limit or higher, a strong film is likely to be obtained, surface roughness tends to be less likely to occur, and the surface is less likely to be roughened.
When the value is not more than the upper limit, the patterning characteristics tend to be good.
The carbon number of the aliphatic ring group is usually 4 or more, preferably 6 or more, more preferably 8 or more, preferably 40 or less, more preferably 30 or less, further preferably 20 or less, and particularly preferably 15 or less. preferable. When it is set to the lower limit value or more, a strong film tends to be easily obtained and surface roughness tends to be less likely to occur, and when it is set to the upper limit value or less, the patterning property tends to be improved.
Specific examples of the aliphatic ring in the aliphatic ring group include a cyclohexane ring, a cycloheptane ring, and the like.
Cyclodecane ring, cyclododecane ring, norbornane ring, isobornane ring, adamantane ring, cyclododecane ring and the like can be mentioned. Among these, the adamantane ring is preferable from the viewpoint of strong film properties.

On the other hand, the number of rings contained in the aromatic ring group is not particularly limited, but is usually 1 or more, preferably 2 or more, more preferably 3 or more, and usually 10 or less, preferably 5 or less. When it is set to the lower limit value or more, a strong film tends to be easily obtained and surface roughness tends to be less likely to occur, and when it is set to the upper limit value or less, the patterning property tends to be improved.
Examples of the aromatic ring group include an aromatic hydrocarbon ring group and an aromatic heterocyclic group. Further, the number of carbon atoms of the aromatic ring group is usually 4 or more, preferably 5 or more, more preferably 6 or more, and also.
30 or less is preferable, 20 or less is more preferable, and 15 or less is further preferable. When it is set to the lower limit value or more, a strong film tends to be easily obtained and surface roughness tends to be less likely to occur, and when it is set to the upper limit value or less, the patterning property tends to be improved.
Specific examples of the aromatic ring in the aromatic ring group include a benzene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring, a fluorene ring and the like. Among these, the fluorene ring is preferable from the viewpoint of development solubility.

Examples of the substituent that the cyclic hydrocarbon group may have include a methyl group, an ethyl group, an n-propyl group, an iso-propyl group, an n-butyl group, a sec-butyl group, a tert-butyl group and an amyl group. Examples thereof include an alkyl group having 1 to 5 carbon atoms such as an iso-amyl group; an alkoxy group having 1 to 5 carbon atoms such as a methoxy group and an ethoxy group; a hydroxyl group; a nitro group; a cyano group; and a carboxy group. Of these, no substitution is preferable from the viewpoint of ease of synthesis.

Although p represents an integer of 1 or more, 2 or more is preferable, and 3 or less is preferable. When it is at least the above lower limit value, the film curing degree and the residual film ratio tend to be good, and when it is at least the above upper limit value, the developability tends to be good.

Among these, from the viewpoint of strong film hardening degree, R ^α is preferably a monovalent aliphatic ring group, and more preferably an adamantyl group.

As described above, the benzene ring in the formula (b1-II-1) may be further substituted with an arbitrary substituent. Examples of the substituent include a hydroxy group, a methyl group, a methoxy group, and the like.
Ethyl group, ethoxy group, propyl group, propoxy group and the like can be mentioned. The number of substituents is not particularly limited, and may be one or two or more.
Among these, it is preferable that it is not substituted from the viewpoint of patterning characteristics.

Specific examples of the partial structure represented by the above formula (b1-II-1) will be given below.

Further, the partial structure represented by the general formula (b1-II) is a partial structure represented by the following general formula (b1-II-2) from the viewpoint of skeletal rigidity and membrane hydrophobicity. Is preferable.

In formula (b1-II-2), R ¹³ , R ¹⁵ , R ¹⁶ , m and n are synonymous with the above formula (b1-II), and R ^β is a divalent group which may have a substituent. Represents the cyclic hydrocarbon group of, and * represents the bond. The benzene ring in the formula (b1-II-2) may be further substituted with an arbitrary substituent.

(R ^β )
In the formula (b1-II-2), R ^β represents a divalent cyclic hydrocarbon group which may have a substituent.
Examples of the cyclic hydrocarbon group include an aliphatic ring group and an aromatic ring group.

The number of rings contained in the aliphatic ring group is not particularly limited, but is usually 1 or more, preferably 2 or more, and usually 10 or less, preferably 5 or less. When it is set to the upper limit value or more, a strong film tends to be easily obtained and surface roughness tends to be less likely to occur, and when it is set to the upper limit value or less, deterioration of sensitivity and film loss during development can be easily suppressed. The resolution tends to improve.
The carbon number of the aliphatic ring group is usually 4 or more, preferably 6 or more, more preferably 8 or more, preferably 40 or less, more preferably 35 or less, still more preferably 30 or less. When it is set to the lower limit value or more, there is a tendency to suppress film roughness during development, and when it is set to the upper limit value or less, it is easy to suppress deterioration of sensitivity and film loss during development, and resolution is improved. Tend.
Specific examples of the aliphatic ring in the aliphatic ring group include a cyclohexane ring, a cycloheptane ring, a cyclodecane ring, a cyclododecane ring, a norbornane ring, an isobornane ring, an adamantane ring, a cyclododecane ring and the like. Among these, the adamantane ring is preferable from the viewpoint of film reduction during development and resolution.

On the other hand, the number of rings contained in the aromatic ring group is not particularly limited, but is usually 1 or more, preferably 2 or more, more preferably 3 or more, and usually 10 or less, preferably 5 or less. When it is set to the upper limit value or more, a strong film is likely to be obtained and surface roughness tends to be less likely to occur, and when it is set to the upper limit value or less, deterioration of sensitivity and film loss are easily suppressed, and resolution is achieved. Tends to improve.
Examples of the aromatic ring group include an aromatic hydrocarbon ring group and an aromatic heterocyclic group. The carbon number of the aromatic ring group is usually 4 or more, preferably 6 or more, more preferably 8 or more, further preferably 10 or more, still preferably 40 or less, more preferably 30 or less, and further preferably 20 or less. It is preferable, and 15 or less is particularly preferable. When it is set to the upper limit value or more, a strong film is likely to be obtained and surface roughness tends to be less likely to occur, and when it is set to the upper limit value or less, deterioration of sensitivity and film loss are easily suppressed, and resolution is achieved. Tends to improve.
Specific examples of the aromatic ring in the aromatic ring group include a benzene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring, a fluorene ring and the like. Among these, the fluorene ring is preferable from the viewpoint of developability.

Examples of the substituent that the cyclic hydrocarbon group may have include a methyl group, an ethyl group, an n-propyl group, an iso-propyl group, an n-butyl group, a sec-butyl group, a tert-butyl group and an amyl group. Examples thereof include an alkyl group having 1 to 5 carbon atoms such as an iso-amyl group; an alkoxy group having 1 to 5 carbon atoms such as a methoxy group and an ethoxy group; a hydroxyl group; a nitro group; a cyano group; and a carboxy group. Of these, no substitution is preferable from the viewpoint of simplicity of synthesis.

Among these, from the viewpoint of suppressing membrane loss and resolvability, R ^β is preferably a divalent aliphatic ring group, and more preferably a divalent adamantane ring group.
On the other hand, from the viewpoint of patterning characteristics, R ^β is preferably a divalent aromatic ring group, and more preferably a divalent fluorene ring group.

As described above, the benzene ring in the formula (b1-II-2) may be further substituted with an arbitrary substituent. Examples of the substituent include a hydroxy group, a methyl group, a methoxy group, and the like.
Ethyl group, ethoxy group, propyl group, propoxy group and the like can be mentioned. The number of substituents is not particularly limited, and may be one or two or more.
Further, two benzene rings may be linked via a substituent. Examples of the substituent in this case include divalent groups such as -O-, -S-, -NH-, and -CH _2-.
Among these, it is preferable that it is not substituted from the viewpoint of patterning characteristics. Further, from the viewpoint of making it difficult for film loss and the like to occur, methyl group substitution is preferable.

Specific examples of the partial structure represented by the above formula (b1-II-2) will be given below. Note that * in the example indicates a bond.

On the other hand, the partial structure represented by the formula (b1-II) is preferably a partial structure represented by the following formula (b1-II-3) from the viewpoint of the coating film residual film ratio and the patterning characteristics. ..

In the formula (b1-II-3), R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ , m and n are the above formula (b1-II).
Synonymous with, R ^Z represents a hydrogen atom or a polybasic acid residue.

The polybasic acid residue means a monovalent group obtained by subtracting one OH group from the polybasic acid or its anhydride. ^{In addition, another OH group may be removed and shared with R Z} in another molecule represented by the formula (b1-II-3), that is, a plurality of formulas (b1 ^{) may be shared via R Z.} -II-3)
May be connected.
Polybasic acids include maleic acid, succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, pyromellitic acid, trimellitic acid, benzophenone tetracarboxylic acid, methylhexahydrophthalic acid, endomethylenetetrahydrophthalic acid. One or more selected from acid, chlorendic acid, methyltetrahydrophthalic acid and biphenyltetracarboxylic acid can be mentioned.
Among these, from the viewpoint of patterning properties, maleic acid, succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, pyromellitic acid,
Trimellitic acid and biphenyltetracarboxylic acid, more preferably tetrahydrophthalic acid and biphenyltetracarboxylic acid.

(B1-II) The above formula (b1) contained in one molecule of an epoxy (meth) acrylate resin.
The partial structure represented by 1-II-3) may be one kind or two or more kinds. For example, even if R ^Z is a hydrogen atom and R ^Z is a polybasic acid residue. good.

The number of partial structures represented by the formula (b1-II) contained in one molecule of the (b1-II) epoxy (meth) acrylate resin is not particularly limited, but 1 or more is preferable, and 3
The above is more preferable, 20 or less is preferable, 15 or less is more preferable, and 10 or less is further preferable. When it is set to the upper limit value or more, a strong film is likely to be obtained and surface roughness tends to be less likely to occur, and when it is set to the upper limit value or less, deterioration of sensitivity and film loss are easily suppressed, and resolution is achieved. Tends to improve.

The polystyrene-equivalent weight average molecular weight (Mw) of the (b1-II) epoxy (meth) acrylate resin measured by gel permeation chromatography (GPC) is not particularly limited, but is preferably 1000 or more, more preferably 2000 or more. , Also 3000
0 or less is preferable, 20000 or less is more preferable, and 10000 or less is further preferable.
More preferably 7,000 or less, and particularly preferably 5,000 or less. When it is at least the lower limit value, the patterning characteristics tend to be good, and when it is at least the upper limit value, a strong film is likely to be obtained and surface roughness tends to be less likely to occur.

The acid value of the (b1-II) epoxy (meth) acrylate resin is not particularly limited, but 1
0 mgKOH / g or more is preferable, 20 mgKOH / g or more is more preferable, and 40 mgK
OH / g or more is more preferable, 60 mgKOH / g or more is even more preferable, 80 m.
GKOH / g or more is particularly preferable, 100 mgKOH / g or more is most preferable, and 2
00 mgKOH / g or less is preferable, 150 mgKOH / g or less is more preferable, 120
It is more preferably gKOH / g or less. When it is at least the above lower limit value, a strong film tends to be easily obtained, and when it is at least the above upper limit value, the development solubility is improved and the resolution tends to be good.

Even if one type of carboxy group-containing epoxy (meth) acrylate resin is used alone, 2
You may use a mixture of more than one kind of resin.
Further, a part of the above-mentioned carboxy group-containing epoxy (meth) acrylate resin may be replaced with another binder resin. That is, a carboxy group-containing epoxy (meth) acrylate resin may be used in combination with another binder resin. In this case, (b) the ratio of the carboxy group-containing epoxy (meth) acrylate-based resin in the alkali-soluble resin is preferably 50% by mass or more, more preferably 60% by mass or more, and 7
It is more preferably 0% by mass or more, and particularly preferably 80% by mass or more.
It is usually 100% by mass or less.

Further, (b) as an alkali-soluble resin, (b) from the viewpoint of compatibility with pigments, dispersants and the like.
2) It is preferable to use an acrylic copolymer resin, and those described in JP-A-2014-137466 can be preferably used.

Examples of the acrylic copolymer resin include an ethylenically unsaturated monomer having one or more carboxy groups (hereinafter referred to as “unsaturated monomer (b2-1)”) and other copolymerizable ethylene. Examples thereof include a copolymer with a sex-unsaturated monomer (hereinafter referred to as "unsaturated monomer (b2-2)").
Examples of the unsaturated monomer (b2-1) include (meth) acrylic acid, crotonic acid, and α-.
Unsaturated monocarboxylic acids such as chloroacrylic acid and cinnamic acid; maleic acid, maleic anhydride, etc.
Unsaturated dicarboxylic acids such as fumaric acid, citraconic acid, citraconic anhydride, mesaconic acid or their anhydrides; monosuccinic acid [2- (meth) acryloyloxyethyl], mono phthalate [2-
Mono [(meth) acryloyloxyalkyl] ester of divalent or higher valent carboxylic acid such as (meth) acryloyloxyethyl]; carboxy group and hydroxyl group at both ends of ω-carboxypolycaprolactone mono (meth) acrylate etc. Mono (meth) acrylate of a polymer having and; p-vinylbenzoic acid and the like can be mentioned.
These unsaturated monomers (b2-1) can be used alone or in admixture of two or more.

Further, as the unsaturated monomer (b2-2), for example, N-substituted maleimide such as N-phenylmaleimide and N-cyclohexylmaleimide;
Aromatic vinyl compounds such as styrene, α-methylstyrene, p-hydroxystyrene, p-hydroxy-α-methylstyrene, p-vinylbenzylglycidyl ether, and acenaphthylene;

Methyl (meth) acrylate, n-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, allyl (meth) acrylate, benzyl (meth) acrylate, polyethylene glucol (degree of polymerization 2) -10
) Methyl ether (meth) acrylate, polypropylene glucol (degree of polymerization 2-10)
Methyl ether (meth) acrylate, polyethylene glycol (degree of polymerization 2-10) mono (meth) acrylate, polypropylene glycol (degree of polymerization 2-10) 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,
3-[(Meta) acryloyloxymethyl] -3-ethyl (meth) acrylic acid ester such as oxetane;

Cyclohexyl vinyl ether, isobornyl vinyl ether, tricyclo [5.2.
1.0 ^2,6 ] Vinyl ethers such as decane-8-yl vinyl ether, pentacyclopentadecanyl vinyl ether, 3- (vinyloxymethyl) -3-ethyloxetane;
Examples thereof include macromonomers having a mono (meth) acryloyl group at the end of polymer molecular chains such as polystyrene, polymethyl (meth) acrylate, poly-n-butyl (meth) acrylate, and polysiloxane.
These unsaturated monomers (b2-2) can be used alone or in admixture of two or more.

