JP7031598B2 - Photosensitive coloring composition, cured product, coloring spacer, image display device - Google Patents

Description

The present invention relates to a photosensitive coloring composition and the like. Specifically, for example, a photosensitive coloring composition preferably used for forming a coloring spacer or the like in an image display device, a cured product obtained by curing the photosensitive coloring composition, a coloring spacer formed from the cured product, and the like. The present invention relates to an image display device provided with a colored spacer.
The specification of Japanese Patent Application No. 2016-202679 filed with the Japan Patent Office on October 14, 2016, and Japanese Patent Application No. 2017-172544 filed with the Japan Patent Office on September 7, 2017, The scope of claims, drawings, and the entire contents of the abstract, and a part or all of the contents disclosed in the documents cited in the present specification are cited here and incorporated as the disclosed contents of the present specification.

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 cell of the LCD is often formed by a method using a photosensitive composition represented by photolithography. 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 using the photosensitive composition, the voltage applied to the liquid crystal is not maintained due to the influence of the electrical characteristics of the photosensitive composition itself and the impurities contained in the photosensitive composition, which causes uneven display on the display. Problems may occur. In particular, in a color liquid crystal display, a member closer to the liquid crystal layer, for example, a member used for keeping the distance between two substrates in a liquid crystal panel constant, a so-called columnar spacer, a photo spacer, or the like has a great influence.

Conventionally, when a transparent spacer 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, for example, Patent Document 1 describes a method of using a spacer (colored spacer) having a light-shielding property. Further, in Patent Document 2, a specific combination is provided as a colored spacer that can control the shape and the step while ensuring the light-shielding property and the voltage retention rate of the liquid crystal display and has excellent adhesion to the substrate. Colored photosensitive compositions containing the above pigments have been proposed.

On the other hand, the photosensitive composition for a display may be required to have high curability and excellent mechanical properties. When manufacturing a liquid crystal panel, the color filter and the substrate are crimped under high temperature and high pressure, so that the physical properties of the color filter and the substrate are required to be maintained without being deformed by the high temperature and high pressure conditions at the time of crimping. That is, even if it is deformed by an external pressure, mechanical properties such as a recovery rate and an elastic restoration rate are required as a spacer to return to the original shape when the external pressure is removed. Conventionally, as a material satisfying this mechanical property, a resin composition or the like in which the content of the polyfunctional acrylate monomer is in a specific range has been proposed (see Patent Document 3).
Further, a curable composition containing a specific resin has been proposed as having excellent mechanical properties, pattern accuracy, and substrate adhesion (see Patent Document 4).

Japanese Patent Application Laid-Open No. 8-234212 International Publication No. 2013/115268 Japanese Patent Application Laid-Open No. 2002-174812 Japanese Patent Application Laid-Open No. 2006-312704

In recent years, with the change of the panel structure, there is a demand to further improve the light-shielding property of the colored spacer. Examples of the method for increasing the light-shielding property include a method for increasing the content ratio of the colorant in the photosensitive coloring composition. As a result of the study by the present inventors, when a colored spacer is formed by using a photosensitive coloring composition having a high content ratio of the colorant, the colorant is derived from the solvent for forming the alignment film to be the upper layer film thereof. It has been found that there is a problem that the elution amount of the impurities in the liquid crystal increases, and as a result, the display reliability of the LCD is deteriorated. Furthermore, it has also been found that as the content of the colorant increases, the curable component that contributes to the curing of the spacer decreases, so that there is a problem that the mechanical properties of the spacer deteriorate.

The present invention has been made in view of the above circumstances, and the present invention provides a photosensitive coloring composition capable of forming a pattern having high light-shielding property and excellent solvent resistance and mechanical properties. The purpose is.

As a result of diligent studies to solve the above-mentioned problems, the present inventors have solved the above-mentioned problems by using a specific alkali-soluble resin in the photosensitive coloring composition in which the content ratio of the colorant is a specific value or more. We found that it could be solved and came up with the present invention.

That is, the present invention has the following configurations [1] to [16].

[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 content of the (a) colorant in the total solid content of the photosensitive coloring composition is 20% by mass or more.
A photosensitive coloring composition, wherein the alkali-soluble resin (b) contains an alkali-soluble resin (b-1) having a partial structure (1) represented by the following formula (I).

(In formula (I), R ¹ represents a hydrogen atom or a methyl group;
R ² , R ³ , R ⁵ and R ⁶ each independently represent an alkylene group which may have a substituent;
R ⁴ represents an n + 1 valent linking group;
R ⁷ represents an alkylene group which may have a substituent, an alkenylene group which may have a substituent or an aromatic ring group which may have a substituent;
l and m each independently represent an integer from 0 to 12;
n represents an integer greater than or equal to 3;
* Represents a bond. )

[2] 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 content of the (a) colorant in the total solid content of the photosensitive coloring composition is 20% by mass or more.
(B) A photosensitive coloring composition, wherein the alkali-soluble resin contains an alkali-soluble resin (b-1) having a double bond equivalent of 400 or less.

[3] The photosensitive coloring composition according to [1] or [2], wherein the alkali-soluble resin (b-1) has a polystyrene-equivalent weight average molecular weight of 1000 or more as measured by gel permeation chromatography.
[4] The item according to any one of [1] to [3], wherein the content of the alkali-soluble resin (b-1) in the total solid content of the photosensitive coloring composition is 1% by mass or more. Photosensitive coloring composition.
[5] The photosensitive coloring composition according to any one of [1] to [4], wherein the alkali-soluble resin (b) further contains an epoxy (meth) acrylate resin (b-2).
[6] The epoxy (meth) acrylate resin (b-2) is an epoxy (meth) acrylate resin (b-2-ii) having a partial structure represented by the following general formula (ii), [5]. The photosensitive coloring composition according to.

(In formula (ii), R ^c each independently represents a hydrogen atom or a methyl group;
R ^d represents a divalent hydrocarbon group having a cyclic hydrocarbon group as a side chain;
^Re and R ^f each independently represent a divalent aliphatic group which may have a substituent;
m and n each independently represent an integer of 0 to 2;
* Represents a bond. )

[7] The photosensitive coloring composition according to any one of [1] to [6], wherein the (a) colorant contains an organic coloring pigment.
[8] The organic coloring pigment contains at least one selected from the group consisting of red pigments and orange pigments, and at least one selected from the group consisting of blue pigments and purple pigments, according to [7]. Photosensitive coloring composition.
[9] The photosensitive coloring composition according to any one of [1] to [8], wherein the (a) colorant contains a black pigment.
[10] The photosensitive coloring composition according to [9], wherein the black pigment contains one or both of carbon black and an organic black pigment.
[11] The organic black pigment is at least one selected from the group consisting of a compound represented by the following general formula (1), a geometric isomer of the compound, a salt of the compound, and a salt of the geometric isomer of the compound. The photosensitive coloring composition according to [10], which is an organic black pigment containing seeds.

(In formula (1), R ¹¹ and R ¹⁶ each independently represent a hydrogen atom, CH ₃ , CF ₃ , a fluorine atom or a chlorine atom;
R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁷ , R ¹⁸ , R ¹⁹ and R ²⁰ are independent hydrogen atoms, halogen atoms, 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 ²² , 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- ^, SO ₂ NH ₂ , SO ₂ NHR Represents ²¹ or SO ₂ NR ²¹ R ²² ;
And at least one combination selected from the group consisting of R ¹² and R ¹³ , R ¹³ and R ¹⁴ , R ¹⁴ and R ¹⁵ , R ¹⁷ and R ¹⁸ , R ¹⁸ and R ¹⁹ , and R ¹⁹ and R ²⁰ They can be bonded directly to each other or to each other by oxygen, sulfur, NH or NR ²¹ bridges;
Each of R ²¹ and R ²² independently has an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms, an alkenyl group having 2 to 12 carbon atoms, a cycloalkenyl group having 3 to 12 carbon atoms, or a carbon number of carbon atoms. It is an alkynyl group of 2 to 12. )

[12] The photosensitive coloring composition according to any one of [1] to [11], wherein the optical density per 1 μm of the cured coating film is 1.0 or more.
[13] The photosensitive coloring composition according to any one of [1] to [12], which is used for forming a coloring spacer.

[14] A cured product obtained by curing the photosensitive coloring composition according to any one of [1] to [13].
[15] A colored spacer formed from the cured product of [14].
[16] An image display device including the colored spacers of [15].

According to the present invention, it is possible to provide a photosensitive coloring composition having high light-shielding property and capable of forming a pattern having excellent solvent resistance and mechanical properties. Further, it is possible to provide a cured product and a colored spacer having excellent light-shielding property, solvent resistance and mechanical properties, and further, it is possible to provide an image display device provided with such a colored spacer.

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 "one or both of acrylic and methacrylic", and the same applies to "(meth) acrylate" and "(meth) acryloyl".

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

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

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

[Photosensitive coloring composition]
The photosensitive coloring composition of the present invention is
(A) Colorant (b) Alkali-soluble resin (c) Photopolymerization initiator (d) Ethylene unsaturated compound (e) Solvent (f) Dispersant is contained as an essential component.
Further, the photosensitive coloring composition of the present invention further comprises an adhesion improver such as a silane coupling agent, a surfactant (coatability improver), a pigment derivative, a photoacid generator, a cross-linking agent, and a mercapto, if necessary. It may contain other compounding components such as compounds, development improvers, ultraviolet absorbers, antioxidants, etc., and each compounding component is usually used in a state of being dissolved or dispersed in a solvent.

The photosensitive coloring composition according to the first aspect of the present invention has (a) a colorant content of 20% by mass or more in the total solid content of the photosensitive coloring composition, and (b) alkali-soluble. The resin contains an alkali-soluble resin (b-1) having a partial structure (1) represented by the formula (I) described later.
On the other hand, in the photosensitive coloring composition according to the second aspect of the present invention, the content ratio of the (a) colorant in the total solid content of the photosensitive coloring composition is 20% by mass or more, and (b). The alkali-soluble resin contains an alkali-soluble resin (b-1) having a double bond equivalent of 400 or less.
Hereinafter, unless otherwise specified, the "photosensitive coloring composition of the present invention" refers to both the photosensitive coloring composition according to the first aspect and the photosensitive coloring composition according to the second aspect. Unless otherwise specified, the "alkali-soluble resin (b-1)" refers to the "alkali-soluble resin (b-1)" according to the first aspect and the "alkali-soluble resin (b-1)" according to the second aspect. 1) ”both.

<(A) Colorant>
The photosensitive coloring composition of the present invention contains (a) a colorant. (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, in the photosensitive coloring composition of the present invention, the content ratio of the (a) colorant in the total solid content is 20% by mass or more. By containing (a) a colorant in a predetermined amount or more in this way, the light-shielding property of the obtained cured product, particularly the colored spacer, is enhanced. On the other hand, while the ratio of the colorant in the total solid content is high, the content ratio of curable components such as resins and monomers that contribute to photocuring is relatively low, and the content ratio of the colorant is high. As a result, the proportion of ultraviolet light absorbed by the colorant during exposure also tends to increase, and as a result, the crosslink density of the cured product tends to decrease, and solvent resistance and mechanical properties tend to deteriorate. ..

The type of (a) colorant used in the present invention is not particularly limited, and a pigment may be used 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 kind alone or two or more kinds. In particular, from the viewpoint of uniformly shading in the visible region, 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 pigments and inorganic pigments. Among these, it is preferable to use an organic pigment from the viewpoint of suppressing a decrease in the voltage retention rate of the liquid crystal display and suppressing absorption of ultraviolet rays to facilitate control of the shape and the step.
Examples of the organic pigment include an organic coloring pigment and an organic black pigment. 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 organic pigments, it is preferable to use an organic coloring pigment from the viewpoint of light-shielding property and ultraviolet absorption.
As the organic coloring pigment, one kind may be used alone, or two or more kinds may be used in combination. In particular, when used for light-shielding applications, it is more preferable to use a combination of organic coloring pigments having different colors, and it is further preferable to use a combination of organic coloring pigments having a color close to black.

The chemical structure of these organic pigments is not particularly limited, and examples thereof include azo-based, phthalocyanine-based, quinacridone-based, benzimidazolone-based, isoindolinone-based, dioxazine-based, indanthrone-based, and perylene-based. 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).

As the red pigment, C.I. I. Pigment Red 1, 2, 3, 4, 5, 6, 7, 8, 9, 12, 14, 15, 16, 17, 21, 22, 23, 31, 32, 37, 38, 41, 47, 48, 48: 1, 48: 2, 48: 3, 48: 4, 49, 49: 1, 49: 2, 50: 1, 52: 1, 52: 2, 53, 53: 1, 53: 2, 53: 3, 57, 57: 1, 57: 2, 58: 4, 60, 63, 63: 1, 63: 2, 64, 64: 1, 68, 69, 81, 81: 1, 81: 2, 81: 3, 81: 4, 83, 88, 90: 1, 101, 101: 1, 104, 108, 108: 1, 109, 112, 113, 114, 122, 123, 144, 146, 147, 149, 151, 166, 168, 169, 170, 172, 173, 174, 175, 176, 177, 178, 179, 181, 184, 185, 187, 188, 190, 193, 194, 200, 202, 206, 207, 208, 209, 210, 214, 216, 220, 221, 224, 230, 231, 232, 233, 235, 236, 237, 238, 239, 242, 243, 245, 247, 249, 250, 251, 253, 254, 255, 256, 257, 258, 259, 260, 262, 263, 264, 265, 266, 267, 268, 269, 270, 271, 272, 273, 274, 275, 276 can be mentioned. Among these, C.I. I. Pigment Red 48: 1, 122, 149, 168, 177, 179, 194, 202, 206, 207, 209, 224, 242, 254, more preferably C.I. I. Pigment Red 177, 209, 224, 254 can be mentioned. In terms of dispersibility and light-shielding property, C.I. I. Pigment Red 177, 254, 272 are preferably used, and when the photosensitive coloring composition 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, 74, 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 is preferably used, and when the photosensitive coloring composition is cured with ultraviolet rays, it is preferable to use an orange pigment having a low ultraviolet absorption rate, and from this viewpoint. C. I. It is more preferable to use Pigment Oranges 64 and 72.

As the blue pigment, C.I. I. Pigment Blue 1, 1: 2, 9, 14, 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, 16, 17, 19, 25, 27, 28, 29, 33, 35, 36, 56, 56: 1, 60, 61, 61: 1, 62, 63, 66, 67, 68, 71, 72, 73, 74, 75, 76, 78, 79 can be mentioned. Among these, from the viewpoint of light-shielding property, C.I. I. Pigment Blue 15, 15: 1, 15: 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 a blue pigment. 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, more preferably C.I. I. Pigment Violet 23 can be mentioned.
In terms of dispersibility and light-shielding property, C.I. I. Pigment Violet 23, 29 is preferably used, and when the photosensitive coloring composition 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 organic coloring pigments that can be used in addition to red pigments, orange pigments, blue pigments, and purple pigments include green pigments and yellow pigments.
Examples of the green pigment include C.I. I. Pigment Greens 1, 2, 4, 7, 8, 10, 13, 14, 15, 17, 18, 19, 26, 36, 45, 48, 50, 51, 54, 55 can be mentioned. Among these, preferably C.I. I. Pigment Greens 7 and 36 can be mentioned.
As the yellow pigment, C.I. I. Pigment Yellow 1, 1: 1, 2, 3, 4, 5, 6, 9, 10, 12, 13, 14, 16, 17, 24, 31, 32, 34, 35, 35: 1, 36, 36: 1,37,37: 1,40,41,42,43,48,53,55,61,62,62: 1,63,65,73,74,75,81,83,87,93,94, 95, 97, 100, 101, 104, 105, 108, 109, 110, 111, 116, 117, 119, 120, 126, 127, 127: 1, 128, 129, 133, 134, 136, 138, 139, 142, 147, 148, 150, 151, 153, 154, 155, 157, 158, 159, 160, 161, 162, 163, 164, 165, 166, 167, 168, 169, 170, 172, 173, 174, 175, 176, 180, 181, 182, 183, 184, 185, 188, 189, 190, 191, 191: 1, 192, 193, 194, 195, 196, 197, 198, 199, 200, 202, 203, 204, 205, 206, 207, 208 can be mentioned. Among these, preferably C.I. I. Pigment Yellow 83, 117, 129, 138, 139, 150, 154, 155, 180, 185, more preferably C.I. I. Pigment Yellow 83, 138, 139, 150, 180 can be mentioned.

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

Among these, from the viewpoint of light-shielding property and control of shape and step, it is preferable to contain at least one of the following pigments.
Red pigment: Color Index Pigment Red 177, 254, 272
Orange pigment: Color Index Pigment Orange 43, 64, 72
Blue pigment: Color Index Pigment Blue 15: 6, 60
Purple Pigment: Color Index 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 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, and examples thereof include a combination of a red pigment and a blue pigment, a combination of a blue pigment and an orange pigment, and a combination of a blue pigment and an orange pigment and a purple pigment from the viewpoint of light-shielding property. ..

Further, in addition to these organic coloring pigments, black pigments may be used. Further, in addition to the organic coloring pigment, a black pigment may be further used.
Examples of the black pigment include inorganic black pigments and organic black pigments, but from the viewpoint of light-shielding properties, it is preferable to contain one or both of carbon black and organic black pigments.

Among the black pigments, it is preferable to use an organic black pigment from the viewpoint of suppressing a decrease in the voltage retention rate of the liquid crystal and suppressing the absorption of ultraviolet rays to make it easier to control the shape and the step, and particularly the light-shielding property. From the viewpoint of the above, the compound represented by the following general formula (1) (hereinafter, also referred to as “compound (1)”), the geometric isomer of the compound (1), the salt of the compound (1), and the compound (1). ), It is preferable to use an organic black pigment containing at least one selected from the group consisting of salts of the geometric isomers (hereinafter, may be referred to as "organic black pigment represented by the general formula (1)"). ..

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 are independent hydrogen atoms, halogen atoms, 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 ²² , 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- ^, SO ₂ NH ₂ , SO ₂ NHR Represents ²¹ or SO ₂ NR ²¹ R ²² ; and from R ¹² and R ¹³ , R ¹³ and R ¹⁴ , R ¹⁴ and R ¹⁵ , R ¹⁷ and R ¹⁸ , R ¹⁸ and R ¹⁹ , and R ¹⁹ and R ²⁰ . At least one combination selected from the group can be bonded directly to each other or to each other by an oxygen atom, a sulfur atom, an NH or NR ²¹ bridge; R ²¹ and R ²² each independently have 1 to 1 carbon atoms. It is an alkyl group having 12 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms, an alkenyl group having 2 to 12 carbon atoms, a cycloalkenyl group having 3 to 12 carbon atoms, or an alkynyl group having 2 to 12 carbon atoms.

The geometric 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 considered to be non-absorbent and do not 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, preferably hydrogen atom, NO ₂ , OCH ₃ , OC ₂ H ₅ , bromine atom, chlorine atom, CH ₃ , C ₂ H ₅ , N (CH ₃ ) ₂ , N (CH). ₃ ) (C ₂ H ₅ ), N (C ₂ H ₅ ) ₂ , α-naphthyl, β-naphthyl, SO ₃ H or SO _3- ^, more preferably hydrogen atom or SO ₃ H, particularly preferred. Is a hydrogen atom.

Each of R ¹¹ and R ¹⁶ is 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 R ²⁰ . It is the same.

The alkyl group having 1 to 12 carbon atoms is, for example, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, an isobutyl group, a tert-butyl group, a 2-methylbutyl group, or n-. Pentyl group, 2-pentyl group, 3-pentyl group, 2,2-dimethylpropyl group, n-hexyl group, n-heptyl group, n-octyl group, 1,1,3,3-tetramethylbutyl group, 2 -Ethylhexyl group, nonyl group, decyl group, undecyl group or dodecyl group.

The cycloalkyl group having 3 to 12 carbon atoms is, for example, a cyclopropyl group, a cyclopropylmethyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cyclohexylmethyl group, a trimethylcyclohexyl group, a tudyl group, a norbornyl group, a boronyl group, or a norcaryl group. , Caryl group, mentyl group, norpinyl group, pinyl group, 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, a 2-propen-2-yl group, a 2-butene-1-yl group, a 3-buten-1-yl group, or a 1,3-butadiene. -2-yl group, 2-penten-1-yl group, 3-penten-2-yl group, 2-mentyl-1-buten-3-yl group, 2-methyl-3-buten-2-yl group, It is a 3-methyl-2-buten-1-yl group, a 1,4-pentadiene-3-yl group, a hexenyl group, an octenyl group, a nonenyl group, a decenyl group or a 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 -Il group, 7,7-dimethyl-2,4-norbornediene-3-yl group or canphenyl group.

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

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

The 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 bodies.

Specific examples of such an organic black pigment include Irgaphor (registered trademark) Black S 0100 CF (manufactured by BASF) under the trade name.
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 thereof. It is preferable to include.

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, 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, # 970, # 980, # 990, # 1000, # 2200, # 2300, # 2350, # 2400, # 2600, # 2650, # 3030, # 3050, # 3150, # 3250, # 3400, # 3600, # 3750, # 3950, # 4000, # 4010, OIL7B, OIL9B , OIL11B, OIL30B, OIL31B
Made by Degusa: Printex (registered trademark, the same applies hereinafter) 3, Printex3OP, Printex30, Printex30OP, Printex40, Printex45, Printex55, Printex60, Printex75, Printex80, Printex85, Printex90, PrintexA U, Printex V, PrintexG, SpecialBlack550, SpecialBlack350, SpecialBlack250, SpecialBlack100, SpecialBlack6, SpecialBlack5, SpecialBlack5, SpecialBlackBlackBlBlBlack4, Col
FW2V, Color Black FW18, Color Black FW18, Color Black FW200, Color Black S160, Color Black S170
Made by Cabot: Monarch (registered trademark, the same shall apply hereinafter) 120, Monarch280, Monarch460, Monarch800, Monarch880, Monarch900, Monarch1000, Monarch1100, Monarch1300, Monarch1400, Monarch4630, REGAL (registered trademark, the same shall apply hereinafter). REGAL415R, REGAL250, REGAL250R, REGAL330, REGAL400R, REGAL55R0, REGAL660R, BLACK PEARLS480, PEARLS130, VULCAN (registered trademark, the same shall apply hereinafter) XC72R, ELFTEX (registered trademark) -8
Made by Biller: RAVEN (registered trademark, the same shall apply hereinafter) 11, RAVEN14, RAVEN15, RAVEN16, RAVEN22RAVEN30, RAVEN35, RAVEN40, RAVEN410, RAVEN420, RAVEN450, RAVEN500, RAVEN780, RAVEN450, RAVEN500, RAVEN780, RAVEN810RAVEN10URA , RAVEN1170, 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 Japanese Patent Application Laid-Open No. 09-71733 can be preferably used. Resin-coated carbon black is preferably used in terms of volume resistance and dielectric constant.

The carbon black to be subjected to the coating treatment with the resin preferably has a total content of Na and Ca of 100 ppm or less. Carbon black is usually raw material oil or combustion oil (or gas) at the time of production, reaction stop water, granulation water, Na, Ca, K, Mg, Al, Fe, etc. mixed from the reactor material of the reactor. Contains ash having the composition of. 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 these Na and Ca-containing ash, carefully select the raw material oil, fuel oil (or gas) and reaction stop water used in the production of carbon black, which have the lowest possible content. It is possible by doing so and by reducing the amount of alkaline substances added to adjust the structure as much as possible. As another method, there is a method of washing the carbon black produced from the furnace with water, hydrochloric acid or the like to dissolve and remove Na and Ca.

Specifically, when carbon black is mixed and dispersed in water, hydrochloric acid, or hydrogen peroxide solution, and then a sparingly soluble solvent is added to water, the carbon black moves to the solvent side and completely separates from water. Most of the Na and Ca present in the carbon black are dissolved and removed in water and acid. In order to reduce the total amount of Na and Ca to 100 ppm or less, it may be possible to use the carbon black manufacturing process alone, in which the raw materials are carefully selected, 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 up to 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. It means the equivalent circle diameter obtained by.

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

The type of resin to be coated is not particularly limited, but synthetic resin is common, and a resin having a benzene ring in its structure has a stronger action as an amphoteric surfactant. It is preferable from the viewpoint of dispersibility and dispersion stability.
Specific synthetic resins include thermocurable 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 sulfopolyphenylensulphon, polyarylate, and polyether ether ketone can be used. The amount of the coating resin is preferably 1 to 30% by mass with respect to the total amount of carbon black and the resin. There is a tendency that the coating can be made sufficient by setting it to the lower limit value or more. On the other hand, by setting the value to the upper limit or less, 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 colorant 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 light-shielding rate and a low surface reflectance tends to be formed at low cost. It is also presumed that by coating the surface of the carbon black with a resin, the ash containing Na and Ca has a function of being contained 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.
The average particle size of the pigment is a value obtained from the pigment particle size measured by dynamic light scattering (DLS). The particle size is measured by a sufficiently diluted 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, , According to the concentration), and measure at 25 ° C.

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 colorants include azo dyes, anthraquinone dyes, phthalocyanine dyes, quinone imine dyes, quinoline dyes, nitro dyes, carbonyl dyes, and methine dyes.
Examples of the azo dye include C.I. I. Acid Yellow 11, C.I. I. Acid Orange 7, C.I. I. Acid Red 37, C.I. I. Acid Red 180, C.I. I. Acid Blue 29, C.I. I. Direct Red 28, C.I. I. Direct Red 83, C.I. I. Direct Yellow 12, C.I. I. Direct Orange 26, C.I. I. Direct Green 28, C.I. I. Direct Green 59, C.I. I. Reactive Yellow 2, C.I. I. Reactive Red 17, C.I. I. Reactive Red 120, C.I. I. Reactive Black 5, C.I. I. Disperse Orange 5, C.I. I. Disperse thread 58, C.I. I. Disperse Blue 165, C.I. I. Basic Blue 41, C.I. I. Basic Red 18, C.I. I. Moldant Red 7, C.I. I. Moldant Yellow 5, C.I. I. Examples include Moldant Black 7.

