TWI829830B - Photosensitive coloring composition, hardened material, coloring spacer, and image display device - Google Patents

Abstract

The present invention provides a photosensitive coloring composition capable of forming a colored spacer having excellent surface roughness and mechanical properties. The photosensitive coloring composition of the present invention contains (a) a coloring agent, (b) an alkali-soluble resin, (c) a photopolymerization initiator, and (d) an ethylenically unsaturated compound, and the above-mentioned (a) coloring agent The content ratio of the above-mentioned (a) colorant contains a purple pigment in the total solid content of the photosensitive coloring composition is 2 to 20% by mass, and the content ratio of the above-mentioned purple pigment in the above-mentioned (a) colorant is 50% by mass. %above.

Description

Photosensitive coloring composition, hardened material, coloring spacer, and image display device

The present invention relates to a photosensitive coloring composition and the like. Specifically, the present invention relates to a photosensitive coloring composition that can be preferably used to form colored spacers and the like in color filters of liquid crystal displays and the like, and a cured product obtained by curing the photosensitive coloring composition. Objects and colored spacers, and image display devices provided with the colored spacers. The contents disclosed in the specification, patent scope, drawings and abstract of Japanese Patent Application No. 2018-236121 filed with the Japan Patent Office on December 18, 2018, as well as the documents cited in this specification. Part or all of them are cited in this article and incorporated as the disclosure content of this specification.

Liquid crystal displays (LCDs) have the property of switching the arrangement of liquid crystal molecules by turning on and off the voltage applied to the liquid crystal. Most of the components constituting the liquid crystal panel are formed by a method using a photosensitive composition represented by photolithography. As an example, a so-called spacer is used to maintain a constant distance between two substrates in a liquid crystal panel.

Previously, when a transparent spacer was used in a TFT (Thin Film Transistor, thin film transistor) LCD, there was a case where the TFT, which was a switching element, malfunctioned due to light transmitted through the spacer. In order to prevent this, for example, Patent Document 1 describes a method of using a light-shielding spacer (colored spacer). Furthermore, in Patent Document 2, it is proposed to use a pigment containing a specific combination in order to obtain a colored spacer that can control the shape or step difference and has excellent adhesion to the substrate after ensuring light-shielding properties and voltage retention of the liquid crystal. Colored photosensitive composition.

In addition, when manufacturing a liquid crystal panel, there is a step of press-bonding two substrates under high temperature and high pressure. Therefore, it is required that the spacer will not be deformed due to the high temperature and high pressure conditions during the press bonding and maintain the function of the spacer. That is, mechanical characteristics such as recovery rate or elastic recovery rate that allow the material to return to its original shape when the external pressure is removed are required even if it is deformed due to external pressure. For example, Patent Document 3 describes that the mechanical properties at high film thickness can be improved by using a specific photopolymerization initiator, and Patent Document 4 describes that by using a compound containing a specific unsaturated group, Can improve mechanical properties.

On the other hand, Patent Document 5 describes that contamination of the liquid crystal layer caused by the colorant is reduced by using a coloring composition containing a purple colorant and/or a brown colorant, and a specific blue colorant. [Prior technical literature] [Patent Document]

[Patent Document 1] Japanese Patent Application Laid-Open No. 8-234212 [Patent Document 2] International Publication No. 2013/115268 [Patent Document 3] Japanese Patent Application Publication No. 2015-38607 [Patent Document 4] Japanese Patent Application Laid-Open No. 2005-165294 [Patent Document 5] Japanese Patent Application Publication No. 2018-9132

[Problem to be solved by the invention]

In order to suppress display defects of a liquid crystal display, it is necessary for the colored spacer to have low surface roughness and excellent smoothness. The present inventors conducted research and found out that it is difficult to obtain a colored spacer that achieves both surface roughness and mechanical properties from the photosensitive coloring composition described in Patent Document 2 or 5.

There is no description about colored spacers in Patent Documents 3 and 4, and the impact of containing a coloring agent in the spacer is not yet clear.

The present invention was made in view of the above-mentioned circumstances, and an object thereof is to provide a photosensitive coloring composition capable of forming a colored spacer having excellent surface roughness and mechanical properties. [Technical means to solve problems]

The inventors of the present invention conducted diligent research in order to solve the above-mentioned problems, and as a result, they found that the content ratio of the colorant in the total solid content should be within a specific range, and a specific pigment should be used as the colorant, and the content ratio of the colorant in the total solid content should be within a specific range. By setting the ratio within a specific range, the above-mentioned problems can be solved, and the present invention has been completed. That is, the present invention has the following structures [1] to [9].

[1] A photosensitive coloring composition characterized by containing (a) a colorant, (b) an alkali-soluble resin, (c) a photopolymerization initiator, and (d) an ethylenically unsaturated compound, and The content ratio of the colorant (a) mentioned above is 2 to 20% by mass in the total solid content of the photosensitive coloring composition, The colorant (a) above contains a purple pigment, and The content ratio of the purple pigment in the colorant (a) is 50% by mass or more. [2] The photosensitive coloring composition according to [1], wherein the purple pigment contains at least one selected from the group consisting of C.I. Pigment Violet 29 and C.I. Pigment Violet 23. [3] The photosensitive coloring composition according to [1] or [2], wherein the coloring agent (a) further contains an orange pigment. [4] The photosensitive coloring composition according to any one of [1] to [3], wherein the content ratio of the above-mentioned (b) alkali-soluble resin relative to 100 parts by mass of the above-mentioned (d) ethylenically unsaturated compound is: 150 parts by mass or less. [5] The photosensitive coloring composition according to any one of [1] to [4], wherein the photopolymerization initiator (c) contains a hexaarylbimidazole compound. [6] The photosensitive coloring composition according to any one of [1] to [5], which is used to form a colored spacer.

[7] A cured product obtained by curing the photosensitive coloring composition according to any one of [1] to [6]. [8] A colored spacer composed of the hardened material described in [7]. [9] An image display device provided with the colored spacer as described in [8]. [Effects of the invention]

According to the present invention, it is possible to provide a photosensitive coloring composition capable of forming a color spacer having excellent surface roughness and mechanical properties, a cured product, a color spacer composed of the same, and an image display including such a color spacer. device.

Hereinafter, embodiments of the present invention will be described in detail. However, the present invention is not limited to the following embodiments and can be implemented with various modifications within the scope of the spirit. In addition, in the present invention, "(meth)acrylic acid" means "acrylic acid and/or methacrylic acid", and the same applies to "(meth)acrylate" and "(meth)acrylyl".

The so-called "(co)polymer" refers to both homopolymer (homopolymer) and copolymer (copolymer), and the so-called "acid (anhydride)" and "...acid (anhydride)" refer to both acid and its anhydride. By. Moreover, in the present invention, "acrylic resin" means a (co)polymer containing (meth)acrylic acid and a (co)polymer containing (meth)acrylic acid ester having a carboxyl group.

In addition, in the present invention, the so-called "monomer" is a term relative to the so-called high molecular substance (polymer), and in addition to the monomer (monomer) in the narrow sense, it also includes dimers, trimers, and low-polymers. The meaning of polymer etc. In the present invention, "total solid content" refers to all components other than the solvent contained in the photosensitive coloring composition or the ink described below. In the present invention, the "weight average molecular weight" refers to the weight average molecular weight (Mw) converted to polystyrene using GPC (gel permeation chromatography). In addition, in the present invention, the so-called "amine value", unless otherwise specified, means the amine value converted from the effective solid content, which is the mass of the alkali per 1 g of the solid content of the dispersant and the equivalent mass of KOH. the value represented. In addition, the measurement method will be described below. On the other hand, the so-called "acid value" means the acid value in terms of effective solid content unless otherwise specified, and is calculated by neutralization titration.

In addition, in this specification, the percentage or part expressed by "mass" has the same meaning as the percentage or part expressed by "weight". In addition, in this specification, specific examples of pigments may be expressed by pigment numbers, and terms such as "C.I. Pigment Red 2" refer to color index (C.I.).

[Photosensitive coloring composition] The photosensitive coloring composition of the present invention contains the following components as essential components: (a)Coloring agent (b)Alkali-soluble resin (c) Photopolymerization initiator (d) Ethylenically unsaturated compounds, If necessary, it further contains adhesion enhancers such as silane coupling agents, surfactants (coatability enhancers), pigment derivatives, photoacid generators, cross-linking agents, sulfhydryl compounds, polymerization inhibitors, development improvers, and ultraviolet absorbers. For other formulation ingredients such as antioxidants and antioxidants, each formulation ingredient is usually used in a state of being dissolved or dispersed in a solvent.

＜(a) Colorant＞ The photosensitive coloring composition of the present invention contains (a) colorant. By containing (a) the colorant, moderate light absorbing properties can be obtained, and in particular, when used to form a light-shielding member such as a colored spacer, moderate light-shielding properties can be obtained. Moreover, in the photosensitive coloring composition of this invention, the content ratio of (a) coloring agent is 2-20 mass % in total solid content. By containing the colorant (a) in a specific amount in this manner, the obtained cured product, especially the colored spacer, can achieve both light-shielding properties and high mechanical properties.

(a) The content ratio of the colorant is not particularly limited as long as it is 2 to 20% by mass in the total solid content. From the viewpoint of light-shielding properties, it is preferably 3% by mass or more, and more preferably 4% by mass. or more, and more preferably 5 mass% or more. On the other hand, from the viewpoint of mechanical properties, it is preferably 18 mass% or less, more preferably 15 mass% or less, further preferably 12 mass% or less, still more preferably 10 mass% or less, and particularly preferably 8% by mass or less. For example, 3 to 18 mass % is preferred, 3 to 15 mass % is more preferred, 4 to 12 mass % is still more preferred, 4 to 10 mass % is still more preferred, and 5 to 8 mass % is particularly preferred.

(a) As the coloring agent, pigments or dyes may be used. Among them, from the viewpoint of durability, the use of pigments is preferred.

In the photosensitive coloring composition of the present invention, (a) the coloring agent contains a purple pigment, and the content ratio of the purple pigment in the (a) coloring agent is 50 mass % or more. It is considered that by including 50% by mass or more of the purple pigment in the colorant (a), the dispersion of the pigment in the coating film becomes uniform, so that the solubility in the developer during development becomes uniform, and the surface roughness becomes uniform. Get good. In addition, since the purple pigment has a maximum absorption wavelength with an absorption peak near 500 to 600 nm in the absorption spectrum, it is also effective in that the optical density (OD) can be easily increased by including the purple pigment. On the other hand, since there is less absorption at wavelengths less than 400 nm, there is less overlap with the absorption wavelength of (c) the photopolymerization initiator, and it is also more effective from the viewpoint of photohardenability and sensitivity. In addition, since there is less absorption at the wavelength of 450 nm, it is also more effective from the viewpoint of light resistance against blue light strongly irradiated from the backlight of the liquid crystal display.

Examples of purple pigments include: C.I. Pigment Violet 1, 1:1, 2, 2:2, 3, 3:1, 3:3, 5, 5:1, 14, 15, 16, 19, 23, 25 ,27,29,31,32,37,39,42,44,47,49,50. Among them, from the viewpoint of light-shielding properties, C.I. Pigment Violet 19, 23, and 29 are preferred, and C.I. Pigment Violet 23 and 29 are more preferred. On the other hand, from the viewpoint of dispersibility or light resistance, it is preferable to use C.I. Pigment Violet 29.