In the copolymer of the unsaturated monomer (b2-1) and the unsaturated monomer (b2-2), the copolymerization ratio of the unsaturated monomer (b2-1) in the copolymer is preferable. Is 5 to 50% by mass, more preferably 10 to 40% by mass. By copolymerizing the unsaturated monomer (b2-1) in such a range, it tends to be possible to obtain a photosensitive coloring composition having excellent alkali developability and storage stability.

As a specific example of the copolymer of the unsaturated monomer (b2-1) and the unsaturated monomer (b2-2),
For example, Japanese Patent Application Laid-Open No. 7-140654, Japanese Patent Application Laid-Open No. 8-259876, Japanese Patent Application Laid-Open No. 10-
31308, 10-300922, 11-174224, 11-258415, 2000-56118, 2004-
Examples thereof include copolymers disclosed in Japanese Patent Application Laid-Open No. 101728.
A copolymer of an unsaturated monomer (b2-1) and an unsaturated monomer (b2-2) can be produced by a known method. For example, JP-A-2003-222717, JP-A-2003-222717 2006
The structure, Mw, and Mw / Mn can also be controlled by the methods disclosed in Japanese Patent Application Laid-Open No. 259680, International Publication No. 2007/029871 and the like.

In addition, International Publication No. 2016/194619, International Publication No. 2017/1544
The resin described in Japanese Patent Application Laid-Open No. 39 may be used.

<(C) Photopolymerization initiator>
(C) The photopolymerization initiator is a component having a function of directly absorbing light, causing a decomposition reaction or a hydrogen abstraction reaction, and generating a polymerization active radical. If necessary, an additive such as a polymerization accelerator (chain transfer agent) or a sensitizing dye may be added and used.
Examples of the photopolymerization initiator include JP-A-59-152396 and JP-A-61-15.
A metallocene compound containing the titanocene compound described in Japanese Patent Application Laid-Open No. 1197;
Hexaaryl imidazole derivatives described in Japanese Patent Application Laid-Open No. 118; JP-A-10-39503
Halomethylated oxadiazole derivatives and halomethyl-s-triazine derivatives described in JP-A; α-aminoalkylphenone derivatives; JP-A-2000-80068, JP-A-2
Examples thereof include oxime ester compounds described in Japanese Patent Application Laid-Open No. 006-36750.

Specifically, for example, examples of the metallocene compound include dicyclopentadienyl titanium dichloride, dicyclopentadienyl titanium bisphenyl, and dicyclopentadienyl titanium bis (2,3,4,5,6-pentafluoropheni). -1-yl), dicyclopentadienyl titanium bis (2,3,5,6-tetrafluoropheni-1-yl), dicyclopentadienyl titanium bis (2,4,6-trifluoropheni-1) -Il),
Dicyclopentadienyl Titanium Di (2,6-difluoropheni-1-yl), Dicyclopentadienyl Titanium Di (2,4-difluoropheni-1-yl), Di (Methylcyclopentadienyl) Titanium Bis (2,3,4,5,6-Pentafluoropheni-1
-Il), di (methylcyclopentadienyl) titanium bis (2,6-difluorophenyl-1-yl), dicyclopentadienyl titanium [2,6-di-fluoro-3- (pyro-1-yl) ) -Pheni-1-yl] and the like.

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

In addition, as halomethylated oxadiazole derivatives, 2-trichloromethyl-5-
(2'-benzofuryl) -1,3,4-oxadiazole, 2-trichloromethyl-5-
[Β- (2'-benzofuryl) vinyl] -1,3,4-oxadiazole, 2-trichloromethyl-5-[β- (2'-(6''-benzofuryl) vinyl)]-1,3 , 4-Oxadiazole, 2-trichloromethyl-5-furyl-1,3,4-oxadiazole and the like.

The 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)
Examples thereof include -4,6-bis (trichloromethyl) -s-triazine and 2- (4-ethoxycarbonylnaphthyl) -4,6-bis (trichloromethyl) -s-triazine.

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

As the photopolymerization initiator, an oxime ester compound is particularly effective in terms of sensitivity and plate-making property, and when an alkali-soluble resin containing a phenolic hydroxyl group is used, an oxime ester compound having such excellent sensitivity is particularly effective. Compounds are useful. Oxime ester compounds are
Since the structure has a structure that absorbs ultraviolet rays, a structure that transmits light energy, and a structure that generates radicals, it is highly sensitive with a small amount and stable against thermal reactions.
It is possible to obtain a highly sensitive photosensitive coloring composition in a small amount.

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

In the above formula (IV), R ^21a represents a hydrogen atom, an alkyl group which may have a substituent, or an aromatic ring group which may have a substituent.
R ^21b represents any substituent containing an aromatic ring.
R ^22a represents an alkanoyl group which may have a substituent or an allyloyl group which may have a substituent.
n represents an integer of 0 or 1.

The ^{number of carbon atoms of the alkyl group in R 21a} is not particularly limited, but from the viewpoint of solubility in a solvent and sensitivity, it is usually 1 or more, preferably 2 or more, and usually 20 or less, preferably 15 or less, more preferably 10 or less. Is. Specific examples of the alkyl group include a methyl group, an ethyl group, a propyl group, a cyclopentylethyl group and the like.
Substituents that the alkyl group may have include aromatic ring groups, hydroxyl groups, carboxy groups, and the like.
Halogen atom, amino group, amide group, 4- (2-methoxy-1-methyl) ethoxy-2-
Examples thereof include a methylphenyl group and an N-acetyl-N-acetoxyamino group, which are preferably unsubstituted from the viewpoint of easiness of synthesis.

Examples of the aromatic ring group in R ^21a include an aromatic hydrocarbon ring group and an aromatic heterocyclic group. The number of carbon atoms of the aromatic ring group is not particularly limited, but is preferably 5 or more from the viewpoint of solubility in the photosensitive coloring composition. Further, from the viewpoint of developability, it is preferably 30 or less, more preferably 20 or less, and further preferably 12 or less.

Specific examples of the aromatic ring group include a phenyl group, a naphthyl group, a pyridyl group, a frill group and the like. Among these, a phenyl group or a naphthyl group is preferable, and a phenyl group is more preferable, from the viewpoint of developability.
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, a group in which these substituents are linked, and the like, and the group is developed. From the viewpoint of properties, an alkyl group, an alkoxy group, and a group in which these are linked are preferable, and a linked alkoxy group is more preferable.
Among these, from the viewpoint of developability, R ^21a is preferably an aromatic ring group which may have a substituent, and further preferably an aromatic ring group having a linked alkoxy group as a substituent. preferable.

In addition, ^{examples of R 21b} include a optionally substituted carbazolyl group, an optionally substituted thioxanthonyl group, and an optionally substituted diphenylsulfide group. Among these, a carbazolyl group which may be substituted is preferable from the viewpoint of sensitivity. On the other hand, from the viewpoint of electrical reliability, a diphenyl sulfide group which may be substituted is preferable.

The carbon number of the alkanoyl group in R ^22a is not particularly limited, but is usually 2 or more, preferably 3 or more, and usually 20 or less, preferably 1 from the viewpoint of solubility in a solvent and sensitivity.
It is 5 or less, more preferably 10 or less, still more preferably 5 or less.
Specific examples of the alkanoyl group include an acetyl group, a propanoyl group, a butanoyl group and the like.
Examples of the substituent that the alkanoyl group may have include an aromatic ring group, a hydroxyl group, a carboxy group, a halogen atom, an amino group, an amide group and the like, and from the viewpoint of easiness of synthesis, the substituent should be unsubstituted. Is preferable.

The ^{number of carbon atoms of the allylloyl group in R 22a} is not particularly limited, but from the viewpoint of solubility in a solvent and sensitivity, it is usually 7 or more, preferably 8 or more, and usually 20 or less, preferably 1.
It is 5 or less, more preferably 10 or less. Specific examples of the allylloyl group include a benzoyl group and a naphthoyl group.
Examples of the substituent that the allylloyl group may have include a hydroxyl group, a carboxy group, a halogen atom, an amino group, an amide group, an alkyl group and the like, and from the viewpoint of easiness of synthesis, it is preferably unsubstituted. ..
Among these, from the viewpoint of sensitivity, R ^22a is preferably an alkanoyl group which may have a substituent, more preferably an unsubstituted alkanoyl group, and further preferably an acetyl group.

Further, the initiator described in JP-A-2016-133574 is also preferably used from the viewpoint of reducing the contamination of the liquid crystal layer by the colorant.

As the photopolymerization initiator, one type may be used alone, or two or more types may be used in combination.
If necessary, the photopolymerization initiator may be blended with a sensitizing dye and a polymerization accelerator according to the wavelength of the image exposure light source for the purpose of increasing the sensitivity. As a sensitizing dye, Japanese Patent Application Laid-Open No. 4-2
Xanthene dyes described in JP-A-21958 and JP-A-4-219756, JP-A-3-
A coumarin dye having a heterocycle described in JP-A-239703 and JP-A-5-289335, a 3-ketocoumarin compound described in JP-A-3-239703 and JP-A-5-289335, JP-A-6-19240. Pyrromethene dyes described in Japanese Patent Application Laid-Open No. 4
7-2528, 54-155292, 45-373777, 48-84183, 52-12681, 58-15
503, 60-88805, 59-56403, 2-69, 57-16888, 5-107761, 5 Examples thereof include dyes having a dialkylaminobenzene skeleton described in JP-A-210240 and JP-A-4-288818.

Among these sensitizing dyes, preferable ones are amino group-containing sensitizing dyes, and more preferable ones are compounds having an amino group and a phenyl group in the same molecule. Particularly preferred are, for example, 4,4'-dimethylaminobenzophenone, 4,4'-diethylaminobenzophenone, 2-aminobenzophenone, 4-aminobenzophenone, 4,4'-diaminobenzophenone, 3,3'-diaminobenzophenone. , 3,4-Diaminobenzophenone and other benzophenone compounds; 2- (p-dimethylaminophenyl) benzoxazole, 2- (p-diethylaminophenyl) benzoxazole, 2- (p-dimethylaminophenyl) benzo [4,5 ] Benzophenone, 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-diethylamino) P such as (phenyl) quinoline, (p-dimethylaminophenyl) pyrimidine, (p-diethylaminophenyl) pyrimidine, etc.
-Dialkylaminophenyl group-containing compound and the like. The most preferable of these is 4,
It is a 4'-dialkylaminobenzophenone.
As the sensitizing dye, one type may be used alone, or two or more types may be used in combination.

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

<(D) Ethylene unsaturated compound>
The photosensitive coloring composition of the present invention contains (d) an ethylenically unsaturated compound. (D) Sensitivity is improved by containing an ethylenically unsaturated compound.
The ethylenically unsaturated compound used in the present invention is a compound having at least one ethylenically unsaturated group in the molecule. Specifically, for example, (meth) acrylic acid, (meth) acrylic acid alkyl ester, acrylonitrile, styrene, carboxylic acid having one ethylenically unsaturated bond, monoester of polyvalent or monovalent alcohol, etc. Can be mentioned.

In the present invention, it is particularly desirable to use a polyfunctional ethylenic monomer having two or more ethylenically unsaturated groups in one molecule. The number of ethylenically unsaturated groups contained in 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 5 or more. The number is 8 or less, more preferably 7 or less. When it is set to the lower limit value or more, the sensitivity tends to be high, and when it is set to the upper limit value or less, the solubility in a solvent tends to be improved.
Examples of polyfunctional ethylenic monomers include, for example, esters of aliphatic polyhydroxy compounds and unsaturated carboxylic acids; esters of aromatic polyhydroxy compounds and unsaturated carboxylic acids;
Examples thereof include an ester obtained by an esterification reaction of a polyvalent hydroxy compound such as an aliphatic polyhydroxy compound and an aromatic polyhydroxy compound with an unsaturated carboxylic acid and a polybasic carboxylic acid.

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

Examples of the ester of the aromatic polyhydroxy compound and the unsaturated carboxylic acid include an acrylic acid ester and a methacrylic acid ester of an aromatic polyhydroxy compound such as hydroquinone diacrylate, hydroquinone dimethacrylate, resorcindiacrylate, resorcindimethacrylate, and pyrogallol triacrylate. And so on.

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

In addition, as an example of the polyfunctional ethylenic monomer used in the present invention, a polyisocyanate compound and a hydroxyl group-containing (meth) acrylic acid ester or a polyisocyanate compound and a polyol and a hydroxyl group-containing (meth) acrylic acid ester are reacted. Urethane (meth) acrylates as obtained; polyvalent epoxy compounds and hydroxy (meth) acrylates or (
Meta) Epoxy acrylates such as an addition reaction product with acrylic acid; acrylamides such as ethylene bisacrylamide; allyl esters such as diallyl phthalate; vinyl group-containing compounds such as divinyl phthalate are useful.

Examples of the urethane (meth) acrylates include DPHA-40H and UX-5.
000, UX-5002D-P20, UX-5003D, UX-5005 (manufactured by Nippon Kayaku Co., Ltd.), U-2PPA, U-6LPA, U-10PA, U-33H, UA-53H, UA-3
2P, UA-1100H (manufactured by Shin Nakamura Chemical Industry Co., Ltd.), UA-306H, UA-510H, U
F-8001G (manufactured by Kyoeisha Chemical Co., Ltd.), UV-1700B, UV-7600B, UV-76
05B, UV-7630B, UV7640B (manufactured by Nippon Synthetic Chemical Industry Co., Ltd.) and the like can be mentioned.

Among these, from the viewpoint of curability, it is preferable to use (meth) acrylic acid alkyl ester as the (d) ethylenically unsaturated compound, and it is more preferable to use dipentaerythritol hexaacrylate.
One of these may be used alone, or two or more thereof may be used in combination.