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

<(B) Alkaline-soluble resin>
{Alkali-soluble resin (b-1)}
(First aspect)
In the photosensitive coloring composition of the present invention according to the first aspect, the alkali-soluble resin (b) is an alkali-soluble resin (b-1) having a partial structure (1) represented by the following formula (I) (hereinafter, , The "alkali-soluble resin (b-1)" in the first aspect may be referred to as "alkali-soluble resin (b-1-1)"). Since the alkali-soluble resin (b-1-1) has three or more (meth) acryloyloxy groups in the partial structure represented by the formula (I), the amount of ethylenic double bonds in one molecule of the resin is large. When a colored spacer is formed using the photosensitive coloring composition containing the resin, the crosslink density is increased, the elution of impurities into the solvent is suppressed, high display reliability can be ensured, and the crosslink density of the spacer is also increased. It is considered that the mechanical properties are also excellent.

(Partial structure (1))

In formula (I) above, R ¹ represents a hydrogen atom or a methyl group;
R ² , R ³ , R ⁵ and R ⁶ each independently represent an alkylene group which may have a substituent;
R ⁴ represents an n + 1 valent linking group;
R ⁷ represents an alkylene group which may have a substituent, an alkenylene group which may have a substituent, or an aromatic ring group which may have a substituent;
l and m each independently represent an integer from 0 to 12;
n represents an integer greater than or equal to 3;
* Represents a bond.

(R ² , R ³ , R ⁵ and R ⁶ )
In the formula (I), R ² , R ³ , R ⁵ and R ⁶ each independently represent an alkylene group which may have a substituent.
The alkylene group may be linear, branched, cyclic, or a combination thereof. The carbon number is not particularly limited, but is 1 or more, and is usually 6 or less, preferably 4 or less, and more preferably 2 or less. By setting the value to the upper limit or less, the compatibility with other components tends to be good. The combination of the upper limit and the lower limit is preferably 1 to 6, more preferably 1 to 4, and even more preferably 1 to 2.

Specific examples of the alkylene group include a methylene group, an ethylene group, a propylene group, a butylene group and a cyclohexylene group, and a methylene group or an ethylene group is preferable from the viewpoint of compatibility with other components, and a methylene group is more preferable. ..

Examples of the substituent that the alkylene group may have include an alkoxy group, a halogen atom (-F, -Cl, -Br, -I), a hydroxy group, a carboxyl group, and the like, and from the viewpoint of easiness of synthesis, there are examples. It is preferably unsubstituted.

(R ⁴ )
In the general formula (I), R ⁴ represents an n + 1 valent linking group. The chemical structure of the n + 1-valent linking group is not particularly limited, and examples thereof include n + 1-valent hydrocarbon groups which may have a substituent. The hydrocarbon group may be an aliphatic hydrocarbon group or an aromatic hydrocarbon group, and is preferably an aliphatic hydrocarbon group from the viewpoint of developability. Further, the carbon-carbon single bond in the hydrocarbon group may be interrupted by at least one selected from the group consisting of —O—, CO— and —NH—.

Specific examples of the n + 1 valent linking group include the following. * In the chemical formula represents the bond.

(R ⁷ )
In the formula (I), R ⁷ has an alkylene group which may have a substituent, an alkaneylene group which may have a substituent, or a divalent aromatic ring which may have a substituent. Represents a group.

The alkylene group in R ⁷ may be linear, branched, cyclic, or a combination thereof. The number of carbon atoms is not particularly limited, but is 1 or more, preferably 2 or more, and usually 8 or less, preferably 6 or less, and more preferably 4 or less. When it is set to the lower limit value or more, the development adhesion tends to be good, and when it is set to the upper limit value or less, the curability tends to be good. The combination of the upper limit and the lower limit is preferably 1 to 8, more preferably 1 to 6, and even more preferably 2 to 4.

Specific examples of the alkylene group include a methylene group, an ethylene group, a propylene group, a hexylene group and a cyclohexylene group. From the viewpoint of curability, a methylene group or an ethylene group is preferable, and an ethylene group is more preferable.

Examples of the substituent that the alkylene group may have include an alkoxy group, a halogen atom (-F, -Cl, -Br, -I), a hydroxy group, a carboxyl group, and the like, and from the viewpoint of curability, there is no substituent. It is preferably a substitution.

The alkenylene group in R ⁷ may be linear, branched, cyclic, or a combination thereof. The number of carbon atoms is not particularly limited, but is 2 or more, preferably 4 or more, and usually 8 or less, preferably 6 or less. When it is set to the lower limit value or more, the development adhesion tends to be good, and when it is set to the upper limit value or less, the curability tends to be good. The combination of the upper limit and the lower limit is preferably 2 to 8, and more preferably 4 to 6.

Specific examples of the alkenylene group include an ethenylene group, a propenylene group, a butenylene group, and a cyclohexenylene group. From the viewpoint of curability, an ethenylene group or a cyclohexenylene group is preferable, and an ethenylene group is more preferable.

Examples of the substituent that the alkenylene group may have include an alkoxy group, a halogen atom (-F, -Cl, -Br, -I), a hydroxy group, a carboxyl group, and the like, and from the viewpoint of curability, there is no substituent. It is preferably a substitution.

Examples of the divalent aromatic ring group in R ⁷ 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 40 or less, more preferably 30 or less, further preferably 20 or less, still more preferably 15 or less, and 10 or less. Especially preferable. When it is set to the lower limit value or more, the development adhesion tends to be good, and when it is set to the upper limit value or less, the curability tends to be good. As the combination of the upper limit and the lower limit, 4 to 40 is preferable, 5 to 30 is more preferable, 6 to 20 is more preferable, 6 to 15 is more preferable, and 6 to 10 is particularly preferable.

The aromatic hydrocarbon ring in the divalent aromatic hydrocarbon ring group may be a monocyclic ring or a condensed ring. Examples of the divalent 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, and a chrysene ring, which have two free atomic valences. Examples thereof include groups such as a triphenylene ring, an acenaphthene ring, a fluorene ring, and a fluorene ring.
Further, the aromatic heterocycle in the divalent aromatic heterocyclic group may be a monocyclic ring or a condensed ring. Examples of the divalent 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, and an indol, which have two free atomic valences. Ring, carbazole ring, pyrrolobylmidazole ring, pyrrolopyrazole ring, pyrolopyrrole ring, thienopyrazole ring, thienothiophene ring, flopyrol ring, flofran ring, thienofran ring, benzoisoxazole ring, benzoisothiazole ring, benzimidazole ring, pyridine ring, Examples include groups such as pyrazine ring, pyridazine ring, pyrimidin ring, triazine ring, quinoline ring, isoquinoline ring, synolin ring, quinoxalin ring, phenanthridine ring, benzimidazole ring, perimidine ring, quinazoline ring, quinazolinone ring, and azulene ring. ..
Among these, from the viewpoint of photocurability, a benzene or 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 an alkyl group, an alkoxy group, a halogen atom (-F, -Cl, -Br, -I), a hydroxy group, a carboxyl group and the like. .. Of these, no substitution is preferable from the viewpoint of curability.

Among these, from the viewpoint of curability, R ⁷ is preferably an alkylene group which may have a substituent, more preferably an unsubstituted alkylene group, and further preferably an ethylene group.

(L and m)
In the general formula (I), l and m each independently represent an integer of 0 to 12. From the viewpoint of development adhesion, it is preferably 0 or more, more preferably 1 or more, and from the viewpoint of curability, it is preferably 8 or less, more preferably 6 or less, and 4 The following is more preferable, and 2 or less is particularly preferable. As the combination of the upper limit and the lower limit, 0 to 8 is preferable, 1 to 6 is more preferable, 1 to 4 is more preferable, and 1 to 2 is particularly preferable. On the other hand, it is preferably 0 from the viewpoint of curability.

(N)
In the general formula (I), n represents an integer of 3 or more. n is preferably 4 or more, more preferably 5 or more, preferably 10 or less, more preferably 8 or less, further preferably 7 or less, and particularly preferably 6 or less. When it is at least the above lower limit value, the curability tends to be good, and when it is at least the above upper limit value, the development solubility tends to be good. As the combination of the upper limit and the lower limit, 3 to 10 is preferable, 4 to 8 is more preferable, 5 to 7 is more preferable, and 5 to 6 is particularly preferable.

(Partial structure (2))
Further, the alkali-soluble resin (b-1-1) preferably has a partial structure (2) represented by the following formula (II) from the viewpoint of development solubility.

In the above formula (II), R ⁸ represents an alkylene group which may have a substituent, an alkenylene group which may have a substituent, or an aromatic ring group which may have a substituent. ;
* Represents a bond.

(R ⁸ )
In the formula (II), R ⁸ has an alkylene group which may have a substituent, an alkaneylene group which may have a substituent, or a divalent aromatic ring which may have a substituent. Represents a group.

The alkylene group in R ⁸ may be linear, branched, cyclic, or a combination thereof. The number of carbon atoms is not particularly limited, but is 1 or more, preferably 2 or more, and usually 8 or less, preferably 6 or less. When it is set to the lower limit value or more, the development adhesion tends to be good, and when it is set to the upper limit value or less, the curability tends to be good. The combination of the upper limit and the lower limit is preferably 1 to 8, and more preferably 2 to 6.

Specific examples of the alkylene group include a methylene group, an ethylene group, a propylene group, a hexylene group and a cyclohexylene group. From the viewpoint of curability, a methylene group or an ethylene group is preferable, and an ethylene group is more preferable.

Examples of the substituent that the alkylene group may have include an alkoxy group, a halogen atom (-F, -Cl, -Br, -I), a hydroxy group, a carboxyl group, and the like, and from the viewpoint of curability, there is no substituent. It is preferably a substitution.

The alkenylene group in R ⁸ may be linear, branched, cyclic, or a combination thereof. The number of carbon atoms is not particularly limited, but is 2 or more, preferably 4 or more, and usually 8 or less, preferably 6 or less. When it is set to the lower limit value or more, the development adhesion tends to be good, and when it is set to the upper limit value or less, the curability tends to be good.

Specific examples of the alkenylene group include an ethenylene group, a propenylene group, a butenylene group, and a cyclohexenylene group. From the viewpoint of curability, an ethenylene group or a cyclohexenylene group is preferable, and a cyclohexenylene group is more preferable.

Examples of the substituent that the alkenylene group may have include an alkoxy group, a halogen atom (-F, -Cl, -Br, -I), a hydroxy group, a carboxyl group, and the like, and from the viewpoint of curability, there is no substituent. It is preferably a substitution.

Examples of the divalent aromatic ring group in R ⁸ 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 40 or less, more preferably 30 or less, further preferably 20 or less, still more preferably 15 or less, and 10 or less. Especially preferable. When it is set to the lower limit value or more, the development adhesion tends to be good, and when it is set to the upper limit value or less, the curability tends to be good. As the combination of the upper limit and the lower limit, 4 to 40 is preferable, 5 to 30 is more preferable, 6 to 20 is more preferable, 6 to 15 is more preferable, and 6 to 10 is particularly preferable.

The aromatic hydrocarbon ring in the divalent aromatic hydrocarbon ring group may be a monocyclic ring or a condensed ring. Examples of the divalent 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, and a chrysene ring, which have two free atomic valences. Examples thereof include groups such as a triphenylene ring, an acenaphthene ring, a fluorene ring, and a fluorene ring.
Further, the aromatic heterocycle in the divalent aromatic heterocyclic group may be a monocyclic ring or a condensed ring. Examples of the divalent 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, and an indol, which have two free atomic valences. Ring, carbazole ring, pyrrolobylmidazole ring, pyrrolopyrazole ring, pyrolopyrrole ring, thienopyrazole ring, thienothiophene ring, flopyrol ring, flofran ring, thienofran ring, benzoisoxazole ring, benzoisothiazole ring, benzimidazole ring, pyridine ring, Examples include groups such as pyrazine ring, pyridazine ring, pyrimidin ring, triazine ring, quinoline ring, isoquinoline ring, synolin ring, quinoxalin ring, phenanthridine ring, benzimidazole ring, perimidine ring, quinazoline ring, quinazolinone ring, and azulene ring. ..
Among these, from the viewpoint of photocurability, a benzene or 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 an alkyl group, an alkoxy group, a halogen atom (-F, -Cl, -Br, -I), a hydroxy group, a carboxyl group and the like. .. Of these, no substitution is preferable from the viewpoint of curability.

Among these, from the viewpoint of curability, R ⁸ is preferably an alkenylene group which may have a substituent, more preferably an unsubstituted alkenylene group, and further preferably a cyclohexenylene group. preferable.

Specific examples of the partial structure (2) represented by the formula (II) include the following. * In the chemical formula represents the bond.

(Partial structure (3))
Further, the alkali-soluble resin (b-1-1) preferably has a partial structure (3) represented by the following formula (III) from the viewpoint of curability.

In the above formula (III), R ⁹ represents an epoxy resin residue;
p represents an integer greater than or equal to 1;
* Represents a bond.

(R ⁹ )
In the above formula (III), R ⁹ represents an epoxy resin residue. The epoxy resin residue means a residue obtained by removing an epoxy group from an epoxy resin.
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 higher phenolic hydroxyl group, and may be a monomer or a polymer.
Specifically, for example, bisphenol A epoxy resin, bisphenol F epoxy resin, bisphenol S epoxy resin, phenol novolac epoxy resin, cresol novolac epoxy resin, biphenyl novolac epoxy resin, trisphenol epoxy resin, polymerization of phenol with dicyclopentane. Epoxy resin, dihydrooxylfluorene type epoxy resin, dihydrooxylalkyleneoxylfluorene type epoxy resin, 9,9-bis (4'-hydroxyphenyl) fluorene diglycidyl etherified product, 1,1-bis (4'-hydroxy) Examples thereof include diglycidyl etherified product of phenyl) adamantan, and those having an aromatic ring in the main chain such as these can be preferably used.

(P)
In the above equation (III), p represents an integer of 1 or more. From the viewpoint of achieving both curability and develop solubility, p is preferably 2. On the other hand, from the viewpoint of curability, p is preferably 2 or more, more preferably 3 or more, further preferably 5 or more, and 20 or less from the viewpoint of development solubility. Is preferable, and it is more preferably 15 or less, and further preferably 10 or less. When it is at least the above lower limit value, the curability tends to be good, and when it is at least the above upper limit value, the development solubility tends to be good. The combination of the upper limit and the lower limit is preferably 1 to 20, more preferably 2 to 15, and even more preferably 2 to 10.

(Partial structure (3-1))
The partial structure (3) represented by the formula (III) is preferably a partial structure (3-1) represented by the following formula (III-1) from the viewpoint of development solubility.

In the above formula (III-1), γ represents a divalent linking group;
The benzene ring in formula (III-1) may be further substituted with any substituent;
* Represents a bond.

(Γ)
In the formula (III-1), γ represents a divalent linking group. Examples of the divalent linking group include a single bond, an alkylene group which may have a substituent, -CO- or -SO _2- , from the viewpoint of development solubility.
The alkylene group may be linear, branched, cyclic, or a combination thereof. The number of carbon atoms is not particularly limited, but is preferably 1 or more, preferably 2 or more, and usually 8 or less, preferably 6 or less. When it is set to the lower limit value or more, the development adhesion tends to be good, and when it is set to the upper limit value or less, the curability tends to be good. The combination of the upper limit and the lower limit is preferably 1 to 8, and more preferably 2 to 6.

Specific examples of the alkylene group include a methylene group, an ethylene group, a propylene group, a butylene group, a hexylene group, a cyclohexylene group, a heptylene group, an octylene group and a dodecylene group, and a methylene group or a propylene group may be used from the viewpoint of curability. Preferably, a propylene group is more preferred, and a propane-2,2-diyl group is even more preferred.

Examples of the substituent that the alkylene group may have include an alkoxy group, a halogen atom (-F, -Cl, -Br, -I), a hydroxy group, a carboxyl group, and the like, and from the viewpoint of curability, there is no substituent. It is preferably a substitution.
When having a substituent, the number thereof is not limited and may be 1 or 2 or more.

Further, when the two hydrogen atoms of the methylene group (-CH _2- ) in the alkylene group are both substituted with a substituent, even if the two substituents are linked to each other to form a hydrocarbon ring. good. Specific examples of γ in that case include a group represented by the following formula (IV) and a group represented by the following formula (V). * In the chemical formula represents the bond.

In the above formula (IV) and the above formula (V), * represents a bond.
Among them, the resin having the structure represented by the formula (IV) is preferable from the viewpoint of curability.

Further, examples of the optional substituent that the benzene ring in the above formula (III-1) may have include a hydroxyl group, a methyl group, a methoxy group, an ethyl group, an ethoxy group, a propyl group, a propoxy group and the like. Can be mentioned. The number of substituents is not particularly limited, and may be one or two or more. When the benzene ring in the above formula (III-1) has a substituent, the two benzene rings in the formula (III-1) may be linked by the substituent. For example, they may be connected by —O—.

Among these, as one embodiment, from the viewpoint of curability, γ is preferably an alkylene group which may have a substituent, more preferably an unsubstituted alkylene group, and a propylene group. Is more preferable, and propane-2,2-diyl is even more preferable. Further, as another aspect, from the viewpoint of curability, it is preferable that γ is a group represented by the formula (IV).

(Partial structure (3-2))
The partial structure (3) represented by the formula (III) is preferably a partial structure (3-2) represented by the following formula (III-2) from the viewpoint of curability.

In the above formula (III-2), the benzene ring in the above formula (III-2) may be further substituted with any substituent;
* Represents a bond.

Examples of the optional substituent that the benzene ring in the above formula (III-2) may have include a hydroxyl group, an alkyl group, an alkoxy group and the like. The number of substituents is not particularly limited, and may be one or two or more. Among these, an alkyl group is preferable, a cycloalkyl group is more preferable, and an adamantyl group is further preferable, from the viewpoint of development adhesion.

(Partial structure (3-3))
The partial structure (3) represented by the formula (III) preferably contains the partial structure (3-3) represented by the following formula (III-3) from the viewpoint of curability.

In the above formula (III-3), R ¹⁰ represents a divalent hydrocarbon group which may have a substituent;
The benzene ring in formula (III-3) may be further substituted with any substituent;
* Represents a bond.

(R ¹⁰ )
In the formula (III-3), R ¹⁰ 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 one or more divalent aliphatic groups and one or more divalent aromatic ring groups 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, while cyclic ones are preferable from the viewpoint of development adhesion. The number of carbon atoms is 1 or more, preferably 3 or more, more preferably 6 or more, more preferably 20 or less, still more preferably 15 or less, still more preferably 10 or less. When it is set to the lower limit value or more, the development adhesion tends to be good, and when it is set to the upper limit value or less, the curability tends to be good. The combination of the upper limit and the lower limit is preferably 1 to 20, more preferably 3 to 15, and even more preferably 6 to 10.

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-hexylene group, an n-heptylene group and the like. Among these, a methylene group is preferable from the viewpoint of curability.
Specific examples of the divalent branched chain aliphatic group include the above-mentioned divalent linear aliphatic group, and as side chains, a methyl group, an ethyl group, an n-propyl group, an iso-propyl group, and n-butyl. Examples thereof include a structure having a group, an iso-butyl group, a sec-butyl group, a tert-butyl group and the like.
The number of rings contained in the divalent cyclic aliphatic group is not particularly limited, but is preferably 1 or more, preferably 2 or more, and usually 20 or less, 10 or less, more preferably 5 or less. When it is set to the lower limit value or more, the development adhesion tends to be good, and when it is set to the upper limit value or less, the curability tends to be good. The combination of the upper limit and the lower limit is preferably 1 to 20, and more preferably 2 to 10. Specific examples of the divalent cyclic aliphatic group include two hydrogen atoms removed from a ring such as a cyclohexane ring, a cycloheptane ring, a cyclodecane ring, a cyclododecane ring, a norbornane ring, an isobornane ring, an adamantane ring, or a 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; a carboxyl group and the like. Among these, unsubstituted is preferable from the viewpoint of easiness of synthesis.

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, more preferably 20 or less, still more preferably 15 or less, still more preferably 10 or less. When it is set to the lower limit value or more, the development adhesion tends to be good, and when it is set to the upper limit value or less, the curability tends to be good. The combination of the upper limit and the lower limit is preferably 4 to 20, more preferably 5 to 15, and even more preferably 6 to 10.

The aromatic hydrocarbon ring in the divalent aromatic hydrocarbon ring group may be a monocyclic ring or a condensed ring. Examples of the divalent 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, and a chrysene ring, which have two free atomic valences. Examples thereof include groups such as a triphenylene ring, an acenaphthene ring, a fluorene ring, and a fluorene ring.
Further, the aromatic heterocycle in the divalent aromatic heterocyclic group may be a monocyclic ring or a condensed ring. Examples of the divalent 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, and an indol, which have two free atomic valences. Ring, carbazole ring, pyrrolobylmidazole ring, pyrrolopyrazole ring, pyrolopyrrole ring, thienopyrazole ring, thienothiophene ring, flopyrol ring, flofran ring, thienofran ring, benzoisoxazole ring, benzoisothiazole ring, benzimidazole ring, pyridine ring, Examples include groups such as pyrazine ring, pyridazine ring, pyrimidin ring, triazine ring, quinoline ring, isoquinoline ring, synolin ring, quinoxalin ring, phenanthridine ring, benzimidazole ring, perimidine ring, quinazoline ring, quinazolinone ring, and azulene ring. ..
Among these, from the viewpoint of photocurability, 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 hydroxyl 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 curability.

Further, as a group in which one or more divalent aliphatic groups and one or more divalent aromatic ring groups are linked, the above-mentioned divalent aliphatic group is 1 or more, and the above-mentioned divalent aromatic group is used. Examples thereof include a group in which one or more ring groups are linked.
The number of divalent aliphatic groups is not particularly limited, but is preferably 1 or more, preferably 2 or more, usually 10 or less, 5 or less, and more preferably 3 or less. When it is at least the lower limit value, the curability tends to be good, and when it is at least the upper limit value, the developability tends to be good. The combination of the upper limit and the lower limit is preferably 1 to 10, more preferably 2 to 5, and even more preferably 2 to 3.
The number of divalent aromatic ring groups is not particularly limited, but is preferably 1 or more, preferably 2 or more, usually 10 or less, 5 or less, and more preferably 3 or less. When it is at least the lower limit value, the curability tends to be good, and when it is at least the upper limit value, the developability tends to be good. The combination of the upper limit and the lower limit is preferably 1 to 10, more preferably 2 to 5, and even more preferably 2 to 3.

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 (III-3-A) to (III-3-E). The groups to be used are mentioned. Among these, the group represented by the following formula (III-3-A) is preferable from the viewpoint of development solubility. * In the chemical formula represents the bond.

As described above, the benzene ring in the formula (III-3) may be further substituted with any substituent. Examples of the substituent include a hydroxyl 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, from the viewpoint of curability, it is preferably unsubstituted.

(Partial structure (3-4))
From the viewpoint of curability, the partial structure (3) represented by the formula (III) preferably contains the partial structure (3-4) represented by the following formula (III-4).

In the above formula (III-4), γ represents a divalent linking group;
The benzene ring in formula (III-4) may be further substituted with any substituent;
* Represents a bond.

As the γ in the formula (III-4), the one described as γ in the formula (III-1) can be preferably adopted.
Further, as an arbitrary substituent that the benzene ring in the formula (III-4) may have, as an arbitrary substituent that the benzene ring in the formula (III-1) may have. The described ones can be preferably adopted.

The alkali-soluble resin (b-1-1) has a partial structure (3-1) among the partial structures (3-1) to the partial structure (3-4) from the viewpoint of development solubility. Is preferable.

(Production method)
In the photosensitive coloring composition of the present invention according to the first aspect, (b) the alkali-soluble resin contains an alkali-soluble resin (b-1-1), and the alkali-soluble resin (b-1-1). For example, after reacting a compound (p1) having an ethylenically unsaturated group-containing carbonyloxy group obtained from the epoxy resin (A) with an isocyanate group-containing compound (p3), a polyvalent carboxylic acid and the like thereof. A method of reacting one or both of the anhydrides (p2) can be mentioned.

(Epoxy resin (A))
As the epoxy resin (A), the epoxy resin described as the epoxy resin in the epoxy resin residue of ^R9 of the above formula (III) can be used, and specifically, the epoxy resin described in the following formula (III-5). Can be used.

(In formula (III-5), R ⁹ represents an epoxy resin residue;
p represents an integer greater than or equal to 1;
* Represents a bond. )

(Compound having an ethylenically unsaturated group-containing carbonyloxy group (p1))
The compound (p1) having an ethylenically unsaturated group-containing carbonyloxy group obtained from the above-mentioned epoxy resin (A) is a reaction using the above-mentioned epoxy resin (A) as a raw material, resulting in an ethylenically unsaturated group. As long as the contained carbonyloxy group is formed, the production method thereof is not limited, but specifically, the ethylenically unsaturated group-containing carboxylic acid (B) is reacted with the above-mentioned epoxy resin (A). A method for forming an ethylenically unsaturated group-containing carbonyloxy group by a subsequent reaction after first reacting the above-mentioned epoxy resin with a carboxylic acid (C) containing no ethylenically unsaturated group, for example, producing. Examples thereof include a method of reacting the compound (D) having a functional group that reacts with the hydroxyl group to form an ethylenically unsaturated group-containing carbonyloxy group.