If the content ratio of the purple pigment in (a) the colorant is 50 mass% or more, it is not particularly limited. From the viewpoint of improving surface roughness, it is preferably 55 mass% or more, and more preferably 58 mass% or more. , more preferably 60 mass% or more, still more preferably 62 mass% or more, particularly preferably 65 mass% or more. On the other hand, from the viewpoint of broadening the absorption band by utilizing the optical properties of colorants other than purple pigments, the content is preferably 90 mass% or less, more preferably 80 mass% or less, and still more preferably 75 mass% or less. For example, 50 to 90 mass % is preferred, 55 to 90 mass % is more preferred, 58 to 80 mass % is still more preferred, 60 to 80 mass % is still more preferred, and 62 to 75 mass % is particularly preferred. Particularly preferred is 65 to 75% by mass.

(a) The content ratio of C.I. Pigment Violet 29 in the colorant is not particularly limited. From the viewpoint of improving surface roughness and light resistance, it is preferably 50 mass% or more, more preferably 55 mass% or more, and further preferably Preferably, it is 60 mass % or more, More preferably, it is 62 mass % or more, Most preferably, it is 65 mass % or more. On the other hand, from the viewpoint of broadening the absorption band by utilizing the optical properties of colorants other than C.I. Pigment Violet 29, 90 mass % or less is preferred, 80 mass % or less is more preferred, and 75 mass % or less is still more preferred. %the following. For example, 50 to 90 mass % is preferred, 55 to 90 mass % is more preferred, 58 to 80 mass % is still more preferred, 60 to 80 mass % is still more preferred, and 62 to 75 mass % is particularly preferred. Particularly preferred is 65 to 75% by mass.

(a) The coloring agent may include coloring agents other than purple pigments (hereinafter referred to as "other coloring agents"). Examples of other colorants include pigments and dyes. Pigments are preferred from the viewpoint of heat resistance, and organic pigments are preferred from the viewpoints of hue, photocurability, and sensitivity.

Examples of pigments include organic colored pigments such as yellow pigments, orange pigments, red pigments, blue pigments, green pigments, and brown pigments. Examples of yellow pigments include: C.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. Among them, from the viewpoint of dispersion and reliability, C.I. Pigment Yellow 83, 117, 129, 138, 139, 150, 154, 155, 180, and 185 are preferred, and C.I. Pigment Yellow 138, 139, 150. From the perspective of light-shielding properties, C.I. Pigment Yellow 139 is particularly preferred.

Examples of orange pigments include: C.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. Among them, C.I. Pigment Orange 13, 43, 64, and 72 are preferably used in terms of dispersibility or light-shielding properties. When the photosensitive coloring composition is cured by ultraviolet rays, as an orange pigment, C.I. Pigment Orange 13, 43, 64, and 72 are preferably used. From this point of view, it is more preferable to use C.I. Pigment Orange 64 or 72, especially C.I. Pigment Orange 64, which has a low ultraviolet absorption rate.

Examples of red pigments include: C.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 . Among them, from the viewpoint of light-shielding properties and dispersion properties, preferred examples include: C.I. Pigment Red 48:1, 122, 149, 168, 177, 179, 194, 202, 206, 207, 209, 224, 242 , 254, and more preferably include: C.I. Pigment Red 177, 209, 224, 254. Furthermore, from the viewpoint of dispersibility or light-shielding properties, it is preferable to use C.I. Pigment Red 177, 254, and 272. When the photosensitive coloring composition is cured by ultraviolet rays, it is preferable to use ultraviolet rays as the red pigment. From this point of view, it is more preferable to use C.I. Pigment Red 254 or 272 when the production absorption rate is low.

Examples of blue pigments include: C.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. Among them, from the viewpoint of light-shielding properties, preferred examples include C.I. Pigment Blue 15, 15:1, 15:2, 15:3, 15:4, 15:6, 16, and 60, and further preferred ones are Examples include C.I. Pigment Blue 15:6 and 16. Furthermore, in terms of dispersibility or light-shielding properties, it is preferable to use C.I. Pigment Blue 15:6, 16, and 60. When the photosensitive coloring composition is cured by ultraviolet rays, it is preferable as a blue pigment. In order to use one with a low ultraviolet absorption rate, from this point of view, it is more preferable to use C.I. Pigment Blue 60. On the other hand, as described in Korean Registered Patent No. 10-1840984, from the viewpoint of reliability, light-shielding properties, and elastic recovery rate, it is preferable to use C.I. Pigment Blue 16.

Examples of green pigments include: C.I. Pigment Green 1, 2, 4, 7, 8, 10, 13, 14, 15, 17, 18, 19, 26, 36, 45, 48, 50, 51, 54, 55 ,58. Among them, from the viewpoint of dispersibility, C.I. Pigment Green 7 and 36 are preferred.

Examples of brown pigments include C.I. Pigment Brown 23, 25, 26, 28, 38, 41, 83, and 93. Among them, from the viewpoint of achieving both near-infrared ray transmittance and light-shielding properties, C.I. Pigment Brown 26, 28, 83, and 93 are preferred.

Among these organic color pigments, the orange pigment is preferred in that it has an absorption band around a wavelength of 400 to 500 nm that is different from the absorption band of the purple pigment. When an orange pigment is included, the content ratio of the orange pigment in (a) the colorant is not particularly limited, but is preferably 5 mass% or more, more preferably 10 mass% or more, and further preferably 20 mass% or more, In particular, it is 30 mass % or more, more preferably 50 mass % or less, more preferably 45 mass % or less, further preferably 40 mass % or less, especially 35 mass % or less. For example, 5 to 50 mass% is preferred, 10 to 45 mass% is more preferred, 20 to 40 mass% is further more preferred, and 30 to 35 mass% is particularly preferred. By setting the value above the lower limit, the optical density (OD) tends to increase, and by setting the value below the upper limit, the surface roughness tends to become good.

On the other hand, when an orange pigment is included, the light resistance tends to deteriorate. Therefore, from the viewpoint of improving the light resistance, the content ratio of the orange pigment in the (a) colorant is preferably 50 mass % or less, and more preferably It is preferably 40 mass% or less, further preferably 30 mass% or less, still more preferably 20 mass% or less, particularly preferably 10 mass% or less, and most preferably 0 mass%.

In addition, when a blue pigment is included, the surface roughness tends to deteriorate, so the content ratio of the blue pigment in the colorant (a) is preferably 50 mass% or less, more preferably 40 mass% or less, and further The content is preferably 30 mass% or less, more preferably 20 mass% or less, particularly preferably 10 mass% or less, and most preferably 0 mass%.

When C.I. Pigment Blue 60 is included in the blue pigment, the surface roughness tends to deteriorate, so the content ratio of C.I. Pigment Blue 60 in (a) the colorant is preferably 50 mass % or less, more preferably 40 % by mass or less, more preferably 30 % by mass or less, still more preferably 20 % by mass or less, still more preferably 10 % by mass or less, and most preferably 0 % by mass.

Moreover, as other colorants, a black pigment may also be included. Examples of the black pigment include organic black pigments and inorganic black pigments. Examples of the organic black pigment include a group selected from the group consisting of a compound represented by the following formula (1), a geometric isomer of the compound, a salt of the compound, and a salt of the geometric isomer of the compound. At least one of the organic black pigments.

[Chemical 1]

In formula (1), R ¹ and R ⁶ are independently hydrogen atoms, CH ₃ , CF ₃ , fluorine atoms or chlorine atoms; R ² , R ³ , R ⁴ , R ⁵ , R ⁷ , R ⁸ , R ⁹ and R ¹⁰ are independently a hydrogen atom, a halogen atom, R ¹¹ , COOH, COOR ¹¹ , COO ^- , CONH ₂ , CONHR ¹¹ , CONR ¹¹ R ¹² , CN, OH, OR ¹¹ , COCR ¹¹ , OOCNH ₂ , OOCNHR ¹¹ , OOCNR ¹¹ R ¹² , NO ₂ , NH ₂ , NHR ¹¹ , NR ¹¹ R ¹² , NHCOR ¹² , NR ¹¹ COR ¹² , N=CH ₂ , N=CHR ¹¹ , N=CR ¹¹ R ¹² , SH, SR ¹¹ , SOR ¹¹ , SO ₂ R ¹¹ , SO ₃ R ¹¹ , SO ₃ H, SO ₃ ^- , SO ₂ NH ₂ , SO ₂ NHR ¹¹ or SO ₂ NR ¹¹ R ¹² ; and, selected from R ² and R ³ , R ³ At least one combination of the group consisting of R ⁴ , R ⁴ and R ⁵ , R ⁷ and R ⁸ , R ⁸ and R ⁹ , and R ⁹ and R ¹⁰ may be directly bonded to each other, or an oxygen atom may be used. , sulfur atom, NH or NR ¹¹ are bridged and bonded to each other; R ¹¹ and R ¹² are independently an alkyl group with 1 to 12 carbon atoms, a cycloalkyl group with 3 to 12 carbon atoms, and an alkene group with 2 to 12 carbon atoms. group, a cycloalkenyl group having 3 to 12 carbon atoms or an alkynyl group having 2 to 12 carbon atoms.

The geometric isomers of the compound represented by general formula (1) have the following core structure (where the substituents in the structural formula are omitted), and the trans-trans isomer may be the most stable.

[Chemicalization 2]

When the compound represented by the general formula (1) is anionic, it is preferable to use any known suitable cation, such as metal, organic, inorganic or metal-organic cations, specifically, alkali metals, alkaline earth metals, transition metals , primary ammonium, secondary ammonium, tertiary ammonium such as trialkylammonium, quaternary ammonium such as tetraalkylammonium or organic metal complexes to compensate for their charge. Furthermore, when the geometric isomer of the compound represented by general formula (1) is anionic, the same salt is preferred.

Among the substituents of the general formula (1) and their definitions, the following are preferred in terms of the tendency to increase the shielding rate. The reason is that the following substituents are considered to have no absorption and will not affect the hue of the pigment. R ² , R ⁴ , R ⁵ , R ⁷ , R ⁹ and R ¹⁰ are each independently preferably a hydrogen atom, a fluorine atom or a chlorine atom, and more preferably a hydrogen atom. R ³ and R ⁸ are each independently preferably a hydrogen atom, NO ₂ , OCH ₃ , OC ₂ H ₅ , a bromine atom, a chlorine atom, CH ₃ , C ₂ H ₅ , N(CH ₃ ) ₂ , N(CH ₃ )(C ₂ H ₅ ), N(C ₂ H ₅ ) ₂ , α-naphthyl group, β-naphthyl group, SO ₃ H or SO ₃ ^- , and more preferably a hydrogen atom or SO ₃ H.

R ¹ and R ⁶ are each independently preferably a hydrogen atom, CH ₃ or CF ₃ , and more preferably a hydrogen atom. Preferably, at least one combination selected from the group consisting of R ¹ and R ⁶ , R ² and R ⁷ , R ³ and R ⁸ , R ⁴ and R ⁹ , and R ⁵ and R ¹⁰ is the same, and more preferably ^R1 is the same as ^R6 , ^R2 is the same as ^R7 , ^R3 is the same as ^R8 , ^R4 is the same as ^R9 , and ^R5 is the same as ^R10 .