<(E) Solvent>
The photosensitive coloring composition of the present invention contains (e) a solvent. (E) By containing the solvent, the pigment can be dispersed in the solvent, and the coating becomes easy.
The photosensitive coloring composition of the present invention usually contains (a) a colorant, (b) an alkali-soluble resin, and (c).
) Photopolymerization initiator, (d) ethylenically unsaturated compound, (f) dispersant, and various other materials used as needed are used in a state of being dissolved or dispersed in a solvent. Among the solvents
An organic solvent is preferable from the viewpoint of dispersibility and coatability.

Among the organic solvents, those having a boiling point in the range of 100 to 300 ° C. are preferably selected, and those having a boiling point in the range of 120 to 280 ° C. are more preferably selected from the viewpoint of coatability. The boiling point referred to here means the boiling point at a pressure of 1013.25 hPa, and the following boiling points are all the same.

Examples of such an organic solvent include the following.
Ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-n-butyl ether, propylene glycol-t-butyl ether, diethylene glycol monomethyl Ether, diethylene glycol monoethyl ether, diethylene glycol mono-n-butyl ether, methoxymethylpentanol, dipropylene glycol monoethyl ether, dipropylene glycol monomethyl ether, 3-methoxybutanol, 3-methyl-3-methoxybutanol, triethylene glycol monomethyl Glycol monoalkyl ethers such as ethers, triethylene glycol monoethyl ethers, tripropylene glycol methyl ethers;
Glycoldialkyl ethers such as ethylene glycol dimethyl ether, ethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, dipropylene glycol dimethyl ether;

Ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol mono-n-butyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, propylene glycol monobutyl ether acetate, methoxybutyl Acetate, 3-methoxybutyl acetate, methoxypentyl acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol mono-n-butyl ether acetate, dipropylene glycol monomethyl ether acetate, triethylene glycol monomethyl ether acetate, triethylene glycol monoethyl Glycolalkyl ether acetates such as ether acetate, 3-methyl-3-methoxybutyl acetate;
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;

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

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

Examples of commercially available organic solvents corresponding to the above include Mineral Spirit, Balsol # 2, Apco # 18 Solvent, Apco Thinner, and Socal Solvent No. 1 and No. 2. Solvento # 150, Shell TS28 Solvent, Carbitol, Ethyl Carbitol, Butyl Carbitol, Methyl Cellosolve (“Cerosolve” is a registered trademark; the same shall apply hereinafter), Ethyl Cellosolve, Ethyl Cellosolve Acetate, Methyl Cellosolve Acetate, Diglime (
Both are product names) and the like.
These organic solvents may be used alone or in combination of two or more.

When forming a colored spacer by a photolithography method, it is preferable to select an organic solvent having a boiling point in the range of 100 to 200 ° C. More preferably 120-170
It has a boiling point of ° C.

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

In addition, an organic solvent having a boiling point of 150 ° C. or higher (hereinafter, may be referred to as a "high boiling point solvent").
It is also preferable to use in combination. By using such a high boiling point solvent in combination, the photosensitive coloring composition becomes difficult to dry, but there is an effect of preventing the uniformly dispersed state of the pigment in the composition from being destroyed by rapid drying. That is, for example, at the tip of the slit nozzle.
It has the effect of preventing the occurrence of foreign matter defects due to the precipitation and solidification of colorants 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 preferable because of their high effects.

When a high boiling point solvent is used in combination, the content ratio of the high boiling point solvent in the organic solvent is preferably 3% by mass to 50% by mass, more preferably 5% by mass to 40% by mass, and particularly preferably 5% by mass to 30% by mass. preferable. By setting it to the above lower limit value or more, for example, it tends to be possible to suppress the precipitation and solidification of the coloring material and the like at the tip of the slit nozzle to cause foreign matter defects, and by setting it to the above upper limit value or less, the drying temperature of the composition. There is a tendency to suppress the slowdown of the temperature, and to suppress problems such as poor tact in the vacuum drying process and pin marks of prebake.

The high boiling point solvent having a boiling point of 150 ° C. or higher may be glycol alkyl ether acetates or glycol alkyl ethers. In this case, the boiling point is 1.
It is not necessary to separately contain a high boiling point solvent of 50 ° C. or higher.
As a preferable high boiling solvent, for example, among the various solvents described above, diethylene glycol mono-n-butyl ether acetate, diethylene glycol monoethyl ether acetate, dipropylene glycol methyl ether acetate, 1,3-butylene glycol diacetate, 1,6-hexanoldi Examples include acetate and triacetin.

<(F) Dispersant>
The photosensitive coloring composition of the present invention contains (f) a dispersant. By containing (f) a dispersant, (a) the colorant can be stably dispersed.
The dispersant (f) in the photosensitive coloring composition of the present invention may be referred to as a dispersant (f1) having a repeating unit represented by the following general formula (1) (hereinafter, referred to as “dispersant (f1)”). ) Is contained.

(In the formula (1), R ¹ and R ² are each independently an alkyl group which may have a substituent or an aryl group which may have a substituent, and R ¹ and R ² are They may be combined with each other to form an annular structure.
R ³ is an alkylene group.
R ⁴ is a polycyclic aromatic hydrocarbon group which may have a substituent.
R ⁵ is a hydrogen atom or a methyl group.
X is a divalent linking group.
Y is a halogen atom. )

The dispersant (f1) is a dispersant having an ammonium group having a polycyclic aromatic hydrocarbon group and a counter anion of a halogen ion. A dispersant having an ammonium group may be released by breaking some of the bonds constituting the ammonium group when irradiated with ultraviolet rays, but the dispersant (f)
Since the polycyclic aromatic hydrocarbon group in 1) is UV-absorbent, it is presumed that the bond is not easily broken and released even when irradiated with ultraviolet rays, and the voltage retention rate after irradiation with ultraviolet rays is not easily affected.

On the other hand, as described later, a solvent (N-methylpyrrolidone, NMP) is used when forming the alignment film.
) May be used, but the dispersant (f1) has chemical resistance to the solvent (NMP resistance).
Tends to be good. It is presumed that the chemical resistance is improved because the dispersant has a highly hydrophobic and low-polarity functional group such as a polycyclic aromatic hydrocarbon group, which reduces the solubility of the dispersant in NMP.

(R ¹ and R ² )
In the above formula (1), R ¹ and R ² are each independently an alkyl group which may have a substituent or an aryl group which may have a substituent.
Examples ^{of the alkyl group in R 1} and R ² include a linear, branched or cyclic alkyl group, and the linear group is preferable from the viewpoint of voltage retention after ultraviolet irradiation and NMP resistance.
The number of carbon atoms of the alkyl group is not particularly limited, but is preferably 10 or less, more preferably 6 or less, further preferably 2 or less, and usually 1 or more. By setting the value to the upper limit or less, the stability of the dispersion liquid with time tends to be improved.
Specific examples of the alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group and the like. From the viewpoint of stability of the dispersion with time, a methyl group and an ethyl group are preferable, and a methyl group is preferable. Is more preferable.
The substituents that the alkyl group may have include an alkoxy group such as a methoxy group and an ethoxy group; a halogen atom such as a fluorine atom, a chlorine atom and a bromine atom; an aralkyl group such as a benzyl group and a phenethyl group; a phenyl group, Examples thereof include an aryl group such as a naphthyl group, which is preferably unsubstituted from the viewpoint of dispersibility.

Examples of the aryl group in R ¹ and R ² include a monovalent aromatic hydrocarbon ring group and a monovalent aromatic heterocyclic group.
The number of carbon atoms of the aryl group is not particularly limited, but is preferably 24 or less, more preferably 18 or less, further preferably 12 or less, and usually 6 or more. The dispersibility tends to be improved by setting the value to the upper limit or less.
Specific examples of the aryl group include a phenyl group, a naphthyl group, an anthracenyl group and the like. From the viewpoint of dispersibility, a phenyl group and a naphthyl group are preferable, and a phenyl group is more preferable.
Substituents that the aryl group may have include an alkyl group such as a methyl group and an ethyl group; an alkoxy group such as a methoxy group and an ethoxy group; a halogen atom such as a fluorine atom, a chlorine atom and a bromine atom; a benzyl group, Examples thereof include an aralkyl group such as a phenethyl group, which is preferably unsubstituted from the viewpoint of dispersibility.

In the above formula (1), R ¹ and R ² may be bonded to each other to form a cyclic structure, and the cyclic structure includes, for example, a 5- to 7-membered nitrogen-containing heterocyclic monocycle or 2 thereof. Examples thereof include a fused ring formed by individual condensation. The nitrogen-containing heterocycle is preferably one having no aromaticity, and more preferably a saturated ring. Specifically, the following can be mentioned.

(These cyclic structures may further have a substituent. * Indicates a bond.)

Among these, from the viewpoint of voltage retention after ultraviolet irradiation and NMP resistance, R ¹ and R ² are preferably alkyl groups which may have substituents independently, and are unsubstituted alkyl groups. Is more preferable, a methyl group or an ethyl group is further preferable, and a methyl group is particularly preferable.

(R ³ )
In the formula (1), R ³ is an alkylene group.
Examples of the alkylene group include a linear, branched or cyclic alkyl group, and the linear group is preferable from the viewpoint of easiness of synthesis.
The number of carbon atoms of the alkylene group is not particularly limited, but is preferably 10 or less, more preferably 6 or less, further preferably 2 or less, and usually 1 or more. When it is set to the upper limit or less, the synthesis tends to be easy.
Specific examples of the alkylene group include a methylene group, an ethylene group, a propylene group, a butylene group, a pentylene group, a hexylene group and the like. From the viewpoint of easiness of synthesis, a methylene group and an ethylene group are preferable, and a methylene group is more preferable. ..

(R ⁴ )
In the formula (1), R ⁴ is a polycyclic aromatic hydrocarbon group which may have a substituent.
The polycyclic aromatic hydrocarbon group is a group in which aromatic hydrocarbon rings are condensed, and the number of rings of the polycyclic aromatic hydrocarbon group is not particularly limited as long as it is 2 or more, preferably 5 or less, and 4 or less. The following is more preferable, and 3 or less is further preferable. When it is set to the lower limit value or more, the NMP resistance and the voltage retention rate after ultraviolet irradiation tend to be good, and when it is set to the upper limit value or less, the dispersibility tends to be good.

Further, the number of aromatic rings contained in the polycyclic aromatic hydrocarbon group is not particularly limited, and is not particularly limited as long as it is usually 2 or more, preferably 5 or less, more preferably 4 or less, still more preferably 3 or less. When it is set to the lower limit value or more, the NMP resistance and the voltage holding rate after ultraviolet irradiation tend to be good, and when it is set to the upper limit value or less, the dispersibility tends to be good.

When the polycyclic aromatic hydrocarbon group has a benzene ring, the number of benzene rings is not particularly limited, and is usually 1 or more, 2 or more, preferably 5 or less, more preferably 4 or less, and 3 or less. Is even more preferable. When it is set to the lower limit value or more, the NMP resistance and the voltage holding rate after ultraviolet irradiation tend to be good, and when it is set to the upper limit value or less, the dispersibility tends to be good.

The number of carbon atoms of the polycyclic aromatic hydrocarbon group is also not particularly limited, but 7 or more is preferable, 8 or more is more preferable, 9 or more is further preferable, 18 or less is more preferable, 16 or less is more preferable, and 14 or less is further preferable. It is preferable, and 12 or less is particularly preferable. When it is set to the lower limit value or more, the NMP resistance and the voltage holding rate after ultraviolet irradiation tend to be good, and when it is set to the upper limit value or less, the dispersibility tends to be good.

Specific examples of the polycyclic aromatic hydrocarbon group include an azulenyl group, a naphthyl group, an anthrasenyl group, a phenanthrenyl group, a fluorenyl group, a tetrasenyl group, a chrysenyl group, a benzfluorenyl group, and the like, from the viewpoint of NMP resistance. , Naphtyl group, anthracenyl group,
Is preferable, and a naphthyl group is more preferable.

Substituents that the polycyclic aromatic hydrocarbon group may have include an alkyl group such as a methyl group and an ethyl group; an alkoxy group such as a methoxy group and an ethoxy group; and a halogen such as a fluorine atom, a chlorine atom and a bromine atom. Atomic: An aralkyl group such as a benzyl group or a phenethyl group can be mentioned, and it is preferable that the group is unsubstituted from the viewpoint of easiness of synthesis.

Specific examples of the polycyclic aromatic hydrocarbons constituting the polycyclic aromatic hydrocarbon group are described below.

(X)
In the formula (1), X is a divalent linking group.
Examples of the divalent linking group include a single bond, an alkylene group having 1 to 10 carbon atoms, and 6 to 10 carbon atoms.
12 arylene group, -CONH-R ⁶ - group, -COOR ⁷ - group (wherein, R ⁶ and R ⁷ each independently represent a single bond, an alkylene group having 1 to 10 carbon atoms, or 2 to 10 carbon atoms Ether group (
Alkyloxy alkyl group)), and the like, -COOR ⁷ from the viewpoint of dispersibility - group. Among R ⁷ , from the viewpoint of the stability of the dispersion with time, an alkylene group having 1 to 10 carbon atoms is preferable, an alkylene group having 1 to 5 carbon atoms is more preferable, and an alkylene group having 1 to 3 carbon atoms is further preferable.

(Y)
In the formula (1), Y is a halogen atom.
Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. From the viewpoint of easiness of synthesis, a chlorine atom and a bromine atom are preferable, and a chlorine atom is more preferable.

The dispersant (f1) has a repeating unit represented by the general formula (1), but may further have other repeating units.
The dispersant (f1) preferably has a repeating unit represented by the following general formula (2) from the viewpoint of difficulty in generating foreign substances (resolubility) when the die coat is applied.

(In the formula (2), R ⁸ and R ⁹ are each independently an alkyl group which may have a substituent or an aryl group which may have a substituent. R ⁸ and R ⁹ are. They may be combined with each other to form an annular structure.
R ¹⁰ is a hydrogen atom or a methyl group.
Z is a divalent linking group. )

In the above formula (2), R ⁸ and R ⁹ are each independently an alkyl group which may have a substituent or an aryl group which may have a substituent. As the alkyl group which may have a substituent and the aryl group which may have a substituent ^{, those listed as R 1 to} R ³ in the above formula (1) can be preferably adopted.