(Ethylene unsaturated group-containing carboxylic acids (B))
Examples of the ethylenically unsaturated group-containing carboxylic acid (B) include unsaturated carboxylic acid having an ethylenically unsaturated double bond, and specific examples thereof include (meth) acrylic acid, crotonic acid, o-, and m. -, P-vinyl benzoic acid, α-position haloalkyl of (meth) acrylic acid, monocarboxylic acids such as alkoxyls, halogens, nitros and cyano substituents, reaction products of (meth) acrylic acids with lactones or polylactones;
Acrylate succinic acid, Acrylate anhydride, Maleic anhydride, Fumaric anhydride, Itaconic anhydride, Tetrahydrophthalic anhydride, Methyltetrahydrochloride phthalic acid, Hexahydrochloride phthalic acid, Methylhexahydrochloride phthalic acid, Methylendomethylenetetrahydrochloride phthalic acid , Saturated or unsaturated dicarboxylic acid anhydrides such as maleic anhydride, hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, polyethylene glycol mono (meth) acrylate, glycerinji (meth) One or more in one molecule of (meth) acrylate such as acrylate, trimethylolpropane di (meth) acrylate, pentaerythritol di (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, etc. Semi-esters obtained by reacting with a (meth) acrylate derivative having a hydroxyl group of
Saturated or unsaturated dicarboxylic acid anhydride, phenylglycidyl ether, glycidyl (meth) acrylate, 3,4-epoxycyclohexylmethyl (meth) acrylate, 8,9-epoxy [bicyclo [4.3.0] nonane-3- Semi-ester obtained by reacting with an unsaturated group-containing glycidyl compound such as yl] (meth) acrylate and 8,9-epoxy [bicyclo [4.3.0] nonane-3-yl] oxymethyl (meth) acrylate. Kind; etc.
Among these, in the present invention, semi-esters obtained by reacting with pentaerythritol tri (meth) acrylate, dipentaerythritol penta (meth) acrylate and the like are particularly preferable.
These may be used alone or in combination of two or more.

(Carvone acids (C) containing no ethylenically unsaturated group)
Examples of the carboxylic acid (C) containing no ethylenically unsaturated group include hydroxyl group-containing carboxylic acids such as lactic acid and dihydroxypropionic acid and their anhydrides, dicarboxylic acids such as succinic acid, phthalic acid and tartaric acid and their anhydrides. Be done.
These may be used alone or in combination of two or more.

(Compound (D) having a functional group that reacts with a hydroxyl group or a carboxyl group)
The above-mentioned epoxy resin (A) is reacted with a carboxylic acid (C) that does not contain an ethylenically unsaturated group, and then a compound (D) having a functional group that reacts with the generated hydroxyl group or carboxyl group is reacted. As the compound (D) having a functional group that reacts with a hydroxyl group or a carboxyl group, which is used when forming an ethylenically unsaturated group-containing carbonyloxy group, a compound having an epoxy group, a carboxyl group and an isocyanate group is preferable. Specific examples thereof include, but are not limited to, the above-mentioned ethylenically unsaturated group-containing carboxylic acids and the above-mentioned ethylenically unsaturated group-containing compounds such as the unsaturated group-containing glycidyl compound.
These may be used alone or in combination of two or more.

(Isocyanate group-containing compound (p3))
In order to adjust the developability of the obtained photosensitive coloring composition, the compound (p1) having an ethylenically unsaturated group-containing hydroxyl group obtained from the epoxy resin (A) is optionally added to the isocyanate group-containing compound (p3). ) May be reacted.

Examples of the isocyanate group-containing compound (p3) include organic monoisocyanates such as butane isocyanate, 3-chlorobenzene isocyanate, cyclohexane isocyanate, 3-isopropenoyl-α, and α-dimethylbenzyl isocyanate; paraphenylenedi isocyanate and 2,4-tolylene diisocyanate. , 2,6-tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, naphthalene-1,5-diisocyanate, trizine diisocyanate and other aromatic diisocyanates; hexamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, dimer acid Aliphatic diisocyanates such as diisocyanates; alicyclic diisocyanates such as isophorone diisocyanates, 4,4'-methylenebis (cyclohexylisocyanate), ω, ω'-diisocyanate dimethylcyclohexane; xylylene diisocyanates, α, α, α', α An aliphatic diisocyanate having an aromatic ring such as'-tetramethylxylylene diisocyanate; lysine ester triisocyanate, 1,6,11-undecantriisocyanate, 1,8-diisocyanate-4-isocyanatemethyloctane, 1,3,6- Triisocyanates such as hexamethylene triisocyanate, bicycloheptane triisocyanate, tris (isocyanatephenylmethane), tris (isocyanatephenyl) thiophosphate; and trimerics thereof, water adducts, polyol adducts thereof and the like can be mentioned. .. Of these, the dimer or trimer of organic diisocyanate is preferable, and the trimerylpropane adduct of tolylene diisocyanate, the trimer of tolylene diisocyanate, and the trimer of isophorone diisocyanate are most preferable. ..
These may be used alone or in combination of two or more.

(One or both of the polyvalent carboxylic acid and its anhydride (p2))
The alkali-soluble resin (b-1-1) is a compound (p1) having an ethylenically unsaturated group-containing carbonyloxy group obtained from the epoxy resin (A), and in some cases, the above-mentioned isocyanate group-containing compound (p3). Can be obtained by reacting one or both (p2) of a polyvalent carboxylic acid having substantially no tetravalent or higher carboxylic acid and its anhydride and its anhydride.

Examples of the polyvalent carboxylic acid and its anhydride (p2) include succinic acid, maleic acid, itaconic acid, tetrahydrophthalic acid, methyltetrahydrophthalic acid, hexahydrophthalic acid, methylhexahydrophthalic acid, and methylendomethylenetetrahydrophthalic acid. Saturated or unsaturated dicarboxylic acids such as acids and phthalic acids and their acid anhydrides; trimellitic acid and its anhydrides, and pyromellitic acid, benzophenone tetracarboxylic acid, biphenyl tetracarboxylic acid, biphenyl ether tetracarboxylic acid, butane. Examples thereof include tetracarboxylic acids such as tetracarboxylic acid and their acid anhydrides, among which dicarboxylic acids such as succinic acid, tetrahydrophthalic acid and phthalic acid and their acid anhydrides, trimellitic acid and its anhydrides. , Etc. Use a carboxylic acid compound having a valence of 3 or less. With a carboxylic acid compound having a valence of 4 or more, the storage stability of the obtained ethylenically unsaturated group and carboxyl group-containing compound tends to deteriorate. Among the carboxylic acid compounds having a trivalent or lower valence, an acid anhydride of a polyvalent carboxylic acid having an acid dissociation constant (first dissociation constant) of 3.5 or more is particularly preferable from the viewpoint of development solubility. The acid dissociation constant is further preferably 3.8 or more, and particularly preferably 4.0 or more. As such acid anhydrides, acid anhydrides of succinic acid and tetrahydrophthalic acid are particularly preferable.

For the acid dissociation constant, refer to Determination of Organic Structures by Physical Methods, Academic Press, New York, 1955 (Brown, HC et al.).
In the present invention, the polyvalent carboxylic acid and its acid anhydride (p2) may be used alone or in combination of two or more.

Further, the alkali-soluble resin (b-1-1) is further added to a part of the carboxyl group in the compound obtained by reacting one or both (p2) of the polyvalent carboxylic acid and its anhydride in this way. It may be a compound to which the above-mentioned epoxy resin (A) is added.

As a specific method for producing the alkali-soluble resin (b-1-1), the methods described in Japanese Patent Application Laid-Open No. 2006-312704 and Japanese Patent Application Laid-Open No. 2007-119718 can be adopted.

As described above, the alkali-soluble resin (b-1-1) having a partial structure derived from the epoxy resin and the one obtained by modifying the epoxy resin as a raw material have been described in detail. Not limited. For example, an acrylic resin having a glycidyl ether group in a side chain to which the ethylenically unsaturated group-containing carboxylic acid (B) is added may be mentioned.

(Molecular weight)
The polystyrene-equivalent weight average molecular weight measured by gel permeation chromatography of the alkali-soluble resin (b-1) contained in the photosensitive coloring composition of the present invention according to the first aspect is not particularly limited, but may be 1000 or more. Preferably, 1500 or more is more preferable, 2000 or more is further preferable, 2500 or more is particularly preferable, 6000 or less is preferable, 5000 or less is more preferable, 4000 or less is further preferable, and 3500 or less is particularly preferable. When it is set to the lower limit value or more, the development adhesion tends to be good, and when it is set to the upper limit value or less, the curability tends to be good. As the combination of the upper limit and the lower limit, 1000 to 6000 is preferable, 1500 to 5000 is more preferable, 2000 to 4000 is further preferable, and 2500 to 3500 is particularly preferable.

(Acid value)
The acid value of the alkali-soluble resin (b-1) contained in the photosensitive coloring composition of the present invention according to the first aspect is not particularly limited, but is preferably 5 mgKOH / g or more, more preferably 10 mgKOH / g or more. 15 mgKOH / g or more is further preferable, 20 mgKOH / g or more is particularly preferable, 60 mgKOH / g or less is preferable, 50 mgKOH / g or less is more preferable, 40 mgKOH / g or less is further preferable, and 30 mgKOH / g or less is particularly preferable. When it is at least the above lower limit value, the development solubility tends to be good, and when it is at least the above upper limit value, the curability tends to be good. As the combination of the upper limit and the lower limit, 5 to 60 mgKOH / g is preferable, 10 to 50 mgKOH / g is more preferable, 15 to 40 mgKOH / g is further preferable, and 20 to 30 mgKOH / g is particularly preferable.

(Double bond equivalent)
The double bond equivalent of the alkali-soluble resin (b-1) contained in the photosensitive coloring composition of the present invention according to the first aspect is not particularly limited, but is preferably 20 or more, more preferably 50 or more, and more preferably 80 or more. Is particularly preferable, 100 or more is particularly preferable, 600 or less is preferable, 400 or less is more preferable, 300 or less is further preferable, 200 or less is further preferable, 180 or less is particularly preferable, and 150 or less is most preferable. When it is at least the above lower limit value, the development solubility tends to be good, and when it is at least the above upper limit value, the curability tends to be good. As the combination of the upper limit and the lower limit, 20 to 600 is preferable, 50 to 400 is more preferable, 80 to 300 is further preferable, and 100 to 200 is particularly preferable.
Further, the double bond equivalent of the alkali-soluble resin (b-1) can be calculated from the following formula (x).

(Double bond equivalent of alkali-soluble resin (b-1))
= (Molecular weight of resin (b-1)) / (Number of ethylenically unsaturated double bonds per molecule of resin (b-1)) ... (x)

(Number of ethylenically unsaturated double bonds)
The number of ethylenically unsaturated double bonds contained in one molecule of the alkali-soluble resin (b-1) contained in the photosensitive coloring composition of the present invention according to the first aspect is not particularly limited, but is 2 or more. Is preferable, 3 or more is more preferable, 4 or more is further preferable, 6 or more is more preferable, 8 or more is particularly preferable, 20 or less is more preferable, 18 or less is more preferable, 14 or less is further preferable, and 12 or less is more preferable. Especially preferable. When it is at least the above lower limit value, the curability tends to be good, and when it is at least the above upper limit value, the development solubility tends to be good. As the combination of the upper limit and the lower limit, 2 to 20 is preferable, 4 to 18 is more preferable, 6 to 14 is more preferable, and 8 to 12 is particularly preferable.

As described above, in the photosensitive coloring composition of the present invention according to the first aspect, (b) the alkali-soluble resin has an alkali-soluble resin (b-) having a partial structure (1) represented by the above formula (I). Although it contains 1), the alkali-soluble resin (b-1) may contain one kind alone or a combination of two or more kinds.

(Second aspect)
In the photosensitive coloring composition of the present invention according to the second aspect, the alkali-soluble resin (b) is an alkali-soluble resin (b-1) having a double bond equivalent of 400 or less (hereinafter, "" in the second aspect. "Alkali-soluble resin (b-1)" may be referred to as "alkali-soluble resin (b-1-2)"). Since the alkali-soluble resin (b-1-2) has a double bond equivalent of 400 or less, the amount of ethylenic double bonds in one molecule of the resin is large, and the alkali-soluble resin (b-1-2) is colored using a photosensitive coloring composition containing the resin. It is considered that when the spacer is formed, the cross-linking density becomes high, the elution of impurities into the solvent is suppressed, high display reliability can be ensured, and similarly, the cross-linking density of the spacer becomes high, so that the mechanical properties are also excellent.

(Molecular weight)
The polystyrene-equivalent weight average molecular weight measured by gel permeation chromatography of the alkali-soluble resin (b-1) contained in the photosensitive coloring composition of the present invention according to the second aspect is not particularly limited, but may be 1000 or more. Preferably, 1500 or more is more preferable, 2000 or more is further preferable, 2500 or more is particularly preferable, 6000 or less is preferable, 5000 or less is more preferable, 4000 or less is further preferable, and 3500 or less is particularly preferable. When it is set to the lower limit value or more, the development adhesion tends to be good, and when it is set to the upper limit value or less, the curability tends to be good. As the combination of the upper limit and the lower limit, 1000 to 6000 is preferable, 1500 to 5000 is more preferable, 2000 to 4000 is further preferable, and 2500 to 3500 is particularly preferable.

(Acid value)
The acid value of the alkali-soluble resin (b-1) contained in the photosensitive coloring composition of the present invention according to the second aspect is not particularly limited, but is preferably 5 mgKOH / g or more, more preferably 10 mgKOH / g or more. 15 mgKOH / g or more is further preferable, 20 mgKOH / g or more is particularly preferable, 60 mgKOH / g or less is preferable, 50 mgKOH / g or less is more preferable, 40 mgKOH / g or less is further preferable, and 30 mgKOH / g or less is particularly preferable. When it is at least the above lower limit value, the development solubility tends to be good, and when it is at least the above upper limit value, the curability tends to be good. As the combination of the upper limit and the lower limit, 5 to 60 mgKOH / g is preferable, 10 to 50 mgKOH / g is more preferable, 15 to 40 mgKOH / g is further preferable, and 20 to 30 mgKOH / g is particularly preferable.

(Double bond equivalent)
The double bond equivalent of the alkali-soluble resin (b-1) contained in the photosensitive coloring composition of the present invention according to the second aspect is not particularly limited as long as it is 400 or less, but 20 or more is preferable, and 50 or more is preferable. More preferably, 80 or more is further preferable, 100 or more is particularly preferable, 350 or less is preferable, 300 or less is next, 300 or less is more preferable, 180 or less is more preferable, 160 or less is further preferable, and 150 or less is more preferable. Is particularly preferable, 140 or less is particularly preferable, and 130 or less is most preferable. When it is at least the above lower limit value, the development solubility tends to be good, and when it is at least the above upper limit value, the curability tends to be good. As the combination of the upper limit and the lower limit, 20 to 400 is preferable, 50 to 400 is more preferable, 80 to 300 is further preferable, and 100 to 200 is particularly preferable.
Further, the double bond equivalent of the alkali-soluble resin (b-1) in the second aspect can be calculated from the above formula (x).

(Number of ethylenically unsaturated double bonds)
The number of ethylenically unsaturated double bonds contained in one molecule of the alkali-soluble resin (b-1) contained in the photosensitive coloring composition of the present invention according to the second aspect is not particularly limited, but 2 The above is preferable, 3 or more is more preferable, 4 or more is further preferable, 6 or more is more preferable, 8 or more is particularly preferable, 20 or less is more preferable, 18 or less is more preferable, 14 or less is further preferable, and 12 or less is preferable. Is particularly preferable. When it is at least the above lower limit value, the curability tends to be good, and when it is at least the above upper limit value, the development solubility tends to be good. As the combination of the upper limit and the lower limit, 2 to 20 is preferable, 4 to 18 is more preferable, 6 to 14 is more preferable, and 8 to 12 is particularly preferable.

The alkali-soluble resin (b-1) contained in the photosensitive coloring composition of the present invention according to the second aspect is the alkali-soluble resin contained in the photosensitive coloring composition of the present invention according to the first aspect. Those listed as (b-1) can be preferably used.

The alkali-soluble resin (b-1) contained in the photosensitive coloring composition of the present invention according to the second aspect is not particularly limited as long as its double bond equivalent is 400 or less, and is not particularly limited. An alkali-soluble resin other than the alkali-soluble resin (b-1) according to the embodiment can also be adopted. For example, an acrylic resin containing a repeating unit containing an ethylenic double bond in the side chain in an amount such that the double bond equivalent is 400 or less can be mentioned. Examples of the repeating unit containing an ethylenic double bond in the side chain include a repeating unit represented by the following formula (IV).

In formula (IV) above, R ¹¹ and R ¹² each independently represent a hydrogen atom or a methyl group;
* Represents a bond.

{Epoxy (meth) acrylate resin (b-2)}
In the photosensitive coloring composition of the present invention, the alkali-soluble resin (b) is further an epoxy (meth) acrylate resin (b-2) other than the alkali-soluble resin (b-1) (hereinafter, “epoxy (meth) acrylate resin”). (B-2) "may be abbreviated.)" May be contained.
It is considered that the acid value of the photosensitive coloring composition can be increased by containing the epoxy (meth) acrylate resin (b-2), and there is a tendency that both development solubility and curability can be achieved at the same time.

In the epoxy (meth) acrylate resin (b-2), an ethylenically unsaturated monocarboxylic acid or an ester compound is added to the epoxy resin, and an isocyanate group-containing compound is optionally reacted, and then a polybasic acid or an anhydride thereof is further added. It is a resin obtained by reacting with. For example, by opening and adding a carboxyl group of an unsaturated monocarboxylic acid to the epoxy group of an epoxy resin, an ethylenically unsaturated bond is added to the epoxy compound via an ester bond (-COO-), and at the same time, an ethylenically unsaturated bond is added. Examples thereof include a hydroxyl group generated at that time to which one carboxy group of the polybasic acid anhydride is added. Further, when the polybasic acid anhydride is added, the polyhydric alcohol may be added at the same time to add the polyhydric acid anhydride.
Further, the epoxy (meth) acrylate resin (b-2) also contains a resin obtained by reacting the carboxyl group of the resin obtained by the above reaction with a compound having a functional group capable of further reacting.
As described above, the epoxy (meth) acrylate resin has substantially no epoxy group due to its chemical structure and is not limited to "(meth) acrylate", but the epoxy compound (epoxy resin) is the raw material. Yes, and since "(meth) acrylate" is a typical example, it is named in this way according to convention.

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.
Specifically, for example, bisphenol A epoxy resin, bisphenol F epoxy resin, bisphenol S epoxy resin, phenol novolac epoxy resin, cresol novolac epoxy resin, biphenyl novolac epoxy resin, trisphenol epoxy resin, polymerization of phenol and dicyclopentane. Epoxy resin, dihydrooxylfluorene type epoxy resin, dihydrooxylalkyleneoxylfluorene type epoxy resin, 9,9-bis (4'-hydroxyphenyl) fluorene diglycidyl etherified product, 1,1-bis (4'-hydroxy) Examples thereof include diglycidyl etherified product of phenyl) adamantan, and those having an aromatic ring in the main chain as described above can be preferably used.

Among them, from the viewpoint of compatibility, bisphenol A epoxy resin, phenol novolac epoxy resin, biphenyl novolak epoxy resin, cresol novolac epoxy resin, polymerized epoxy resin of phenol and dicyclopentadiene, 9,9-bis (4'-hydroxyphenyl). ) A diglycidyl etherified product of fluorene, an epoxy resin having an adamantyl group, and the like are preferable, and an epoxy resin having an adamantyl group is more preferable.

Examples of the ethylenically unsaturated monocarboxylic acid include (meth) acrylic acid, crotonic acid, maleic acid, fumaric acid, itaconic acid, citraconic acid and the like, and pentaerythritol tri (meth) acrylate anhydride succinic acid adduct, penta. Ellis Ritol Tri (Meta) Acrylate Tetrahydro Acrylate Additive, Dipenta Erythritol Penta (Meta) Acrylate Acrylate Additive, Dipenta Erythritol Penta (Meta) Acrylate Acrylate Additive, Dipenta Erythritol Penta (Meta) Acrylate Tetrahydro Examples thereof include phthalic acid anhydride adducts, reaction products of (meth) acrylic acid and ε-caprolactone. Of these, (meth) acrylic acid is preferable, and acrylic acid is more preferable, from the viewpoint of sensitivity.

Examples of the polybasic acid (anhydride) include succinic acid, maleic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, 3-methyltetrahydrophthalic acid, 4-methyltetrahydrophthalic acid, 3-ethyltetrahydrophthalic acid, and 4 -Ethyltetrahydrophthalic acid, hexahydrophthalic acid, 3-methylhexahydrophthalic acid, 4-methylhexahydrophthalic acid, 3-ethylhexahydrophthalic acid, 4-ethylhexahydrophthalic acid, trimellitic acid, pyromellitic acid , Benzophenone tetracarboxylic acid, biphenyltetracarboxylic acid, and anhydrides thereof. Among them, succinic acid anhydride, maleic acid anhydride, tetrahydrophthalic acid anhydride, hexahydrophthalic acid anhydride or biphenyltetracarboxylic acid dianhydride is preferable, and succinic acid anhydride and tetrahydrophthalic acid are preferable from the viewpoint of development solubility. An anhydride or biphenyltetracarboxylic acid dianhydride is more preferred, and tetrahydrophthalic acid anhydride or biphenyltetracarboxylic acid dianhydride is even more preferred.

By using a polyhydric alcohol, the molecular weight of the epoxy (meth) acrylate resin can be increased, branching can be introduced into the molecule, and there is a tendency that the molecular weight and the viscosity can be balanced. In addition, the rate of introduction 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.
The polyhydric alcohol may be, for example, one or more polyhydric alcohols selected from trimethylolpropane, ditrimethylolpropane, pentaerythritol, dipentaerythritol, trimethylolethane, and 1,2,3-propanetriol. It is preferable to have.

The acid value of the epoxy (meth) acrylate resin (b-2) is not particularly limited, but is preferably 10 mgKOH / g or more, more preferably 20 mgKOH / g or more, further preferably 50 mgKOH / g or more, and further preferably 80 mgKOH / g or more. Preferably, 90 mgKOH / g or more is particularly preferable, 100 mgKOH / g or more is most preferable, 300 mgKOH / g or less is preferable, 200 mgKOH / g or less is more preferable, 150 mgKOH / g or less is further preferable, and 130 mgKOH / g or less is particularly preferable. .. When it is at least the lower limit value, the development solubility tends to be good, and when it is at least the upper limit value, the development adhesion tends to be good. As the combination of the upper limit and the lower limit, 10 to 300 mgKOH / g is preferable, 20 to 200 mgKOH / g is more preferable, 50 to 150 mgKOH / g is further preferable, and 80 to 130 mgKOH / g is particularly preferable.

The weight average molecular weight (Mw) of the epoxy (meth) acrylate resin (b-2) is not particularly limited, but is usually 1000 or more, preferably 2000 or more, more preferably 3000 or more, still more preferably 4000 or more, still more preferably 5000. As described above, it is particularly preferably 6000 or more, and usually 30,000 or less, preferably 20,000 or less, more preferably 15,000 or less, still more preferably 10,000 or less, and particularly preferably 8,000 or less. When it is at least the lower limit value, the development adhesion tends to be good, and when it is at least the upper limit value, the development solubility tends to be good. The combination of the upper limit and the lower limit is preferably 1000 to 30000, more preferably 2000 to 20000, still more preferably 3000 to 15000, still more preferably 4000 to 10000, and particularly preferably 5000 to 8000.

The double bond equivalent of the epoxy (meth) acrylate resin (b-2) is not particularly limited, but is preferably 400 or more, more preferably 450 or more, further preferably 500 or more, still preferably 800 or less, and more preferably 700 or less. It is preferably 600 or less, and more preferably 600 or less. When it is at least the above lower limit value, the development solubility tends to be good, and when it is at least the above upper limit value, the sensitivity tends to be high. The double bond equivalent of the epoxy (meth) acrylate resin (b-2) can be calculated in the same manner as in the above formula (x). The combination of the upper limit and the lower limit is preferably 400 to 800, more preferably 450 to 700, and even more preferably 500 to 600.

The epoxy (meth) acrylate resin (b-2) can be synthesized by a conventionally known method. Specifically, the epoxy resin is dissolved in an organic solvent, and in the coexistence of a catalyst and a thermal polymerization inhibitor, the acid or ester compound having an ethylenically unsaturated bond is added and subjected to an addition reaction, and then a polybasic acid or a polybasic acid thereof or the like thereof is added. A method of adding an anhydride and continuing the reaction can be used.

Here, examples of the organic solvent used in the reaction include one or more organic solvents such as methyl ethyl ketone, cyclohexanone, diethylene glycol ethyl ether acetate, and propylene glycol monomethyl ether acetate.
Examples of the catalyst include tertiary amines such as triethylamine, benzyldimethylamine and tribenzylamine, tetramethylammonium chloride, methyltriethylammonium chloride, tetraethylammonium chloride, tetrabutylammonium chloride, trimethylbenzylammonium chloride and the like. Examples thereof include one or more of quaternary ammonium salts, phosphorus compounds such as triphenylphosphine, and stibins such as triphenylstibine.
Further, examples of the thermal polymerization inhibitor include one or more of hydroquinone, hydroquinone monomethyl ether, methylhydroquinone and the like.

The acid or ester compound having an ethylenically unsaturated bond is usually 0.7 to 1.3 chemical equivalents, preferably 0.9 to 1.1 chemical equivalents, relative to one chemical equivalent of the epoxy group of the epoxy resin. It can be an amount that becomes. The temperature at the time of the addition reaction is usually 60 to 150 ° C, preferably 80 to 120 ° C. Further, the amount of the polybasic acid (anhydride) used is usually 0.1 to 1.2 chemical equivalents, preferably 0.2 to 1.1, relative to one chemical equivalent of the hydroxyl group generated in the addition reaction. It can be an amount that is a chemical equivalent.

The chemical structure of the epoxy (meth) acrylate resin (b-2) is not particularly limited, but from the viewpoint of curability, the epoxy (meth) acrylate resin (b-2) having a repeating unit structure represented by the following formula (i). -I) and one or both of the epoxy (meth) acrylate resin (b-2-ii) having a partial structure represented by the following formula (ii) are preferable. Further, from the viewpoint of display reliability, an epoxy (meth) acrylate resin having a partial structure represented by the following formula (ii) is more preferable.