Examples of alkyl groups having 1 to 12 carbon atoms include methyl, ethyl, n-propyl, isopropyl, n-butyl, 2-butyl, isobutyl, 3-butyl, and 2-methylbutyl. base, n-pentyl, 2-pentyl, 3-pentyl, 2,2-dimethylpropyl, n-hexyl, heptyl, n-octyl, 1,1,3,3-tetramethylbutyl, 2-Ethylhexyl, nonyl, decyl, undecyl or dodecyl.

Examples of the cycloalkyl group having 3 to 12 carbon atoms include: cyclopropyl, cyclopropylmethyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclohexylmethyl, trimethylcyclohexyl, base, norpinyl, 𦯉yl, norcarboryl, carbinyl, menthyl, norpinenyl, pinyl, 1-adamantyl or 2-adamantyl.

Examples of alkenyl groups having 2 to 12 carbon atoms include vinyl, allyl, 2-propen-2-yl, 2-buten-1-yl, 3-buten-1-yl, and 1,3- Butadien-2-yl, 2-penten-1-yl, 3-penten-2-yl, 2-menthyl-1-buten-3-yl, 2-methyl-3-butene- 2-yl, 3-methyl-2-buten-1-yl, 1,4-pentadien-3-yl, hexenyl, octenyl, nonenyl, decenyl or dodecenyl .

Examples of the cycloalkenyl group having 3 to 12 carbon atoms include 2-cyclobuten-1-yl, 2-cyclopenten-1-yl, 2-cyclohexen-1-yl, and 3-cyclohexen-yl. 1-yl, 2,4-cyclohexadien-1-yl, 1-p-menthene-8-yl, 4(10)-limonene-10-yl, 2-norbornene-1-yl, 2 , 5-nor 𦯉 dien-1-yl, 7,7-dimethyl-2,4-norcarboradien-3-yl or camphenyl.

Examples of the alkynyl group having 2 to 12 carbon atoms include 1-propyn-3-yl, 1-butyn-4-yl, 1-pentyn-5-yl, and 2-methyl-3-butyn- 2-yl, 1,4-pentyn-3-yl, 1,3-pentyn-5-yl, 1-hexyn-6-yl, cis-3-methyl-2-penten-4-yne -1-yl, trans-3-methyl-2-penten-4-yn-1-yl, 1,3-hexyn-5-yl, 1-octyn-8-yl, 1-nonyne -9-yl, 1-decyn-10-yl or 1-dodecyn-12-yl.

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 above general formula (1) is preferably a compound represented by the following general formula (2) and/or a geometric isomer of the compound.

[Chemical 3]

As a specific example of such an organic black pigment, the trade name is Irgaphor (registered trademark) Black S 0100 CF (manufactured by BASF Corporation). The organic black pigment is preferably dispersed using the following dispersants, solvents, and methods. Furthermore, if a sulfonic acid derivative of a compound represented by the above general formula (2) or a geometric isomer of the compound is present during dispersion, dispersibility or storage properties may be improved. In addition, as the organic black pigment, from the viewpoint of optical properties and reliability, it is preferable to use the organic black pigment described in Korean Patent Publication No. 10-2018-0052502, or Korean Patent Publication No. 10-2018- Organic black pigments described in Gazette No. 0052864.

Examples of other organic black pigments include aniline black, cyanine black, and perylene black. In addition, carbon black, an inorganic black pigment, can also be used. Examples of carbon black include the following carbon blacks.

Manufactured 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 Manufactured by Degussa: Printex (registered trademark, the same below) 3, Printex3OP, Printex30, Printex30OP, Printex40, Printex45, Printex55, Printex60, Printex75, Printex80, Printex85, Printex90, Printex A, Printex L, Printex G, Printex P, Printex U , Printex V, SpecialBlack550, SpecialBlack350, SpecialBlack250, SpecialBlack100, SpecialBlack6, SpecialBlack5, SpecialBlack4, Color Black FW1, Color Black FW2, Color Black FW2V, Color Black FW18, Color Black FW200, Color Black S160, Color Black S170 Manufactured by Cabot Company: Monarch (registered trademark, the same below) 120, Monarch280, Monarch460, Monarch800, Monarch880, Monarch900, Monarch1000, Monarch1100, Monarch1300, Monarch1400, Monarch4630, REGAL (registered trademark, the same below) 99, REGAL99R, REGAL415, REGAL415R, REGAL250, REGAL250R, REGAL330, REGAL400R, REGAL55R0, REGAL660R, BLACK PEARLS480, PEARLS130, VULCAN (registered trademark) XC72R, ELFTEX (registered trademark)-8 Made by Birla: RAVEN (registered trademark, the same below) 11, RAVEN14, RAVEN15, RAVEN16, RAVEN22, RAVEN30, RAVEN35, RAVEN40, RAVEN410, RAVEN420, RAVEN450, RAVEN500, RAVEN780, RAVEN850, RAVEN890H, RAVEN1000, RAVEN1020, RAVEN1040, RAVEN1060U , RAVEN1080U, RAVEN1170, RAVEN1190U, RAVEN1250, RAVEN1500, RAVEN2000, RAVEN2500U, RAVEN3500, RAVEN5000, RAVEN5250, RAVEN5750, RAVEN7000

Carbon black may be coated with resin. If resin-coated carbon black is used, there is an effect of improving the adhesion to the glass substrate or the volume resistance value. As the resin-coated carbon black, for example, the carbon black described in Japanese Patent Application Laid-Open No. 09-71733 can be suitably used. In terms of volume resistance or dielectric constant, resin-coated carbon black can be suitably used.

These pigments are preferably dispersed and used so that the average particle diameter is usually 1 μm or less, preferably 0.5 μm or less, further preferably 0.25 μm or less. Here, the basis of the average particle diameter is the number of pigment particles. In addition, in the photosensitive coloring composition, the average particle diameter of a pigment is a value calculated from the pigment particle diameter measured by dynamic light scattering (DLS). The particle size measurement is performed on a sufficiently diluted photosensitive coloring composition (usually diluted to prepare a pigment concentration of about 0.005 to 0.2% by mass. If there is a recommended concentration based on the measurement equipment, the concentration is used), and Measurement was performed at 25°C.

In addition to the above-mentioned pigments, dyes may also be used. Examples of dyes include azo dyes, anthraquinone dyes, phthalocyanine dyes, quinone imine dyes, quinoline dyes, nitro dyes, carbonyl dyes, methine dyes, and the like. Examples of azo dyes include: C.I. Acid Yellow 11, C.I. Acid Orange 7, C.I. Acid Red 37, C.I. Acid Red 180, C.I. Acid Blue 29, C.I. Direct Red 28, C.I. Direct Red 83, C.I. Direct Yellow 12 , C.I. Direct Orange 26, C.I. Direct Green 28, C.I. Direct Green 59, C.I Reactive Yellow 2, C.I Reactive Red 17, C.I Reactive Red 120, C.I Reactive Black 5, C.I. Disperse Orange 5, C.I. Disperse Red 58, C.I. Disperse Blue 165 , C.I. basic blue 41, C.I. basic red 18, C.I. mordant red 7, C.I. mordant yellow 5, C.I. mordant black 7, etc.

Examples of anthraquinone dyes include: C.I. Vat Blue 4, C.I. Acid Blue 40, C.I. Acid Green 25, C.I Reactive Blue 19, C.I Reactive Blue 49, C.I. Disperse Red 60, C.I. Disperse Blue 56, C.I. Disperse Blue 60 wait. In addition, examples of phthalocyanine-based dyes include C.I. Vat Blue 5, etc. Examples of quinoneimine-based dyes include C.I. Basic Blue 3, C.I. Basic Blue 9, etc. Examples of quinoline-based dyes Examples of nitro dyes include C.I. Solvent Yellow 33, C.I. Acid Yellow 3, C.I. Disperse Yellow 64, and the like. Examples of nitro dyes include C.I. Acid Yellow 1, C.I. Acid Orange 3, C.I. Disperse Yellow 42, and the like.

＜(b) Alkali-soluble resin＞ The alkali-soluble resin (b) used in the present invention is not particularly limited as long as it contains a carboxyl group or a hydroxyl group. Examples thereof include: epoxy (meth)acrylate resin, acrylic resin, resin containing Carboxyl group epoxy resin, carboxyl group-containing urethane resin, novolak-based resin, polyvinylphenol-based resin, etc. Among them, from the viewpoint of excellent plate-making properties, the following can be suitably used: (b1) Epoxy (meth)acrylate resin (b2) Copolymer resin. These can be used individually by 1 type, or in mixture of a plurality of types.

＜(b1) Epoxy (meth)acrylate resin＞ (b1) Epoxy (meth)acrylate resin is a combination of epoxy resin (epoxy compound) and α,β-unsaturated monocarboxylic acid and/or α,β-unsaturated monocarboxylic acid ester having a carboxyl group The reactants are resins obtained by reacting the hydroxyl groups generated by the reaction with polybasic acids and/or their anhydrides. Furthermore, before reacting the above-mentioned polybasic acid and/or its acid anhydride with a hydroxyl group, a compound having two or more substituents capable of reacting with the hydroxyl group is reacted, and then the polybasic acid and/or its acid anhydride is reacted to obtain The resin is also included in the above-mentioned (b1) epoxy (meth)acrylate resin.

Furthermore, a compound having a reactive functional group is reacted with the carboxyl group of the resin obtained in the above reaction, and the resin obtained is also included in the above-mentioned (b1) epoxy (meth)acrylate resin. In this way, the epoxy (meth)acrylate-based resin does not substantially have an epoxy group in its chemical structure and is not limited to "(meth)acrylate". However, since an epoxy compound (epoxy resin) is used as a raw material , and "(meth)acrylate" is a representative example, so it is named as such based on convention.

As the (b1) epoxy (meth)acrylate resin used in the present invention, specifically, from the viewpoint of developability and reliability, the following epoxy (meth)acrylate can be suitably used. resin (b1-1) and/or epoxy (meth)acrylate resin (b1-2) (hereinafter sometimes referred to as "carboxyl group-containing epoxy (meth)acrylate resin").

<Epoxy (meth)acrylate resin (b1-1)> Alkali solubility obtained by adding α,β-unsaturated monocarboxylic acid and/or α,β-unsaturated monocarboxylic acid ester with carboxyl group to epoxy resin, and then reacting polybasic acid and/or its anhydride resin. <Epoxy (meth)acrylate resin (b1-2)> By adding α,β-unsaturated monocarboxylic acid and/or α,β-unsaturated monocarboxylic acid ester with carboxyl groups to the epoxy resin, and then combining it with polyols, polybasic acids and/or their anhydrides Alkali-soluble resin obtained by reaction.