In the above formula (2), R ⁸ and R ⁹ may be combined with each other to form an annular structure. Examples of the cyclic structure include a nitrogen-containing heterocyclic monocycle having a 5- to 7-membered ring or a fused ring formed by condensing two of them. The nitrogen-containing heterocycle is preferably one having no aromaticity, and more preferably a saturated ring. Specifically, the following can be mentioned.

(These cyclic structures may further have a substituent. * Indicates a bond.)

In the formula (2), Z is a divalent linking group. As the divalent linking group, the above formula (1)
) Can be preferably adopted as X.

Further, the dispersant (f1) preferably has a repeating unit represented by the following general formula (3) from the viewpoint of increasing the compatibility with the solvent or the alkali-soluble resin and improving the dispersion stability.

(In the formula (3), R ¹¹ is a hydrogen atom, an alkyl group which may have a substituent, or an aryl group which may have a substituent.
R ¹² is a hydrogen atom or a methyl group. )

(R ¹¹ )
Examples ^{of the alkyl group in R 11} include linear, branched, and cyclic alkyl groups, which are preferably linear from the viewpoint of compatibility with solvents and alkali-soluble resins, and are suitable for pigments. From the viewpoint of affinity, it is preferably branched chain.
The number of carbon atoms of the alkyl group is not particularly limited, but is usually 1 or more, preferably 2 or more, and 4
The above is more preferable, 10 or less is preferable, 8 or less is more preferable, and 6 or less is further preferable. By setting the value to the lower limit or higher, the affinity for the pigment tends to be increased, and the affinity with the pigment tends to be increased.
By setting the value to the upper limit or less, the compatibility with the solvent or the alkali-soluble resin tends to be improved and the dispersibility tends to be improved.
Specific examples of the alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, an ethylhexyl group, and the like, from the viewpoint of compatibility with a solvent or an alkali-soluble resin. Therefore, a methyl group and an ethyl group are preferable, and a methyl group is more preferable.
Examples of the substituent that the alkyl group may have include an alkoxy group such as a methoxy group and an ethoxy group; a halogen atom such as a fluorine atom, a chlorine atom and a bromine atom; and an aryl group such as a phenyl group and a naphthyl group. , It is preferable that it is unsubstituted from the viewpoint of compatibility with a solvent or an alkali-soluble resin, and it is preferable that it is a phenyl group from the viewpoint of affinity with a pigment.

Examples of the aryl group in R ¹¹ include a monovalent aromatic hydrocarbon ring group and a monovalent aromatic heterocyclic group.
The number of carbon atoms of the aryl group is not particularly limited, but is usually 6 or more, preferably 16 or less, more preferably 12 or less, still more preferably 6 or less. By setting the value to the upper limit or less, the affinity for the pigment tends to be increased.
Specific examples of the aryl group include a phenyl group, a naphthyl group, an anthracenyl group and the like. From the viewpoint of dispersibility, a phenyl group and a naphthyl group are preferable, and a phenyl group is more preferable.
Substituents that the aryl group may have include an alkyl group such as a methyl group and an ethyl group; an alkoxy group such as a methoxy group and an ethoxy group; a halogen atom such as a fluorine atom, a chlorine atom and a bromine atom; a phenyl group, An aryl group such as a naphthyl group; an aralkyl group such as a benzyl group and a phenethyl group can be mentioned, and it is preferable that the group is unsubstituted from the viewpoint of dispersibility.

Among these, from the viewpoint of compatibility with a solvent or an alkali-soluble resin, R ¹¹ is preferably an alkyl group which may have a substituent, and more preferably an unsubstituted alkyl group.
A methyl group, a butyl group, or an ethylhexyl group is more preferable.

Further, the dispersant (f1) preferably has a repeating unit represented by the following general formula (4) from the viewpoint of compatibility with a solvent or an alkali-soluble resin.

In formula (4), R ¹³ is a methylene group, an ethylene group, or a propylene group.
R ¹⁴ is a methyl group, an ethyl group, or a propyl group.
R ¹⁵ is a hydrogen atom or a methyl group.
n is an integer of 1 to 20. )

R ¹³ is a methylene group, an ethylene group, or a propylene group, but an ethylene group is preferable from the viewpoint of compatibility with a solvent or an alkali-soluble resin.
R ¹⁴ is a methyl group, an ethyl group, or a propyl group, but from the viewpoint of compatibility with a solvent or an alkali-soluble resin, a methyl group or an ethyl group is preferable, and an ethyl group is more preferable.

n is an integer of 1 to 20, but 1 or more is preferable, 2 or more is more preferable, and 10
The following is preferable, and 5 or less is more preferable. When it is at least the above lower limit value, the compatibility with the solvent or the alkali-soluble resin tends to be improved, and when it is at least the above upper limit value, the affinity for the pigment is enhanced and the dispersibility tends to be improved.

The content ratio of the repeating unit represented by the general formula (1) (hereinafter, may be referred to as “repeating unit (1)”) in the dispersant (f1) is not particularly limited, but is included in all the repeating units. 1 mol% or more is preferable, 4 mol% or more is more preferable, 6 mol% or more is further preferable, 8 mol% or more is particularly preferable, 40 mol% or less is preferable, 20 mol% or less is more preferable, and 15 mol. % Or less is more preferable, and 10 mol% or less is particularly preferable.
When it is at least the lower limit value, the stability of the dispersion liquid with time tends to be good, and when it is at least the upper limit value, the dispersibility tends to be good.

When the dispersant (f1) contains a repeating unit represented by the general formula (2) (hereinafter, may be referred to as a “repeating unit (2)”), the content ratio thereof is not particularly limited.
1 mol% or more is preferred, 5 mol% or more is more preferred, and 10 mol% in all repeating units.
The above is further preferable, 15 mol% or more is particularly preferable, 50 mol% or less is preferable, 40 mol% or less is more preferable, 30 mol% or less is further preferable, and 20 mol% or less is particularly preferable. When the value is not less than the lower limit value, the dispersibility tends to be good, and when the value is not more than the upper limit value, the stability of the dispersion liquid with time tends to be good.

When the dispersant (f1) contains the repeating unit (2), the content ratio of the repeating unit (1) to the total of the repeating unit (1) and the repeating unit (2) is usually 5 mol% or more, and 10 More than mol% is preferable, 20 mol% or more is more preferable, 25 mol% or more is further preferable, 30 mol% or more is particularly preferable, and usually 100 mol% or less, 80 mol% or less is preferable, and 60 mol% is preferable. The following is more preferable, 50 mol% or less is further preferable, and 40% or less is particularly preferable. When it is at least the above lower limit value, the stability of the dispersion liquid with time tends to be good, and when it is at least the above upper limit value, the voltage retention rate after ultraviolet irradiation and NMP
Tolerance tends to be good.

When the dispersant (f1) contains a repeating unit represented by the general formula (3) (hereinafter, may be referred to as a “repeating unit (3)”), the content ratio thereof is not particularly limited.
In all repeating units, 20 mol% or more is preferable, 40 mol% or more is more preferable, 50 mol% or more is further preferable, 60 mol% or more is particularly preferable, 90 mol% or less is preferable, and 80 mol% or less is 80 mol% or less. More preferably, 75 mol% or less is further preferable. When it is at least the above lower limit value, it tends to increase the affinity for pigments, and when it is at least the above upper limit value, it tends to increase the compatibility with solvents and alkali-soluble resins.

When the dispersant (f1) contains a repeating unit represented by the general formula (4) (hereinafter, may be referred to as a “repeating unit (4)”), the content ratio thereof is not particularly limited.
0.5 mol% or more is preferable, 1 mol% or more is more preferable, 2 mol% or more is further preferable, 2.5 mol% or more is particularly preferable, and 10 mol% or less is preferable, and 8 mol% or less is preferable in all repeating units. More preferably, it is mol% or less, further preferably 5 mol% or less, and particularly preferably 3 mol% or less. The lower limit value or more tends to increase the compatibility with the solvent or the alkali-soluble resin, and the upper limit value or less tends to increase the affinity with the pigment.

When the dispersant (f1) has a repeating unit (1) and a repeating unit (2), from the viewpoint of dispersibility, a B block having the repeating unit (1) and the repeating unit (2), and the repeating unit (1) and It is preferably a block copolymer having an A block having no repeating unit (2). The block copolymer is preferably an AB block copolymer or an ABA block copolymer.

In the B block, the repeating unit (1) and the repeating unit (2) may be contained in any aspect of random copolymerization and block copolymerization. In addition, the repeating unit (1)
And two or more kinds of repeating units (2) may be contained in the B block, and in that case, each repeating unit is contained in the B block in any mode of random copolymerization or block copolymerization. May be.

If the dispersant (f1) has a repeating unit (3) or a repeating unit (4), they are A.
It may be contained in a block, and may be contained in any aspect of random copolymerization and block copolymerization. Further, two or more kinds of repeating units (3) and repeating units (4) may be contained in the A block, and in that case, each repeating unit is a random copolymerization or a block copolymerization in the A block. It may be contained in any of the above embodiments.

Repeating units other than the repeating unit (3) and the repeating unit (4) may be contained in the A block, and examples of such repeating units include styrene-based monomers such as styrene and α-methylstyrene. (Meta) acrylate-based monomers such as (meth) acrylic acid chloride; (meth) acrylamide-based monomers such as (meth) acrylamide and N-methylol acrylamide; vinyl acetate; acrylonitrile; allylglycidyl ether, croton Glycidyl acid acid ether; repeat units derived from monomers such as N-methacryloylmorpholine.

The amine value of the dispersant (f1) is not particularly limited, but is preferably 20 mgKOH / g or more, more preferably 30 mgKOH / g or more, still more preferably 40 mgKOH / g or more.
50 mgKOH / g or more is particularly preferable, and 150 mgKOH / g or less is particularly preferable.
100 mgKOH / g or less is more preferable, and 80 mgKOH / g or less is further preferable.
70 mgKOH / g or less is particularly preferable. When it is at least the above lower limit value, NMP resistance and dispersibility tend to be good, and when it is at least the above upper limit value, the stability over time of the dispersion liquid tends to be improved. The amine value is K, which is equivalent to the amount of base per 1 g of solid content of the dispersant (f1).
It is represented by the mass of OH.

The acid value of the dispersant (f1) is not particularly limited, but from the viewpoint of dispersibility, 10 mgKOH / g
The following is preferable, 5 mgKOH / g or less is more preferable, 1 mgKOH / g or less is further preferable, and 0 mgKOH / g is particularly preferable.

The weight average molecular weight of the dispersant (f1) is not particularly limited, but is preferably 3000 or more, and 5
More than 000 is more preferable, 7,000 or more is further preferable, 100,000 or less is more preferable, 50,000 or less is more preferable, and 10,000 or less is further preferable. When it is at least the lower limit value, the dispersibility tends to be improved, and when it is at least the upper limit value, the stability over time of the dispersion liquid tends to be improved.
In the dispersant of the present invention (f1), the counter anion (Y ^-) by the presence, may weight average molecular weight can not be sufficiently measured, in which case the counter anion ^- before granting (Y) The theoretical molecular weight calculated from the weight average molecular weight value of is sometimes used.
The theoretical molecular weight of the dispersant (f1) is not particularly limited, but is preferably 3000 or more, preferably 500.
0 or more is more preferable, 7,000 or more is further preferable, 100,000 or less is preferable, 50,000 or less is more preferable, and 10,000 or less is further preferable. When it is at least the lower limit value, the dispersibility tends to be improved, and when it is at least the upper limit value, the stability over time of the dispersion liquid tends to be improved.

The method for producing the dispersant (f1) is not particularly limited, and a known method can be adopted. For example, a precursor of the dispersant (f1) containing the repeating unit (2) can be produced, and the precursor can be reacted with a compound represented by the following general formula (1') to produce the precursor. can.

(In the formula (1'), R ³ , R ⁴ , and Y are synonymous with the above formula (1).

The (f) dispersant in the photosensitive coloring composition of the present invention may contain a dispersant other than the dispersant (f1) (hereinafter, may be referred to as “other dispersants”).

Examples of other dispersants include the following dispersants.
Carboxy groups; or these bases; primary, secondary or tertiary amino groups;
Quaternary ammonium base; groups derived from nitrogen-containing heterocycles such as pyridine, pyrimidine, and pyrazine,
A dispersant having a functional group such as is preferable. Among them, a dispersant having a basic functional group such as a primary, secondary or tertiary amino group; a quaternary ammonium base; a group derived from a nitrogen-containing heterocycle such as pyridine, pyrimidine, or pyrazine, etc. can be mentioned.
Further, a polymer dispersant is preferable from the viewpoint that the pigment can be dispersed with a small amount of dispersant.

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

As a specific example of such a polymer dispersant, the trade name is EFKA (registered trademark. BASF).
Made by the company. ), DISPERBYK (registered trademark, manufactured by Big Chemie), Disparon (registered trademark, manufactured by Kusumoto Kasei), SOLSPERSE (registered trademark, manufactured by Lubrizol), K
P (manufactured by Shin-Etsu Chemical Co., Ltd.), Polyflow (manufactured by Kyoeisha Chemical Co., Ltd.), Ajispar (registered trademark, manufactured by Ajinomoto Co., Inc.) and the like can be mentioned.

Examples of urethane-based and acrylic-based polymer dispersants include DISPERBYK160 ~.
166, 182 series (all urethane type), DISPERBYK2000, 200
1. BYK-LPN21116 and the like (all are acrylic) (all of which are manufactured by Big Chemie).

As the other dispersant, one type may be used, or two or more types may be used in combination.

<Other ingredients of the photosensitive coloring composition>
In addition to the above-mentioned components, the photosensitive coloring composition of the present invention includes 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 added as appropriate.

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

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

In the above general formulas (g1), (g2) and (g3), R ⁵¹ represents a hydrogen atom or a methyl group, l and l'are integers of 1 to 10, and m is 1, 2 or 3.
These phosphoric acid group-containing compounds may be used alone or in combination of two or more.