One or both of the one having the repeating unit structure represented by the following formula (i) and the one having the partial structure represented by the following formula (ii) have high compatibility with the alkali-soluble resin (b-1). It is considered that the development solubility is improved.

In formula (i), Ra represents ^a hydrogen atom or a methyl group;
R ^b represents a divalent hydrocarbon group which may have a substituent;
The benzene ring in formula (i) may be further substituted with any substituent;
* Represents a bond.

In formula (ii), R ^c each independently represents a hydrogen atom or a methyl group;
R ^d represents a divalent hydrocarbon group having a cyclic hydrocarbon group as a side chain;
^Re and R ^f each independently represent a divalent aliphatic group which may have a substituent;
m and n each independently represent an integer of 0 to 2;
* Represents a bond.

Of these, an epoxy (meth) acrylate resin having a unit structure represented by the following formula (ii-a) is preferable.

(Epoxy (meth) acrylate resin (b-2-i))
Next, an epoxy (meth) acrylate resin having a repeating unit structure represented by the formula (i) (hereinafter, abbreviated as “epoxy (meth) acrylate resin (b-2-i)”) will be described in detail. ..

In formula (i), Ra represents ^a hydrogen atom or a methyl group;
R ^b represents a divalent hydrocarbon group which may have a substituent;
The benzene ring in formula (i) may be further substituted with any substituent;
* Represents a bond.

(R ^b )
In the formula (i), R ^b 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 one or more divalent aliphatic groups and one or more divalent aromatic ring groups 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, while cyclic ones are preferable from the viewpoint of development adhesion. The number of carbon atoms is 1 or more, preferably 3 or more, more preferably 6 or more, more preferably 20 or less, still more preferably 15 or less, still more preferably 10 or less. When it is set to the lower limit value or more, the development adhesion tends to be good, and when it is set to the upper limit value or less, the curability tends to be good. The combination of the upper limit and the lower limit is preferably 1 to 20, more preferably 3 to 15, and even more preferably 6 to 10.

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-hexylene group, an n-heptylene group and the like. Among these, a methylene group is preferable from the viewpoint of curability.
Specific examples of the divalent branched chain aliphatic group include the above-mentioned divalent linear aliphatic group, and as side chains, a methyl group, an ethyl group, an n-propyl group, an iso-propyl group, and n-butyl. Examples thereof include a structure having a group, an iso-butyl group, a sec-butyl group, a tert-butyl group and the like.
The number of rings contained in the divalent cyclic aliphatic group is not particularly limited, but is preferably 1 or more, preferably 2 or more, and usually 10 or less and 5 or less. When it is set to the lower limit value or more, the development adhesion tends to be good, and when it is set to the upper limit value or less, the curability tends to be good. The combination of the upper limit and the lower limit is preferably 1 to 10, and more preferably 2 to 5. Specific examples of the divalent cyclic aliphatic group include two hydrogen atoms removed from a ring such as a cyclohexane ring, a cycloheptane ring, a cyclodecane ring, a cyclododecane ring, a norbornane ring, an isobornane ring, an adamantane ring, or a 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; a carboxyl group and the like. Among these, unsubstituted is preferable from the viewpoint of easiness of synthesis.

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, more preferably 20 or less, still more preferably 15 or less, still more preferably 10 or less. When it is set to the lower limit value or more, the development adhesion tends to be good, and when it is set to the upper limit value or less, the curability tends to be good. The combination of the upper limit and the lower limit is preferably 4 to 20, more preferably 5 to 15, and even more preferably 6 to 10.

The aromatic hydrocarbon ring in the divalent aromatic hydrocarbon ring group may be a monocyclic ring or a condensed ring. Examples of the divalent 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, and a chrysene ring, which have two free atomic valences. Examples thereof include groups such as a triphenylene ring, an acenaphthene ring, a fluorene ring, and a fluorene ring.
Further, the aromatic heterocycle in the divalent aromatic heterocyclic group may be a monocyclic ring or a condensed ring. Examples of the divalent 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, and an indol, which have two free atomic valences. Ring, carbazole ring, pyrrolobylmidazole ring, pyrrolopyrazole ring, pyrolopyrrole ring, thienopyrazole ring, thienothiophene ring, flopyrol ring, flofran ring, thienofran ring, benzoisoxazole ring, benzoisothiazole ring, benzimidazole ring, pyridine ring, Examples include groups such as pyrazine ring, pyridazine ring, pyrimidin ring, triazine ring, quinoline ring, isoquinoline ring, synolin ring, quinoxalin ring, phenanthridine ring, benzimidazole ring, perimidine ring, quinazoline ring, quinazolinone ring, and azulene ring. ..
Among these, from the viewpoint of photocurability, 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 hydroxyl 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 curability.

Further, as a group in which one or more divalent aliphatic groups and one or more divalent aromatic ring groups are linked, the above-mentioned divalent aliphatic group is 1 or more, and the above-mentioned divalent aromatic group is used. Examples thereof include a group in which one or more ring groups are linked.
The number of divalent aliphatic groups is not particularly limited, but is preferably 1 or more, preferably 2 or more, usually 10 or less, 5 or less, and more preferably 3 or less. When it is set to the lower limit value or more, the development adhesion tends to be good, and when it is set to the upper limit value or less, the curability tends to be good. The combination of the upper limit and the lower limit is preferably 1 to 10, more preferably 2 to 5, and even more preferably 2 to 3.
The number of divalent aromatic ring groups is not particularly limited, but is usually preferably 1 or more, 2 or more, usually 10 or less, 5 or less, and more preferably 3 or less. When it is at least the lower limit value, the curability tends to be good, and when it is at least the upper limit value, the curability tends to be good. The combination of the upper limit and the lower limit is preferably 1 to 10, more preferably 2 to 5, and even more preferably 2 to 3.

Specific examples of a group in which one or more divalent aliphatic groups and one or more divalent aromatic ring groups are linked include groups represented by the following formulas (ia) to (iE). Can be mentioned. Among these, the group represented by the following formula (ia) is preferable from the viewpoint of development solubility. * In the chemical formula represents the bond.

As described above, the benzene ring in the formula (i) may be further substituted with any substituent. Examples of the substituent include a hydroxyl 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, from the viewpoint of curability, it is preferably unsubstituted.

Further, the repeating unit structure represented by the formula (i) is preferably a repeating unit structure represented by the following formula (i-1) from the viewpoint of curability.

In formula (i-1), R ^a and R ^b are synonymous with those of formula (i);
RX represents a hydrogen atom or a ^polybasic acid residue;
* Represents a bond;
The benzene ring in formula (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 derived 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. 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 are preferable. Is tetrahydrophthalic acid, biphenyltetracarboxylic acid.

The repeating unit structure represented by the above formula (i-1) contained in one molecule of the epoxy (meth) acrylate resin (b-2-i) may be one kind or two or more kinds, for example, ^RX . A hydrogen atom and a ^polybasic acid residue of RX may be mixed.

Further, the number of repeating unit structures represented by the above formula (i) contained in one molecule of the epoxy (meth) acrylate resin (b-2-i) 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. When it is at least the above lower limit value, the curability tends to be good, and when it is at least the above upper limit value, the development solubility tends to be good. As the combination of the upper limit and the lower limit, 1 to 20 is preferable, and 3 to 15 is more preferable.

The polystyrene-equivalent weight average molecular weight (Mw) of the epoxy (meth) acrylate resin (b-2-i) measured by gel permeation chromatography (GPC) is not particularly limited, but is preferably 1000 or more, more preferably 2000 or more. Preferably, 3000 or more is further preferable, 4000 or more is further preferable, 5000 or more is particularly preferable, 30,000 or less is preferable, 20000 or less is more preferable, 10,000 or less is further preferable, 8000 or less is further preferable, and 7000 or less is more preferable. Especially preferable. When it is at least the lower limit value, the development adhesion tends to be good, and when it is at least the upper limit value, the development solubility tends to be good. The combination of the upper limit and the lower limit is preferably 1000 to 30,000, more preferably 2000 to 20000, still more preferably 3000 to 10000, still more preferably 4000 to 8000, and particularly preferably 5000 to 7000.

The acid value of the epoxy (meth) acrylate resin (b-2-i) is not particularly limited, but is preferably 10 mgKOH / g or more, more preferably 30 mgKOH / g or more, further preferably 60 mgKOH / g or more, and 80 mgKOH / g or more. Is particularly preferable, and 200 mgKOH / g or less is preferable, 180 mgKOH / g or less is more preferable, 150 mgKOH / g or less is further preferable, and 130 mgKOH / g or less is particularly preferable. When it is at least the above lower limit value, the development solubility tends to be good, and when it is at least the above upper limit value, the curability tends to be good. As the combination of the upper limit and the lower limit, 10 to 200 mgKOH / g is preferable, 30 to 180 mgKOH / g is more preferable, 60 to 150 mgKOH / g is further preferable, and 80 to 130 mgKOH / g is particularly preferable.

Specific examples of the epoxy (meth) acrylate resin (b-2-i) are given below.

(Epoxy (meth) acrylate resin (b-2-ii))
Next, an epoxy (meth) acrylate resin having a partial structure represented by the formula (ii) (hereinafter, abbreviated as “epoxy (meth) acrylate resin (b-2-ii)”) will be described in detail.

In formula (ii), R ^c each independently represents a hydrogen atom or a methyl group;
R ^d represents a divalent hydrocarbon group having a cyclic hydrocarbon group as a side chain;
^Re and R ^f each independently represent a divalent aliphatic group which may have a substituent;
m and n each independently represent an integer of 0 to 2;
* Represents a bond.

Of these, an epoxy (meth) acrylate resin having a unit structure represented by the following formula (ii-a) is preferable.

(R ^d )
In the formula (ii), R ^d 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 preferably 1 or more, preferably 2 or more, and usually 10 or less, 5 or less is preferable, and 3 or less is more preferable. When it is set to the lower limit value or more, the development adhesion tends to be good, and when it is set to the upper limit value or less, the curability tends to be good. The combination of the upper limit and the lower limit is preferably 1 to 10, more preferably 2 to 5, and even more preferably 2 to 3.
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, the development adhesion tends to be good, and when it is set to the upper limit value or less, the curability tends to be good. The combination of the upper limit and the lower limit is preferably 4 to 40, more preferably 6 to 30, and even more preferably 8 to 20.
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 display reliability.

On the other hand, the number of rings contained in the aromatic ring group is not particularly limited, but is 1 or more, preferably 2 or more, more preferably 3 or more, and usually 10 or less, 5 or less, and 4 or less. preferable. When it is set to the lower limit value or more, the development adhesion tends to be good, and when it is set to the upper limit value or less, the curability tends to be good. The combination of the upper limit and the lower limit is preferably 1 to 10, more preferably 2 to 5, and even more preferably 3 to 4.
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, still more 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. When it is set to the lower limit value or more, the development adhesion tends to be good, and when it is set to the upper limit value or less, the curability tends to be good. As the combination of the upper limit and the lower limit, 4 to 40 is preferable, 6 to 30 is more preferable, 8 to 20 is more preferable, and 10 to 15 is particularly preferable.
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 fluorene rings. Among these, the fluorene ring is preferable from the viewpoint of patterning characteristics.

Further, 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 compatibility, while a cyclic one is preferable from the viewpoint of display reliability.
The number of carbon atoms of the divalent aliphatic group is 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 lower limit value or more, the development adhesion tends to be good, and when it is set to the upper limit value or less, the curability tends to be good. The combination of the upper limit and the lower limit is preferably 1 to 25, more preferably 3 to 20, and even more preferably 6 to 15.

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-hexylene group, an n-heptylene group and the like. Among these, a methylene group is preferable from the viewpoint of curability.
Specific examples of the divalent branched chain aliphatic group include the above-mentioned divalent linear aliphatic group, and as side chains, a methyl group, an ethyl group, an n-propyl group, an iso-propyl group, and n-butyl. Examples thereof include a structure having a group, an iso-butyl group, a sec-butyl group, a tert-butyl group and the like.
The number of rings contained in the divalent cyclic aliphatic group is not particularly limited, but is preferably 1 or more, preferably 2 or more, and usually 10 or less, preferably 5 or less, still more preferably 3 or less. When it is set to the lower limit value or more, the development adhesion tends to be good, and when it is set to the upper limit value or less, the curability tends to be good. The combination of the upper limit and the lower limit is preferably 1 to 10, more preferably 2 to 5, and even more preferably 2 to 3.
Specific examples of the divalent cyclic aliphatic group include two hydrogen atoms removed from a ring such as a cyclohexane ring, a cycloheptane ring, a cyclodecane ring, a cyclododecane ring, a norbornane ring, an isobornane ring, an adamantane ring, or a cyclododecane ring. The group that was used is mentioned. Among these, from the viewpoint of display reliability, 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; a carboxyl group and the like. Among these, unsubstituted is preferable from the viewpoint of easiness of synthesis.

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 lower limit value or more, the development adhesion tends to be good, and when it is set to the upper limit value or less, the curability tends to be good. The combination of the upper limit and the lower limit is preferably 4 to 30, more preferably 5 to 20, and even more preferably 6 to 15.

The aromatic hydrocarbon ring in the divalent aromatic hydrocarbon ring group may be a monocyclic ring or a condensed ring. Examples of the divalent 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, and a chrysene ring, which have two free atomic valences. Examples thereof include groups such as a triphenylene ring, an acenaphthene ring, a fluorene ring, and a fluorene ring.
Further, the aromatic heterocycle in the divalent aromatic heterocyclic group may be a monocyclic ring or a condensed ring. Examples of the divalent 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, and an indol, which have two free atomic valences. Ring, carbazole ring, pyrrolobylmidazole ring, pyrrolopyrazole ring, pyrolopyrrole ring, thienopyrazole ring, thienothiophene ring, flopyrol ring, flofran ring, thienofran ring, benzoisoxazole ring, benzoisothiazole ring, benzimidazole ring, pyridine ring, Examples include groups such as pyrazine ring, pyridazine ring, pyrimidin ring, triazine ring, quinoline ring, isoquinoline ring, synolin ring, quinoxalin ring, phenanthridine ring, benzimidazole ring, perimidine ring, quinazoline ring, quinazolinone ring, and azulene ring. ..
Among these, from the viewpoint of patterning characteristics, a benzene ring, a naphthalene ring or a fluorene ring having two free valences is preferable, and a fluorene ring having two free valences is more preferable.

Examples of the substituent that the divalent aromatic ring group may have include a hydroxyl 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 and moisture absorption resistance.

Further, as a group in which one or more divalent aliphatic groups and one or more divalent aromatic ring groups are linked, the above-mentioned divalent aliphatic group is 1 or more, and the above-mentioned divalent aromatic group is used. Examples thereof include a group in which one or more ring groups are linked.
The number of divalent aliphatic groups is not particularly limited, but is preferably 1 or more, preferably 2 or more, usually 10 or less, 5 or less, and more preferably 3 or less. When it is set to the lower limit value or more, the development adhesion tends to be good, and when it is set to the upper limit value or less, the curability tends to be good. The combination of the upper limit and the lower limit is preferably 1 to 10, more preferably 2 to 5, and even more preferably 2 to 3.
The number of divalent aromatic ring groups is not particularly limited, but is preferably 1 or more, preferably 2 or more, usually 10 or less, 5 or less, and more preferably 3 or less. When it is set to the lower limit value or more, the development adhesion tends to be good, and when it is set to the upper limit value or less, the curability tends to be good. The combination of the upper limit and the lower limit is preferably 1 to 10, more preferably 2 to 5, and even more preferably 2 to 3.

Specific examples of a group in which one or more divalent aliphatic groups and one or more divalent aromatic ring groups are linked include groups represented by the above formulas (ia) to (iE). Can be mentioned. Among these, the group represented by the above formula (iC) is preferable from the viewpoint of display reliability.

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

(R ^e , R ^f )
In the general formula (ii), ^Re and R ^f 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 number of carbon atoms is 1 or more, preferably 3 or more, more preferably 6 or more, more preferably 20 or less, still more preferably 15 or less, still more preferably 10 or less. When it is set to the 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, and when it is set to the upper limit value or less, the surface smoothness of the film tends to be good. It is easy to suppress the deterioration of the sensitivity and the resolution tends to be improved. The combination of the upper limit and the lower limit is preferably 1 to 20, more preferably 3 to 15, and even more preferably 6 to 10.

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-hexylene group, an n-heptylene group and the like. Among these, a methylene group is preferable from the viewpoint of skeletal rigidity.
Specific examples of the divalent branched chain aliphatic group include the above-mentioned divalent linear aliphatic group, and as side chains, a methyl group, an ethyl group, an n-propyl group, an iso-propyl group, and n-butyl. Examples thereof include a structure having a group, an iso-butyl group, a sec-butyl group, a tert-butyl group and the like.
The number of rings contained in the divalent cyclic aliphatic group is not particularly limited, but is preferably 1 or more, preferably 2 or more, and usually 12 or less and 10 or less. When it is at least the above lower limit value, the film becomes strong and the substrate adhesion tends to be good, and when it is at least the above upper limit value, it is easy to suppress deterioration of the surface smoothness and sensitivity of the film, and the resolution is high. There is a tendency for sex to improve. As the combination of the upper limit and the lower limit, 1 to 12 is preferable, and 2 to 10 is more preferable. 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. The group obtained by dividing two is mentioned. 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; a carboxyl group and the like. Among these, unsubstituted is preferable from the viewpoint of easiness of synthesis.

(M, n)
In the general formula (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 good. From the viewpoint of developability, m and n are preferably 0, while from the viewpoint of patterning suitability and surface roughness, m and n are preferably 1 or 2.

Further, the partial structure represented by the formula (ii) is preferably a partial structure represented by the following formula (ii-1) from the viewpoint of compatibility.

In equation (ii-1), ^Rc is synonymous with equation (ii);
^Rα represents a monovalent cyclic hydrocarbon group which may have a substituent;
n is an integer greater than or equal to 1;
The benzene ring in the formula (ii-1) may be further substituted with any substituent.

(R ^α )
In the formula (ii-1), R ^α represents a monovalent cyclic hydrocarbon group.
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 preferably 1 or more, preferably 2 or more, and usually 6 or less, 4 or less is preferable, and 3 or less is more preferable. When it is set to the lower limit value or more, the development adhesion tends to be good, and when it is set to the upper limit value or less, the curability tends to be good. The combination of the upper limit and the lower limit is preferably 1 to 6, more preferably 2 to 4, and even more preferably 2 to 3.
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, the development adhesion tends to be good, and when it is set to the upper limit value or less, the curability tends to be good. The combination of the upper limit and the lower limit is preferably 4 to 40, more preferably 6 to 30, and even more preferably 8 to 20.
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 compatibility.

On the other hand, the number of rings contained in the aromatic ring group is not particularly limited, but is preferably 1 or more, preferably 2 or more, more preferably 3 or more, and usually 10 or less and 5 or less. When it is set to the lower limit value or more, the development adhesion tends to be good, and when it is set to the upper limit value or less, the curability tends to be good. The combination of the upper limit and the lower limit is preferably 1 to 10, more preferably 2 to 5, and even more preferably 2 to 3.
Examples of the aromatic ring group include an aromatic hydrocarbon ring group and an aromatic heterocyclic group. The aromatic ring group usually has 4 or more carbon atoms, preferably 5 or more, more preferably 6 or more, and more preferably. , 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, the development adhesion tends to be good, and when it is set to the upper limit value or less, the curability tends to be good. The combination of the upper limit and the lower limit is preferably 4 to 30, more preferably 5 to 20, and even more preferably 6 to 15.
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 display reliability.

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; a carboxyl group and the like. Of these, no substitution is preferable from the viewpoint of ease of synthesis.

Although n represents an integer of 1 or more, 2 or more is preferable, and 3 or less is preferable. When it is set to the lower limit value or more, the development adhesion tends to be good, and when it is set to the upper limit value or less, the curability tends to be good. As n, 2 or 3 is preferable, 2 is more preferable in one embodiment, and 3 is more preferable in another embodiment.
When n is 2 or more, R ^α of 2 or more may be the same or different.

Among these, from the viewpoint of compatibility, ^Rα is preferably a monovalent aliphatic ring group, and more preferably an adamantyl group.

As described above, the benzene ring in the formula (ii-1) may be further substituted with any substituent. Examples of the substituent include a hydroxyl 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 unsubstituted from the viewpoint of patterning characteristics.

Specific examples of the partial structure represented by the above formula (ii-1) will be given below. * In the chemical formula represents the bond.

Further, the partial structure represented by the formula (ii) is preferably a partial structure represented by the following formula (ii-2) from the viewpoint of display reliability.

In equation (ii-2), R ^c is synonymous with equation (ii);
^Rβ represents a divalent cyclic hydrocarbon group which may have a substituent;
The benzene ring in formula (ii-2) may be further substituted with any substituent.

(R ^β )
In the formula (ii-2), R ^β represents a divalent cyclic hydrocarbon group.
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 preferably 1 or more, preferably 2 or more, and usually 10 or less and 5 or less. When it is set to the lower limit value or more, the development adhesion tends to be good, and when it is set to the upper limit value or less, the curability tends to be good. The combination of the upper limit and the lower limit is preferably 1 to 10, and more preferably 2 to 5.
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, the development adhesion tends to be good, and when it is set to the upper limit value or less, the curability tends to be good. The combination of the upper limit and the lower limit is preferably 4 to 40, more preferably 6 to 35, and even more preferably 8 to 30.
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 compatibility.

On the other hand, the number of rings contained in the aromatic ring group is not particularly limited, but is preferably 1 or more, preferably 2 or more, more preferably 3 or more, and usually 10 or less and 5 or less. When it is set to the lower limit value or more, the development adhesion tends to be good, and when it is set to the upper limit value or less, the curability tends to be good. The combination of the upper limit and the lower limit is preferably 1 to 10, more preferably 2 to 5, and even more preferably 2 to 3.
Examples of the aromatic ring group include an aromatic hydrocarbon ring group and an aromatic heterocyclic group. The aromatic ring group usually has 4 or more carbon atoms, preferably 6 or more, more preferably 8 or more, and 10 or more. The above is more preferable, 40 or less is preferable, 30 or less is more preferable, 20 or less is further preferable, and 15 or less is particularly preferable. When it is set to the lower limit value or more, the development adhesion tends to be good, and when it is set to the upper limit value or less, the curability tends to be good. As the combination of the upper limit and the lower limit, 4 to 40 is preferable, 6 to 30 is more preferable, 8 to 20 is more preferable, and 10 to 15 is particularly preferable.
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 display reliability.

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; a carboxyl group and the like. Of these, no substitution is preferable from the viewpoint of simplicity of synthesis.

Among these, from the viewpoint of compatibility, 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 display reliability, 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 (ii-2) may be further substituted with any substituent. Examples of the substituent include a hydroxyl 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. Further, the two benzene rings in the formula (ii-2) may be linked via these substituents.
Among these, it is preferable that it is unsubstituted from the viewpoint of patterning characteristics.

Specific examples of the partial structure represented by the above formula (ii-2) will be given below. * In the chemical formula represents the bond.

On the other hand, the partial structure represented by the formula (ii) is preferably a partial structure represented by the following formula (ii-3) from the viewpoint of compatibility.

In equation (ii-3), R ^c and R ^d are synonymous with equation (ii);
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 derived from the polybasic acid or its anhydride. Further, another OH group may be removed and shared with R ^Z in another molecule represented by the formula (ii-3), that is, a plurality of formulas (ii-3) may be shared via R ^Z. ) May be concatenated.
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 are preferable. Is tetrahydrophthalic acid, biphenyltetracarboxylic acid.

The partial structure represented by the above formula (ii-3) contained in one molecule of the epoxy (meth) acrylate resin (b-2-ii) may be one kind or two or more kinds, for example, R ^Z is hydrogen. Atomic ones and those having R ^Z as a polybasic acid residue may be mixed.

Further, the number of partial structures represented by the above formula (ii) contained in one molecule of the epoxy (meth) acrylate resin (b-2-ii) is not particularly limited, but 1 or more is preferable, and 3 or more is more preferable. It is preferable, 20 or less is preferable, 15 or less is more preferable, and 10 or less is further preferable. When it is at least the above lower limit value, the curability tends to be good, and when it is at least the above upper limit value, the development solubility tends to be good. The combination of the upper limit and the lower limit is preferably 1 to 20, more preferably 3 to 15, and even more preferably 3 to 10.

The polystyrene-equivalent weight average molecular weight (Mw) of the epoxy (meth) acrylate resin (b-2-ii) measured by gel permeation chromatography (GPC) is not particularly limited, but is preferably 1000 or more, more preferably 1500 or more. Preferably, 2000 or more is further preferable, 30,000 or less is preferable, 20000 or less is more preferable, 10,000 or less is further preferable, 8000 or less is further preferable, and 5000 or less is particularly preferable. When it is at least the lower limit value, the development adhesion tends to be good, and when it is at least the upper limit value, the development solubility tends to be good. The combination of the upper limit and the lower limit is preferably 1000 to 30000, more preferably 1000 to 20000, still more preferably 1500 to 15000, still more preferably 1500 to 10000, particularly preferably 2000 to 8000, and most preferably 2000 to 5000. Be done.

The acid value of the epoxy (meth) acrylate resin (b-2-ii) is not particularly limited, but is preferably 10 mgKOH / g or more, more preferably 30 mgKOH / g or more, further preferably 60 mgKOH / g or more, and even more preferably 80 mgKOH / g or more. Is particularly preferable, and 200 mgKOH / g or less is preferable, 180 mgKOH / g or less is more preferable, 150 mgKOH / g or less is further preferable, and 130 mgKOH / g or less is particularly preferable. When it is at least the lower limit value, the development solubility tends to be good, and when it is at least the upper limit value, the development adhesion tends to be good. As the combination of the upper limit and the lower limit, 10 to 200 mgKOH / g is preferable, 30 to 180 mgKOH / g is more preferable, 60 to 150 mgKOH / g is further preferable, and 80 to 130 mgKOH / g is particularly preferable.