Here, the term "epoxy resin" includes the raw material compound before being formed into a resin by thermal curing. As the epoxy resin, an appropriate selection can be made from among known epoxy resins and used. In addition, a compound obtained by reacting a phenolic compound and an epihalohydrin can be used as the epoxy resin. As the phenolic compound, a compound having a phenolic hydroxyl group having a divalent or higher valence is preferred, and it may be a monomer or a polymer. As the type of epoxy resin used as a raw material, cresol novolak type epoxy resin, phenolic novolak type epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin, trisphenol type can be suitably used. Methane-type epoxy resin, biphenyl novolak-type epoxy resin, naphthol-type epoxy resin, epoxy which is the complex addition reactant of dicyclopentadiene and phenol or cresol and the reaction product of epihalohydrin Resins, adamantyl group-containing epoxy resins, n-type epoxy resins, etc., those having an aromatic ring in the main chain can be suitably used.

Moreover, as a specific example of the epoxy resin, bisphenol A-type epoxy resin (for example, "jER (registered trademark, the same below)-828", "jER-1001", "jER" manufactured by Mitsubishi Chemical Corporation) can be suitably used. -1002", "jER-1004", "NER-1302" manufactured by Nippon Chemical Company (epoxy equivalent 323, softening point 76°C), etc.), bisphenol F-type resin (such as "jER-" manufactured by Mitsubishi Chemical Corporation) 807", "jER-4004P", "jER-4005P", "jER-4007P", "NER-7406" manufactured by Nippon Kayaku Co., Ltd. (epoxy equivalent 350, softening point 66°C), etc.), bisphenol S type Epoxy resin, biphenyl glycidyl ether (such as "jER-YX4000" manufactured by Mitsubishi Chemical Corporation), phenolic novolak-type epoxy resin (such as "EPPN-201" manufactured by Nippon Chemical Company, Mitsubishi Chemical Corporation) "jER-152", "jER-154", "DEN-438" manufactured by Dow Chemical Co., Ltd.), (ortho, meta, p-) cresol novolak type epoxy resin (such as "EOCN (manufactured by Nippon Chemical Co., Ltd.) Registered trademarks, the same below)-102S", "EOCN-1020", "EOCN-104S"), triglycidyl isocyanurate (such as "TEPIC (registered trademark)" manufactured by Nissan Chemical Co., Ltd.), trisphenolmethane type Epoxy resin (such as "EPPN (registered trademark, the same below)-501", "EPPN-502", "EPPN-503" manufactured by Nippon Kayaku Co., Ltd.), alicyclic epoxy resin ("Celloxide manufactured by Daicel Corporation" (Registered trademark, the same below) 2021P", "Celloxide EHPE"), epoxy resin obtained by glycidylizing a phenol resin using the reaction of dicyclopentadiene and phenol (such as "EXA-7200" manufactured by DIC Corporation , "NC-7300" manufactured by Nippon Kayaku Co., Ltd.), epoxy resins represented by the following general formulas (B1) to (B4), etc. Specifically, "XD-1000" manufactured by Nippon Kayaku Co., Ltd., which is an epoxy resin represented by the following general formula (B1), and "XD-1000", an epoxy resin represented by the following general formula (B2), can be exemplified. "NC-3000" manufactured by Nippon Kayaku Co., Ltd., "ESF-300" manufactured by Nippon Steel & Sumitomo Metal Chemical Co., Ltd., etc. are the epoxy resin represented by the following general formula (B4).

[Chemical 4]

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

[Chemistry 5]

In the above general formula (B2), b is an average value and represents a number from 0 to 10. R ¹²¹ represents any one of a hydrogen atom, a halogen atom, an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, a phenyl group, a naphthyl group, or a biphenyl group. In addition, a plurality of R ¹²¹ present in one molecule may be the same or different.

[Chemical 6]

In the above general formula (B3), X represents a linking group represented by the following general formula (B3-1) or (B3-2). Among them, the molecular structure contains more than one adamantane structure. c means 2 or 3.

[Chemical 7]

In the above general formulas (B3-1) and (B3-2), R ¹³¹ to R ¹³⁴ and R ¹³⁵ to R ¹³⁷ each independently represent an adamantyl group which may have a substituent, a hydrogen atom, and a carbon which may have a substituent. An alkyl group having numbers 1 to 12, or a phenyl group which may have a substituent. *Indicates bonding key.

[Chemical 8]

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

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

Examples of α,β-unsaturated monocarboxylic acid or α,β-unsaturated monocarboxylic acid ester having a carboxyl group include: (meth)acrylic acid, crotonic acid, o-, m- or p-vinylbenzoic acid, (meth)acrylic acid, monocarboxylic acid such as haloalkyl, alkoxy, halogen, nitro, cyano substituents of α-position of acrylic acid, 2-(meth)acryloxyethylsuccinic acid, 2-(meth)propene acyloxyethyladipic acid, 2-(meth)acryloxyethylphthalic acid, 2-(meth)acryloxyethylhexahydrophthalic acid, 2-(methyl) )Acryloxyethylmaleic acid, 2-(meth)acryloxypropylsuccinic acid, 2-(meth)acryloxypropyladipic acid, 2-(methyl) Acryloxypropyltetrahydrophthalic acid, 2-(meth)acryloxypropyl phthalic acid, 2-(meth)acryloxypropylmaleic acid, 2- (Meth)acryloxybutylsuccinic acid, 2-(meth)acryloxybutyladipic acid, 2-(meth)acryloxybutylhydrophthalic acid, 2-(meth)acryloxybutylhydrophthalic acid Meth)acryloxybutyl phthalic acid, 2-(meth)acryloxybutylmaleic acid, ε-caprolactone, β-propiolactone added to (meth)acrylic acid , γ-butyrolactone, δ-valerolactone and other lactone monomers, or hydroxyalkyl (meth)acrylate, pentaerythritol tri(meth)acrylate, dipentaerythritol penta(methyl) ) Monomers, (meth)acrylic acid dimers, etc. formed by adding acids (anhydrides) such as succinic acid (anhydride), phthalic acid (anhydride), and maleic acid (anhydride) to acrylic ester. Among these, from the viewpoint of surface roughness, (meth)acrylic acid is particularly preferred.

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

Furthermore, each of the epoxy resin, α,β-unsaturated monocarboxylic acid and/or α,β-unsaturated monocarboxylic acid ester having a carboxyl group, and the esterification catalyst may be used alone, or two or more may be used in combination. . The usage amount of α,β-unsaturated monocarboxylic acid and/or α,β-unsaturated monocarboxylic acid ester having a carboxyl group is preferably in the range of 0.5 to 1.2 equivalents relative to 1 equivalent of the epoxy group of the epoxy resin, and further Preferably, it is in the range of 0.7 to 1.1 equivalents. By setting the usage amount of α,β-unsaturated monocarboxylic acid and/or α,β-unsaturated monocarboxylic acid ester having a carboxyl group to above the lower limit, it is possible to suppress insufficient introduction of unsaturated groups. And it is easy to make the subsequent reaction with polybasic acid and/or its anhydride also tend to become sufficient. On the other hand, by setting the value below the above upper limit, it was found that the remaining unreacted substances of α,β-unsaturated monocarboxylic acid and/or α,β-unsaturated monocarboxylic acid ester having a carboxyl group can be suppressed. The hardening properties tend to be improved easily.

Examples of the polybasic acid and/or its anhydride include maleic acid, succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, and pyromellitic acid. , trimellitic acid, benzophenone tetracarboxylic acid, methylhexahydrophthalic acid, endomethylenetetrahydrophthalic acid, chlorobactolic acid, methyltetrahydrophthalic acid, biphenyl tetracarboxylic acid One or more types of carboxylic acids and acid anhydrides thereof.

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

Known methods can also be used for the addition reaction of polybasic acids and/or their anhydrides, which can be carried out with α,β-unsaturated monocarboxylic acids and/or α,β-unsaturated monocarboxylic acids with carboxyl groups on epoxy resins. Addition reaction of acid ester Under the same conditions, the target product is obtained by continuing the reaction. The addition amount of the polybasic acid and/or its anhydride component is preferably such that the acid value of the produced carboxyl group-containing epoxy (meth)acrylate resin falls within the range of 10 to 150 mgKOH/g, more preferably If it falls into the range of 20 to 140 mgKOH/g. By setting it as above the said lower limit value, alkali developability tends to become favorable, and by setting it as below the said upper limit value, hardening performance tends to become favorable.

Furthermore, during the addition reaction of the polybasic acid and/or its anhydride, polyhydric alcohols such as trimethylolpropane, pentaerythritol, and dipentaerythritol can be added to introduce a multi-branched structure.

Epoxy (meth)acrylate resins containing carboxyl groups can usually be obtained by the following method: combining epoxy resin with α,β-unsaturated monocarboxylic acid and/or α,β-unsaturated monocarboxylic acid with carboxyl groups After mixing polybasic acid and/or its acid anhydride into the reactant of carboxylic acid ester, or mixing epoxy resin with α,β-unsaturated monocarboxylic acid and/or α,β-unsaturated monocarboxylic acid ester having a carboxyl group. The reactant is mixed with a polybasic acid and/or its acid anhydride and a polyhydric alcohol and then heated. In this case, the mixing order of the polybasic acid and/or its anhydride and the polyhydric alcohol is not particularly limited. By heating, the polybasic acid and/or its anhydride reacts with the reactants and polyols present in the epoxy resin and α,β-unsaturated monocarboxylic acid and/or α,β-unsaturated monocarboxylic acid ester having a carboxyl group. Any hydroxyl group in the mixture undergoes an addition reaction.

Examples of carboxyl group-containing epoxy (meth)acrylate resins other than those mentioned above include Korean Patent Publication No. 10-2013-0022955, Korean Registered Patent No. 10-0965189, and Japanese Unexamined Patent Publication. Those described in Publication No. 2005-165294, Japanese Patent Application Laid-Open No. 2006-312704, etc.

The polystyrene-equivalent weight average molecular weight (Mw) of the epoxy (meth)acrylate resin measured by gel permeation chromatography (GPC) is usually 1,000 or more, preferably 1,500 or more, more preferably 2,000 or above, more preferably 2,500 or more, and usually 10,000 or less, preferably 8,000 or less, more preferably 6,000 or less, further preferably 5,000 or less, and particularly preferably 4,000 or less. For example, 1,000 to 10,000 is preferable, 1,000 to 8,000 is more preferable, 1,500 to 6,000 is still more preferable, 2,000 to 5,000 is still more preferable, and 2,500 to 4,000 is particularly preferable. By setting it to the above-mentioned lower limit value or more, the tendency of the solubility to the developer to become too high can be suppressed, and by setting it to below the above-mentioned upper limit value, it is easy to make the solubility to the developer solution good. tendency.

The acid value of the epoxy (meth)acrylate resin is not particularly limited, but it is preferably 10 mgKOH/g or more, more preferably 20 mgKOH/g or more, and more preferably 200 mgKOH/g or less, more preferably 150 mgKOH/g or less, more preferably 100 mgKOH/g or less, particularly preferably 50 mgKOH/g or less. For example, 10 to 200 mgKOH/g is preferred, 10 to 150 mgKOH/g is more preferred, 20 to 100 mgKOH/g is more preferred, and 20 to 50 mgKOH/g is particularly preferred. By setting it to the above lower limit value or more, moderate development solubility tends to be obtained, and by setting it to below the above upper limit value, development tends not to proceed excessively and film dissolution tends to be suppressed.