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

As the surfactant, for example, various kinds such as anionic type, cationic type, nonionic type, amphoteric surfactant and the like can be used. Among them, it is preferable to use a nonionic surfactant because it is unlikely to adversely affect various properties, and among them, a fluorine-based or silicon-based surfactant is effective in terms of coatability.
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 Big Chemie), KP340 (manufactured by Shinetsu Silicone), F-
470, F-475, F-478, F-554, F-559 (manufactured by DIC Corporation), SH7PA
(Toray Dow Corning), DS-401 (Daikin), L-77 (Nippon Unicar), FC4430 (3M) and the like.
As the surfactant, one type may be used, or two or more types may be used in combination in any combination and ratio.

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

Specific examples of the pigment derivative include a phthalocyanine sulfonic acid derivative, a quinophthalone sulfonic acid derivative, an anthraquinone sulfonic acid derivative, and a quinacridone sulfonic acid derivative.
Examples thereof include a sulfonic acid derivative of diketopyrrolopyrrole and a sulfonic acid derivative of dioxazine. One of these may be used alone, or two or more thereof may be used in combination.

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

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

In formula (6), R ⁶¹ represents −NR ⁶⁶ R ⁶⁷ groups or an aryl group having 6 to 12 carbon atoms, and R ⁶¹ is −
In ^{the case of NR 66} R ⁶⁷ group, one of R ⁶² , R ⁶³ , R ⁶⁴ , R ⁶⁵ , R ⁶⁶ and R ⁶⁷ represents -CH ₂ OR ⁶⁸ group, and when R ⁶¹ is an aryl group having 6 to 12 carbon atoms. One of R ⁶² , R ⁶³ , R ⁶⁴ and R ⁶⁵ represents -CH ₂ OR ⁶⁸ groups, ^{and the rest of R 62} , R ⁶³ , R ⁶⁴ , R ⁶⁵ , R ⁶⁶ and R ⁶⁷ are independent of each other, hydrogen or -CH ₂ OR ^{represents 68} groups, and R ⁶⁸ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.
Here, the aryl group having 6 to 12 carbon atoms is typically a phenyl group, a 1-naphthyl group or 2
-It is a naphthyl group, and a substituent such as an alkyl group, an alkoxy group, or a halogen atom may be bonded to these phenyl group or naphthyl group. The alkyl group and the alkoxy group can each have about 1 to 6 carbon atoms. Among the above, the alkyl group represented by R ⁶⁸ is preferably a methyl group or an ethyl group, particularly a methyl group.

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

In formula (6-1), when one of R ⁶² , R ⁶³ , R ⁶⁴ , R ⁶⁵ , R ⁶⁶ and R ⁶⁷ is an aryl group, one of R ⁶² , R ⁶³ , R ⁶⁴ and R ⁶⁵ is −CH _2. Represents OR ⁶⁸ groups, R ⁶² , R ⁶³ , R ⁶⁴ , R ⁶⁵ ,
The rest of R ⁶⁶ and R ⁶⁷ represent hydrogen atoms or -CH ₂ OR ⁶⁸ groups independently of each other, and R ⁶⁸ represents hydrogen atoms or alkyl groups.

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

Further, a cross-linking agent having a methylol group or a methylol alkyl ether group can also be used. An example is given below.
2,6-bis (hydroxymethyl) -4-methylphenol, 4-tert-butyl-
2,6-bis (hydroxymethyl) phenol, 5-ethyl-1,3-bis (hydroxymethyl) perhydro-1,3,5-triazine-2-one (commonly known as N-ethyldimethyloltriazone) or its dimethyl ether Body, dimethylol trimethylene urea or its dimethyl ether form, 3,5-bis (hydroxymethyl) perhydro-1,3,5-oxadiadin-4-one (commonly known as dimethylolurone) or its dimethyl ether form, tetramethylol glioxal diurein Or its tetramethyl ether form.

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

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

Types of mercapto compounds include 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, 2-mercaptobenzoimidazole, hexanedithiol, decandithiol, 1,4-dimethylmercaptobenzene, butanediol bisthiopropionate, butanediol bis. Thioglycolate, ethylene glycol bisthioglycolate, trimethylolpropanetristhioglycolate, butanediol bisthiopropionate, trimethylolpropanetristhiopropionate, trimethylolpropanetristhioglycolate, pentaerythritol tetrakisthiopropio Nate, pentaerythritol tetraxthioglycolate, trishydroxyethyl tristhiopropionate, ethylene glycol bis (3-mercaptobutyrate), butanediol bis (3)
-Mercaptobutyrate), 1,4-bis (3-mercaptobutyryloxy) butane, trimethylpropanthris (3-mercaptobutyrate), pentaerythritol tetrakis (3-mercaptobutyrate), pentaerythritol tris (3-mercaptobutyrate) Mercaptobutyrate), ethylene glycol bis (3-mercaptoisobutyrate), butanediolbis (3-mercaptoisobutyrate), trimethylpropanthritol (3-mercaptoisobutyrate), 1,3,5-tris (3-mercaptoisobutyrate) 3-Mercaptobutyloxyethyl) -1
, 3,5-Triazine-2,4,6 (1H, 3H, 5H) -trione and other mercapto compounds having a heterocycle, aliphatic polyfunctional mercapto compounds and the like can be mentioned. These can be used alone or in admixture of two or more.

(7) Polymerization Inhibitor The photosensitive coloring composition of the present invention may contain a polymerization inhibitor from the viewpoint of shape control. It is considered that the taper angle (the angle formed by the support and the cured product in the cross section of the cured product) can be controlled because the inclusion of the polymerization inhibitor inhibits the radical polymerization of the lower layer of the coating film.
Examples of the polymerization inhibitor include hydroquinone, hydroquinone monomethyl ether, methylhydroquinone, methoxyphenol, and 2,6-di-tert-butyl-4-cresol (B).
HT) and the like. Among these, from the viewpoint of shape control, 2,6-di-tert-
Butyl-4-cresol is preferred. Further, from the viewpoint of safety to the human body, hydroquinone monomethyl ether and methyl hydroquinone are preferable.
The polymerization inhibitor preferably contains one kind or two or more kinds. (B) When producing an alkali-soluble resin, a polymerization inhibitor may be contained in the resin, which may be used as the polymerization inhibitor of the present invention, or in addition to the polymerization inhibitor in the resin. , The same or different polymerization inhibitor may be added at the time of producing the photosensitive coloring composition.

When the photosensitive coloring composition contains a polymerization inhibitor, its content is not particularly limited, but it is usually 0.0005% by mass or more, preferably 0.001% by mass, in the total solid content of the photosensitive coloring composition.
As described above, it is more preferably 0.01% by mass or more, and usually 0.3% by mass or less, preferably 0.2% by mass or less, and more preferably 0.1% by mass or less. The shape tends to be controlled by setting the value to the lower limit value or more, and the required sensitivity tends to be maintained by setting the value to the upper limit value or less.

<Content ratio of each component in the photosensitive coloring composition>
The content ratio of the (a) colorant 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 more preferably 20% by mass or more in the total solid content of the photosensitive coloring composition. More preferably by mass% or more, more preferably 30% by mass or more, and 35% by mass.
The above is particularly preferable, 70% by mass or less is preferable, 60% by mass or less is more preferable, 50% by mass or less is further preferable, and 45% by mass or less is particularly preferable. When it is set to the lower limit value or more, the light-shielding property tends to be secured, and when it is set to the upper limit value or less, the patterning property tends to be improved.

When the photosensitive coloring composition contains an organic coloring pigment, the content ratio thereof is not particularly limited, but is preferably 5% by mass or more, more preferably 20% by mass or more in the total solid content of the photosensitive coloring composition. , 30% by mass or more is more preferable, 35% by mass or more is particularly preferable, and 7
0% by mass or less is preferable, 60% by mass or less is more preferable, and 50% by mass or less is particularly preferable. When it is set to the lower limit value or more, the light-shielding property tends to be improved while suppressing the loss of ultraviolet light required for curing, and when it is set to the upper limit value or less, the NMP resistance tends to be improved.

(A) When the colorant contains a red pigment and / or an orange pigment, the total content ratio of the red pigment and the orange pigment is not particularly limited, but (a) 5% by mass or more is preferable in the colorant, and 8% by mass is preferable.
The above is more preferable, 10% by mass or more is further 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. By setting the value above the lower limit, the color tone tends to be close to black, and the color tone tends to be close to black.
When it is set to the upper limit or less, the sensitivity tends 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 (a) 30% by mass or more is preferable in the colorant, and 50% by mass is preferable. The above is more preferable, 70% by mass or more is further 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. When it is at least the lower limit value, the light-shielding property tends to be high, and when it is at least the upper limit value, the NMP resistance tends to be good.

When the photosensitive coloring composition contains a black pigment, the content ratio thereof is not particularly limited, but it is preferably 3% by mass or more, more preferably 5% by mass or more, and 10% by mass in the total solid content of the photosensitive coloring composition.
More preferably, it is more preferably mass% or more, 20% by mass or more, particularly preferably 60% by mass or less, more preferably 50% by mass or less, and particularly preferably 40% by mass or less. When it is set to the lower limit value or more, the light-shielding property tends to be improved, and when it is set to the upper limit value or less, NM
P resistance tends to be good.

When the photosensitive coloring composition contains an organic black pigment, the content ratio thereof is not particularly limited, but it is preferably 3% by mass or more, more preferably 5% by mass or more in the total solid content of the photosensitive coloring composition. 10% by mass or more is further 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.
When it is at least the lower limit value, the light-shielding property tends to be high, and when it is at least the upper limit value, the NMP resistance tends to be good.

(A) When the colorant contains an organic black pigment, the content ratio thereof is not particularly limited, but (a)
In the colorant, 5% by mass or more is preferable, 10% by mass or more is more preferable, 15% by mass or more is further preferable, 20% by mass or more is particularly preferable, and 100% by mass or less is preferable.
80% by mass or less is more preferable, and 70% by mass or less is particularly preferable. When it is at least the lower limit value, the light-shielding property tends to be high, and when it is at least the upper limit value, the NMP resistance tends to be good.

When the photosensitive coloring composition contains carbon black as an inorganic black pigment, its content is not particularly limited, but (a) 5% by mass or more is preferable, and 8% by mass or more is more preferable in the colorant. More preferably, it is more than% by mass, and more preferably less than 60% by mass.
0% by mass or less is more preferable, and 40% by mass or less is particularly preferable. When it is at least the lower limit value, the light-shielding property tends to be high, and when it is at least the upper limit value, the NMP resistance tends to be good.

When (a) the colorant contains an organic color pigment and a black pigment, the total content ratio is not particularly limited, but (a) 30% by mass or more is preferable, and 50% by mass or more is more preferable in the colorant. , 70% by mass or more is more preferable, and 90% by mass or more is particularly preferable. Also, 1
It is preferably 00% by mass or less. When the value is equal to or higher than the lower limit, the light-shielding property tends to be improved.
When the value is not more than the upper limit, the NMP resistance tends to be good.

(B) The content ratio of the alkali-soluble resin is not particularly limited, but is 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, still more preferably. Is 50% by mass or less, particularly preferably 45.
It is mass% or less. (B) By setting the content ratio of the alkali-soluble resin to the lower limit value or more, it tends to be possible to suppress a decrease in the solubility of the unexposed portion in the developing solution and suppress development defects.
Further, by setting the value to the upper limit or less, it tends to be possible to maintain an appropriate sensitivity, suppress dissolution of the exposed portion by the developing solution, and suppress deterioration of pattern sharpness and adhesion.

(B1) The content ratio of the epoxy (meth) acrylate resin is not particularly limited, but is usually 10% by mass or more, preferably 20% by mass or more, in the total solid content of the photosensitive coloring composition of the present invention.
It is more preferably 30% by mass or more, further preferably 35% by mass or more, and usually 50% by mass or less, preferably 45% by mass or less, and more preferably 40% by mass or less. When it is set to the lower limit value or more, the solubility of the unexposed portion in the developing solution tends to be secured, and when it is set to the upper limit value or less, the appropriate sensitivity is maintained and the dissolution of the exposed portion by the developing solution is suppressed. Can,
In addition, there is a tendency that deterioration of pattern sharpness and adhesion can be suppressed.

The content ratio of the (b1) epoxy (meth) acrylate-based resin contained in the (b) alkali-soluble resin is not particularly limited, but is usually 20% by mass or more, preferably 40% by mass or more, more preferably 50% by mass or more. Particularly preferably, it is 60% by mass or more, and usually 100% by mass.
Hereinafter, it is preferably 80% by mass or more, and more preferably 70% by mass or more. When it is set to the lower limit value or more, the solubility of the unexposed portion in the developing solution tends to be secured, and when it is set to the upper limit value or less, the appropriate sensitivity is maintained and the dissolution of the exposed portion by the developing solution is suppressed. It can be done, and there is a tendency that deterioration of pattern sharpness and adhesion can be suppressed.

The content ratio of the photopolymerization initiator (c) is not particularly limited, but is 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, still more preferably 6% by mass. % Or less. (C) There is a tendency that the decrease in sensitivity can be suppressed by setting the content ratio of the photopolymerization initiator to the above lower limit value or more, and by setting it to the above upper limit value or less, the decrease in solubility of the unexposed portion in the developing solution is suppressed. , There is a tendency to suppress development defects.

(C) When a polymerization accelerator is used together with the photopolymerization initiator, the content ratio of the polymerization accelerator is not particularly limited, but is preferably 0.05% by mass 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, and the polymerization accelerator is usually 0.1 to 50 parts by mass, particularly 0.1 to 20 parts by mass with respect to 100 parts by mass of the (c) photopolymerization initiator. It is preferable to use in the ratio of. By setting the content ratio of the polymerization accelerator to the lower limit value or more, the decrease in sensitivity to the exposed light tends to be suppressed, and by setting the content ratio to the upper limit value or less, the decrease in the solubility of the unexposed portion in the developing solution is suppressed. However, there is a tendency that development defects can be suppressed.
When (c) a sensitizing dye is used together with the photopolymerization initiator, the content ratio thereof is not particularly limited, but from the viewpoint of sensitivity, it is usually 20% by mass or less, preferably 20% by mass or less, in the total solid content in the photosensitive coloring composition. It is 15% by mass or less, more preferably 10% by mass or less.