<Other alkali-soluble resins>
The alkali-soluble resin (b) used in the present invention may contain other alkali-soluble resins in addition to the alkali-soluble resin (b-1) and the epoxy (meth) acrylate resin (b-2). ..

Examples of other alkali-soluble resins include acrylic resins, carboxyl group-containing epoxy resins, carboxyl group-containing urethane resins, novolak resins, and polyvinylphenol resins.

Among these, acrylic resins are preferably used from the viewpoint of compatibility with pigments, dispersants and the like, and those described in Japanese Patent Application Laid-Open No. 2014-137466 can be preferably used.

The acrylic resin includes, for example, an ethylenically unsaturated monomer having one or more carboxyl groups (hereinafter referred to as “unsaturated monomer (b1)”) and another copolymerizable ethylenically unsaturated monomer (b1). Examples thereof include a copolymer with a monomer (hereinafter referred to as “unsaturated monomer (b2)”).
Examples of the unsaturated monomer (b1) include unsaturated monocarboxylic acids such as (meth) acrylic acid, crotonic acid, α-chloroacrylic acid, and dermal acid; maleic acid, maleic anhydride, fumaric acid, and itacone. Unsaturated dicarboxylic acid such as acid, itaconic acid anhydride, citraconic acid, citraconic acid anhydride, mesaconic acid or its anhydride; monosuccinic acid [2- (meth) acryloyloxyethyl], mono-phthalic acid [2- (meth) Mono-[(meth) acryloyloxyalkyl] ester of a divalent or higher valent carboxylic acid such as [acryloyloxyethyl]; has a carboxy group and a hydroxyl group at both ends of ω-carboxypolycaprolactone mono (meth) acrylate and the like. Polymer mono (meth) acrylate; p-vinylbenzoic acid and the like can be mentioned.
These unsaturated monomers (b1) can be used alone or in admixture of two or more.

Examples of the unsaturated monomer (b2) include N-position substituted maleimides such as N-phenylmaleimide and N-cyclohexylmaleimide; styrene, α-methylstyrene, p-hydroxystyrene, and p-hydroxy-α-. Aromatic vinyl compounds such as methylstyrene, p-vinylbenzylglycidyl ether, 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 (polymerization degree 2 to 10) Methyl ether (meth) acrylate, polyethylene glycol (polymerization degree 2 to 10) mono (meth) acrylate, polypropylene glycol (polymerization degree 2 to 10) ) Mono (meth) acrylate, cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, tricyclo [5.2.1.0 ^2,6 ] decane-8-yl (meth) acrylate, dicyclopentenyl (meth) acrylate, Gglycerol mono (meth) acrylate, 4-hydroxyphenyl (meth) acrylate, ethylene oxide-modified (meth) acrylate of paracumylphenol, glycidyl (meth) acrylate, 3,4-epoxycyclohexylmethyl (meth) acrylate, 3-[(( (Meta) Acryloyloxymethyl] Oxetane, 3-[(Meta) Acryloyloxymethyl] -3-ethyl Oxetane and other (meth) acrylic acid esters;

Vinyl ethers such as cyclohexyl vinyl ether, isobornyl vinyl ether, tricyclo [5.2.1.0 ^2,6 ] decane-8-ylvinyl 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) can be used alone or in admixture of two or more.

In the copolymer of the unsaturated monomer (b1) and the unsaturated monomer (b2), the copolymerization ratio of the unsaturated monomer (b1) in the copolymer is preferably 5 to 50% by mass. , More preferably 10 to 40% by mass. By copolymerizing the unsaturated monomer (b1) in such a range, it tends to be possible to obtain a photosensitive coloring composition having excellent alkali developability and storage stability.

Specific examples of the copolymer of the unsaturated monomer (b1) and the unsaturated monomer (b2) include, for example, Japanese Patent Application Laid-Open No. 7-140654, Japanese Patent Application Laid-Open No. 8-259876, Japan. Japanese Patent Application Laid-Open No. 10-31308, Japanese Patent Application Laid-Open No. 10-300922, Japanese Patent Application Laid-Open No. 11-174224, Japanese Patent Application Laid-Open No. 11-258415, Japanese Patent Application Laid-Open No. 2000-56118, Japan Examples thereof include copolymers disclosed in Japanese Patent Application Laid-Open No. 2004-101728.
The copolymer of the unsaturated monomer (b1) and the unsaturated monomer (b2) can be produced by a known method, and for example, Japanese Patent Application Laid-Open No. 2003-222717, Japanese Patent Application Laid-Open No. 2003-222717, Japanese Patent Laid-Open No. The structure, Mw, and Mw / Mn can also be controlled by the methods disclosed in Japanese Patent Publication No. 2006-259680, Pamphlet No. 2007/029871 and the like.

<(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.

As the photopolymerization initiator, for example, a metallocene compound containing a titanosen compound described in Japanese Patent Application Laid-Open No. 59-152396 and Japanese Patent Application Laid-Open No. 61-151197; The hexaarylbiimidazole derivative described; N-aryl-α-amino acids such as halomethylated oxadiazole derivative, halomethyl-s-triazine derivative, N-phenylglycine, etc. described in JP-A-10-39503 of Japan, N- Radical activators such as aryl-α-amino acid salts and N-aryl-α-amino acid esters, α-aminoalkylphenone derivatives; Examples thereof include the described oxime ester derivatives.

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

Examples of 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-diphenylimidazole dimer, (4'- Methoxyphenyl) -4,5-diphenylimidazole dimer and the like can be mentioned.

Examples of halomethylated oxadiazole derivatives include 2-trichloromethyl-5- (2'-benzofuryl) -1,3,4-oxadiazole and 2-trichloromethyl-5-[β- (2'-). Benzofuryl) vinyl] -1,3,4-oxadiazole, 2-trichloromethyl-5-[β- (2'-(6 "-benzofuryl) vinyl)]-1,3,4-oxadiazole, 2 -Trichloromethyl-5-furyl-1,3,4-oxadiazole and the like can be mentioned.

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

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

As the photopolymerization initiator, oxime ester compounds (oxime ester derivatives) are particularly effective in terms of sensitivity and plate-making property, and when an alkali-soluble resin containing a phenolic hydroxyl group is used, it is disadvantageous in terms of sensitivity. Therefore, such an oxime ester-based compound having excellent sensitivity is particularly useful.
Examples of the oxime ester compound include those described in International Publication No. 2008/0756564, those described in International Publication No. 2009/131189, those described in Japanese Patent Application Laid-Open No. 2011-132215, and International Publication No. Examples thereof include those described in 2008/076878 and those described in Japanese Patent Publication No. 2014-500852.

Among the oxime ester compounds, it is preferable to include the oxime ester compound represented by the following formula (CI) from the viewpoint of high sensitivity.

In the above general formula (CI), R ^c1 represents an aromatic ring group which may have a substituent;
R ^c2 represents an alkanoyl group which may have a substituent or an allyloyl group which may have a substituent;
R ^c3 represents a hydrogen atom or an alkyl group which may have a substituent;
R ^c4 represents an aromatic ring group which may have a substituent;
R ^c5 and R ^c6 each independently represent a benzene ring that may have a substituent or a naphthalene ring that may have a substituent, provided that at least one of R ^c5 and R ^c6 . Is a naphthalene ring which may have a substituent;
At least one of R ^c1 and R ^c4 has a -OR ^c7 group, where R ^c7 represents a halogenoalkyl group;
X represents a direct bond or a carbonyl group;
Z represents a direct bond or a carbonyl group.

Examples of the aromatic ring group in R ^c1 include an aromatic hydrocarbon ring group and an aromatic heterocyclic group. The carbon number is preferably 30 or less, more preferably 12 or less, usually 4 or more, and preferably 6 or more. When it is set to the upper limit value or less, the solubility tends to be good, and when it is set to the lower limit value or more, it tends to be easy to achieve both sensitivity and solubility. The combination of the upper limit and the lower limit is preferably 4 to 30, and more preferably 6 to 12.

The aromatic hydrocarbon ring in the 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 one free atomic value. 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 oxazole ring, an indole ring, and a carbazole ring having one free atomic value. Rings, pyrrolobymidazole rings, pyrrolopyrazole rings, pyrolopyrrole rings, thienopyrrole rings, thienothiophene rings, flopyrol rings, flofran rings, thienoflan rings, benzoisoxazole rings, benzoisothiazole rings, benzimidazole rings, pyridine rings, pyrazine rings, Examples thereof include pyridazine rings, pyrimidine rings, triazine rings, quinoline rings, isoquinoline rings, sinoline rings, quinoxalin rings, phenanthridin rings, benzimidazole rings, perimidine rings, quinazoline rings, quinazolinone rings, and azulene rings.
Examples of the substituent that the aromatic ring group may have include an alkyl group, a hydroxyl group, an alkoxy group, a halogen atom, a halogenoalkyl group, a —OR ^c7 group described later, and the like, and halogen from the viewpoint of surface curability. An atom, a halogenoalkyl group or an —OR ^c7 group is preferable, a —OR ^c7 group is more preferable, and on the other hand, it is preferably unsubstituted from the viewpoint of easiness of synthesis.
Among these, from the viewpoint of sensitivity, an aromatic hydrocarbon ring group which may have a substituent is preferable, and an aromatic hydrocarbon ring group substituted with -OR ^c7 group is more preferable. It is more preferably a benzene ring group substituted with an —OR ^c7 group.

The carbon number of the alkanoyl group in R ^c2 is not particularly limited, but is preferably 2 or more from the viewpoint of sensitivity. Further, from the viewpoint of sensitivity, it is preferably 20 or less, more preferably 12 or less, further preferably 7 or less, further preferably 5 or less, and particularly preferably 3 or less. .. The combination of the upper limit and the lower limit is preferably 2 to 20, more preferably 2 to 12, further preferably 2 to 7, further preferably 2 to 5, and particularly preferably 2 to 3.

Specific examples of the alkanoyl group include an acetyl group, a propanoyl group, a butanoyl group, and the like. Among these, an acetyl group or a propanoyl group is preferable, and an acetyl group is more preferable, from the viewpoint of sensitivity.
Examples of the substituent that the alkanoyl group may have include a hydroxyl group, an alkoxy group, a halogen atom and the like, and it is preferable that the substituent is unsubstituted from the viewpoint of sensitivity.

The carbon number of the allylloyl group in R ^c2 is not particularly limited, but is preferably 7 or more from the viewpoint of sensitivity. Further, from the viewpoint of sensitivity, it is preferably 20 or less, more preferably 12 or less, further preferably 10 or less, and particularly preferably 8 or less. The combination of the upper limit and the lower limit is preferably 7 to 20, more preferably 7 to 12, and even more preferably 7 to 10.

Specific examples of the allylloyl group include a benzoyl group, a methylbenzoyl group, a naphthoyl group and the like, and among these, a benzoyl group is more preferable from the viewpoint of sensitivity.
Examples of the substituent that the allylloyl group may have include a hydroxyl group, an alkoxy group, a halogen atom and the like, and it is preferable that the allyloyl group is unsubstituted from the viewpoint of sensitivity.
Among these, from the viewpoint of sensitivity, R ^c2 is preferably an alkanoyl group which may have a substituent, more preferably an unsubstituted alkanoyl group, and further preferably an acetyl group.

The number of carbon atoms of the alkyl group in R ^c3 is not particularly limited, but is preferably 1 or more, more preferably 2 or more, further preferably 5 or more, and 7 or more from the viewpoint of solubility. Is particularly preferable. Further, from the viewpoint of compatibility, it is preferably 20 or less, more preferably 15 or less, and further preferably 10 or less. The combination of the upper limit and the lower limit is preferably 1 to 20, more preferably 2 to 15, and even more preferably 5 to 10.

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, a 2-ethylhexyl group and the like, and among these, from the viewpoint of solubility, An octyl group or a 2-ethylhexyl group is preferable, and a 2-ethylhexyl group is more preferable.

Examples of the substituent that the alkyl group may have include a hydroxyl group, an alkoxy group, a halogen atom, a phosphoric acid group and the like, and it is more preferable that the substituent is unsubstituted from the viewpoint of easiness of synthesis.
Among these, from the viewpoint of solubility, R ^c3 is preferably an alkyl group which may have a substituent, more preferably an unsubstituted alkyl group, and preferably a 2-ethylhexyl group. More preferred.

Examples of the aromatic ring group in R ^c4 include an aromatic hydrocarbon ring group and an aromatic heterocyclic group. The carbon number is preferably 30 or less, more preferably 12 or less, usually 4 or more, and preferably 6 or more. When it is set to the upper limit value or less, the solubility tends to be good, and when it is set to the lower limit value or more, it tends to be easy to achieve both sensitivity and solubility. The combination of the upper limit and the lower limit is preferably 4 to 30, and more preferably 6 to 12.

The aromatic hydrocarbon ring in the 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 one free atomic value. 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 oxazole ring, an indole ring, and a carbazole ring having one free atomic value. Rings, pyrrolobymidazole rings, pyrrolopyrazole rings, pyrolopyrrole rings, thienopyrrole rings, thienothiophene rings, flopyrol rings, flofran rings, thienoflan rings, benzoisoxazole rings, benzoisothiazole rings, benzimidazole rings, pyridine rings, pyrazine rings, Examples thereof include pyridazine rings, pyrimidine rings, triazine rings, quinoline rings, isoquinoline rings, sinoline rings, quinoxalin rings, phenanthridine rings, benzimidazole rings, perimidine rings, quinazoline rings, quinazolinone rings, and azulene rings.

Examples of the substituent that the aromatic ring group may have include an alkyl group, a hydroxyl group, an alkoxy group, a halogen atom and the like, and an alkyl group or an alkoxy group is preferable from the viewpoint of solubility, and an alkyl group is more preferable. , Methyl group is more preferred. The number of substituents is not particularly limited, but from the viewpoint of solubility, it is preferably 1 or more, more preferably 2 or more, and even more preferably 3 or more. Further, from the viewpoint of compatibility, 10 or less is preferable, 5 or less is more preferable, and 4 or less is further preferable. The combination of the upper limit and the lower limit is preferably 1 to 10, more preferably 2 to 5, and even more preferably 3 to 4.

Among these, from the viewpoint of solubility, R ^c4 is preferably an aromatic hydrocarbon ring group which may have a substituent, and is preferably an aromatic hydrocarbon ring group having two or more methyl groups. Is more preferable, and it is further preferable to use a mesityl group.

R ^c5 and R ^c6 each independently represent a benzene ring or a naphthalene ring which may have a substituent. However, at least one of R ^c5 and R ^c6 is a naphthalene ring which may have a substituent. Specific combinations include a combination in which R ^c5 is a benzene ring which may have a substituent and R ^c6 is a naphthalene ring which may have a substituent, and R ^c5 has a substituent. A combination of naphthalene rings that may be present, where R ^c6 is a benzene ring that may have a substituent, R ^c5 is a naphthalene ring that may have a substituent, and R ^c6 is a substituent. Examples thereof include combinations which are naphthalene rings which may be possessed. Among these, from the viewpoint of absorbance, a combination in which R ^c5 is a naphthalene ring which may have a substituent and R ^c6 is a benzene ring which may have a substituent can be mentioned. ..

In the case of a benzene ring in which R ^c5 may have a substituent, an embodiment in which an N atom is bonded to the 1-position of the benzene ring, R ^c6 is bonded to the 2-position, and X is bonded to the 4-position can be mentioned. Similarly, in the case of a benzene ring in which R ^c6 may have a substituent, an N atom is bonded to the 1-position of the benzene ring, R ^c5 is bonded to the 2-position, and Z is bonded to the 4-position. Can be mentioned.

On the other hand, in the case of a naphthalene ring in which R ^c5 may have a substituent, the X, N atoms and R ^c6 bonded to R ^c5 in the formula (CI) are at the positions of the naphthalene ring represented by R ^c5 . It may be combined. For example, an N atom is bonded to the 1-position of the naphthalene ring, R ^c6 is bonded to the 2-position, and X is bonded to the 4-position, or R ^c6 is bonded to the 1-position of the naphthalene ring and the N atom is bonded to the 2-position. Is bound, and X is bound at the 6-position. Similarly, in the case of a naphthalene ring in which R ^c6 may have a substituent, the Z, N atom and R ⁵ bonded to R ^c6 in the formula (CI) are bonded to the position of the naphthalene ring. May be. For example, an N atom is bonded to the 1-position of the naphthalene ring, R ^c5 is bonded to the 2-position, and Z is bonded to the 4-position, or R ^c5 is bonded to the 1-position of the naphthalene ring and the N atom is bonded to the 2-position. Is bound, and Z is bound at the 6-position.

Examples of the substituent that the benzene ring or naphthalene ring in R ^c5 and R ^c6 may have include a hydroxyl group, an alkoxy group, a halogen atom and the like, and it is more preferable that the substituent is unsubstituted from the viewpoint of sensitivity.

At least one of R ^c1 and R ^c4 has a -OR ^c7 group. R ^c1 may have -OR ^c7 groups, R ^c4 may have -OR ⁷ groups, and R ^c1 and R ^c4 may each independently have -OR ^c7 groups. good. Among these, from the viewpoint of sensitivity, it is preferable that R ^c1 has -OR ^c7 groups.

R ^c7 represents a halogenoalkyl group, and the number of carbon atoms of the halogenoalkyl group in R ^c7 is not particularly limited, but is preferably 1 or more, more preferably 2 or more, and 3 or more from the viewpoint of solubility. Is even more preferable. Further, from the viewpoint of compatibility, it is preferably 10 or less, more preferably 7 or less, and further preferably 5 or less. The combination of the upper limit and the lower limit is preferably 1 to 10, more preferably 2 to 7, and even more preferably 3 to 5.
The carbon chain in the halogenoalkyl group may be a straight chain, a branched chain, or a cyclic chain, but is preferably a straight chain from the viewpoint of ease of production.

The number of halogen atoms contained in the halogenoalkyl group is not particularly limited, but is preferably 1 or more, more preferably 2 or more, and even more preferably 3 or more from the viewpoint of solubility. Further, from the viewpoint of compatibility, it is preferably 7 or less, more preferably 6 or less, and further preferably 5 or less. The combination of the upper limit and the lower limit is preferably 1 to 7, more preferably 2 to 6, and even more preferably 3 to 5.

Specific examples of the halogenoalkyl group include a 2,2,3,3-tetrafluoropropyl group, a 2,2,2-trifluoroethyl group, and a 2,2,3,3,4,5,5-octa. Examples thereof include a fluoropentyl group, and among these, a 2,2,3,3-tetrafluoropropyl group is more preferable from the viewpoint of ease of production.
Examples of the substituent that the halogenoalkyl group may have include a hydroxyl group and an alkoxy group, and it is preferable that the substituent is unsubstituted from the viewpoint of ease of production.

X represents a direct bond or a carbonyl group, and in one embodiment, it is preferably a direct bond from the viewpoint of adhesion, and in another embodiment, it is preferably a carbonyl group from the viewpoint of sensitivity.
Further, Z represents a direct bond or a carbonyl group, and in one embodiment, it is preferably a direct bond from the viewpoint of adhesion, and in another embodiment, it is preferably a carbonyl group from the viewpoint of sensitivity.

On the other hand, among the oxime ester compounds, it is preferable to include the oxime ester compound having a diphenyl sulfide skeleton from the viewpoint of solvent resistance. As described above, it is considered that the inclusion of the oxime ester compound having a diphenyl sulfide skeleton strongly absorbs light at a short wavelength and improves the surface curability, so that it becomes difficult to dissolve in a solvent and the solvent resistance is enhanced. Further, by preventing the penetration of the solvent, it becomes possible to suppress the colorant and the like from leaching out from the inside of the coating film. The oxime ester-based compound having a diphenyl sulfide skeleton has a short conjugate system, high energy of the entire molecule, high radical generation efficiency by thermal decomposition, promotes the polymerization reaction, and further, an unreacted initiator. It is considered that the elution of the initiator itself into the solvent can be suppressed.

The chemical structure of the oxime ester compound having a diphenylsulfide skeleton is not particularly limited, but from the viewpoint of solvent resistance, it is preferable to use one represented by the following general formula (C-II).

In the above general formula (C-II), R ²³ represents an alkyl group which may have a substituent or an aromatic ring group which may have a substituent;
R ²⁴ represents an alkyl group which may have a substituent or an aromatic ring group which may have a substituent;
R ²⁵ represents a hydroxyl group, a carboxyl group, or a group represented by the following general formula (C-II-1);
h represents an integer from 0 to 5;
The benzene ring represented by the formula (C-II) may further have a substituent.

In formula (C-II-1), R ^25a represents -O-, -S-, -OCO- or -COO-;
R ^25b represents an alkylene group which may have a substituent;
The alkylene portion of R ^25b may be interrupted 1-5 times by -O-, -S-, -COO- or -OCO-;
The alkylene moiety of R ²⁵ may have a bifurcated side chain or may be cyclohexylene;
R ^25c represents a hydroxyl group or a carboxyl group.

The number of carbon atoms of the alkyl group in R ²³ is not particularly limited, but is preferably 1 or more from the viewpoint of solubility in the photosensitive coloring composition. Further, from the viewpoint of developability, it is preferably 20 or less, more preferably 10 or less, further preferably 8 or less, further preferably 5 or less, and particularly preferably 3 or less. preferable. As the combination of the upper limit and the lower limit, 1 to 20 is preferable, 1 to 10 is more preferable, 1 to 8 is more preferable, 1 to 5 is more preferable, and 1 to 3 is particularly preferable.

Specific examples of the alkyl group include a methyl group, a hexyl group, a cyclopentylmethyl group and the like. Among these, a methyl group or a hexyl group is preferable, and a methyl group is more preferable, from the viewpoint of developability.
Examples of the substituent that the alkyl group may have include an aromatic ring group, a hydroxyl group, a carboxyl group, a halogen atom, an amino group and an amide group, and a hydroxyl group and a carboxyl group are preferable from the viewpoint of alkali developability. Carboxyl groups are more preferred. Further, from the viewpoint of ease of synthesis, it is preferably unsubstituted.

Examples of the aromatic ring group in R ²³ 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. The combination of the upper limit and the lower limit is preferably 5 to 30, more preferably 5 to 20, and even more preferably 5 to 12.

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 carboxyl group, a halogen atom, an amino group, an amide group and an alkyl group, and a hydroxyl group and a carboxyl group are preferable from the viewpoint of developability, and a carboxyl group is preferable. Groups are more preferred.
Among these, from the viewpoint of developability, R ²³ is preferably an alkyl group which may have a substituent, more preferably an unsubstituted alkyl group, and further preferably a methyl group. ..

The number of carbon atoms of the alkyl group in R ²⁴ is not particularly limited, but is preferably 1 or more from the viewpoint of sensitivity. Further, from the viewpoint of sensitivity, it is preferably 20 or less, more preferably 10 or less, further preferably 5 or less, and particularly preferably 3 or less. As the combination of the upper limit and the lower limit, 1 to 20 is preferable, 1 to 10 is more preferable, 1 to 5 is more preferable, and 1 to 3 is particularly preferable.

Specific examples of the alkyl group include a methyl group, an ethyl group, a propyl group and the like. Among these, a methyl group or an ethyl group is preferable, and a methyl group is more preferable, from the viewpoint of sensitivity.
Examples of the substituent that the alkyl group may have include a halogen atom, a hydroxyl group, a carboxyl group, an amino group and an amide group. From the viewpoint of alkali developability, a hydroxyl group and a carboxyl group are preferable, and a carboxyl group is more preferable. On the other hand, from the viewpoint of ease of synthesis, it is preferably unsubstituted.

Examples of the aromatic ring group in R ²⁴ include an aromatic hydrocarbon ring group and an aromatic heterocyclic group. The carbon number is preferably 30 or less, more preferably 12 or less, usually 4 or more, and preferably 6 or more. When it is set to the upper limit value or less, the sensitivity tends to be high, and when it is set to the lower limit value or more, the sublimation property tends to be low. The combination of the upper limit and the lower limit is preferably 4 to 30, and more preferably 6 to 12.

The aromatic hydrocarbon ring in the 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 one free atomic value. 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 oxazole ring, an indole ring, and a carbazole ring having one free atomic value. Rings, pyrrolobymidazole rings, pyrrolopyrazole rings, pyrolopyrrole rings, thienopyrrole rings, thienothiophene rings, flopyrol rings, flofran rings, thienoflan rings, benzoisoxazole rings, benzoisothiazole rings, benzimidazole rings, pyridine rings, pyrazine rings, Examples thereof include pyridazine rings, pyrimidine rings, triazine rings, quinoline rings, isoquinoline rings, sinoline rings, quinoxalin rings, phenanthridine rings, benzimidazole rings, perimidine rings, quinazoline rings, quinazolinone rings, and azulene rings.
Examples of the substituent that the aromatic ring group may have include an alkyl group, a halogen atom, a hydroxyl group, a carboxyl group and the like.
Among these, from the viewpoint of sensitivity, R ²⁴ is preferably an alkyl group which may have a substituent, more preferably an unsubstituted alkyl group, and further preferably a methyl group.
On the other hand, from the viewpoint of plate-making property, R ²⁴ is preferably an aromatic ring group which may have a substituent, and more preferably an aromatic hydrocarbon group which may have a substituent. , It is more preferably an unsubstituted aromatic hydrocarbon group, and particularly preferably a phenyl group.

R ²⁵ is a hydroxyl group, a carboxyl group, or a group represented by the general formula (C-II-1). Among these, from the viewpoint of sensitivity and developability, the general formula (C-II-1) is used. It is preferably a group represented by.
In the general formula (C-II-1), as described above, R ^25a represents -O-, -S-, -OCO- or -COO-, and among these, from the viewpoint of sensitivity and developability. , -O- or -OCO- is preferable, and -O- is more preferable.