The double bond equivalent of the epoxy (meth)acrylate resin is not particularly limited, but is preferably 800 or less, more preferably 700 or less, further preferably 600 or less, still more preferably 500 or less, and particularly preferably 400. below, preferably 300 or less, more preferably 100 or more, more preferably 150 or more, further preferably 200 or more, particularly preferably 250 or more. For example, 100 to 800 is preferred, 100 to 700 is more preferred, 150 to 600 is still more preferred, 150 to 500 is still more preferred, 200 to 400 is particularly preferred, and 250 to 300 is even more preferred. By setting the value below the upper limit, mechanical properties and surface roughness tend to be improved, and by setting it above the lower limit, storage stability tends to be improved. In addition, the double bond equivalent of the resin can be calculated based on the following formula (x).

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

(b1) The chemical structure of the epoxy (meth)acrylate resin is not particularly limited. From the viewpoint of curability, an epoxy (meth)acrylate resin having a partial structure represented by the following general formula (i) is preferred. epoxy (meth)acrylate resin (b1-A) (hereinafter, sometimes referred to as "epoxy (meth)acrylate resin (b1-A)"), or a part represented by the following general formula (ii) Structure of epoxy (meth)acrylate resin (b1-B) (hereinafter, sometimes referred to as "epoxy (meth)acrylate resin (b1-B)"). Moreover, from the viewpoint of reliability, epoxy (meth)acrylate resin (b1-B) is more preferred.

[Chemical 9]

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

[Chemical 10]

In formula (ii), R ^c 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. *Indicates bonding key.

(R ^b ) In the above formula (i), R ^b represents a divalent hydrocarbon group which may have a substituent. Examples of the divalent hydrocarbon group include a divalent aliphatic group, a divalent aromatic ring group, and a group in which one or more divalent aliphatic groups and one or more divalent aromatic ring groups are connected.

Examples of the divalent aliphatic group include linear, branched, cyclic, and combinations thereof. Among these, a linear one is preferable from the viewpoint of development solubility, and on the other hand, a cyclic one is preferable from the viewpoint of development adhesion. The carbon number is usually 1 or more, preferably 3 or more, more preferably 6 or more, and preferably 20 or less, more preferably 15 or less, still more preferably 10 or less. For example, 1 to 20 are preferable, 3 to 15 are more preferable, and 6 to 10 are still more preferable. By setting it as above the said lower limit value, development adhesion tends to become good, and by setting it as below the said upper limit value, curability tends to become good.

Specific examples of the divalent linear aliphatic group include methylene, ethylene, n-propyl, n-butyl, n-hexyl, n-heptyl, and the like. Among these, from the viewpoint of hardening properties, methylene is preferred. Specific examples of the divalent branched aliphatic group include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, The second butyl group, the third butyl group, etc. serve as side chain structures. The number of rings in the bivalent cyclic aliphatic group is not particularly limited, but is usually 1 or more, preferably 2 or more, and is usually 10 or less, preferably 5 or less. For example, 1 to 10 are preferable, 1 to 5 are more preferable, and 2 to 5 are still more preferable. By setting it as above the said lower limit value, development adhesion tends to become good, and by setting it as below the said upper limit value, curability tends to become good. Specific examples of the bivalent cyclic aliphatic group include a cyclohexane ring, a cycloheptane ring, a cyclodecane ring, a cyclododecane ring, a norbivalent ring, an isobornane ring, and an adamantane ring. A base obtained by removing 2 hydrogen atoms from a ring such as a ring. Among these, from the viewpoint of the rigidity of the skeleton, a group obtained by removing two hydrogen atoms from an adamantane ring is preferred.

Examples of substituents that the divalent aliphatic group may have include: hydroxyl group; alkoxy groups having 1 to 5 carbon atoms such as methoxy group and ethoxy group; nitro group; cyano group; carboxyl group and the like. From the viewpoint of ease of synthesis, unsubstituted is preferred.

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, and preferably 20 or less, more preferably 15 or less, still more preferably 10 or less. For example, 4 to 20 are preferred, 5 to 15 are more preferred, and 6 to 10 are still more preferred. By setting it as above the said lower limit value, development adhesion tends to become good, and by setting it as below the said upper limit value, curability tends to become good.

The aromatic hydrocarbon ring in the divalent aromatic hydrocarbon ring group may be a single ring or a condensed ring. Examples of the divalent aromatic hydrocarbon ring group include: benzene ring, naphthalene ring, anthracene ring, phenanthrene ring, perylene ring, condensed tetraphenyl ring, pyrene ring, benzopyrene ring having two free atom valences, The base of ring, ternary benzene ring, acenaphthene ring, fluoranthene ring, fluoranthene ring, etc. In addition, the aromatic heterocyclic ring in the divalent aromatic heterocyclic group may be a single 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 pyrrole ring, a pyrazole ring, an imidazole ring, and a dioxadiazole having two free atom valences. ring, indole ring, carbazole ring, pyrroloimidazole ring, pyrrolopyrazole ring, pyrrolopyrrole ring, thienopyrrole ring, thienothiophene ring, furopyrrole ring, furofuran ring, thienofuran ring , benzisisothiazole ring, benzisothiazole ring, benzimidazole ring, pyridine ring, pyridine ring, pyrimidine ring, pyrimidine ring, triphenylene ring, quinoline ring, isoquinoline ring, 㖕line ring, The base of quinoline ring, phenanthridine ring, phenidine ring, quinazoline ring, quinazolinone ring, azulene ring, etc. Among these, from the viewpoint of photohardenability, a benzene ring or a naphthalene ring having a valency of two free atoms is preferred, and a benzene ring having a valency of two free atoms is more preferred.

Examples of substituents that the divalent aromatic ring group may have include hydroxyl, methyl, methoxy, ethyl, ethoxy, propyl, propoxy, and the like. From the viewpoint of hardening properties, unsubstituted is preferred.

Moreover, as a group which connects one or more divalent aliphatic groups and one or more divalent aromatic ring groups, one or more of the above-mentioned divalent aliphatic groups and one or more of the above-mentioned divalent aromatic ring groups are used. The base formed by connecting the family ring bases. The number of divalent aliphatic groups is not particularly limited, but is usually 1 or more, preferably 2 or more, usually 10 or less, preferably 5 or less, and more preferably 3 or less. For example, 1 to 10 are preferable, 1 to 5 are more preferable, 1 to 3 are still more preferable, and 2 to 3 are still more preferable. By setting it as above the said lower limit value, development adhesion tends to become good, and by setting it as below the said upper limit value, curability tends to become good. The number of divalent aromatic ring groups is not particularly limited, but is usually 1 or more, preferably 2 or more, usually 10 or less, preferably 5 or less, and more preferably 3 or less. For example, 1 to 10 are preferable, 1 to 5 are more preferable, 1 to 3 are still more preferable, and 2 to 3 are still more preferable. By setting it as above the said lower limit value, the hardenability tends to become good, and by setting it as below the said upper limit value, the hardenability tends to become good.

Specific examples of the group in which one or more divalent aliphatic groups and one or more divalent aromatic ring groups are connected include groups represented by the following formulas (i-A) to (i-E). Among these, from the viewpoint of development solubility, a group represented by the following formula (i-A) is preferred. The * in the chemical formula represents the bond.

[Chemical 11]

As mentioned above, the benzene ring in formula (i) may be further substituted by 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 1 or 2 or more. From the viewpoint of hardening properties, unsubstituted is preferred.

Moreover, from the viewpoint of hardenability, the partial structure represented by the above general formula (i) is preferably a partial structure represented by the following general formula (i-1).

[Chemical 12]

In the formula (i-1), R ^a and R ^b have the same meaning as in the above formula (i). R ^X represents a hydrogen atom or a polybasic acid residue. *Indicates bonding key. The benzene ring in formula (i-1) may be further substituted by any substituent.

The so-called polybasic acid residue refers to a monovalent group obtained by removing one OH group from a polybasic acid or its anhydride. Examples of the polybasic acid include maleic acid, succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, pyromellitic acid, and trimellitic acid. , 1 of benzophenone tetracarboxylic acid, methyl hexahydrophthalic acid, endomethylene tetrahydrophthalic acid, chlorobacterial acid, methyl tetrahydrophthalic acid, and biphenyl tetracarboxylic acid One or more species. Among these, from the viewpoint of patterning properties, as the polybasic acid, maleic acid, succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, and hexahydrophthalic acid are preferred. dicarboxylic acid, pyromellitic acid, trimellitic acid, biphenyltetracarboxylic acid, more preferably tetrahydrophthalic acid and biphenyltetracarboxylic acid.

The partial structure represented by the above formula (i-1) contained in one molecule of the epoxy (meth)acrylate resin (b1-A) may be one type or two or more types. For example, ^R is a hydrogen atom and R ^X is a polybasic acid residue.

In addition, the number of partial structures represented by the above formula (i) contained in one molecule of the epoxy (meth)acrylate resin (b1-A) is not particularly limited, but is preferably 1 or more, and more preferably 3. The above is preferably 20 or less, and more preferably 15 or less. For example, 1 to 20 are preferred, and 3 to 15 are more preferred. By setting it as above the said lower limit value, hardenability tends to become favorable, and by setting it as below the said upper limit value, the development solubility tends to become favorable.

Specific examples of the epoxy (meth)acrylate resin (b1-A) are given below.

[Chemical 13]

[Chemical 14]

[Chemical 15]

[Chemical 16]

(R ^d ) In the above 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 the aliphatic cyclic group has is not particularly limited, but is usually 1 or more, preferably 2 or more, and is usually 10 or less, preferably 5 or less, and more preferably 3 or less. For example, 1 to 10 are preferable, 1 to 5 are more preferable, 1 to 3 are still more preferable, and 2 to 3 are still more preferable. By setting it as above the said lower limit value, development adhesion tends to become good, and by setting it as below the said upper limit value, curability tends to become good. In addition, the number of carbon atoms in the aliphatic ring group is usually 4 or more, preferably 6 or more, more preferably 8 or more, and preferably 40 or less, more preferably 30 or less, further preferably 20 or less, and particularly preferably 15 or less. For example, 4 to 40 is preferred, 4 to 30 is more preferred, 6 to 20 is more preferred, 6 to 15 is still more preferred, and 8 to 15 is still more preferred. By setting it as above the said lower limit value, development adhesion tends to become good, and by setting it as below the said upper limit value, curability tends to become good. Specific examples of the aliphatic ring in the aliphatic ring group include: cyclohexane ring, cycloheptane ring, cyclodecane ring, cyclododecane ring, norbisane ring, isobornane ring, and adamantine ring. Alkane ring etc. Among these, an adamantane ring is preferable from the viewpoint of reliability.