(D) The content ratio of the ethylenically unsaturated compound is not particularly limited, but is usually 1% by mass or more, preferably 5% by mass or more, more preferably 10 in the total solid content of the photosensitive coloring composition of the present invention.
It is usually 30% by mass or less, preferably 20% by mass or less, and more preferably 15% by mass or less. By setting the value to the lower limit or higher, the appropriate sensitivity can be maintained, dissolution of the exposed portion by the developer can be suppressed, deterioration of pattern sharpness and adhesion tends to be suppressed, and the value is lower than the upper limit. By doing so, it tends to suppress the increase in the permeability of the developing solution into the exposed portion, and it tends to be easy to obtain a good image.

The content ratio of (b) alkali-soluble resin to 100 parts by mass of (d) ethylenically unsaturated compound is usually preferably 80 parts by mass or more, 100 parts by mass or more, more preferably 150 parts by mass or more, and further 200 parts by mass or more. Preferably, 250 parts by mass or more is particularly preferable, and 250 parts by mass or more is particularly preferable.
Usually, 700 parts by mass or less, 500 parts by mass or less is preferable, 400 parts by mass or less is more preferable, and 300 parts by mass or less is further preferable. When it is set to the lower limit value or more, it tends to be in an appropriate melting and developing state without peeling, and when it is set to the upper limit value or less, an appropriate melting time for the developer tends to be obtained. ..

By using the solvent (e), the photosensitive coloring composition of the present invention has a total solid content of usually 5% by mass or more, preferably 10% by mass or more, and more preferably 15% by mass or more. Further, the liquid is usually prepared so as to be 50% by mass or less, preferably 30% by mass or less, and more preferably 25% by mass or less.

The content ratio of the dispersant (f) is not particularly limited, but is usually 1% by mass or more, preferably 3% by mass or more, more preferably 5% by mass or more, and usually in the total solid content of the photosensitive coloring composition. It is preferably 30% by mass or less, 20% by mass or less, more preferably 15% by mass or less, and further preferably 10% by mass or less. When it is set to the lower limit value or more, sufficient dispersibility tends to be obtained, and when it is set to the upper limit value or less, the ratio of other components is relatively reduced, so that the sensitivity, plate-making property, etc. are lowered. Tends to be suppressed.

The content ratio of the dispersant (f1) is not particularly limited, but is usually 1% by mass or more, preferably 3% by mass or more, more preferably 5% by mass or more, and usually in the total solid content of the photosensitive coloring composition. It is preferably 30% by mass or less, 20% by mass or less, more preferably 15% by mass or less, and further preferably 10% by mass or less. When it is at least the lower limit value, the dispersibility tends to be good, and when it is at least the upper limit value, the voltage holding ratio tends to be high.

The content ratio of the dispersant (f1) is not particularly limited, but (f) is usually 10% by mass or more, preferably 40% by mass or more, more preferably 60% by mass or more, and further 80% by mass or more in the dispersant. It is preferable, and usually it is 100% by mass or less. By setting the value to the lower limit or more, the voltage retention rate after ultraviolet irradiation tends to be high, and the NMP resistance tends to be improved.

The content ratio of (f) dispersant to 100 parts by mass of (a) colorant is usually 5 parts by mass or more, more preferably 10 parts by mass or more, further preferably 15 parts by mass or more, and usually 50 parts by mass or less, particularly. It is preferably 30 parts by mass or less. When it is set to the lower limit value or more, sufficient dispersibility tends to be obtained, and when it is set to the upper limit value or less, the ratio of other components is relatively reduced, so that the sensitivity, plate-making property, etc. are lowered. Tends to be suppressed.

When the adhesion improver is used, the content ratio thereof is not particularly limited, but is 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. ..
It is 4 to 2% by mass. By setting the content ratio of the adhesion improver to the lower limit value or more, the effect of improving the adhesion tends to be sufficiently obtained, and when it is set to the upper limit value or less, the sensitivity is lowered or a residue remains after development. There is a tendency to prevent it from becoming a defect.

When a surfactant is used, its content is not particularly limited, but it is usually 0.001 to 10% by mass, preferably 0.005 to 1% by mass, more preferably 0.005 to 1% by mass, in the total solid content of the photosensitive coloring composition. Is 0.01 to 0.5% by mass, most preferably 0.03 to 0.3% by mass.
When the content ratio of the surfactant is at least the above lower limit value, the smoothness and uniformity of the coating film tends to be easily developed, and when it is at least the above upper limit value, the smoothness and uniformity of the coating film are exhibited. Easy,
Deterioration of other properties also tends to be suppressed.

<Physical characteristics of the photosensitive coloring composition>
The photosensitive coloring composition of the present invention has an optical density (OD) of 0.
5 or more. It is more preferably 0.7 or more, further preferably 1.0 or more, further preferably 1.3 or more, particularly preferably 1.5 or more, and usually 4.0 or less. It is preferably 3.0 or less, and more preferably 2.0 or less. When it is set to the lower limit value or more, sufficient light-shielding property tends to be obtained, and when it is set to the upper limit value or less, the voltage retention rate and NMP resistance tend to be improved.
The optical density (OD) per 1 μm of the film thickness of the coating film may be measured by using a coating film obtained by curing the photosensitive coloring composition of the present invention, and a coating film cured by heating at 230 ° C. for 20 minutes is used. Is preferable.
In addition, this optical density means that the spectral sensitivity characteristic of the light receiving part is ISO in the ISO 5-3 standard.
Refers to the transmitted optical density indicated by visual density. Usually, as a light source,
The A light source specified by the CIE (International Commission on Illumination) is used. As a measuring instrument that can be used for measuring the transmitted optical density, for example, X- of Sakata Inx Engineering Co., Ltd.
Rite 361T (V) can be mentioned.

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

The dispersion treatment is usually preferably carried out in a system in which (a) a colorant, (e) a solvent, (f) a dispersant, and (b) a part or all of an alkali-soluble resin are used in combination (hereinafter, dispersion). The composition obtained by the treatment may be referred to as a "pigment dispersion"). In particular, it is preferable to use a polymer dispersant as the dispersant (f) because the thickening of the obtained pigment dispersion liquid and the photosensitive coloring composition with time is suppressed (excellent dispersion stability).
As described above, in the step of producing the photosensitive coloring composition, (a) a colorant, (e) a solvent,
And (f) it is preferable to produce a pigment dispersion liquid containing at least a dispersant.
As the (a) colorant, (e) solvent, and (f) dispersant that can be used in the pigment dispersion, those described as being usable in the photosensitive coloring composition are preferably used. can. Further, as the content ratio of each colorant of (a) colorant in the pigment dispersion liquid, those described as the content ratio in the photosensitive coloring composition can be preferably adopted.

When the liquid containing all the components to be blended in the photosensitive coloring composition is subjected to the dispersion treatment, the highly reactive components may be denatured due to the heat generated during the dispersion treatment. Therefore, it is preferable to carry out the dispersion treatment in a system containing a polymer dispersant.
When (a) the colorant is dispersed with a sand grinder, glass beads or zirconia beads having a particle size of about 0.1 to 8 mm are preferably used. The dispersion treatment conditions are such that the temperature is usually 0 ° C. to 100 ° C., preferably in the range of room temperature to 80 ° C. The dispersion time is appropriately adjusted because the appropriate time varies depending on the composition of the liquid, the size of the dispersion treatment apparatus, and the like. So that the 20-degree mirror gloss (JIS Z8741) of the photosensitive coloring composition is in the range of 50 to 300.
The guideline for dispersion is to control the gloss of the pigment dispersion. When the glossiness of the photosensitive coloring composition is low, the dispersion treatment is not sufficient and coarse pigment (coloring material) particles often remain, resulting in developability.
Adhesion, resolution, etc. may be insufficient. Further, if the dispersion treatment is performed until the gloss value exceeds the above range, the pigment is crushed and a large number of ultrafine particles are generated, so that the dispersion stability tends to be impaired.

The dispersed particle size of the pigment dispersed in the pigment dispersion is usually 0.03 to 0.3 μm, and is measured by a dynamic light scattering method or the like.
Next, the pigment dispersion liquid obtained by the above dispersion treatment and the above other components contained in the photosensitive coloring composition are mixed to obtain a uniform solution. In the manufacturing process of the photosensitive coloring composition, fine dust may be mixed in the liquid, so that it is desirable to filter the obtained photosensitive coloring composition with a filter or the like.

[Pigment dispersion for image display devices]
The pigment dispersion liquid for the image display device of the present invention contains (a) a colorant, (e) a solvent, and (f) a dispersant, and in particular, the (a) colorant contains a black pigment. Moreover, the dispersant (f) contains the dispersant (f1).
In the pigment dispersion liquid for the image display device of the present invention, (a) a colorant, (e) a solvent, and (f)
) As the dispersant, those listed as the same item in the photosensitive coloring composition of the present invention can be preferably adopted. Similarly, as the black pigment and the dispersant (f1) in the pigment dispersion liquid for the image display device of the present invention, those listed as the same item in the photosensitive coloring composition of the present invention can be preferably adopted.

In the pigment dispersion liquid for the image display device of the present invention, the content ratio of (a) the colorant is not particularly limited, but is preferably 30% by mass or more, more preferably 50% by mass or more in the total solid content of the pigment dispersion liquid. , 60% by mass or more, more preferably 80% by mass or less, more preferably 75% by mass or less, still more preferably 70% by mass or less. When it is at least the above lower limit value, the voltage retention rate and NMP resistance after ultraviolet irradiation tend to be good, and when it is at least the above upper limit value, the dispersibility tends to be good.

In the pigment dispersion liquid for the image display device of the present invention, the content ratio of the black pigment is not particularly limited, but is preferably 30% by mass or more, more preferably 50% by mass or more, and 60% by mass in the total solid content of the pigment dispersion liquid. % Or more is more preferable, 80% by mass or more is particularly preferable, 75% by mass or less is preferable, and 70% by mass or less is more preferable. When it is set to the lower limit value or more, the voltage retention rate and NMP resistance after ultraviolet irradiation tend to be good, and when it is set to the upper limit value or less, the dispersibility tends to be good.

In the pigment dispersion liquid for the image display device of the present invention, among the black pigments, the inclusion of the organic black pigment represented by the general formula (1) is considered from the viewpoint of light-shielding property when used as a photosensitive coloring composition. preferable.
When the pigment dispersion liquid for the image display device contains an organic black pigment represented by the general formula (1) as a black pigment, the content ratio thereof is not particularly limited, but (a) 10% by mass or more is preferable in the colorant. , 40% by mass or more is more preferable, 70% by mass or more is further preferable, 90% by mass or more is particularly preferable, and 98% by mass or more is even more preferable.
In the pigment dispersion liquid for the image display device of the present invention, the content ratio of the dispersant (f) is not particularly limited, but is preferably 1% by mass or more, more preferably 5% by mass or more in the total solid content of the pigment dispersion liquid. , 8% by mass or more is more preferable, 10% by mass or more is particularly preferable, 35% by mass or less is more preferable, 30% by mass or less is more preferable, and 20% by mass or less is further preferable.
It is particularly preferably 15% by mass or less. When it is at least the lower limit value, the dispersibility tends to be good, and when it is at least the upper limit value, the voltage retention rate and NMP resistance after ultraviolet irradiation tend to be good.

In the pigment dispersion liquid for the image display device of the present invention, the content ratio of the dispersant (f1) is not particularly limited, but is preferably 5% by mass or more, more preferably 8% by mass or more in the total solid content of the pigment dispersion liquid. 10% by mass or more is further preferable, 35% by mass or less is preferable, 30% by mass or less is more preferable, 20% by mass or less is further preferable, and 15% by mass or less is particularly preferable. When it is at least the above lower limit value, the dispersibility tends to be good, and when it is at least the above upper limit value, the voltage retention rate and NMP resistance after ultraviolet irradiation when used as a photosensitive coloring composition are good. Tends to be.

The content ratio of the dispersant (f1) is not particularly limited, but (f) is usually 10% by mass or more, preferably 40% by mass or more, more preferably 60% by mass or more, and further 80% by mass or more in the dispersant. It is preferable, and usually it is 100% by mass or less. By setting it to the above lower limit value or more, the voltage retention rate after ultraviolet irradiation when used as a photosensitive coloring composition tends to be good, and the NMP resistance tends to be improved.

By using the solvent (e), the pigment dispersion liquid for the image display device of the present invention has a total solid content of usually 10% by mass or more, preferably 15% by mass or more, and more preferably 20% by mass. % Or more, usually 40% by mass or less, preferably 35% by mass or less, and more preferably 30% by mass or less.

[Cured product]
A cured product can be obtained by curing the photosensitive coloring composition of the present invention. A cured product obtained by curing the photosensitive coloring composition can be suitably used as a coloring spacer.

[Colored spacer]
Next, a colored spacer using the photosensitive coloring composition of the present invention will be described according to a method for producing the colored spacer.

(1) Support The material of the support for forming the colored spacer is not particularly limited as long as it has an appropriate strength. A transparent substrate is mainly used, and as the material, for example, a polyester resin such as polyethylene terephthalate, a polyolefin resin such as polypropylene and polyethylene, a thermoplastic resin sheet such as polycarbonate, polymethylmethacrylate and polysulphon, and epoxy. Resin, unsaturated polyester resin, poly (meth)
Examples thereof include a thermosetting resin sheet such as an acrylic resin, and various types of glass. Among these, glass and heat-resistant resin are preferable from the viewpoint of heat resistance. Also, ITO, IZ on the surface of the substrate
A transparent electrode such as O may be formed. Other than the transparent substrate, it can be formed on the TFT array.

The support may be subjected to corona discharge treatment, ozone treatment, silane coupling agent, thin film formation treatment of various resins such as urethane-based resin, and the like, if necessary, in order to improve surface physical properties such as adhesiveness. ..
The thickness of the transparent substrate is usually in the range of 0.05 to 10 mm, preferably 0.1 to 7 mm. When thin film formation treatment of various resins is performed, the film thickness is usually in the range of 0.01 to 10 μm, preferably 0.05 to 5 μm.

(2) Coloring Spacer The photosensitive coloring composition of the present invention is used for the same purposes as the known photosensitive coloring composition for color filters, but hereinafter, when it is used as a coloring spacer (black photo spacer). , A specific example of a method for forming a black photo spacer using the photosensitive coloring composition of the present invention will be described.

Usually, the photosensitive coloring composition is supplied in a film or pattern on a substrate on which a black photo spacer should be provided by a method such as coating, and the solvent is dried. Subsequently, pattern formation is performed by a method such as a photolithography method in which exposure-development is performed. Then, if necessary, additional exposure or thermosetting treatment is performed to form a black photo spacer on the substrate.