As described above, R ^25b represents an alkylene group which may have a substituent.
The number of carbon atoms of the alkylene group in R ^25b is not particularly limited, but is preferably 1 or more, more preferably 2 or more, and 20 or less from the viewpoint of solubility in the photosensitive coloring composition. Is more preferable, 10 or less is more preferable, 5 or less is further preferable, and 3 or less is particularly preferable. As the combination of the upper limit and the lower limit, 1 to 20 is preferable, 1 to 10 is more preferable, 2 to 5 is more preferable, and 2 or 3 is particularly preferable.
The alkylene group may be linear, may be branched, or may contain an aliphatic ring. Among these, a straight chain is preferable from the viewpoint of solubility in the photosensitive coloring composition.

Specific examples of the alkylene group include a methylene group, an ethylene group, a propylene group and the like, and among these, an ethylene group is more preferable from the viewpoint of solubility in a photosensitive coloring composition.

As described above, R ^25c is a hydroxyl group or a carboxyl group. From the viewpoint of solvent resistance (liquid crystal contamination resistance), it is preferable that R ^25c is a hydroxyl group.

In the general formula (C-II), h represents an integer of 0 to 5. In particular, from the viewpoint of developability, h is preferably 1 or more, preferably 4 or less, more preferably 3 or less, still more preferably 2 or less, and preferably 1. Most preferred. The combination of the upper limit and the lower limit is preferably 0 to 4, more preferably 1 to 3, and even more preferably 1 to 2.
On the other hand, from the viewpoint of ease of synthesis, h is preferably 0.

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

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

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

<(D) Ethylene unsaturated compound>
The photosensitive coloring composition of the present invention contains (d) an ethylenically unsaturated compound. (D) The sensitivity is improved by containing the 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. Specific examples thereof include (meth) acrylic acid, (meth) acrylic acid alkyl ester, acrylonitrile, styrene, and a carboxylic acid having one ethylenically unsaturated bond, and an ester of a polyvalent or monovalent alcohol. Be done.

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 ethylenically 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 at least the lower limit value, the sensitivity tends to be high, and when it is at least the upper limit value, the solubility in a solvent tends to be improved. The combination of the upper limit and the lower limit is preferably 1 to 8, more preferably 2 to 8, and even more preferably 5 to 7.
Examples of the polyfunctional ethylenic monomer include, for example, an ester of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid; an ester of an aromatic polyhydroxy compound and an unsaturated carboxylic acid; an aliphatic polyhydroxy compound, an aromatic poly. Examples thereof include an ester obtained by an esterification reaction between a polyvalent hydroxy compound such as a hydroxy compound and an unsaturated carboxylic acid and a polybasic carboxylic acid.

Examples of the ester of the aliphatic polyhydroxy compound and the unsaturated carboxylic acid include ethylene glycol diacrylate, triethylene glycol diacrylate, trimethylolpropane triacrylate, 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 itacon acid ester instead of itaconate, a crotonic acid ester instead of clonate, a maleic acid ester instead of maleate, and the like can be mentioned.

Examples of the ester of the aromatic polyhydroxy compound and the unsaturated carboxylic acid include acrylic acid esters and methacrylic acid esters of aromatic polyhydroxy compounds such as hydroquinone diacrylate, hydroquinone dimethacrylate, resorcindiacrylate, resorcindimethacrylate, and pyrogalloltriacrylate. And so on.

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

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

Examples of the urethane (meth) acrylates include DPHA-40H, UX-5000, UX-5002D-P20, UX-5003D, UX-5005 (manufactured by Nippon Kayaku Co., Ltd.), U-2PPA, U-6LPA, U. -10PA, U-33H, UA-53H, UA-32P, UA-1100H (manufactured by Shin Nakamura Chemical Industry Co., Ltd.), UA-306H, UA-510H, UF-8001G (manufactured by Kyoeisha Chemical Co., Ltd.), UV-1700B , UV-7600B, UV-7605B, UV-7630B, UV7640B (manufactured by Nippon Kayaku Kagaku Co., Ltd.) and the like.

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.
These may be used alone or in combination of two or more.

<(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 application becomes easy.
The photosensitive coloring composition of the present invention usually comprises (a) a colorant, (b) an alkali-soluble resin, (c) a photopolymerization initiator, (d) an ethylenically unsaturated compound, (f) a dispersant, and necessary. Various other materials used according to the above 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 here means the boiling point at a pressure of 1013.25 hPa.

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;
Glycol diacetates such as ethylene glycol diacetate, 1,3-butylene glycol diacetate, 1,6-hexanol diacetate;
Alkyl acetates such as cyclohexanol acetate;
Ethers such as amyl ether, diethyl ether, dipropyl ether, diisopropyl ether, dibutyl ether, diamil ether, ethylisobutyl ether, dihexyl ether;

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

Aromatic hydrocarbons such as benzene, toluene, xylene, cumene;
Amilformate, ethylformate, ethyl acetate, butyl acetate, propyl acetate, amyl acetate, methylisobutyrate, ethylene glycol acetate, ethylpropionate, propylpropionate, butyl butyrate, isobutyl butyrate, methyl isobutyrate, ethyl Caprilate, butyl stearate, ethyl benzoate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, propyl 3-methoxypropionate, 3-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 amilkloride;
Etheretones 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 Sokal Solvent No. 1 and No. 2. Solvento # 150, Shell TS28 Solvent, Carbitol, Ethyl Carbitol, Butyl Carbitol, Methyl Cellosolve (“Cellosolve” is a registered trademark; the same shall apply hereinafter), Ethyl Cellosolve, Ethyl Cellosolve Acetate, Methyl Cellosolve Acetate, Diglime (any of them). Also the product name) and so on.
These organic solvents may be used alone or in combination of two or more.

When forming a 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. (under pressure 1013.25 hPa conditions; hereinafter, the boiling points are all the same). More preferably, it has a boiling point of 120 to 170 ° C.

Among the above organic solvents, glycol alkyl ether acetates are preferable, and propylene glycol monomethyl ether acetate is more preferable, from the viewpoint that the balance between coatability and surface tension is good and the solubility of the constituent components in the composition is relatively high. Glycol alkyl ether acetates may be used alone.
Glycol alkyl ether acetates may be used alone or in combination with other organic solvents. Glycol monoalkyl ethers are particularly preferable as the organic solvent to be used in combination. Of these, propylene glycol monomethyl ether is preferable, and 3-methoxybutanol is more preferable, because of the solubility of the constituents in the composition.
Glycol monoalkyl ethers have high polarity, and if the amount added is too large, the pigment tends to aggregate, and the viscosity of the colored resin composition obtained later tends to increase, and the storage stability tends to decrease. When glycol monoalkyl ethers are used in combination, the proportion of glycol monoalkyl ethers in the solvent is preferably 5% by mass to 30% by mass, more preferably 5% by mass to 20% by mass.

It is also preferable to use an organic solvent having a boiling point of 150 ° C. or higher (hereinafter, may be referred to as “high boiling point solvent”) in combination. By using such a high boiling point solvent in combination, the 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, there is an effect of preventing the generation of foreign matter defects due to precipitation and solidification of coloring materials and the like at the tip of the slit nozzle. Among the above-mentioned various solvents, diethylene glycol mono-n-butyl ether, diethylene glycol mono-n-butyl ether acetate, and diethylene glycol monoethyl ether acetate are particularly preferable because of such a high effect.

The content of the high boiling point solvent in the organic solvent is preferably 3% by mass to 50% by mass, more preferably 5% by mass to 40% by mass, and particularly preferably 5% by mass to 30% by mass. 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 coloring materials 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 time in the vacuum drying process and pin marks of prebake (drying unevenness caused by the pins for supporting the substrate of the prebake device).

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

<(F) Dispersant>
The photosensitive coloring composition of the present invention contains (f) a dispersant because (a) it is important to finely disperse the colorant and stabilize the dispersed state thereof in order to ensure quality stability. ..
(F) As the dispersant, a polymer dispersant having a functional group is preferable, and further, from the viewpoint of dispersion stability, a carboxyl group; a phosphate group; a sulfonic acid group; or these groups; a primary, secondary or tertiary. A polymer dispersant having a functional group such as an amino group; a quaternary ammonium base; a group derived from a nitrogen-containing heterocycle such as pyridine, pyrimidin, or pyrazine is preferable. In particular, a polymer 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 disperses the pigment. It is particularly preferable from the viewpoint that it 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 consisting of monomers having amino groups and macromonomers, and polyoxyethylene alkyl ethers. Examples thereof include a system dispersant, a polyoxyethylene diester dispersant, a polyether phosphate dispersant, a polyester phosphoric acid dispersant, a sorbitan aliphatic ester dispersant, and an aliphatic modified polyester dispersant.

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

The weight average molecular weight (Mw) of the polymer dispersant is usually 700 or more, preferably 1000 or more, and usually 100,000 or less, preferably 50,000 or less.
Of these, from the viewpoint of pigment dispersibility, the dispersant (f) preferably contains one or both of a urethane-based polymer dispersant having a functional group and an acrylic polymer dispersant, and acrylic polymer dispersants. It is particularly preferable to include an agent.
Further, from the viewpoint of dispersibility and storage stability, a polymer dispersant having a basic functional group and having one or both of a polyester bond and a polyether bond is preferable.

Examples of urethane-based and acrylic-based polymer dispersants include DISPERBYK-160 to 167, 182 series (all urethane-based), DISPERBYK-2000, 2001, BYK-LPN21116, etc. (all acrylic-based) (all manufactured by Big Chemie). ).
To specifically exemplify a preferable chemical structure as a urethane-based polymer dispersant, for example, it is the same as a polyisocyanate compound and a compound having one or two hydroxyl groups in the molecule and having a number average molecular weight of 300 to 10,000. Examples thereof include a dispersed resin having a weight average molecular weight of 1,000 to 200,000, which is obtained by reacting an active hydrogen with a compound having a tertiary amino group in the molecule. By treating these with a quaternary agent such as benzyl chloride, all or part of the tertiary amino group can be converted into a quaternary ammonium base.

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

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

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

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

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

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

The number average molecular weight of the compound having one or two hydroxyl groups in the same molecule is usually 300 to 10,000, preferably 500 to 6,000, and more preferably 1,000 to 4,000.

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

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

When the tertiary amino group has a nitrogen-containing heterocyclic structure, the nitrogen-containing heterocycle includes a pyrazole ring, an imidazole ring, a triazole ring, a tetrazole ring, an indole ring, a carbazole ring, an indazole ring, a benzimidazole ring, and a benzo. Nitrogen-containing hetero 5-membered ring such as triazole ring, benzoxazole ring, benzothiazole ring, benzothiasiazole ring, pyridine ring, pyridazine ring, pyrimidine ring, triazine ring, quinoline ring, aclysine ring, isoquinoline ring and other nitrogen-containing hetero 6-membered ring. Ring is mentioned. Of these nitrogen-containing heterocycles, the imidazole ring or the triazole ring is preferable.

Specific examples of these compounds having an imidazole ring and an amino group include 1- (3-aminopropyl) imidazole, histidine, 2-aminoimidazole, 1- (2-aminoethyl) imidazole and the like. Specific examples of the compound having a triazole ring and an amino group include 3-amino-1,2,4-triazole and 5- (2-amino-5-chlorophenyl) -3-phenyl-1H-1. , 2,4-Triazole, 4-amino-4H-1,2,4-Triazole-3,5-diol, 3-amino-5-phenyl-1H-1,3,4-triazole, 5-amino-1 , 4-Diphenyl-1,2,3-triazole, 3-amino-1-benzyl-1H-2,4-triazole and the like. Among them, N, N-dimethyl-1,3-propanediamine, N, N-diethyl-1,3-propanediamine, 1- (3-aminopropyl) imidazole, 3-amino-1,2,4-triazole preferable.
These may be used alone or in combination of two or more.

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

The urethane-based polymer dispersant is produced according to a known method for producing a polyurethane resin. The solvent used for production is usually ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclopentanone, cyclohexanone and isophorone, esters such as ethyl acetate, butyl acetate and cellosolve acetate, benzene, toluene, xylene and hexane. Hydrocarbons such as, diacetone alcohol, isopropanol, second butanol, some alcohols such as tertiary butanol, chlorides such as methylene chloride and chloroform, ethers such as tetrahydrofuran and diethyl ether, dimethylformamide, N-methyl. An aprotonic polar solvent such as pyrrolidone or dimethylsulfoxide is used. These may be used alone or in combination of two or more.

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

The amount of the compound having active hydrogen and a tertiary amino group in the same molecule is preferably controlled in the range of 1 to 100 mgKOH / g in terms of the amine value after the reaction. More preferably, it is in the range of 5 to 95 mgKOH / g. The amine value is a value expressed by the number of mg of KOH corresponding to the acid value by neutralizing and titrating the basic amino group with an acid. When the value is equal to or higher than the lower limit, the dispersibility tends to be improved, and when the value is equal to or higher than the upper limit, the developability tends to be improved.

When the isocyanate group remains in the polymer dispersant by the above reaction, it is preferable to crush the isocyanate group with an alcohol or an amino compound because the stability of the product with time is improved.
The weight average molecular weight (Mw) of the urethane-based polymer dispersant is usually in the range of 1,000 to 200,000, preferably 2,000 to 100,000, and more preferably 3,000 to 50,000. When it is at least the above lower limit value, the dispersibility and dispersion stability tend to be improved, and when it is at least the above upper limit value, the solubility is improved and the dispersibility tends to be improved.

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

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

Examples of the unsaturated group-containing monomer having no functional group include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, and isobutyl ( Meta) acrylate, t-butyl (meth) acrylate, benzyl (meth) acrylate, phenyl (meth) acrylate, cyclohexyl (meth) acrylate, phenoxyethyl (meth) acrylate, phenoxymethyl (meth) acrylate, 2-ethylhexyl (meth) Acrylate, Isobornyl (meth) acrylate, Tricyclodecane (meth) acrylate, Tetrahydrofurfuryl (meth) acrylate, N-vinylpyrrolidone, styrene and its derivatives, α-methylstyrene, N-cyclohexylmaleimide, N-phenylmaleimide, N -N-substituted maleimides such as benzylmaleimide, acrylonitrile, vinyl acetate and polymethyl (meth) acrylate macromonomers, polystyrene macromonomers, poly2-hydroxyethyl (meth) acrylate macromonomers, polyethylene glycol macromonomers, polypropylene glycol macromonomers, poly Examples thereof include macromonomers such as caprolactone macromonomers. These may be used alone or in combination of two or more.

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

The B block is composed of a partial structure derived from the unsaturated group-containing monomer that does not contain the functional group, but one B block contains a partial structure derived from two or more kinds of monomers. Also, these may be contained in the B block in any mode of random copolymerization or block copolymerization.
The AB or BAB block copolymer is prepared, for example, by the living polymerization method shown below.
The living polymerization method includes an anion living polymerization method, a cationic living polymerization method, and a radical living polymerization method. Among them, in the anion living polymerization method, the polymerization active species is an anion, and is represented by, for example, the following scheme.

In the above scheme, Ar ¹ is a monovalent organic group, Ar ² is a monovalent organic group different from Ar ¹ , M is a metal atom, and s and t are integers of 1 or more, respectively.

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

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

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

The acrylic polymer dispersant that can be used in the present invention may be an AB block copolymer or a BAB block copolymer, and the A block constituting the copolymer may be used. The / B block ratio is preferably 1/99 to 80/20, particularly 5/95 to 60/40 (mass ratio), and by setting it within this range, the balance between dispersibility and storage stability can be ensured. Tend.
Further, the amount of the quaternary ammonium base in 1 g of the AB block copolymer and the BAB block copolymer that can be used in the present invention is usually preferably 0.1 to 10 mmol, and this is preferable. There is a tendency to ensure good dispersibility by keeping it within the range.

In addition, such a block copolymer may usually contain an amino group generated in the production process, but its amine value is about 1 to 100 mgKOH / g, and from the viewpoint of dispersibility, it is considered. It is preferably 10 mgKOH / g or more, more preferably 30 mgKOH / g or more, still more preferably 50 mgKOH / g or more, preferably 90 mgKOH / g or less, more preferably 80 mgKOH / g or less, still more preferably 75 mgKOH / g or less.
Here, the amine value of the dispersant such as these block copolymers is expressed by the amount of base per 1 g of solid content excluding the solvent in the dispersant sample and the equivalent amount of KOH, and is measured by the following method.
Weigh 0.5-1.5 g of the dispersant sample into a 100 mL beaker and dissolve in 50 mL of acetic acid. This solution is neutralized and titrated with 0.1 mol / L HClO ₄ acetic acid solution using an automated titrator equipped with a pH electrode. The amine value is calculated by the following equation with the inflection point of the titration pH curve as the titration end point.

Aminin value [mgKOH / g] = (561 × V) / (W × S) [However, W: Dispersant sample weighing amount [g], V: Titration quantification at the titration end point [mL], S: Dispersant Represents the solid content concentration [mass%] of the sample. ]
The acid value of this block copolymer depends on the presence or absence and type of an acidic group that is the source of the acid value, but is generally preferably low, usually 10 mgKOH / g or less, and its weight average molecular weight (Mw). ) Is preferably in the range of 1000 to 100,000. Within the above range, good dispersibility tends to be ensured.

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

In the above formula (i), R ³¹ to R ³³ each independently have a hydrogen atom, an alkyl group which may have a substituent, an aryl group which may have a substituent, or a substituent. Represents an Aralkyl group that may be;
Two or more of R ³¹ to R ³³ may be combined with each other to form a cyclic structure;
R ³⁴ is a hydrogen atom or a methyl group;
X is a divalent linking group;
Y ^- is a counter anion.

The number of carbon atoms of the alkyl group which may have a substituent in R ³¹ to R ³³ of the above formula (i) is not particularly limited, but is preferably 1 or more and preferably 10 or less, and 6 The following is more preferable. Specific examples of the alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group and the like, and among these, a methyl group, an ethyl group, a propyl group and a butyl group. It is preferably a group, a pentyl group, or a hexyl group, and more preferably a methyl group, an ethyl group, a propyl group, or a butyl group. Further, it may be linear or branched. Further, it may contain a cyclic structure such as a cyclohexyl group or a cyclohexylmethyl group.

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

The number of carbon atoms of the aralkyl group which may have a substituent in R ³¹ to R ³³ of the above formula (i) is not particularly limited, but is usually 7 or more, preferably 16 or less, and is preferably 12 or less. The following is more preferable. Specific examples of the aralkyl group include a phenylmethyl group (benzyl group), a phenylethyl group (phenethyl group), a phenylpropyl group, a phenylbutyl group, a phenylisopropyl group and the like, and among these, a phenylmethyl group and a phenylethyl group. A group, a phenylpropyl group, or a phenylbutyl group is preferable, and a phenylmethyl group or a phenylethyl group is more preferable.

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

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

In the above formula (ii), R ³⁵ and R ³⁶ each independently have a hydrogen atom, an alkyl group which may have a substituent, an aryl group which may have a substituent, or a substituent. It is an Aralkyl group that may be;
R ³⁵ and R ³⁶ may combine with each other to form a cyclic structure;
R ³⁷ is a hydrogen atom or a methyl group;
Z is a divalent linking group.

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

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

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

In the above formulas (i) and (ii), the divalent linking groups X and Z include, for example, an alkylene group having 1 to 10 carbon atoms, an arylene group having 6 to 12 carbon atoms, and -CONH-R ⁴³ -group. -COOR ⁴⁴ -group [However, R ⁴³ and R ⁴⁴ are a single bond, an alkylene group having 1 to 10 carbon atoms, or an ether group having 2 to 10 carbon atoms (alkyloxyalkyl group)] and the like are preferable. Is a -COO-R ⁴⁴ -group.
Further, in the above formula (i), examples of the counter anion Y ⁻ include Cl ⁻ , Br ⁻ , I ⁻ , ClO ₄ ⁻ , BF ₄ ⁻ , CH ₃ COO ⁻ , PF ₆ ^{− and} the like.

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

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

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

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

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

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

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

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

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

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

The number of carbon atoms of the alkyl group which may have a substituent in R ³⁸ of the above formula (iv) is not particularly limited, but is preferably 1 or more, preferably 2 or more, and preferably 4 or more. More preferably, it is preferably 10 or less, and more preferably 8 or less.
Specific examples of the alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group and the like, and among these, a methyl group, an ethyl group, a propyl group and a butyl group. It is preferably a group, a pentyl group, or a hexyl group, and more preferably a methyl group, an ethyl group, a propyl group, or a butyl group. Further, it may be linear or branched. Further, it may contain a cyclic structure such as a cyclohexyl group or a cyclohexylmethyl group.

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

The carbon number of the aralkyl group which may have a substituent in R ³⁸ of the above formula (iv) is not particularly limited, but is usually 7 or more, preferably 16 or less, and preferably 12 or less. More preferably, it is more preferably 10 or less. Specific examples of the aralkyl group include a phenylmethyl group (benzyl group), a phenylethyl group (phenethyl group), a phenylpropyl group, a phenylbutyl group, a phenylisopropyl group and the like, and among these, a phenylmethyl group and a phenylethyl group. A group, a phenylpropyl group, or a phenylbutyl group is preferable, and a phenylmethyl group or a phenylethyl group is more preferable.

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

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

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

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

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

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

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

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

<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 (coatability improvers), pigment derivatives, photoacid generators, cross-linking agents, and mercapto compounds. , Development improver, ultraviolet absorber, antioxidant and the like can be appropriately blended.

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

In the above general formulas (g1), (g2) and (g3), R ⁵¹ represents a hydrogen atom or a methyl group;
l and l'represent an integer from 1 to 10;
m represents 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 agents such as anionic type, cationic type, nonionic type and amphoteric surfactant can be used. Of these, nonionic surfactants are preferable because they are less likely to adversely affect various properties, and fluorine-based and silicon-based surfactants are particularly effective in terms of coatability.
Examples of such a surfactant include TSF4460 (manufactured by GE Toshiba Silicone Co., Ltd.), DFX-18 (manufactured by Neos Co., Ltd.), BYK-300, BYK-325, BYK-330 (manufactured by Big Chemie), and KP340 (Shinetsu Silicone Co., Ltd.). (Manufactured by), Megafuck F-470, F-475, F-478, F-559 (manufactured by DIC), SH7PA (manufactured by Torre Silicone), DS-401 (manufactured by Daikin), L-77 (manufactured by Nippon Unicar) (Manufactured by Sumitomo 3M), FC4430 (manufactured by Sumitomo 3M) and the like.
As the surfactant, one type may be used, or two or more types may be used in combination in any combination and ratio.

(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-based, phthalocyanine-based, quinacridone-based, benzimidazolone-based, quinophthalone-based, isoindoleinone-based, dioxazine-based, anthraquinone-based, indanthrone-based, perylene-based, perinone-based, diketopyrrolopyrrole-based, and dioxazine. Derivatives such as phthalocyanines can be mentioned, but phthalocyanine-based and quinophthalone-based derivatives are preferable.
As the substituent of the pigment derivative, a sulfonic acid group, a sulfonamide group and a quaternary salt thereof, a phthalimidemethyl group, a dialkylaminoalkyl group, a hydroxyl group, a carboxyl group, an amide group and the like are directly on the pigment skeleton or an alkyl group, an aryl group or a complex. Examples thereof include those bonded via a ring group or the like, and a sulfonic acid group is preferable. Further, a plurality of these substituents may be substituted into one pigment skeleton.

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

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

(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 aryl groups having 6 to 12 carbon atoms;
If R ⁶¹ is -NR ⁶⁶ R ⁶⁷ , one of R ⁶² , R ⁶³ , R ⁶⁴ , R ⁶⁵ , R ⁶⁶ and R ⁶⁷ represents -CH ₂ OR ⁶⁸ ;
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 group;
The rest of R ⁶² , R ⁶³ , R ⁶⁴ , R ⁶⁵ , R ⁶⁶ and R ⁶⁷ each independently represent hydrogen or -CH ₂ OR ⁶⁸ groups;
R ⁶⁸ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.
The aryl group having 6 to 12 carbon atoms in R ⁶¹ is typically a phenyl group, a 1-naphthyl group or a 2-naphthyl group, and these phenyl groups and naphthyl groups include an alkyl group, an alkoxy group and a halogen atom. Substituents such as may be bonded. The alkyl group and the alkoxy group can each have about 1 to 6 carbon atoms. Among the above, the alkyl group represented by R ⁶⁸ is preferably a methyl group or an ethyl group, particularly a methyl group.

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

In formula (6-1), 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;
The rest of R ⁶² , R ⁶³ , R ⁶⁴ , R ⁶⁵ , R ⁶⁶ and R ⁶⁷ each independently represent a hydrogen atom or -CH ₂ OR ⁶⁸ groups;
R ⁶⁸ represents a hydrogen atom or an alkyl group.

Further, the guanamine compound corresponding to the general formula (6), that is, the compound in which R ⁶¹ is an aryl having 6 to 12 carbon atoms in the general formula (6) includes tetramethylolbenzoguanamine, tetramethoxymethylbenzoguanamine, and trimethoxymethyl. Includes benzoguanamine, tetraethoxymethylbenzoguanamine and the like.

Further, a cross-linking agent having a methylol group or a methylol alkyl ether group can also be used. Examples are 2,6-bis (hydroxymethyl) -4-methylphenol, 4-tert-butyl-2,6-bis (hydroxymethyl) phenol, 5-ethyl-1,3-bis (hydroxymethyl). Perhydro-1,3,5-triazine-2-one (commonly known as N-ethyldimethyloltriazone) or its dimethyl ether form, dimethylol trimethylene urea or its dimethyl ether form, 3,5-bis (hydroxymethyl) perhydro-1 , 3,5-oxadiadin-4-one (commonly known as dimethylolurone) or a dimethyl ether form thereof, tetramethylol glioxaldiurein or a tetramethyl ether form thereof can be mentioned.