On the other hand, the number of rings in the aromatic ring group is not particularly limited, but it is usually 1 or more, preferably 2 or more, more preferably 3 or more, and usually 10 or less, preferably 5 or less, and more The best value is below 4. For example, 1 to 10 is preferred, 1 to 5 is more preferred, 1 to 4 is still more preferred, 2 to 4 is still more preferred, and 3 to 4 is particularly preferred. By setting it as above the said lower limit value, development adhesion tends to become good, and by setting it as below the said upper limit value, curability tends to become good. Examples of the aromatic ring group include an aromatic hydrocarbon ring group and an aromatic heterocyclic group. Moreover, the carbon number of the aromatic ring group is usually 4 or more, preferably 6 or more, more preferably 8 or more, further preferably 10 or more, especially 12 or more, and preferably 40 or less, even more preferably It is 30 or less, more preferably 20 or less, especially 15 or less. For example, 4 to 40 is preferred, 6 to 30 is more preferred, 8 to 20 is still more preferred, 10 to 15 is still more preferred, and 12 to 15 is particularly preferred. By setting it as above the said lower limit value, development adhesion tends to become good, and by setting it as below the said upper limit value, curability tends to become good. Specific examples of the aromatic ring in the aromatic ring group include benzene ring, naphthalene ring, anthracene ring, phenanthrene ring, perylene ring, condensed tetraphenyl ring, pyrene ring, benzopyrene ring, ring, ternaryphenyl ring, acenaphthene ring, fluoranthene ring, fluoranthene ring, etc. Among them, from the viewpoint of patterning characteristics, the ring is preferable.

In addition, the divalent hydrocarbon group among the divalent hydrocarbon groups having a cyclic hydrocarbon group as a side chain is not particularly limited, and examples thereof include a divalent aliphatic group, a divalent aromatic ring group, and one or more divalent aliphatic groups linked together. A base formed by a base and one or more divalent aromatic ring groups.

Examples of the divalent aliphatic group include linear, branched, cyclic, and combinations thereof. Among these, linear ones are preferred from the viewpoint of compatibility, and cyclic ones are preferred from the viewpoint of reliability. The carbon number is usually 1 or more, preferably 3 or more, more preferably 6 or more, and preferably 25 or less, more preferably 20 or less, still more preferably 15 or less. For example, 1 to 25 is preferred, 3 to 20 is more preferred, and 6 to 15 is still more preferred. By setting it as above the said lower limit value, development adhesion tends to become good, and by setting it as below the said upper limit value, curability tends to become good.

Specific examples of the divalent linear aliphatic group include methylene, ethylene, n-propyl, n-butyl, n-hexyl, n-heptyl, and the like. Among these, from the viewpoint of hardening properties, methylene is preferred. Specific examples of the divalent branched aliphatic group include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, The second butyl group, the third butyl group, etc. serve as side chain structures. The number of rings in the bivalent cyclic aliphatic group is not particularly limited, but is usually 1 or more, preferably 2 or more, and usually 10 or less, 5 or less, and still more preferably 3 or less. For example, 1 to 10 are preferable, 1 to 5 are more preferable, 1 to 3 are still more preferable, and 2 to 3 are still more preferable. By setting it as above the said lower limit value, development adhesion tends to become good, and by setting it as below the said upper limit value, curability tends to become good. Specific examples of the bivalent cyclic aliphatic group include a cyclohexane ring, a cycloheptane ring, a cyclodecane ring, a cyclododecane ring, a norbivalent ring, an isobornane ring, and an adamantane ring. A base obtained by removing 2 hydrogen atoms from a ring such as a ring. Among these, from the viewpoint of reliability, a group obtained by removing two hydrogen atoms from an adamantane ring is preferred.

Examples of the substituent that may have a divalent aliphatic group include a hydroxyl group; an alkoxy group having 1 to 5 carbon atoms such as a methoxy group and an ethoxy group; a nitro group; a cyano group; a carboxyl group; and the like. From the viewpoint of ease of synthesis, unsubstituted is preferred.

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, and preferably 30 or less, more preferably 20 or less, and still more preferably 15 or less. For example, 4 to 30 are preferable, 5 to 20 are more preferable, and 6 to 15 are still more preferable. By setting it as above the said lower limit value, development adhesion tends to become good, and by setting it as below the said upper limit value, curability tends to become good.

The aromatic hydrocarbon ring in the divalent aromatic hydrocarbon ring group may be a single ring or a condensed ring. Examples of the divalent aromatic hydrocarbon ring group include: benzene ring, naphthalene ring, anthracene ring, phenanthrene ring, perylene ring, condensed tetraphenyl ring, pyrene ring, benzopyrene ring having two free atom valences, The base of ring, ternary benzene ring, acenaphthene ring, fluoranthene ring, fluoranthene ring, etc. In addition, the aromatic heterocyclic ring in the aromatic heterocyclic group may be a single 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 pyrrole ring, a pyrazole ring, an imidazole ring, and a dioxadiazole having two free atom valences. ring, indole ring, carbazole ring, pyrroloimidazole ring, pyrrolopyrazole ring, pyrrolopyrrole ring, thienopyrrole ring, thienothiophene ring, furopyrrole ring, furofuran ring, thienofuran ring , benzisisothiazole ring, benzisothiazole ring, benzimidazole ring, pyridine ring, pyridine ring, pyrimidine ring, pyrimidine ring, triphenylene ring, quinoline ring, isoquinoline ring, 㖕line ring, The base of quinoline ring, phenanthridine ring, phenidine ring, quinazoline ring, quinazolinone ring, azulene ring, etc. Among the divalent aromatic ring groups, from the viewpoint of patterning properties, a benzene ring, a naphthalene ring or a fluorine ring having a valence of two free atoms is preferred, and a fluorine ring having a valence of two free atoms is more preferred.

Examples of substituents that the divalent aromatic ring group may have include hydroxyl, methyl, methoxy, ethyl, ethoxy, propyl, propoxy, and the like. From the viewpoint of development solubility and moisture absorption resistance, unsubstituted is preferred.

Moreover, as a group formed by linking one or more divalent aliphatic groups and one or more divalent aromatic ring groups, examples of the group that link one or more divalent aliphatic groups and one or more divalent aromatic ring groups can be exemplified. A base formed from a valent aromatic ring base. The number of divalent aliphatic groups is not particularly limited, but is usually 1 or more, preferably 2 or more, usually 10 or less, preferably 5 or less, and more preferably 3 or less. For example, 1 to 10 are preferable, 1 to 5 are more preferable, 1 to 3 are still more preferable, and 2 to 3 are still more preferable. By setting it as above the said lower limit value, development adhesion tends to become good, and by setting it as below the said upper limit value, curability tends to become good. The number of divalent aromatic ring groups is not particularly limited, but is usually 1 or more, preferably 2 or more, usually 10 or less, preferably 5 or less, and more preferably 3 or less. For example, 1 to 10 are preferable, 1 to 5 are more preferable, 1 to 3 are still more preferable, and 2 to 3 are still more preferable. By setting it as above the said lower limit value, development adhesion tends to become good, and by setting it as below the said upper limit value, curability tends to become good.

Specific examples of the group in which one or more divalent aliphatic groups and one or more divalent aromatic ring groups are connected include groups represented by the above formulas (i-A) to (i-E). Among these, from the viewpoint of reliability, the base represented by the above formula (i-C) is preferred.

The bonding state of the cyclic hydrocarbon group as the side chain with respect to the divalent hydrocarbon group is not particularly limited. For example, one hydrogen atom of the aliphatic group or aromatic cyclic group is replaced by the side chain. Or, it may contain one carbon atom of an aliphatic group to form a cyclic hydrocarbon group as a side chain.

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

[Chemical 17]

In formula (ii-1), R ^c has the same meaning as in the above formula (ii). R ^α represents a monovalent cyclic hydrocarbon group which may have a substituent. n is an integer above 1. *Indicates bonding key. The benzene ring in formula (ii-1) may be further substituted by any substituent.

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

The number of rings the aliphatic cyclic group has is not particularly limited, but is usually 1 or more, preferably 2 or more, and usually 6 or less, preferably 4 or less, and more preferably 3 or less. For example, 1 to 6 are preferred, 1 to 4 are more preferred, 1 to 3 are still more preferred, and 2 to 3 are even more preferred. By setting it as above the said lower limit value, development adhesion tends to become good, and by setting it as below the said upper limit value, curability tends to become good. In addition, the number of carbon atoms in the aliphatic ring group is usually 4 or more, preferably 6 or more, more preferably 8 or more, and preferably 40 or less, more preferably 30 or less, further preferably 20 or less, and particularly preferably 15 or less. For example, 4 to 40 is preferred, 4 to 30 is more preferred, 6 to 20 is further preferred, and 8 to 15 is particularly preferred. By setting it as above the said lower limit value, development adhesion tends to become good, and by setting it as below the said upper limit value, curability tends to become good. Specific examples of the aliphatic ring in the aliphatic ring group include: cyclohexane ring, cycloheptane ring, cyclodecane ring, cyclododecane ring, norbisane ring, isobornane ring, and adamantine ring. Alkane ring etc. Among these, an adamantane ring is preferable from the viewpoint of compatibility.

On the other hand, the number of rings in the aromatic ring group is not particularly limited, but is usually 1 or more, preferably 2 or more, more preferably 3 or more, and is usually 10 or less, preferably 5 or less. For example, 1 to 10 are preferable, 1 to 5 are more preferable, 2 to 5 are still more preferable, and 3 to 5 are still more preferable. By setting it as above the said lower limit value, development adhesion tends to become good, and by setting it as below the said upper limit value, curability tends to become good. Examples of the aromatic ring group include an aromatic hydrocarbon ring group and an aromatic heterocyclic group. The number of carbon atoms in the aromatic ring group is usually 4 or more, preferably 5 or more, more preferably 6 or more, and more preferably Preferably it is 30 or less, more preferably 20 or less, still more preferably 15 or less. For example, 4 to 30 are preferable, 5 to 20 are more preferable, and 6 to 15 are still more preferable. By setting it as above the said lower limit value, development adhesion tends to become good, and by setting it as below the said upper limit value, curability tends to become good. Specific examples of the aromatic ring in the aromatic ring group include benzene ring, naphthalene ring, anthracene ring, phenanthrene ring, fluorine ring, and the like. Among them, from the viewpoint of reliability, Fuhuan is preferable.

Examples of substituents that the cyclic hydrocarbon group may have include: hydroxyl, methyl, ethyl, n-propyl, isopropyl, n-butyl, second butyl, third butyl, pentyl, and isopentyl. Alkyl groups with 1 to 5 carbon atoms; methoxy, ethoxy and other alkoxy groups with 1 to 5 carbon atoms; nitro group; cyano group; carboxyl group, etc. From the viewpoint of ease of synthesis, unsubstituted is preferred.

n represents an integer of 1 or more, preferably 2 or more, and preferably 3 or less. For example, 1 to 3 are preferred, and 2 to 3 are more preferred. By setting it as above the said lower limit value, development adhesion tends to become good, and by setting it as below the said upper limit value, curability tends to become good.

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

As mentioned above, the benzene ring in formula (ii-1) may be further substituted by 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 1 or 2 or more. From the viewpoint of patterning properties, unsubstituted is preferred.

Specific examples of the partial structure represented by the above formula (ii-1) are given below.

[Chemical 18]

[Chemical 19]

[Chemistry 20]

[Chemistry 21]

[Chemistry 22]

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

[Chemistry 23]

In formula (ii-2), R ^c has the same meaning as in the above formula (ii). ^Rβ represents a divalent cyclic hydrocarbon group which may have a substituent. *Indicates bonding key. The benzene ring in formula (ii-2) may be further substituted by any substituent.