(3) Formation of Colored Spacer [1] Method of Supplying 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. As the supply method, a conventionally known method, for example, a spinner method, a wire bar method, a flow coating method, a die coating method, a roll coating method, a spray coating method, or the like can be used. Further, it may be supplied in a pattern by an inkjet method, a printing method, or the like. Above all, according to the die coating method, the amount of the coating liquid used is significantly reduced, there is no influence of mist adhering when the spin coating method is used, and the generation of foreign substances is suppressed. Preferred from the point of view.

The coating amount varies depending on the application, but in the case of a black photo spacer, for example, the dry film thickness is usually 0.5 μm to 10 μm, preferably 1 μm to 9 μm, and particularly preferably 1 μm.
It is in the range of ~ 7 μm. It is also important that the dry film thickness or the height of the finally formed spacer is uniform over the entire substrate. If the variation is large, unevenness defects will occur in the liquid crystal panel.

However, when the photosensitive coloring composition of the present invention is used to collectively form black photospacers having different heights by a photolithography method, the heights of the finally formed black photospacers are different.

As the substrate, a known substrate such as a glass substrate can be used. Further, it is preferable that the surface of the substrate is flat.

[2] Drying method Drying after supplying the photosensitive coloring composition on the substrate is preferably performed by a drying method using a hot plate, an IR oven, or a convection oven. Alternatively, a vacuum drying method may be combined in which drying is performed in a vacuum chamber without raising the temperature.

The drying conditions can be appropriately selected according to the type of solvent component, the performance of the dryer used, and the like. The drying time usually depends on the type of solvent component, the performance of the dryer used, etc.
Selected at a temperature of 40 ° C. to 130 ° C. for 15 seconds to 5 minutes, preferably 50 ° C. to 110 ° C.
It is selected in the range of 30 seconds to 3 minutes at the temperature of.

[3] Exposure Method Exposure is performed by superimposing a negative mask pattern on a coating film of a photosensitive coloring composition and irradiating a light source of ultraviolet rays or visible light through the mask pattern. When exposure is performed using an exposure mask, the exposure mask may be placed close to the coating film of the photosensitive coloring composition, or the exposure mask may be placed at a position away from the coating film of the photosensitive coloring composition. The method of projecting the exposure light through the mask may also be used. Further, a scanning exposure method using a laser beam that does not use a mask pattern may be used. At this time, if necessary, in order to prevent the sensitivity of the photopolymerizable layer from being lowered by oxygen, the exposure is performed in a deoxidized atmosphere or after forming an oxygen blocking layer such as a polyvinyl alcohol layer on the photopolymerizable layer. You may do it.

As a preferred embodiment of the present invention, when black photospacers having different heights are simultaneously formed by a photolithography method, for example, a light-shielding portion (light transmittance of 0%) and a plurality of openings have the highest average light transmittance. An exposure mask having an opening (intermediate transmittance) having a small average light transmittance with respect to a high opening (completely transmitting aperture) is used. By this method, a step is generated by the difference in the average light transmittance between the intermediate transmission opening and the complete transmission opening, that is, the difference in the exposure amount.
For example, a method of creating an intermediate transmission opening by a matrix-like light-shielding pattern having a minute polygonal light-shielding unit is known. Further, as an absorber, a method of controlling the light transmittance by a film of a material such as chromium-based, molybdenum-based, tungsten-based, or silicon-based is known.

The light source used for the above exposure is not particularly limited. Examples of the light source include xenon lamps, halogen lamps, tungsten lamps, high-pressure mercury lamps, and 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, excima lasers, nitrogen lasers, helium cadmium lasers, bluish purple semiconductor lasers, near infrared semiconductor lasers, etc. Examples include a laser light source. An optical filter can also be used when irradiating light of a specific wavelength for use.

The optical filter may be, for example, a type in which the light transmittance at the exposure wavelength can be controlled with a thin film, and the material in that case is, for example, a Cr compound (Cr oxide, nitride, oxynitride, fluoride, etc.). Examples thereof include MoSi, Si, W and Al.

Energy of exposure generally, 1 mJ / cm ² or more, preferably 5 mJ / cm ² or more, more preferably 10 mJ / cm ² or more, usually 300 mJ / cm ² or less, preferably 200mJ
It is / cm ² or less, more preferably 150 mJ / cm ² or less.
Further, in the case of the proximity exposure method, the distance between the exposure target and the mask pattern is usually 1.
0 μm or more, preferably 50 μm or more, more preferably 75 μm or more, usually 500
It is μm or less, preferably 400 μm or less, and more preferably 300 μm or less.

[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 can further contain a surfactant, an organic solvent, a buffer, a complexing agent, a dye or a pigment.

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

Examples of the surfactant include nonionic surfactants such as polyoxyethylene alkyl ethers, polyoxyethylene alkylaryl ethers, polyoxyethylene alkyl esters, sorbitan alkyl esters, and monoglyceride alkyl esters; alkylbenzene sulfone. Anionic surfactants such as acid salts, alkylnaphthalene sulfonates, alkyl sulfates, alkyl sulfonates, sulfosuccinic acid ester salts; and amphoteric surfactants such as alkyl betaines and amino acids.

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

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

[5] Post-exposure and thermosetting treatment If necessary, the substrate after development may be subjected to post-exposure by the same method as the above-mentioned exposure method, or may be subjected to thermosetting treatment. The thermosetting treatment conditions at this time are that the temperature is 100 ° C to 2
It is selected in the range of 80 ° C., preferably 150 ° C. to 250 ° C., and the time is selected in the range of 5 minutes to 60 minutes.

The size, shape, etc. of the colored spacer of the present invention are appropriately adjusted according to the specifications of the color filter to which the colored spacer is applied. It is useful for forming black photospacers with different colors at the same time, in which case the height of the spacers is usually about 2-7 μm.
The sub-spacer usually has a height of about 0.2 to 1.5 μm lower than that of the spacer.
Further, the optical density (OD) per μm of the colored spacer of the present invention is preferably 1.2 or more, more preferably 1.5 or more, still more preferably 1.8 or more, from the viewpoint of light-shielding property.
It is usually 4.0 or less, preferably 3.0 or less. Here, the optical density (OD) is a value measured by a method described later.

[Septum]
The photosensitive coloring composition of the present invention can be suitably used for forming a partition wall, particularly a partition wall for partitioning an organic layer of an organic electroluminescent device. Examples of the organic layer used for the organic electroluminescent device include a hole injection layer, a hole transport layer, or a hole transport layer on the hole injection layer as described in Japanese Patent Application Laid-Open No. 2016-165396. Examples include the organic layer used.
Next, the partition wall using the photosensitive coloring composition of the present invention will be described according to the manufacturing method thereof.

(1) Support As the support and the substrate for forming the partition wall, the same support and the substrate for forming the colored spacer as described above can be used.

(2) Septum The case of being used as a partition will be described below with reference to a specific example of a method for forming a partition using the photosensitive coloring composition of the present invention.

Usually, the photosensitive coloring composition is supplied in a film or pattern by a method such as coating on a substrate on which a partition wall should be provided, and the solvent is dried. Subsequently, pattern formation is performed by a method such as a photolithography method in which exposure-development is performed. Then, if necessary, additional exposure or thermosetting treatment is performed to form a partition wall on the substrate.

(3) Formation of partition wall In the method for forming a partition wall using the photosensitive coloring composition of the present invention, a method of supplying the photosensitive coloring composition to a substrate, a drying method, an exposure method, a developing method, a follow-up exposure, and a thermosetting treatment. The specific method of
A method similar to the above-mentioned formation of the colored spacer can be adopted.

The size, shape, etc. when the present invention is used as a partition wall are appropriately adjusted according to the specifications of the organic electroluminescent device to which the present invention is applied, but the height of the partition wall formed from the photosensitive coloring composition of the present invention is It is usually about 0.5 to 10 μm.
Further, the optical density (OD) per μm as the partition wall of the present invention is determined from the viewpoint of light-shielding property.
0.7 or more is preferable, 1.2 or more is more preferable, 1.5 or more is further preferable, and 1.
8 or more is particularly preferable. Further, it is usually 4.0 or less, preferably 3.0 or less.
Here, the optical density (OD) is a value measured by a method described later.

[Organic electroluminescent device]
The organic electroluminescent device of the present invention includes a cured product composed of the above-mentioned photosensitive coloring composition, for example, a partition wall.
For example, various organic electroluminescent devices are manufactured using a substrate having a partition wall pattern manufactured by the method described above. The method for forming the organic electroluminescent device is not particularly limited, but preferably, after forming a partition wall pattern on the substrate by the above method, the functional material is sublimated in a vacuum state and within the region surrounded by the partition wall on the substrate. A vapor deposition method that forms a film by adhering to
An organic electroluminescent device is manufactured by forming an organic layer such as a pixel by a wet process such as a casting method, a spin coating method, or an inkjet printing method.

Examples of the type of the organic electroluminescent element include a bottom emission type and a top emission type.
In the bottom emission type, for example, a partition wall is formed on a glass substrate on which transparent electrodes are laminated, 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 wall. NS. On the other hand, in the top emission type, for example, a partition wall is formed on a glass substrate on which a metal electrode layer is laminated, and an electron transport layer, a light emitting layer, a hole transport layer, and a transparent electrode layer are laminated in an opening surrounded by the partition wall. Is created.
Examples of the light emitting layer include an organic electroluminescent layer as described in Japanese Patent Application Laid-Open No. 2009-146691 and Japanese Patent No. 5734681. In addition, Japanese Patent No. 5653387
Quantum dots as described in Japanese Patent Application Laid-Open No. 5653101 may 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 laminated structure consisting of two or more layers from the viewpoint of luminous efficiency. The thickness of each layer is not particularly limited, but is usually 1 to 500 nm from the viewpoint of luminous efficiency and brightness.

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

When an organic electroluminescent element is used as a pixel of an image display device, it is necessary to prevent the light of the light emitting layer of one pixel from leaking to another pixel, and further, when the electrode or the like is metal, it is outside. Since it is necessary to prevent deterioration of image quality due to light reflection, it is preferable to impart light-shielding property to the partition wall constituting the organic electroluminescent element.
Further, in the organic electroluminescent element, since it is necessary to provide electrodes on the upper surface and the lower surface of the partition wall, the partition wall preferably has high resistance and low dielectric constant from the viewpoint of insulating property. Therefore, when a colorant is used to impart light-shielding properties to the partition wall, 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 includes the cured product of the present invention as described above.
For example, the present invention is formed by forming an alignment film on a liquid crystal drive substrate (array substrate) having a colored spacer of the present invention, bonding the alignment film to the counter electrode substrate to form a liquid crystal cell, and injecting liquid crystal into the formed liquid crystal cell. It is possible to manufacture an image display device such as a liquid crystal display device provided with the colored spacers of.
On the other hand, the colored spacer of the present invention is installed on the counter electrode substrate side, and the liquid crystal drive substrate (array substrate).
An image display device such as a liquid crystal display device provided with the colored spacer of the present invention can also be manufactured by injecting liquid crystal into the formed liquid crystal cell.
Further, for example, as described in Japanese Patent Application Laid-Open No. 2014-215614, the liquid crystal orientation can be improved by irradiating the liquid crystal cell with ultraviolet rays after injecting the liquid crystal into the liquid crystal cell using a specific alignment substance.

Next, the present invention will be described in more detail with reference to Examples and Comparative Examples, but the present invention is not limited to the following Examples as long as the gist of the present invention is not exceeded.
The components of the pigment dispersion and the photosensitive coloring composition used in the following Examples and Comparative Examples, and their evaluation methods are as follows.

<Alkali-soluble resin-I>
145 parts by mass of propylene glycol monomethyl ether acetate was stirred while substituting with nitrogen, and the temperature was raised to 120 ° C. Here, 10 parts by mass of styrene, glycidyl methacrylate 8
Monomethacrylate having 5.2 parts by mass and tricyclodecane skeleton (FA manufactured by Hitachi Kasei Co., Ltd.)
−513M) 66 parts by mass was added dropwise, then 8.47 parts by mass of 2,2′-azobis-2-methylbutyronitrile was added dropwise over 3 hours, and stirring was continued at 90 ° C. for 2 hours. Next, the inside of the reaction vessel was replaced with air, 0.7 parts by mass of trisdimethylaminomethylphenol and 0.12 parts by mass of hydroquinone were added to 43.2 parts by mass of acrylic acid, and the reaction was continued at 100 ° C. for 12 hours. Then, 56.2 parts by mass of tetrahydrophthalic anhydride (THPA) and 0.7 parts by mass of triethylamine were added, and the mixture was reacted at 100 ° C. for 3.5 hours. The weight average molecular weight Mw of the alkali-soluble resin-I thus obtained measured by GPC is 8400, and the acid value is 80 mg.
It was KOH / g.

<Alkali-soluble resin-II>
300 parts by mass of "XD1000" (polyglycidyl ether of dicyclopentadiene phenol polymer, epoxy equivalent 252) manufactured by Nippon Kayakusha, 87 parts by mass of acrylic acid, 0.2 parts by mass of p-methoxyphenol, 5 parts by mass of triphenylphosphine. Parts and 255 parts by mass of propylene glycol monomethyl ether acetate were charged into a reaction vessel, and the mixture was stirred at 100 ° C. until the acid value reached 3.0 mgKOH / g. Then further tetrahydrophthalic anhydride 145
Parts by mass were added and reacted at 120 ° C. for 4 hours. Alkali-soluble resin thus obtained-
The weight average molecular weight Mw measured by GPC of II is 2600, and the acid value is 106 mgKOH /.
It was g.

<Pigment-I>
C. I. Pigment Blue 60
<Pigment-II>
C. I. Pigment Orange 64
<Pigment-III>
C. I. Pigment Violet 29
<Pigment-IV>
Black S 0100 CF, manufactured by BASF, Irgaphor®. It contains an organic black pigment having a chemical structure represented by the following general formula (2).

<Dispersant-I>
A methacrylic ABA triblock copolymer composed of an A block containing a repeating unit having a parent solvent group and a B block containing a repeating unit having a pigment adsorbing group. The following formula (a)
It has a repeating unit of ~ (g). The amine value is 61 mgKOH / g. The theoretical molecular weight is 8,600, and it has a repeating unit represented by the general formula (1).