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

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

Types of mercapto compounds include 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, 2-mercaptobenzoimidazole, hexanedithiol, decandithiol, 1,4-dimethylmercaptobenzene, butanediol bisthiopropionate, butanediol bis. Thioglycolate, Ethylene Glycol Bisthioglycolate, Trimethylol Propantristhioglycolate, Butanediol Bisthiopropionate, Trimethylol Propanistristhiopropionate, Trimethylol Propanistristhioglycolate, Pentaerythritol Tetrakissthiopropio Nate, pentaerythritol tetrakisthioglycolate, trishydroxyethyltristhiopropionate, ethylene glycol bis (3-mercaptobutyrate), butanediolbis (3-mercaptobutyrate), 1,4-bis (3-mercaptobutyrate) Liloxy) Butane, Trimethylol Propantris (3-Mercaptobutyrate), Pentaerythritol Tetrakiss (3-Mercaptobutyrate), Pentaerythritol Tris (3-Mercaptobutyrate), Ethylene Glycolbis (3-Mercaptoisobutyrate) , Butanediol bis (3-mercaptoisobutyrate), trimethylpropanthris (3-mercaptoisobutyrate), 1,3,5-tris (3-mercaptobutyloxyethyl) -1,3,5-triazine- Examples thereof include mercapto compounds having a heterocycle such as 2,4,6 (1H, 3H, 5H) -trione, or aliphatic polyfunctional mercapto compounds.
Various of these can be used individually by 1 type or in combination of 2 or more types.

<Amount of ingredients in the photosensitive coloring composition>
In the photosensitive coloring composition of the present invention, the content of the (a) colorant in the total solid content of the photosensitive coloring composition is 20% by mass or more, preferably 30% by mass or more, preferably 35% by mass. The above is more preferable, 40% by mass or more is particularly preferable, and usually 60% by mass or less is preferable, and 50% by mass or less is more preferable. (A) Sufficient optical density (OD) tends to be obtained by setting the content ratio of the colorant to the above lower limit value or more, and sufficient plate making characteristics and solvent resistance by setting it to the above upper limit value or less. , There is a tendency to ensure mechanical properties. The combination of the upper limit and the lower limit is preferably 20 to 60% by mass, more preferably 30 to 50% by mass, further preferably 35 to 50% by mass, and particularly preferably 40 to 50% by mass.

When (a) the colorant contains an organic color pigment, the content ratio of the organic color pigment in (a) the colorant is preferably 20% by mass or more, more preferably 40% by mass or more. , 60% by mass or more, more preferably 80% by mass or more, preferably 99% by mass or less, more preferably 90% by mass or less, and 85% by mass or less. Is more preferable. When it is at least the above lower limit value, a sufficient optical density (OD) tends to be obtained, and when it is at least the above upper limit value, solvent resistance and mechanical properties tend to be ensured. The combination of the upper limit and the lower limit is preferably 20 to 99% by mass, more preferably 40 to 90% by mass, further preferably 60 to 85% by mass, and particularly preferably 80 to 85% by mass.

Further, the total content ratio of at least one pigment selected from the group consisting of red pigment and orange pigment in (a) colorant is preferably 1% by mass or more, and preferably 2% by mass or more. More preferably, it is more preferably 3% by mass or more, further preferably 30% by mass or less, further preferably 20% by mass or less, further preferably 15% by mass or less, and 10% by mass. It is more preferably% or less, and particularly preferably 8% by mass or less. Sufficient optical density (OD) tends to be obtained when the value is equal to or higher than the lower limit value, and plate-making characteristics tend to be ensured when the value is equal to or higher than the upper limit value. The combination of the upper limit and the lower limit is preferably 1 to 30% by mass, more preferably 2 to 20% by mass, further preferably 3 to 15% by mass, still more preferably 3 to 10% by mass, and 3 to 8% by mass. Particularly preferred.

Further, (a) the total content of at least one pigment selected from the group consisting of blue pigments and purple pigments in the colorant is preferably 20% by mass or more, and preferably 30% by mass or more. More preferably, it is more preferably 40% by mass or more, further preferably 50% by mass or more, particularly preferably 60% by mass or more, most preferably 70% by mass or more, and more preferably. It is preferably 95% by mass or less, more preferably 90% by mass or less, further preferably 85% by mass or less, and particularly preferably 80% by mass or less. 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 plate-making characteristic tends to be secured. The combination of the upper limit and the lower limit is preferably 20 to 95% by mass, more preferably 30 to 90% by mass, further preferably 40 to 85% by mass, further preferably 50 to 85% by mass, and 60 to 85% by mass. It is particularly preferable, and 70 to 80% by mass is most preferable.

When (a) the colorant contains a black pigment, the content of the black pigment in (a) the colorant is preferably 1% by mass or more, more preferably 5% by mass or more, and 10%. It is more preferably 5% by mass or more, particularly preferably 15% by mass or more, preferably 50% by mass or less, more preferably 40% by mass or less, and 30% by mass or less. It is more preferably 20% by mass or less, and most preferably 20% by mass or less. When it is set to the lower limit value or more, a sufficient optical density (OD) tends to be obtained, and when it is set to the upper limit value or less, plate making characteristics and mechanical characteristics tend to be secured. As the combination of the upper limit and the lower limit, 1 to 50% by mass is preferable, 5 to 40% by mass is more preferable, and 10 to 30% by mass and 15 to 20% by mass are mentioned.

When the (a) colorant contains an organic black pigment, the content ratio of the organic black pigment in the (a) colorant is preferably 5% by mass or more, more preferably 10% by mass or more, 20 It is more preferably 5% by mass or more, more preferably 50% by mass or less, further preferably 40% by mass or less, further preferably 30% by mass or less, and 20% by mass or less. Is particularly preferred. Sufficient optical density (OD) tends to be obtained when the value is equal to or higher than the lower limit value, and plate-making characteristics tend to be ensured when the value is equal to or higher than the upper limit value. As the combination of the upper limit and the lower limit, 5 to 50% by mass is preferable, 10 to 40% by mass is more preferable, and 10 to 30% by mass is further preferable.

When the (a) colorant contains carbon black, the content of carbon black in the (a) colorant is preferably 1% by mass or more, more preferably 5% by mass or more, and 10% by mass. The above is more preferably, 15% by mass or more is particularly preferable, 50% by mass or less is preferable, 40% by mass or less is more preferable, and 30% by mass or less is preferable. It is more preferably 20% by mass or less, and particularly preferably 20% by mass or less. When it is at least the lower limit value, a sufficient optical density (OD) tends to be obtained, and when it is at least the upper limit value, plate-making characteristics and mechanical characteristics tend to be secured. As the combination of the upper limit and the lower limit, 1 to 50% by mass is preferable, 5 to 40% by mass is more preferable, and 10 to 30% by mass is further preferable.

The content of the (b) alkali-soluble resin in the total solid content of the photosensitive coloring composition is usually 5% by mass or more, preferably 10% by mass or more, more preferably 20% by mass or more, still more preferably 25. It is usually 80% by mass or less, preferably 70% by mass or less, more preferably 50% by mass or less, still more preferably 40% by 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 solubility of the unexposed portion in a developing solution and suppress development defects. Further, by setting the value to the upper limit or less, it is possible to suppress the increase in the permeability of the developing solution into the exposed portion, and it tends to be possible to suppress the deterioration of the sharpness and the adhesion of the pixels. The combination of the upper limit and the lower limit is preferably 10 to 80% by mass, more preferably 20 to 70% by mass, further preferably 25 to 50% by mass, and particularly preferably 25 to 40% by mass.

The content of the alkali-soluble resin (b-1) in the total solid content of the photosensitive coloring composition is usually 1% by mass or more, preferably 2% by mass or more, more preferably 3% by mass or more, and usually 30. It is mass% or less, preferably 20% by mass or less, more preferably 15% by mass or less, still more preferably 10% by mass or less. Sufficient solvent resistance and mechanical properties tend to be obtained by setting the content ratio of the alkali-soluble resin (b-1) to the lower limit or higher, and developing the unexposed portion by setting the content to the upper limit or lower. There is a tendency to secure sex. As the combination of the upper limit and the lower limit, 1 to 30% by mass is preferable, 2 to 20% by mass is more preferable, 3 to 15% by mass is further preferable, and 3 to 10% by mass is particularly preferable.

(B) When the alkali-soluble resin contains an epoxy (meth) acrylate resin (b-2), the content ratio of the epoxy (meth) acrylate resin (b-2) in the total solid content of the photosensitive coloring composition is usually normal. 1% by mass or more, preferably 5% by mass or more, more preferably 8% by mass or more, further preferably 10% by mass or more, usually 50% by mass or less, preferably 40% by mass or less, more preferably 30% by mass. % Or less, more preferably 20% by mass or less. By setting the content ratio of the alkali-soluble resin (b-2) to the lower limit value or more, the developability of the unexposed portion tends to improve, and by setting the content ratio to the upper limit value or less, the developability, solvent resistance and machine There is a tendency to control the characteristics. The combination of the upper limit and the lower limit is preferably 1 to 50% by mass, more preferably 5 to 40% by mass, further preferably 8 to 30% by mass, and particularly preferably 10 to 20% by mass.

The content of the (c) photopolymerization initiator in the total solid content of the photosensitive coloring composition is usually 0.1% by mass or more, preferably 0.5% by mass or more, more preferably 2% by mass or more, and further. It is preferably 4% by mass or more, particularly preferably 6% by mass or more, usually 15% by mass or less, preferably 10% by mass or less, and further preferably 8% 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 be equal to or higher than the lower limit value, and suppressing the decrease in solubility of the unexposed portion in the developing solution by setting the content ratio to be equal to or lower than the upper limit value. , There is a tendency to suppress development defects. The combination of the upper limit and the lower limit is preferably 0.1 to 15% by mass, more preferably 0.5 to 15% by mass, further preferably 2 to 10% by mass, and particularly preferably 4 to 8% by mass.

(C) When the photopolymerization initiator contains the oxime ester compound represented by the formula (CI), the content ratio of the oxime ester compound to the total solid content of the photosensitive coloring composition is usually 0. .5% by mass or more, preferably 1% by mass or more, more preferably 2% by mass or more, further preferably 3% by mass or more, usually 10% by mass or less, preferably 8% by mass or less, more preferably. Is 6% by mass or less, more preferably 5% by mass or less. By setting the content ratio of the oxime ester compound represented by the formula (C-1) to the lower limit value or more, the sensitivity decrease tends to be suppressed, and by setting the content ratio to the upper limit value or less, the unexposed portion is developed. There is a tendency to suppress a decrease in solubility in a liquid and suppress development defects. The combination of the upper limit and the lower limit is preferably 0.5 to 10% by mass, more preferably 1 to 8% by mass, further preferably 2 to 6% by mass, and particularly preferably 3 to 5% by mass.

(C) When the photopolymerization initiator contains an oxime ester compound having a diphenyl sulfide skeleton, the content ratio of the oxime ester compound in the total solid content of the photosensitive coloring composition is usually 0.5% by mass or more, preferably 0.5% by mass or more. Is 1% by mass or more, more preferably 2% by mass or more, usually 10% by mass or less, preferably 8% by mass or less, still more preferably 5% by mass or less. Sufficient solvent resistance tends to be obtained by setting the content ratio of the oxime ester compound having a diphenylsulfide skeleton to the above lower limit value or more, and by setting it to the above upper limit value or less, the unexposed portion is dissolved in the developing solution. There is a tendency to suppress deterioration of properties and suppress development defects. As the combination of the upper limit and the lower limit, 0.5 to 10% by mass is preferable, 1 to 8% by mass is more preferable, and 2 to 5% by mass is further preferable.

(C) When a polymerization accelerator is used together with the photopolymerization initiator, the content ratio of the polymerization accelerator to the total solid content of the photosensitive coloring composition is preferably 0.05% by mass or more, and usually 10% by mass or less. It is preferably 5% by mass or less, and the polymerization accelerator is usually used in a ratio of 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. preferable. 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 to suppress development defects.
Further, the mixing ratio of the sensitizing dye in the photosensitive coloring composition of the present invention is usually 20% by mass or less, preferably 15% by mass or less, more preferably 15% by mass or less, based on the total solid content in the photosensitive coloring composition from the viewpoint of sensitivity. It is preferably 10% by mass or less.

The content of the (d) ethylenically unsaturated compound in the total solid content of the photosensitive coloring composition is usually 30% by mass or less, preferably 20% by mass or less. (D) By setting the content ratio of the ethylenically unsaturated compound to the above upper limit value or less, it is possible to suppress the increase in the permeability of the developing solution to the exposed portion, and it tends to be easy to obtain a good image. be. The lower limit of the content ratio of (d) the ethylenically unsaturated compound is usually 1% by mass or more, preferably 5% by mass or more. As the combination of the upper limit and the lower limit, 1 to 30% by mass is preferable, and 5 to 20% by mass is more preferable.

(D) The content ratio of the alkali-soluble resin to 100 parts by mass of the ethylenically unsaturated compound is not particularly limited, but is preferably 100 parts by mass or more, more preferably 150 parts by mass or more, further preferably 200 parts by mass or more, and 250 parts by mass. The above is particularly preferable, 800 parts by mass or less is preferable, 600 parts by mass or less is more preferable, 500 parts by mass or less is further preferable, and 400 parts by mass or less is particularly preferable. When it is set to the lower limit value or more, the non-image area tends to be uniformly dissolved in the developing solution, and when it is set to the upper limit value or less, the sensitivity tends to be increased. The combination of the upper limit and the lower limit is preferably 100 to 800 parts by mass, more preferably 150 to 600 parts by mass, further preferably 200 to 500 parts by mass, and particularly preferably 250 to 400 parts by mass.

The photosensitive coloring composition of the present invention is prepared by using the solvent (e) so that the solid content concentration is usually 5 to 50% by mass, preferably 10 to 30% by mass.

The content of the dispersant (f) in the total solid content of the photosensitive coloring composition is usually 1% by mass or more, preferably 3% by mass or more, more preferably 5% by mass or more, and usually 30% by mass or less. 20% by mass or less is preferable, and 15% by mass or less is particularly preferable. As the combination of the upper limit and the lower limit, 1 to 30% by mass is preferable, 3 to 20% by mass is more preferable, and 5 to 15% by mass is further preferable.
Further, the content ratio of (f) dispersant to 100 parts by mass of (a) colorant is usually 5 parts by mass or more, particularly preferably 10 parts by mass or more, and usually 50 parts by mass or less, particularly 30 parts by mass or less. preferable. As the combination of the upper limit and the lower limit, 5 to 50 parts by mass is preferable, and 10 to 30 parts by mass is more preferable. (F) When the content ratio of the dispersant is set to the lower limit value or more, sufficient dispersibility tends to be easily obtained, and when the content ratio is set to the upper limit value or less, the ratio of other components is relatively reduced. There is a tendency that deterioration of sensitivity, plate-making property, etc. can be suppressed.

When the adhesion improver is used, the content ratio of the adhesion improver in the total solid content of the photosensitive coloring composition is usually 0.1 to 5% by mass, preferably 0.2 to 3% by mass, and more preferably 0.4. ~ 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 by setting the content ratio to the upper limit value or less, the sensitivity is lowered or the residue remains after development. There is a tendency to prevent it from becoming a defect.

When a surfactant is used, the content of the surfactant in the total solid content of the photosensitive coloring composition is usually 0.001 to 10% by mass, preferably 0.005 to 1% by mass, and more preferably 0. It is 0.01 to 0.5% by mass, most preferably 0.03 to 0.3% by mass. When the content of the surfactant is at least the above lower limit value, the smoothness and uniformity of the coating film tend to be easily developed, and when it is at least the above upper limit value, the smoothness and uniformity of the coating film are developed. It is easy and tends to suppress deterioration of other characteristics.

<Physical characteristics of the photosensitive coloring composition>
The photosensitive coloring composition of the present invention can be suitably used for forming a coloring spacer, and is preferably black from the viewpoint of being used as a coloring spacer. Further, the optical density (OD) per 1 μm of the cured coating film is preferably 1.0 or more, more preferably 1.2 or more, and further preferably 1.5 or more. It is particularly preferably 1.8 or more, usually 4.0 or less, and more preferably 3.0 or less. The combination of the upper limit and the lower limit is preferably 1.0 to 4.0, more preferably 1.2 to 4.0, still more preferably 1.5 to 3.0, and particularly preferably 1.8 to 3.0. Can be mentioned.

<Manufacturing method of photosensitive coloring composition>
The photosensitive coloring composition of the present invention (hereinafter, may be referred to as "resist") is produced according to a conventional method.
Usually, (a) the colorant is preferably dispersed in advance using a paint conditioner, a sand grinder, a ball mill, a roll mill, a stone mill, a jet mill, a homogenizer, or the like. Since the (a) colorant 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, and (f) a dispersant, and (b) a part or all of an alkali-soluble resin are used in combination (hereinafter, dispersion). The mixture to be treated and the composition obtained by the dispersion treatment may be referred to as "ink", "colorant dispersion" or "pigment dispersion"). In particular, it is preferable to use a polymer dispersant as the (f) dispersant because the thickening of the obtained ink and resist over time is suppressed and the dispersion stability is excellent.
As described above, in the step of producing the resist, it is preferable to produce a colorant dispersion liquid containing at least (a) a colorant, (e) a solvent, and (f) a dispersant. As the (a) colorant, (e) organic solvent, and (f) dispersant that can be used in the colorant dispersion liquid, those described as those that can be used in the photosensitive coloring composition are preferably used. be able to.

When the liquid containing all the components to be blended in the photosensitive coloring composition is subjected to the dispersion treatment, the highly reactive component may be denatured due to the heat generated during the dispersion treatment. Therefore, it is preferable to perform the dispersion treatment in a system containing a polymer dispersant.
When (a) the colorant is dispersed by 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 varies depending on the composition of the liquid, the size of the dispersion treatment device, etc., and is appropriately adjusted. The guideline for dispersion is to control the gloss of the ink so that the 20-degree mirror gloss (JIS Z8741) of the resist is in the range of 50 to 300. When the glossiness of the resist is low, the dispersion treatment is not sufficient and rough pigment (coloring material) particles often remain, which may result in insufficient developability, adhesion, resolution, etc. .. Further, if the dispersion treatment is performed until the gloss value exceeds the above range, the pigment is crushed and a large number of ultrafine particles are generated, so that the dispersion stability tends to be impaired.

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

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

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

(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, polyester resin such as polyethylene terephthalate, polyolefin resin such as polypropylene and polyethylene, thermoplastic resin sheet such as polycarbonate, polymethylmethacrylate and polysulphon, and epoxy. Examples thereof include a heat-curable resin sheet such as a resin, an unsaturated polyester resin, a poly (meth) acrylic resin, and various types of glass. Among these, glass and heat-resistant resin are preferable from the viewpoint of heat resistance. Further, a transparent electrode such as ITO or IZO may be formed on the surface of the substrate. Other than the transparent substrate, it can be formed on the TFT array.

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

(2) Coloring Spacer The photosensitive coloring composition of the present invention is used for the same purpose as a known photosensitive coloring composition for a color filter, but hereinafter, when 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 the form of a film or a 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 and development are performed. After that, a black photo spacer is formed on the substrate by performing additional exposure and heat curing treatment as necessary.

(3) Formation of Coloring Spacer [1] Method of Supplying to a 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 coat method, a die coat method, a roll coat method, a spray coat 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, and there is no influence of mist or the like adhering when the spin coating method is used, and the generation of foreign substances is suppressed. 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 in the range of 0.5 μm to 10 μm, preferably 1 μm to 9 μm, and particularly preferably 1 μm to 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 photo spacers having different heights by a photolithography method, the heights of the finally formed black photo spacers 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 onto 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 is usually selected in the range of 15 seconds to 5 minutes at a temperature of 40 ° C. to 130 ° C., preferably 50 ° C. to 110 ° C., depending on the type of solvent component, the performance of the dryer used, and the like. The temperature is selected in the range of 30 seconds to 3 minutes.

[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. It may also be a method of projecting an exposure light through a mask. 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 deoxidizing 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 0%) and a plurality of openings have the highest average light transmittance. An exposure mask having an opening (intermediate transmittance opening) having a small average light transmittance with respect to a high opening (complete transmission opening) is used. By this method, the difference in the average light transmittance between the intermediate transmission opening and the complete transmission opening, that is, the difference in the exposure amount causes a difference in the residual film ratio.
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 a lamp light source such as a xenon lamp, a halogen lamp, a tungsten lamp, a high pressure mercury lamp, an ultrahigh pressure mercury lamp, a metal halide lamp, a medium pressure mercury lamp, a low pressure mercury lamp, a carbon arc, and a fluorescent lamp, an argon ion laser, and a YAG laser. Examples thereof include laser light sources such as an excima laser, a nitrogen laser, a helium cadmium laser, a blue-violet semiconductor laser, and a near-infrared semiconductor laser. An optical filter can also be used when irradiating light of a specific wavelength for use.

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

The exposure amount is usually 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 200 mJ / cm ² or less, more preferably. It is 150 mJ / cm ² or less.
In the case of the proximity exposure method, the distance between the exposure target and the mask pattern is usually 10 μm or more, preferably 50 μm or more, more preferably 75 μm or more, usually 500 μm or less, preferably 400 μm or less, more preferably. It is 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 may further contain a surfactant, an organic solvent, a buffer, a complexing agent, a dye or a pigment.

Examples of alkaline compounds include sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium carbonate, potassium carbonate, sodium hydrogencarbonate, potassium hydrogencarbonate, sodium silicate, potassium silicate, sodium metasilicate, sodium phosphate, and potassium phosphate. , Inorganic alkaline compounds such as sodium hydrogen phosphate, potassium hydrogen phosphate, sodium dihydrogen phosphate, potassium dihydrogen phosphate, ammonium hydroxide, monoethanolamine, diethanolamine or triethanolamine, monomethylamine, dimethylamine or trimethylamine. , Monoethylamine, diethylamine or triethylamine, monoisopropylamine or diisopropylamine, n-butylamine, monoisopropanolamine, diisopropanolamine or triisopropanolamine, ethyleneimine, ethylenediimine, tetramethylammonium hydroxide (TMAH), choline, etc. Examples include organic alkaline compounds.
These alkaline compounds may be a mixture of two or more kinds.

Examples of the surfactant include nonionic surfactants such as polyoxyethylene alkyl ethers, polyoxyethylene alkylaryl ethers, polyoxyethylene alkyl esters, sorbitan alkyl esters, and monoglyceride alkyl esters; alkylbenzene sulfone. Anionic surfactants such as acid salts, alkylnaphthalene sulfonates, alkyl sulfates, alkyl sulfonates, sulfosuccinic acid ester salts; 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 can be used alone or in combination with an aqueous solution.

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

[5] Additional exposure and thermosetting treatment If necessary, the substrate after development may be subjected to additional 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 selected in the range of 100 ° C. to 280 ° C., preferably 150 ° C. to 250 ° C., and the time is selected in the range of 5 minutes to 60 minutes.

The size and shape 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 different black photospacers at the same time, in which case the height of the spacer is usually about 2-7 μm, and the sub-spacer is usually about 0.2-1.5 μm lower than the spacer. Has a photolithography.
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, further preferably 1.8 or more, and usually 4. It is 0 or less, preferably 3.0 or less. Here, the optical density (OD) is a value measured by a method described later.

[Color filter]
The color filter of the present invention includes the coloring spacer of the present invention as described above, for example, on a glass substrate as a transparent substrate, a black matrix, a red, green, and blue pixel coloring layer, and an overcoat layer. And are laminated to form a colored spacer, and then an alignment film is formed. The pixel coloring layer and the coloring spacer may be formed on the liquid crystal drive side substrate, or may be formed separately on the transparent substrate and the liquid crystal drive side substrate.

[Image display device]
A liquid crystal display provided with the colored spacer of the present invention is formed by bonding a color filter having such a colored spacer of the present invention and a liquid crystal drive side substrate to form a liquid crystal cell, and injecting liquid crystal into the formed liquid crystal cell. An image display device such as a display device can be manufactured. Similarly, the case where the pixel colored layer and the colored spacer are formed on the liquid crystal drive side substrate can be manufactured in the same manner.

Hereinafter, 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 constituents of the photosensitive coloring composition used in the following Examples and Comparative Examples 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. To this, 10 parts by mass of styrene, 85.2 parts by mass of glycidyl methacrylate and 66 parts by mass of monomethacrylate (FA-513M manufactured by Hitachi Chemical Co., Ltd.) having a tricyclodecane skeleton were added dropwise, and 2,2'-azobis-2-methyl. 8.47 parts by mass of butyronitrile was added dropwise over 3 hours, and stirring was continued at 90 ° C. for 2 hours. Next, the inside of the reaction vessel was replaced with air, 0.7 parts by mass of trisdimethylaminomethylphenol and 0.12 parts by mass of hydroquinone were added to 43.2 parts by mass of acrylic acid, and the reaction was continued at 100 ° C. for 12 hours. Then, 56.2 parts by mass of tetrahydrophthalic anhydride (THPA) and 0.7 parts by mass of triethylamine were added, and the mixture was reacted at 100 ° C. for 3.5 hours. The weight average molecular weight Mw of the alkali-soluble resin-I thus obtained measured by GPC was about 8400, the acid value was 80 mgKOH / g, and the double bond equivalent was 480 g / mol.

<Alkali-soluble resin-II>
"ZCR-1642H" manufactured by Nippon Kayaku Co., Ltd. (Mw = 6500, acid value = 98 mgKOH / g, double bond equivalent = 560 g / mol)

<Alkali-soluble resin-III>

50 g of an epoxy compound (epoxy equivalent 264) having the above structure, 13.65 g of acrylic acid, 60.5 g of methoxybutyl acetate, 0.936 g of triphenylphosphine, and 0.032 g of paramethoxyphenol were attached with a thermometer, a stirrer, and a cooling tube. The mixture was placed in a flask and reacted at 90 ° C. with stirring until the acid value became 5 mgKOH / g or less. The reaction took 12 hours to obtain an epoxy acrylate solution.
25 parts by mass of the epoxy acrylate solution, 0.76 parts by mass of trimethylolpropane (TMP), 3.3 parts by mass of biphenyltetracarboxylic acid anhydride (BPDA), 3.5 parts by mass of tetrahydrophthalic acid anhydride (THPA). Was placed in a flask equipped with a thermometer, a stirrer, and a cooling tube, and the temperature was slowly raised to 105 ° C. while stirring to react.
When the resin solution became transparent, it was diluted with methoxybutyl acetate to prepare a solid content of 50% by mass, and the acid value was 113 mgKOH / g, the polystyrene-equivalent weight average molecular weight (Mw) was 2600 measured by GPC, and the double. A carboxyl group-containing epoxy acrylate resin (alkali-soluble resin-III) having a binding equivalent of 520 g / mol was obtained.