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

The number of rings the aliphatic cyclic group has is not particularly limited, but is usually 1 or more, preferably 2 or more, and is usually 10 or less, preferably 5 or less. For example, 1 to 10 are preferable, 1 to 5 are more preferable, and 2 to 5 are still more preferable. By setting it as above the said lower limit value, development adhesion tends to become good, and by setting it as below the said upper limit value, curability tends to become good. Moreover, the carbon number of the aliphatic ring group is usually 4 or more, preferably 6 or more, more preferably 8 or more, and preferably 40 or less, more preferably 35 or less, still more preferably 30 or less. For example, 4 to 40 are preferred, 6 to 35 are more preferred, and 8 to 30 are still more preferred. By setting it as above the said lower limit value, development adhesion tends to become good, and by setting it as below the said upper limit value, curability tends to become good. Specific examples of the aliphatic ring in the aliphatic ring group include: cyclohexane ring, cycloheptane ring, cyclodecane ring, cyclododecane ring, norbisane ring, isobornane ring, and adamantine ring. Alkane ring etc. Among these, an adamantane ring is preferable from the viewpoint of compatibility.

On the other hand, the number of rings in the aromatic ring group is not particularly limited, but is usually 1 or more, preferably 2 or more, more preferably 3 or more, and is usually 10 or less, preferably 5 or less. For example, 1 to 10 are preferable, 1 to 5 are more preferable, 2 to 5 are still more preferable, and 3 to 5 are still more preferable. By setting it as above the said lower limit value, development adhesion tends to become good, and by setting it as below the said upper limit value, curability tends to become good. Examples of the aromatic ring group include an aromatic hydrocarbon ring group and an aromatic heterocyclic group. The number of carbon atoms in the aromatic ring group is usually 4 or more, preferably 6 or more, more preferably 8 or more, and still more preferably It is 10 or more, and preferably it is 40 or less, more preferably 30 or less, further preferably 20 or less, especially 15 or less. For example, 4 to 40 is preferred, 6 to 30 is more preferred, 8 to 20 is further preferred, and 10 to 15 is particularly preferred. By setting it as above the said lower limit value, development adhesion tends to become good, and by setting it as below the said upper limit value, curability tends to become good. Specific examples of the aromatic ring in the aromatic ring group include benzene ring, naphthalene ring, anthracene ring, phenanthrene ring, fluorine ring, and the like. Among them, from the viewpoint of reliability, Fuhuan is preferable.

Examples of substituents that the cyclic hydrocarbon group may have include: hydroxyl, methyl, ethyl, n-propyl, isopropyl, n-butyl, second butyl, third butyl, pentyl, and isopentyl. Alkyl groups with 1 to 5 carbon atoms; methoxy, ethoxy and other alkoxy groups with 1 to 5 carbon atoms; nitro group; cyano group; carboxyl group, etc. From the viewpoint of ease of synthesis, unsubstituted is preferred.

Among them, from the viewpoint of compatibility, ^Rβ is preferably a divalent aliphatic ring group, and more preferably a divalent adamantane ring group. On the other hand, from the viewpoint of reliability, R ^β is preferably a divalent aromatic ring group, more preferably a divalent fluorocyclic group.

As mentioned above, the benzene ring in formula (ii-2) may be further substituted by 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 1 or 2 or more. Moreover, two benzene rings in formula (ii-2) may be connected via these substituents. From the viewpoint of patterning properties, unsubstituted is preferred.

Specific examples of the partial structure represented by the above formula (ii-2) are given below.

[Chemistry 24]

[Chemical 25]

[Chemical 26]

[Chemical 27]

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

[Chemical 28]

In formula (ii-3), R ^c and R ^d have the same meanings as in the above formula (ii). R ^Z represents a hydrogen atom or a polybasic acid residue.

The so-called polybasic acid residue refers to a monovalent group obtained by removing one OH group from a polybasic acid or its anhydride. Furthermore, another OH group can be removed and shared with R ^Z in other molecules represented by formula (ii-3), that is, multiple formulas (ii-3) can be connected via R ^Z. Examples of the polybasic acid include maleic acid, succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, pyromellitic acid, and trimellitic acid. , 1 of benzophenone tetracarboxylic acid, methyl hexahydrophthalic acid, endomethylene tetrahydrophthalic acid, chlorobacterial acid, methyl tetrahydrophthalic acid, and biphenyl tetracarboxylic acid One or more species. Among these, from the viewpoint of patterning properties, as the polybasic acid, maleic acid, succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, and hexahydrophthalic acid are preferred. dicarboxylic acid, pyromellitic acid, trimellitic acid, biphenyltetracarboxylic acid, more preferably tetrahydrophthalic acid and biphenyltetracarboxylic acid.

The partial structure represented by the above formula (ii-3) contained in one molecule of the epoxy (meth)acrylate resin (b1-B) may be one type or two or more types. For example, R may be mixed. ^X is a hydrogen atom and R ^Z is a polybasic acid residue.

In addition, the number of partial structures represented by the above formula (ii) contained in one molecule of the epoxy (meth)acrylate resin (b1-B) is not particularly limited, but is preferably 1 or more, and more preferably 3. The above is preferably 20 or less, more preferably 15 or less, and still more preferably 10 or less. For example, 1 to 20 is preferred, 1 to 15 is more preferred, 3 to 15 is more preferred, and 3 to 10 is even more preferred. By setting it as above the said lower limit value, hardenability tends to become favorable, and by setting it as below the said upper limit value, the development solubility tends to become favorable.

On the other hand, as (b) the alkali-soluble resin, from the viewpoint of compatibility with a colorant, a dispersant, etc., it is preferable to use (b2) copolymer resin.

＜(b2) Copolymer resin＞ (b2) The copolymer resin is not particularly limited as long as it contains a carboxyl group or a hydroxyl group, but one having an ethylenically unsaturated group in the side chain is preferred. By having an ethylenically unsaturated group, photohardening by exposure makes film reduction due to an alkaline developer less likely to occur during development, and surface roughness tends to become better.

(Partial structure represented by general formula (I)) In the case where (b2) the copolymer resin has an ethylenically unsaturated group in the side chain, the partial structure including the side chain having the ethylenically unsaturated group is not particularly limited, as the free radicals are easily dispersed due to the flexibility of the film. From the viewpoint of properties, for example, it is preferable to have a partial structure represented by the following general formula (I).

[Chemical 29]

In formula (I), R ¹ and R ² each independently represent a hydrogen atom or a methyl group. *Indicates bonding key.

Moreover, among the partial structures represented by the above-mentioned formula (I), from the viewpoint of sensitivity or alkaline developability, a partial structure represented by the following general formula (I') is preferred.

[Chemical 30]

In formula (I'), R ¹ and R ² each independently represent a hydrogen atom or a methyl group. R ^X represents a hydrogen atom or a polybasic acid residue.

The so-called polybasic acid residue refers to a monovalent group obtained by removing one OH group from a polybasic acid or its anhydride. Examples of the polybasic acid include maleic acid, succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, pyromellitic acid, and trimellitic acid. , 1 of benzophenone tetracarboxylic acid, methyl hexahydrophthalic acid, endomethylene tetrahydrophthalic acid, chlorobacterial acid, methyl tetrahydrophthalic acid, and biphenyl tetracarboxylic acid One or more species. Among these, from the viewpoint of patterning properties, preferred are maleic acid, succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, and homogeneous acid. Promellitic acid, trimellitic acid and biphenyltetracarboxylic acid, more preferably tetrahydrophthalic acid and biphenyltetracarboxylic acid.

When the copolymer resin (b2) contains a partial structure represented by the above-mentioned general formula (I), the content ratio is not particularly limited, but is preferably 10 mol% or more, more preferably 30 mol% or more, and still more preferably It is preferably 50 mol% or more, more preferably 70 mol% or more, especially 80 mol% or more, and more preferably 98 mol% or less, more preferably 95 mol% or less. For example, 10 to 98 mol% is preferred, 30 to 98 mol% is more preferred, 50 to 98 mol% is still more preferred, 70 to 98 mol% is still more preferred, and 80 to 98 mol% is particularly preferred. 95 mol%. By setting it to the above-mentioned lower limit value or more, mechanical characteristics tend to be improved, and by setting it to below the above-mentioned upper limit value, residues tend to be reduced.

When the copolymer resin (b2) contains a partial structure represented by the general formula (I'), the content ratio is not particularly limited, but is preferably 10 mol% or more, more preferably 30 mol% or more, and further It is preferably 50 mol% or more, more preferably 70 mol% or more, especially 80 mol% or more, and more preferably 98 mol% or less, more preferably 95 mol% or less. For example, 10 to 98 mol% is preferred, 30 to 98 mol% is more preferred, 50 to 98 mol% is still more preferred, 70 to 98 mol% is still more preferred, and 80 to 98 mol% is particularly preferred. 95 mol%. By setting it as above the said lower limit value, alkali developability and mechanical characteristics tend to become favorable easily, and by setting it as below the said upper limit value, surface roughness tends to improve and residues tend to be reduced.

(Partial structure represented by general formula (II)) When the copolymer resin (b2) contains a partial structure represented by the above-mentioned general formula (I), the other partial structures contained are not particularly limited. From the viewpoint of development adhesion, for example, it is also preferred to have the following Describe the partial structure represented by general formula (II).

[Chemical 31]

In the above formula (II), R ³ represents a hydrogen atom or a methyl group, and R ⁴ represents an optionally substituted alkyl group, an optionally substituted aromatic ring group, or an optionally substituted alkenyl group.

(R ⁴ ) In the above formula (II), R ⁴ represents an alkyl group which may have a substituent, an aromatic ring group which may have a substituent, or an alkenyl group which may have a substituent. Examples of the alkyl group in R ⁴ include linear, branched or cyclic alkyl groups. The number of carbon atoms is preferably 1 or more, more preferably 3 or more, further preferably 5 or more, especially 8 or more, and preferably 20 or less, more preferably 18 or less, still more preferably 16 or less, and still more preferably 16 or less. It is more preferably 14 or less, and particularly preferably 12 or less. For example, 1 to 20 is preferred, 1 to 18 is more preferred, 3 to 16 is still more preferred, 5 to 14 is still more preferred, and 8 to 12 is particularly preferred. By setting it to the above lower limit value or more, surface roughness tends to increase, and by setting it to below the above upper limit value, residues tend to decrease.

Specific examples of the alkyl group include methyl, ethyl, cyclohexyl, dicyclopentyl, dodecyl, and the like. Among these, from the viewpoint of developability, dicyclopentyl or dodecyl is preferred, and dicyclopentyl is more preferred. In addition, examples of substituents that the alkyl group may have include: methoxy group, ethoxy group, chlorine group, bromo group, fluorine group, hydroxyl group, amino group, epoxy group, oligoglycol group, and phenyl group. , carboxyl group, acrylyl group, methacrylyl group, etc., from the viewpoint of developability, hydroxyl group and oligoglycol group are preferred.