The content ratios of the repeating units of the following formulas (a) to (g) in all the repeating units are (a) 40.4 mol%, (b) 13.8 mol%, (c) 9.2 mol%, respectively. (D) is 7.6 mol%, (e) is 2.7 mol%, (f) is 17.1 mol%, and (g) is 9.2 mol%.

<Dispersant-II>
A methacrylic ABA triblock copolymer composed of an A block containing a repeating unit having a parent solvent group and a B block containing a repeating unit having a pigment adsorbing group. The following formula (a)
It has a repeating unit of ~ (g). The amine value is 66 mgKOH / g. The theoretical molecular weight is 8,600, and it does not have a repeating unit represented by the general formula (1).

The content ratios of the repeating units of the following formulas (a) to (g) in all the repeating units are (a) 40.4 mol%, (b) 13.8 mol%, (c) 9.2 mol%, respectively. (D) is 7.6 mol%, (e) is 2.7 mol%, (f) is 17.1 mol%, and (g) is 9.2 mol%.

<Solvent-I>
PGMEA: Propylene Glycol Monomethyl Ether Acetate <Solvent-II>
MB: 3-Methoxy-1-butanol

<Photopolymerization Initiator-I>
Oxime ester-based photopolymerization initiator having the following chemical structure

<Photopolymerization Initiator-II>
Oxime ester compounds having the following chemical structure (4-acetoxyimino-5-[9-ethyl-6- (2-methylbenzoyl) -9H-carbazole-3-yl] -5-oxopentanoate methyl)

<Ethylene unsaturated compound>
DPHA: Dipentaerythritol hexaacrylate manufactured by Nippon Kayaku Co., Ltd. <Surfactant>
DIC Mega Fvck F-559
<Additives>
KAYAMER PM-21 manufactured by Nippon Kayaku Co., Ltd. (phosphate containing methacryloyl group)

<Evaluation of viscosity>
The viscosity of the prepared pigment dispersion is determined by the RE-85L viscometer manufactured by Toki Sangyo Co., Ltd. (Measurement condition: 23).
℃, 20 rpm).

<Measurement of optical density per unit film thickness (unit OD value)>
The optical density per unit film thickness was measured by the following procedure.
First, the prepared photosensitive coloring composition is applied to a glass substrate with a spin coater so that the film thickness after heat curing is 3.0 μm, dried under reduced pressure for 1 minute, and then 90 ° C. on a hot plate.
Was dried for 140 seconds. The obtained coating film was exposed without using an exposure mask.
As the irradiation light source, a high-pressure mercury lamp having an intensity of 45 mW / cm ^{2 at a wavelength of 365 nm was used.}
The exposure amount was 50 mJ / cm ² . Subsequently, the resist-coated substrate 1 was obtained by heat-curing at 230 ° C. for 20 minutes.
The optical density (OD value) of the obtained resist-coated substrate 1 was adjusted to 361T (V) manufactured by X-Rite.
The film thickness is measured using a transmission densitometer (color temperature of the illumination light source: about 2850K (equivalent to CIE standard light source A), spectral sensitivity characteristics of the light receiving part: ISO visual density according to the ISO 5-3 standard), and the film thickness is determined by the rhombus system. VertScan, a non-contact surface / layer cross-sectional shape measurement system manufactured by the company.
The optical density (unit OD value) per unit film thickness (1 μm) was calculated from the optical density (OD value) and the film thickness as measured by (R) 2.0. The OD value is a numerical value indicating the light-shielding ability, and the larger the value, the higher the light-shielding property.

<Evaluation of voltage retention (VHR) and ion density>
Empty cells were created by the method described in WO 2018/151079.
A liquid crystal display (MLC-6608 manufactured by Merck Japan Co., Ltd.) was injected into the obtained empty cell, and the peripheral portion was sealed with a UV curable sealant. The liquid crystal cell was annealed (heated at 105 ° C. for 2.5 hours in a hot air circulation furnace) to complete the liquid crystal cell for measurement.

A voltage was applied to the created liquid crystal cell for measurement at a voltage of 5 V, 0.6 Hz, and a frame time of 1667 msec, and the voltage retention rate before ultraviolet irradiation was measured with a "liquid crystal property evaluation device-6254 type" manufactured by Toyo Corporation. .. The voltage holding ratio is an index of electrical reliability. Further, the higher the voltage holding ratio, the more preferable.
Then, using the same device, the current when a triangular wave having a frequency of 0.1 Hz and ± 3 V was applied to the liquid crystal cell for measurement was measured over time to obtain a waveform of the time change of the current. The area of the impurity ion peak in the waveform was measured, and the ion density (pC) before irradiation with ultraviolet rays was measured.

Next, the liquid crystal cell for measurement was irradiated with ultraviolet rays ^{at 18 J / cm 2} and an illuminance of 40 mW / cm ^{2 with a high-pressure mercury lamp.} Using the measurement liquid crystal cell after the ultraviolet irradiation, the voltage retention rate after the ultraviolet irradiation and the ion density after the ultraviolet irradiation were measured by the same procedure as described above.

<NMP resistance evaluation>
N-methylpyrrolidone (NMP) resistance was evaluated by the following procedure.
First, the prepared photosensitive coloring composition was applied to an IZO substrate with a spin coater so that the film thickness after heat curing was 3.0 μm, dried under reduced pressure for 1 minute, and then dried at 90 ° C. for 140 seconds on a hot plate. It was dry. The obtained coating film was exposed without using an exposure mask. As the irradiation light source, a high-pressure mercury lamp having an intensity of 45 mW / cm ² at a wavelength of 365 nm was used, and the exposure amount was 50 mJ / cm ² . Subsequently, a developing solution consisting of an aqueous solution containing 0.05% by mass of potassium hydroxide and 0.08% by mass of a nonionic surfactant (“A-60” manufactured by Kao Co., Ltd.) was used, and the water pressure was 0 at 25 ° C. After shower development at 0.05 MPa, the development was stopped with pure water and washed with a water-washing spray. The shower development time was set to 1.6 times the time in which the unexposed coating film was dissolved and removed in advance. After that, the oven temperature is 230 ° C.
The resist-coated substrate 2 was obtained by heat-curing for 20 minutes. Two measurement substrates (2.5 cm × 1.0 cm square) were cut out from the prepared resist-coated substrate 2 and immersed in a 10 mL vial containing 8 mL of NMP. Then, the vial containing the measurement substrate is placed in a hot bath at 80 ° C. 4
The NMP dissolution test was carried out in a state of being allowed to stand for 0 minutes. After allowing to stand for 40 minutes, remove the vial from the heat bath and measure the absorbance of the NMP elution solution with a spectrophotometer (UV-31 manufactured by Shimadzu Corporation).
It was measured every 1 nm in the wavelength range of 300 to 800 nm by 00PC). A halogen lamp and a deuterium lamp (switching wavelength 360 nm) are used as a light source, and a photomal is used as a detector, and a slit width of 2 nm is a measurement condition. Also, the sample solution (N
MP elution solution) was placed in a 1 cm square quartz cell and measured. Absorbance is, in spectroscopy,
It is a dimensionless quantity that indicates how much the light intensity is attenuated when light passes through a certain object, and is defined by the following equation.

A (absorbance) = -log ₁₀ (I / I ₀ ) (I: transmitted light intensity, I ₀ : incident light intensity)

Further, when light is incident on the sample solution and the NMP single solution from the same light source, the light intensity transmitted through the NMP single solution _{can be regarded as I 0,} and the light intensity transmitted through the sample solution can be regarded as I. Therefore, (I / I ₀ ) in the above equation represents the light transmittance, and the absorbance A is a logarithmic representation of the reciprocal of the transmittance. Absorbance A is a notation used when calculating the concentration of a substance contained in a sample solution. When the absorbance A = 0, it indicates a state in which no light is absorbed (transmittance 100%), and when the absorbance A = ∞, it indicates a state in which no light is transmitted (transmittance 0%). become. That is, the higher the absorbance, the more resist coating film components are eluted into NMP, indicating that the NMP resistance is poor. The spectral area of the measured absorbance was calculated, and NMP resistance was evaluated according to the following criteria. The spectral area of the absorbance, which is the evaluation standard, can be expressed by the sum of the absorbances at each wavelength, and means the sum of the eluted resist components.

NMP resistance evaluation criteria: Judgment by spectral area value of absorbance (wavelength 300-800 nm)
)
A: 70 or less B: 70 over 100 or less

<Preparation of pigment dispersions 1 to 3>
The pigments, dispersants, alkali-soluble resins, and solvents shown in Table 1 were mixed so as to have the mass ratios shown in Table 1. This mixed solution was dispersed with a paint shaker in the range of 25 to 45 ° C. for 3 hours. As the beads, 0.5 mmφ zirconia beads were used, and a mass 2.5 times that of the dispersion was added. After the dispersion is completed, the beads and the dispersion liquid are separated by a filter.
Pigment dispersions 1 and 2 were prepared.
The amount of the solvent in Table 1 also includes the amount of the solvent derived from the dispersant and the alkali-soluble resin. Table 1 shows the evaluation results of the viscosity of the pigment dispersion liquid measured by the above method.

[Examples 1 and 2 and Comparative Example 1]
Add each component so that the solid content ratio of each component in the total solid content becomes the value shown in Table 2, and further add PGMEA so that the total solid content content ratio becomes 22% by mass, and stir. , To prepare the photosensitive coloring compositions of Examples 1 and 2 and Comparative Example 1. Table 2 shows the evaluation results of the unit OD value, the voltage retention rate (VHR), the ion density, and the NMP resistance measured by the above method.

From Table 2, the photosensitive coloring composition of Comparative Example 1 has insufficient ion density after ultraviolet irradiation, whereas the photosensitive coloring composition of Example 1 has a voltage retention rate and ion density after ultraviolet irradiation. It was good.
In the dispersant-II used in the photosensitive coloring composition of Comparative Example 1, a phenylmethyl group is bonded to a nitrogen atom constituting an ammonium group, but the bond is easily broken by irradiation with ultraviolet rays, and the phenylmethyl radical is easily broken. It is considered that the ion density deteriorated due to the presence in the liquid crystal. On the other hand, the dispersant (f) used in the photosensitive coloring composition of Example 1.
^{In 1), R 4} in the formula (I) is a naphthyl group, that is, a polycyclic aromatic hydrocarbon group. It is considered that since the ultraviolet rays are absorbed by having the polycyclic aromatic hydrocarbon group, the breakage of the bond due to the ultraviolet irradiation is suppressed, and the voltage retention rate and the ion density are improved.

Further, it is considered that the photosensitive coloring composition of Example 2 also contained the dispersant (f1), and the voltage retention rate and the ion density were improved.

Further, as compared with the photosensitive coloring composition of Comparative Example 1, the photosensitive coloring compositions of Examples 1 and 2 have N.
MP resistance was also good. The dispersant-II used in the photosensitive coloring composition of Comparative Example 1 has a phenylmethyl group bonded to a nitrogen atom constituting an ammonium group as described above.
It is presumed that these dispersants themselves are easily dissolved in NMP because they are not highly hydrophobic, and that a large amount of impurities in the pigment are also eluted in NMP. On the other hand, the dispersant (f1) used in the photosensitive coloring composition of Example 1 ^{is hydrophobic because R 4} in the formula (I) is a polycyclic aromatic hydrocarbon group as described above. It is presumed that the dispersant (f1) itself was difficult to dissolve in NMP, and the impurities in the pigment were also difficult to dissolve in NMP.

Claims (12)

A photosensitive coloring composition containing (a) a colorant, (b) an alkali-soluble resin, (c) a photopolymerization initiator, (d) an ethylenically unsaturated compound, (e) a solvent, and (f) a dispersant. There,
The optical density per 1 μm of the cured coating film is 0.5 or more.
The dispersant (f1) has a repeating unit represented by the following general formula (1).
) Is contained in the photosensitive coloring composition.

(In the formula (1), R ¹ and R ² are each independently an alkyl group which may have a substituent or an aryl group which may have a substituent, and R ¹ and R ² are They may be combined with each other to form an annular structure.
R ³ is an alkylene group.
R ⁴ is a polycyclic aromatic hydrocarbon group which may have a substituent.
R ⁵ is a hydrogen atom or a methyl group.
X is a divalent linking group.
Y is a halogen atom. ) The photosensitive coloring composition according to claim 1, wherein the polycyclic aromatic hydrocarbon group in ^{R 4} in the formula (1) has two or more aromatic rings. Claim 1 or 2 said that the colorant (a) includes 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.
The photosensitive coloring composition according to. The photosensitive coloring composition according to any one of claims 1 to 3, wherein the colorant (a) contains a black pigment. The photosensitive coloring composition according to any one of claims 1 to 4, wherein the content ratio of the colorant (a) is 10% by mass or more in the total solid content. The photosensitive coloring composition according to any one of claims 1 to 5, wherein the amine value of the dispersant (f1) is 30 mgKOH / g or more. The photosensitive coloring composition according to any one of claims 1 to 6, which is used for forming a coloring spacer. A cured product obtained by curing the photosensitive coloring composition according to any one of claims 1 to 7. An image display device containing the cured product according to claim 8. A pigment dispersion liquid for an image display device containing (a) a colorant, (e) a solvent, and (f) a dispersant.
The colorant (a) contains a black pigment and contains
The dispersant (f1) has a repeating unit represented by the following general formula (1).
) Is contained in a pigment dispersion liquid for an image display device.

(In the formula (1), R ¹ and R ² are each independently an alkyl group which may have a substituent or an aryl group which may have a substituent, and R ¹ and R ² are They may be combined with each other to form an annular structure.
R ³ is an alkylene group.
R ⁴ is a polycyclic aromatic hydrocarbon group which may have a substituent.
R ⁵ is a hydrogen atom or a methyl group.
X is a divalent linking group.
Y is a halogen atom. ) The pigment dispersion for an image display device according to claim 10, wherein the polycyclic aromatic hydrocarbon group in ^{R 4} in the formula (1) has two or more aromatic rings. Claim 10 or 1 in which the amine value of the dispersant (f1) is 30 mgKOH / g or more.
The pigment dispersion liquid for the image display device according to 1.