<Alkali-soluble resin-IV>
17 parts by mass of succinic anhydride and 350 parts by mass of commercially available dipentaerythritol polyacrylate (A-9550 manufactured by Shin-Nakamura Chemical Co., Ltd.), 1.8 parts by mass of triethylamine, 0.12 parts by mass of 4-methoxyphenol, and propylene glycol monomethyl. By reacting at 85 ° C. for 6 hours in the presence of 91.8 parts by mass of ether acetate, a mixture (a-1) containing a polyfunctional acrylate having one carboxyl group and five acryloyl groups in one molecule was obtained. Obtained.
Subsequently, 32.7 g of a bisphenol A type epoxy resin (jER828 manufactured by Mitsubishi Chemical Corporation, epoxy equivalent 186), 460.7 g of the mixture (a-1), 2,2,6,6-tetramethylpiperidine 1-oxyl 0. 2 g, 8.0 g of triphenylphosphine and 18.9 g of propylene glycol monomethyl ether acetate were stirred at 80 ° C. until the acid value became 2 mgKOH / g or less. Subsequently, 161.6 g of propylene glycol monomethyl ether acetate was added to 520.5 g of the obtained reaction product to dissolve it, and then 24.2 g of 1,2,3,6-tetrahydrophthalic anhydride was added at 90 ° C. The reaction for 4 hours gave an alkali-soluble resin-IV. The obtained alkali-soluble resin-IV had an acid value of 23 mgKOH / g, a polystyrene-equivalent weight average molecular weight (Mw) of 3000, and a double bond equivalent of 120 g / mol as measured by GPC. The alkali-soluble resin-IV contained an alkali-soluble resin having the following structure, and its double bond equivalent was 189 g / mol.

<Alkali-soluble resin-V>
120 parts by mass of succinic anhydride and 596 parts by mass of commercially available pentaerythritol triacrylate were reacted at 100 ° C. for 5 hours in the presence of 2.5 parts by mass of triethylamine and 0.25 parts by mass of hydroquinone to form one molecule. A polyfunctional acrylate mixture (a-2) having an acid value of 94 mgKOH / g consisting of 67% by mass of a polyfunctional acrylate having one carboxyl group and three acryloyl groups and 33% by mass of pentaerythritol triacrylate was obtained.
Next, 231 parts by mass of a diepoxidized product (epoxy equivalent 231) of 9,9-bis (4'-hydroxyphenyl) fluorene, 597 parts by mass of the polyfunctional acrylate mixture (a-2), 17.08 parts by mass of triethylbenzylammonium chloride. , And 0.25 parts by mass of p-methoxyphenol and 219 parts by mass of propylene glycol monomethyl ether acetate were charged and dissolved by heating at 88 to 90 ° C. while blowing air at a rate of 25 mL / min, and the acid value was 0.8 mgKOH / g. The solution was continuously heated and stirred for 8 hours until the temperature reached the above, and a colorless and transparent reaction product was obtained. Subsequently, 137 parts by mass of 1,2,3,6-tetrahydrophthalic anhydride was added to the obtained reaction product and reacted at 88 to 90 ° C. for 4 hours to obtain an alkali-soluble resin-V. The obtained alkali-soluble resin-V had an acid value of 54 mgKOH / g, a polystyrene-equivalent weight average molecular weight (Mw) of 2500 as measured by GPC, and a double bond equivalent of 219 g / mol. The alkali-soluble resin-V contained an alkali-soluble resin having the following structure, and its double bond equivalent was 261 g / mol.

<Organic black pigment>
Made by BASF, Irgaphor (registered trademark) Black S 0100 CF (having a chemical structure represented by the following formula (I-1))

<Dispersant-I>
"BYK-LPN21116" manufactured by Big Chemie (acrylic AB) consisting of an A block having a quaternary ammonium base and a tertiary amino group in the side chain and a B block having no quaternary ammonium base and a tertiary amino group. Block copolymer. Amine value is 70 mgKOH / g. Acid value is 1 mgKOH / g or less.)
The A block of the dispersant-I contains the repeating units of the following formulas (1a) and (2a), and the B block contains the repeating units of the following formula (3a). The content ratios of the repeating units of the following formulas (1a), (2a), and (3a) in the total repeating units of the dispersant-I are 11.1 mol%, 22.2 mol%, and 6.7 mol%, respectively. be.

<Dispersant-II>
"DISPERBYK-167" manufactured by Big Chemie (urethane-based polymer dispersant)

<Pigment derivative>
"Solspec 12000" manufactured by Lubrizor
<Solvent-I>
PGMEA: Propylene Glycol Monomethyl Ether Acetate <Solvent-II>
MB: 3-Methoxybutanol <Photopolymerization Initiator-I>
Irgacure OXE03 (manufactured by BASF)

<Photopolymerization Initiator-II>

<Photopolymerizable monomer>
DPHA: Dipentaerythritol hexaacrylate manufactured by Nippon Kayaku Co., Ltd. <Additive-I>
KAYAMER PM-21 (phosphate containing methacryloyl group) manufactured by Nippon Kayaku Co., Ltd.
<Additive-II>
SH6040 manufactured by Toray Dow Corning
<Surfactant>
DIC Megafuck F-559

The evaluation method and conditions of the photosensitive coloring composition are as follows.

<Measurement of optical density (unit OD value) per unit film thickness>
The optical density per unit film thickness was measured by the following procedure.
The optical density (OD) of the glass substrate having pattern 2 and pattern 2'described later is measured by the transmission densitometer Gretag Macbeth D200-II, and the film thickness is measured by Ryoka System Co., Ltd. non-contact surface / layer cross-sectional shape measurement system VertScan ( R) Measured according to 2.0. The optical density per unit film thickness (unit OD value) was calculated from the optical density (OD) and the film thickness. In Tables 2 and 3, it is expressed as "unit OD". The OD value is a numerical value indicating the light-shielding ability, and the larger the value is, the higher the light-shielding property is.

<NMP dissolution test>
The N-methylpyrrolidone (NMP) dissolution test was performed according to the following procedure.
Two measurement substrates (2.5 cm × 1.0 cm square) were cut out from the glass substrate having pattern 2 and pattern 2 ′ described later, and immersed in a 10 mL vial containing 8 mL of N-methylpyrrolidone (NMP). Then, the NMP elution test was carried out in a state where the vial containing the measurement substrate was allowed to stand in a hot bath at 80 ° C. for 40 minutes. After that, the vial is taken out from the hot bath, and the absorbance is measured every 1 nm in the wavelength range of 300 to 800 nm by a spectrophotometer (“UV-3100PC” manufactured by Shimadzu Corporation) using the NMP elution solution (sample solution). did. A halogen lamp and a deuterium lamp (switching wavelength 360 nm) were used as a light source, and a photomal was used as a detector, and a slit width of 2 nm was set as a measurement condition. The sample solution was placed in a 1 cm square quartz cell for measurement. Absorbance is a dimensionless quantity that indicates how much light intensity is attenuated when light passes through a certain object in spectroscopy, 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 value obtained by logarithmically expressing 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 stronger the absorbance, the more resist coating film components are eluted in NMP, indicating that the NMP resistance is poor. The spectral area (nm) of the measured absorbance was calculated, and NMP resistance was evaluated with an area value of less than 30 (nm) as A and 30 (nm) or more as B. In Tables 2 and 3, it is described as "NMP resistance", and the evaluation result of NMP resistance is shown in the upper row and the actual area value is shown in the lower row. The spectral area of the absorbance can be expressed by the sum of the absorbances at each wavelength, and means the sum of the eluted resist components.

(Evaluation criteria for NMP resistance)
Judgment based on the area value of the absorption spectrum of the NMP elution solution (wavelength 300 to 800 nm)
A: Less than 30 (nm) B: 30 (nm) or more

<Evaluation of compression characteristics>
For the glass substrate having pattern 1 and pattern 1'described later, the elastic recovery rate was measured by the following procedure.
As a micro-hardness meter for load-unloading test, Shimadzu Corporation (Shimadzu dynamic ultra-micro hardness meter DUH-W201S) is used, a plane indenter with a measurement temperature of 23 ° C and a diameter of 50 μm is used, and a constant speed (3.06 gf) is used. A load was applied to the spacer at (/ sec), and when the load reached 30.6 gf, the load was held for 5 seconds, and then the load was unloaded at the same speed to obtain a load-displacement curve. The maximum displacement (μm) and the final displacement (μm) were measured from this load-displacement curve, the elastic recovery rate (%) was calculated by the following formula, and the compression characteristics were evaluated according to the following evaluation criteria.

Elastic recovery rate (%) = {(maximum displacement-final displacement) / maximum displacement} x 100

(Evaluation criteria for compression characteristics)
A: Elastic recovery rate of 85% or more B: Elastic recovery rate of less than 85%

<Evaluation of compatibility>
The obtained photosensitive coloring composition was stored at 35 ° C. for 9 days, and the compatibility was evaluated by the rate of increase in viscosity after storage. The viscosity was measured with an RC80L type viscometer manufactured by Toki Sangyo Co., Ltd. (measurement conditions: 23 ° C., 50 rpm). The viscosity increase rate after storage was calculated by the following formula, and the compatibility was evaluated according to the following evaluation criteria.
Viscosity increase rate (%) = (Viscosity after storage-Viscosity before storage) / Viscosity before storage

(Evaluation criteria for compatibility)
A: Viscosity increase rate 10% or less B: Viscosity increase rate exceeds 10%

<Evaluation of development form>
The development form was evaluated by the following procedure.
The prepared photosensitive coloring composition was applied to a glass substrate with a spin coater so that the final film thickness was 2.3 μm, dried under reduced pressure for 1 minute, and then dried on a hot plate at 80 ° C. for 70 seconds. After that, exposure and development steps were performed, and how the non-image area (unexposed area) was melted during development was visually observed. The non-image area was roughly classified into a type in which the non-image area was uniformly dissolved in the developing solution and a type in which the non-image area was peeled off in the form of a film, and the quality of the developability was judged by the following evaluation criteria. In the peeling type, stripped pieces of resist remain in the developing solution and may be contaminated as particles, which may reduce the yield at the time of manufacturing the colored spacer.

(Evaluation criteria for development form)
AA: Non-image area dissolves uniformly A: Slight peeling is observed, but other than that, it dissolves almost uniformly.
B: Membrane-like peeling is seen.
C: Cannot develop.

<Evaluation of surface smoothness>
The surface smoothness and the following surface roughness were evaluated by the following procedure.
First, the prepared photosensitive coloring composition was applied to a glass substrate with a spin coater so that the final film thickness was 2.3 μm, dried under reduced pressure for 1 minute, and then dried on a hot plate at 80 ° C. for 70 seconds. .. After the exposure and development steps, the resist-coated substrate was obtained by heating in an oven at 230 ° C. for 20 minutes. With respect to the prepared resist-coated substrate, the presence or absence of wrinkles on the surface after heating was observed with an optical microscope in a field of view of 70 μm × 70 μm, and evaluated according to the following evaluation criteria.

(Evaluation criteria for surface smoothness)
A: Micron-order wrinkles are not observed on the surface of the pattern B: Micron-order wrinkles are slightly observed on the surface of the pattern C: Micron-order wrinkles are remarkably noticeable on the surface of the pattern

<Evaluation of surface roughness>
Regarding the resist-coated substrate produced in the above <evaluation of surface smoothness>, a 50x optical lens was used in the three-dimensional non-contact surface shape measurement system Micromap manufactured by Ryoka System Co., Ltd., and the size was 70 μm × 70 μm in Focus mode. Surface roughness Sa (arithmetic mean roughness, μm) was measured in the visual field.

<Preparation of colorant dispersions 1 and 3>
The colorants, dispersants, alkali-soluble resins, and solvents shown in Table 1 were mixed so as to have the mass ratios shown in Table 1.
This mixture was subjected to a dispersion treatment in the range of 25 to 45 ° C. for 3 hours with a paint shaker. As the beads, 0.5 mmφ zirconia beads were used, and a mass 2.5 times that of the dispersion was added. After the dispersion was completed, the beads and the dispersion were separated by a filter to prepare a colorant dispersion 1 and a colorant dispersion 3.

<Preparation of colorant dispersion 2 (carbon black dispersion)>
Carbon black (manufactured by Biller, RAVEN1060U) as a colorant, a dispersant, a dispersion aid and a solvent were mixed so as to have the mass ratios shown in Table 1.
This mixture was sufficiently stirred with a stirrer and premixed. Next, a paint shaker was used to perform a dispersion treatment in the range of 25 to 45 ° C. for 6 hours. As the beads, 0.5 mmφ zirconia beads were used, and the same mass as that of the dispersion was added. After the dispersion was completed, the beads and the dispersion were separated by a filter to prepare a colorant dispersion 2.

The abbreviations in Table 1 have the following meanings.
Or64: C.I. I. Pigment Orange 64,
V29: C.I. I. Pigment Violet 29,
B60: C.I. I. Pigment Blue 60,
CB: Carbon black.
Further, the blending ratios in Table 1 are all represented by parts by mass, and are values converted into solid content except for the solvent.

[Examples 1 to 9 and Comparative Examples 1 and 2]
Using the colorant dispersions 1 to 3 prepared above, each component is added so that the ratio in the solid content becomes the blending ratio shown in Tables 2 to 3, and the total solid content content ratio becomes 19% by mass. PGMEA was added as described above, and the mixture was stirred and dissolved to prepare a photosensitive coloring composition. Using the obtained photosensitive coloring composition, a pattern was prepared by the method described later, and the evaluation was performed by the method described above.

The blending ratios in Tables 2 and 3 are all represented by parts by mass of solid content.

<Method of forming spacer pattern>
The photosensitive coloring compositions of Examples 1 to 4 and Comparative Examples 1 and 2 were applied onto a glass substrate (“AN100” manufactured by Asahi Glass Co., Ltd.) using a spin coater. Then, it was heated and dried on a hot plate at 100 ° C. for 70 seconds to form a coating film having a film thickness of 2.7 μm.
The obtained coating film was exposed to an exposure mask using an exposure mask having a completely transparent opening of a circular pattern having various diameters having a diameter of 5 to 50 μm (every 5 to 20 μm: 1 μm, 25 μm to 50 μm: every 5 μm). .. The exposure gap (distance between the mask and the coated surface) was 300 μm. As the irradiation light, ultraviolet rays having an intensity of 32 mW / cm ² at a wavelength of 365 nm were used, and the exposure amount was 60 mJ / cm ² . In addition, ultraviolet irradiation was performed under air.

Subsequently, a developer 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 performing 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 adjusted between 10 and 120 seconds, and was 1.3 times the time for dissolving and removing the coating film in the unexposed portion.
By these operations, a pattern in which unnecessary parts were removed was obtained. The substrate on which the pattern is formed is heated in an oven at 230 ° C. for 20 minutes to cure the pattern, and a substantially cylindrical spacer pattern (pattern 1) having a height of 2.3 μm and a bottom diameter of 30 ± 2 μm is formed. Obtained. In addition, a full-face covering pattern (Pattern 2) having a film thickness of 2.3 μm was also created by the same procedure except that an exposure mask was not used. The diameter of the bottom surface of the spacer pattern was measured using an ultra-deep color 3D shape measuring microscope "VK-9500" manufactured by KEYENCE CORPORATION. Similarly, in Examples 5 to 9, a coating film having a film thickness of 2.7 μm was formed, and under the same exposure, development, and heating conditions, a substantially cylindrical spacer pattern (pattern) having a bottom surface diameter of 30 ± 2 μm was formed. A pattern of 1') and full coverage (Pattern 2') was created.

Next, the optical density (OD) per unit film thickness (1 μm) of the pattern 2 and the pattern 2'was measured by the above-mentioned method. Moreover, the NMP dissolution test was carried out by the above-mentioned method using the pattern 2 and the pattern 2'. Further, the compression characteristics of the pattern 1 and the pattern 1'were evaluated by the above-mentioned method. The results are shown in Tables 2 and 3, respectively.

Next, the evaluation of surface smoothness and surface roughness was measured by the above-mentioned method. The results of surface smoothness are shown in Tables 2 and 3. The results of surface roughness were 0.003 μm for Example 1, 0.004 μm for Example 2, 0.807 μm for Example 5, 0.001 μm for Example 6, 0.002 μm for Example 7, and Examples. 8 was 0.003 μm and Example 9 was 0.002 μm.

It was confirmed that the coated substrates using the photosensitive coloring compositions of Examples 1 to 9 had a high unit OD, excellent light-shielding property, and excellent NMP elution and mechanical properties.
On the other hand, the coated substrate using the photosensitive coloring composition of Comparative Example 1 has good NMP elution and mechanical properties, but has a low unit OD and insufficient light-shielding property. Further, it was confirmed that Comparative Example 2 had the same unit OD value as that of Example, but had poor NMP elution and mechanical properties.

Generally, as a method for improving the light-shielding property of the colored spacer, there is a method of increasing the pigment concentration. However, when such a method is applied, the curing component that contributes to the curability of the pattern is reduced, so that the cross-linking density of the pattern tends to be low. Therefore, impurities tend to easily elute into NMP, resulting in poor solvent resistance and poor mechanical properties such as compression properties.
When the pigment concentration is low as in Comparative Example 1, NMP elution and mechanical properties are sufficient even when only a resin having few ethylenic double bonds is used, but the resin type is left as it is. Simply increasing the pigment concentration results in insufficient NMP elution and mechanical properties as in Comparative Example 2.

On the other hand, when the pigment concentration is increased as in Examples 1 to 9, by using a resin having more ethylenic double bonds, the crosslink density of the pattern can be increased, and NMP elution and mechanical It is considered that the characteristics can be improved.

Further, from the comparison between Examples 1 to 3 and Example 4, it was found that the development form was improved by using the epoxy (meth) acrylate resin (b-2) together with the alkali-soluble resin (b-1). .. It is considered that the acid value of the photosensitive coloring composition was increased by using the epoxy (meth) acrylate resin (b-2), and the development solubility was improved.
Further, from the comparison between Examples 1 and 2, the compatibility is improved by adopting the epoxy (meth) acrylate resin (b-2) having the partial structure represented by the above formula (ii). I found out that I would do it. It is considered that this is because the compatibility between the epoxy (meth) acrylate resin (b-2) having the partial structure represented by the formula (ii) and the dispersion liquid is good. When the compatibility is good, the storage stability of the photosensitive coloring composition tends to be improved.
Furthermore, from the comparison with Examples 1 and 3, it was found that the NMP elution and compression characteristics were further improved by increasing the content ratio of the alkali-soluble resin (b-1) in the alkali-soluble resin.

Further, from the comparison of Examples 1, 5 and 6, it was found that by using carbon black alone as the colorant, the light-shielding property can be enhanced even with a small content of the colorant, and the NMP elution and the developed form are improved. This is because the content ratio of the colorant can be lowered, so that the content ratio of the alkali-soluble resin in the photosensitive composition is relatively high and the development solubility is improved, and similarly, the content ratio of the ethylenically unsaturated compound is high and the photocurability is high. It is thought that this is because On the other hand, it was found that the surface smoothness was improved by using an organic pigment as a colorant. It is considered that this is because when an organic pigment is used as a colorant, the ultraviolet transmittance of the organic pigment is high, so that the photocurability of the bottom of the film is high and the difference in crosslink density in the film thickness direction is small.

From the comparison of Examples 1 and 7, it was found that the NMP elution and compression characteristics were improved by lowering the content ratio of the alkali-soluble resin to the content ratio of the ethylenically unsaturated compound. It is considered that this is because the content ratio of the ethylenically unsaturated compound is high and the crosslink density of the membrane is high. On the other hand, the development form tended to deteriorate, which is considered to be because the content ratio of the alkali-soluble resin was low and the development solubility deteriorated.

From the comparison between Examples 1 and 8, it was found that the NMP elution and compression characteristics were good even when the alkali-soluble resin V was used instead of the alkali-soluble resin IV.
From the comparison between Examples 1 and 9, it was found that the NMP elution and compression characteristics were good even when the organic black pigment was used as the colorant.

According to the photosensitive coloring composition of the present invention, it is possible to provide a cured product and a coloring spacer having high light-shielding property, excellent solvent resistance and mechanical properties, and further, an image display provided with such a coloring spacer. The device can be provided. Therefore, the present invention has extremely high industrial applicability in the fields of photosensitive coloring compositions, cured products, coloring spacers, and image display devices.

Claims (16)

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 content of the (a) colorant in the total solid content of the photosensitive coloring composition is 20% by mass or more.
The alkali-soluble resin (b) contains an alkali-soluble resin (b-1) having a partial structure (1) represented by the following formula (I), and the alkali-soluble resin (b-1) has the following formula. A photosensitive coloring composition having a partial structure represented by (III) .

(In formula (I), R ¹ represents a hydrogen atom or a methyl group;
R ² , R ³ , R ⁵ and R ⁶ each independently represent an alkylene group which may have a substituent;
R ⁴ represents an n + 1 valent linking group;
R ⁷ represents an alkylene group which may have a substituent, an alkenylene group which may have a substituent or an aromatic ring group which may have a substituent;
l and m each independently represent an integer from 0 to 12;
n represents an integer greater than or equal to 3;
* Represents a bond. )

(In the above formula (III), R ⁹ represents an epoxy resin residue;
p represents an integer greater than or equal to 1;
* Represents a bond. ) The partial structure represented by the formula (III) is represented by the following formula (III-1), the partial structure represented by the following formula (III-2), and the following formula (III-3). The photosensitive coloring composition according to claim 1 , which is at least one selected from the group consisting of the partial structure to be formed and the partial structure represented by the following formula (III-4).

(In the above formula (III-1), γ represents a divalent linking group;
The benzene ring in formula (III-1) may be further substituted with any substituent;
* Represents a bond. )

(In the above formula (III-2), the benzene ring in the above formula (III-2) may be further substituted with an arbitrary substituent;
* Represents a bond. )

(In the above formula (III-3), R ¹⁰ represents a divalent hydrocarbon group which may have a substituent;
The benzene ring in formula (III-3) may be further substituted with any substituent;
* Represents a bond. )

(In the above formula (III-4), γ represents a divalent linking group;
The benzene ring in formula (III-4) may be further substituted with any substituent;
* Represents a bond. ) The photosensitive coloring composition according to claim 1 or 2 , wherein the alkali-soluble resin (b-1) has a polystyrene-equivalent weight average molecular weight of 1000 or more as measured by gel permeation chromatography. The photosensitive coloring composition according to any one of claims 1 to 3 , wherein the content ratio of the alkali-soluble resin (b-1) in the total solid content of the photosensitive coloring composition is 1% by mass or more. .. The photosensitive coloring composition according to any one of claims 1 to 4 , wherein the alkali-soluble resin (b) further contains an epoxy (meth) acrylate resin (b-2). The fifth aspect of the present invention, wherein the epoxy (meth) acrylate resin (b-2) is an epoxy (meth) acrylate resin (b-2-ii) having a partial structure represented by the following general formula (ii). Photosensitive coloring composition.

(In formula (ii), R ^c each independently represents a hydrogen atom or a methyl group;
R ^d represents a divalent hydrocarbon group having a cyclic hydrocarbon group as a side chain;
^Re and R ^f each independently represent a divalent aliphatic group which may have a substituent;
m and n each independently represent an integer of 0 to 2;
* Represents a bond. ) The photosensitive coloring composition according to any one of claims 1 to 6 , wherein the colorant (a) contains an organic coloring pigment. The photosensitive coloring according to claim 7 , wherein the organic coloring pigment contains at least one selected from the group consisting of a red pigment and an orange pigment and at least one selected from the group consisting of a blue pigment and a purple pigment. Composition. The photosensitive coloring composition according to any one of claims 1 to 8 , wherein the colorant (a) contains a black pigment. The photosensitive coloring composition according to claim 9 , wherein the black pigment contains one or both of carbon black and an organic black pigment. The organic black pigment contains at least one selected from the group consisting of a compound represented by the following general formula (1), a geometric isomer of the compound, a salt of the compound, and a salt of the geometric isomer of the compound. The photosensitive coloring composition according to claim 10 , which is an organic black pigment.

(In formula (1), R ¹¹ and R ¹⁶ each independently represent a hydrogen atom, CH ₃ , CF ₃ , a fluorine atom or a chlorine atom;
R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁷ , R ¹⁸ , R ¹⁹ and R ²⁰ are independent hydrogen atoms, halogen atoms, 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 ²² , 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- ^, SO ₂ NH ₂ , SO ₂ NHR Represents ²¹ or SO ₂ NR ²¹ R ²² ;
And at least one combination selected from the group consisting of R ¹² and R ¹³ , R ¹³ and R ¹⁴ , R ¹⁴ and R ¹⁵ , R ¹⁷ and R ¹⁸ , R ¹⁸ and R ¹⁹ , and R ¹⁹ and R ²⁰ They can be bonded directly to each other or to each other by oxygen, sulfur, NH or NR ²¹ bridges;
Each of R ²¹ and R ²² independently has an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms, an alkenyl group having 2 to 12 carbon atoms, a cycloalkenyl group having 3 to 12 carbon atoms, or a carbon number of carbon atoms. It is an alkynyl group of 2 to 12. ) The photosensitive coloring composition according to any one of claims 1 to 11 , wherein the optical density per 1 μm of the cured coating film is 1.0 or more. The photosensitive coloring composition according to any one of claims 1 to 12 , 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 13 . A colored spacer formed from the cured product of claim 14 . An image display device including the colored spacer according to claim 15 .