Examples of the aromatic ring group in R ⁴ include a monovalent aromatic hydrocarbon ring group and a monovalent aromatic heterocyclic group. The carbon number is preferably 6 or more, more preferably 24 or less, more preferably 22 or less, further preferably 20 or less, especially 18 or less. For example, 6 to 24 are preferred, 6 to 22 are more preferred, 6 to 20 are further preferred, and 6 to 18 are particularly preferred. By setting it as above the said lower limit value, the development adhesiveness tends to improve, and by setting it as below the said upper limit value, the residue tends to reduce. The aromatic hydrocarbon ring in the aromatic hydrocarbon ring group can be a single ring or a condensed ring. Examples include: benzene ring, naphthalene ring, anthracene ring, phenanthrene ring, perylene ring, condensed tetraphenyl ring, pyrene ring, benzopyrene ring, ring, ternaryphenyl ring, acenaphthene ring, fluoranthene ring, fluoranthene ring, etc. In addition, the aromatic heterocyclic group among the aromatic heterocyclic groups may be a single ring or a condensed ring. Examples thereof include: furan ring, benzofuran ring, thiophene ring, benzothiophene ring, and pyrrole ring. , pyrazole ring, imidazole ring, dioxadiazole ring, indole ring, carbazole ring, pyrroloimidazole ring, pyrrolopyrazole ring, pyrrolopyrrole ring, thienopyrrole ring, thienothiophene ring, furopyrrole Ring, furanofuran ring, thienofuran ring, benzisisothiazole ring, benzisothiazole ring, benzimidazole ring, pyridine ring, pyridine ring, pyridine ring, pyrimidine ring, trisulfazone ring, quinoline ring, isoquinoline ring, azoline ring, quinoline ring, phenanthridine ring, phenidine ring, quinazoline ring, quinazolinone ring, azulene ring, etc. Among these, from the viewpoint of developability, a benzene ring or a naphthalene ring is preferred, and a benzene ring is more preferred. Examples of substituents that the aromatic ring group may have include methyl, ethyl, propyl, methoxy, ethoxy, chlorine, bromo, fluoro, hydroxyl, amino, and epoxy. group, oligoethylene glycol group, phenyl group, carboxyl group, etc., and from the viewpoint of developability, hydroxyl group and oligoethylene glycol group are preferred.

Examples of the alkenyl group in R ⁴ include linear, branched or cyclic alkenyl groups. The carbon number is preferably 2 or more, preferably 22 or less, more preferably 20 or less, still more preferably 18 or less, still more preferably 16 or less, and particularly preferably 14 or less. For example, 2 to 22 are preferred, 2 to 20 are more preferred, 2 to 18 are still more preferred, 2 to 16 are still more preferred, and 2 to 14 are particularly preferred. By setting it to the above lower limit value or more, surface roughness tends to increase, and by setting it to below the above upper limit value, residues tend to decrease.

In addition, examples of substituents that the alkenyl group may have include: methyl, ethyl, propyl, methoxy, ethoxy, chlorine, bromo, fluoro, hydroxyl, amino, epoxy, Among the oligoethylene glycol group, phenyl group, carboxyl group, etc., from the viewpoint of developability, hydroxyl group and oligoethylene glycol group are preferred.

In this way, R ⁴ represents an alkyl group which may have a substituent, an aryl group which may have a substituent, or an alkenyl group which may have a substituent. Among these, from the viewpoint of developability and film strength, an alkyl group is preferred. group or alkenyl group, more preferably alkyl group.

When the copolymer resin (b2) contains a partial structure represented by the general formula (II), the content ratio is not particularly limited, but is preferably 0.1 mol% or more, more preferably 0.5 mol% or more, and still more preferably It is preferably 1 mol% or more, more preferably 70 mol% or less, more preferably 50 mol% or less, further preferably 30 mol% or less, and particularly preferably 10 mol% or less. For example, it is preferably 0.1 to 70 mol%, more preferably 0.1 to 50 mol%, further preferably 0.5 to 30 mol%, and particularly preferably 1 to 10 mol%. By setting it to the above lower limit value or more, surface roughness tends to increase, and by setting it to below the above upper limit value, residues tend to decrease.

(Partial structure represented by general formula (III)) When the copolymer resin (b2) contains a partial structure represented by the above-mentioned general formula (I), the additional partial structure preferably contains the following general formula (I) from the viewpoint of heat resistance and film strength. III) Partial structure represented.

[Chemical 32]

In the above formula (III), R ⁵ represents a hydrogen atom or a methyl group, R ⁶ represents an optionally substituted alkyl group, an optionally substituted alkenyl group, an optionally substituted alkynyl group, a hydroxyl group, a carboxyl group, or a halogen atom, An alkoxy group, a thiol group which may have a substituent, or an alkyl sulfide group which may have a substituent. t represents an integer from 0 to 5.

(R ⁶ ) In the above formula (III), R ⁶ represents an alkyl group which may have a substituent, an alkenyl group which may have a substituent, an alkynyl group which may have a substituent, a hydroxyl group, a carboxyl group, a halogen atom, or an alkyl group which may have a substituent. Oxygen group, thiol group, or alkyl sulfide group which may have a substituent. Examples of the alkyl group in R ⁶ include linear, branched or cyclic alkyl groups. The carbon number is preferably 1 or more, more preferably 3 or more, still more preferably 5 or more, and preferably 20 or less, more preferably 18 or less, still more preferably 16 or less, still more preferably 14 or less. , especially preferably below 12. For example, 1 to 20 are preferred, 3 to 18 are more preferred, 3 to 16 are still more preferred, 5 to 14 are still more preferred, and 5 to 12 are particularly preferred. By setting it to the above lower limit value or more, surface roughness tends to increase, and by setting it to below the above upper limit value, residues tend to decrease.

Specific examples of the alkyl group include methyl, ethyl, cyclohexyl, dicyclopentyl, dodecyl, and the like. Among these, from the viewpoint of developability and surface roughness, dicyclopentyl or dodecyl is preferred, and dicyclopentyl is more preferred. In addition, examples of substituents that the alkyl group may have include: methoxy group, ethoxy group, chlorine group, bromo group, fluorine group, hydroxyl group, amino group, epoxy group, oligoglycol group, and phenyl group. , carboxyl group, acrylyl group, methacrylyl group, etc., from the viewpoint of developability, hydroxyl group and oligoglycol group are preferred.

Examples of the alkenyl group in R ⁶ include linear, branched or cyclic alkenyl groups. The carbon number is preferably 2 or more, preferably 22 or less, more preferably 20 or less, still more preferably 18 or less, still more preferably 16 or less, and particularly preferably 14 or less. For example, 2 to 22 are preferred, 2 to 20 are more preferred, 2 to 18 are still more preferred, 2 to 16 are still more preferred, and 2 to 14 are particularly preferred. By setting it to the above lower limit value or more, surface roughness tends to increase, and by setting it to below the above upper limit value, residues tend to decrease.

In addition, examples of substituents that the alkenyl group may have include: methyl, ethyl, propyl, methoxy, ethoxy, chlorine, bromo, fluoro, hydroxyl, amino, epoxy, Among the oligoethylene glycol group, phenyl group, carboxyl group, etc., from the viewpoint of developability, hydroxyl group and oligoethylene glycol group are preferred.

Examples of the alkynyl group in R ⁶ include linear, branched or cyclic alkynyl groups. The carbon number is preferably 2 or more, preferably 22 or less, more preferably 20 or less, still more preferably 18 or less, still more preferably 16 or less, and particularly preferably 14 or less. For example, 2 to 22 are preferred, 2 to 20 are more preferred, 2 to 18 are still more preferred, 2 to 16 are still more preferred, and 2 to 14 are particularly preferred. By setting it to the above lower limit value or more, surface roughness tends to increase, and by setting it to below the above upper limit value, residues tend to decrease.

In addition, examples of substituents that the alkynyl group may have include: methyl, ethyl, propyl, methoxy, ethoxy, chlorine, bromo, fluoro, hydroxyl, amino, and epoxy groups. Among the oligoethylene glycol group, phenyl group, carboxyl group, etc., from the viewpoint of developability, hydroxyl group and oligoethylene glycol group are preferred.

Examples of the halogen atom in R ⁶ include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. Among these, a fluorine atom is preferred from the viewpoint of ink repellency.

Examples of the alkoxy group in R ⁶ include linear, branched or cyclic alkoxy groups. The carbon number is preferably 1 or more, more preferably 20 or less, more preferably 18 or less, still more preferably 16 or less, still more preferably 14 or less, and particularly preferably 12 or less. For example, 1 to 20 is preferred, 1 to 18 is more preferred, 1 to 16 is still more preferred, 1 to 14 is still more preferred, and 1 to 12 is particularly preferred. By setting it to the above lower limit value or more, surface roughness tends to increase, and by setting it to below the above upper limit value, residues tend to decrease.

In addition, examples of substituents that the alkoxy group may have include: methoxy group, ethoxy group, chlorine group, bromo group, fluorine group, hydroxyl group, amino group, epoxy group, oligoglycol group, benzene group group, carboxyl group, acrylyl group, methacrylyl group, etc., and from the viewpoint of developability, hydroxyl group and oligoethylene glycol group are preferred.

Examples of the alkyl sulfide group in R ⁶ include linear, branched or cyclic alkyl sulfide groups. The carbon number is preferably 1 or more, more preferably 20 or less, more preferably 18 or less, still more preferably 16 or less, still more preferably 14 or less, and particularly preferably 12 or less. For example, 1 to 20 is preferred, 1 to 18 is more preferred, 1 to 16 is still more preferred, 1 to 14 is still more preferred, and 1 to 12 is particularly preferred. By setting it to the above lower limit value or more, surface roughness tends to increase, and by setting it to below the above upper limit value, residues tend to decrease.

In addition, examples of the substituents that the alkyl group in the alkyl sulfide group may have include: methoxy group, ethoxy group, chlorine group, bromine group, fluorine group, hydroxyl group, amino group, epoxy group, oligo group, Glycol group, phenyl group, carboxyl group, acrylyl group, methacrylyl group, etc., from the viewpoint of developability, hydroxyl group and oligoglycol group are preferred.

Thus, R ⁶ represents an optionally substituted alkyl group, an optionally substituted alkenyl group, an optionally substituted alkynyl group, a hydroxyl group, a carboxyl group, a halogen atom, an alkoxy group, a hydroxyalkyl group, a thiol group, or an optionally substituted alkyl group. Among the alkyl sulfide groups having a substituent, from the viewpoint of developability, a hydroxyl group or a carboxyl group is preferred, and a carboxyl group is more preferred.

In the above formula (III), t represents an integer from 0 to 5, and from the viewpoint of ease of synthesis, t is preferably 0.

When the copolymer resin (b2) contains a partial structure represented by the general formula (III), the content ratio is not particularly limited, but is preferably 0.5 mol% or more, more preferably 1 mol% or more, and further preferably Preferably, it is more than 2 mol%. Moreover, it is preferably 50 mol% or less, more preferably 30 mol% or less, further preferably 20 mol% or less, more preferably 10 mol% or less. For example, 0.5 to 50 mol% is preferred, 1 to 30 mol% is more preferred, 1 to 20 mol% is more preferred, and 2 to 10 mol% is more preferred. By setting it to the above lower limit value or more, surface roughness tends to increase, and by setting it to below the above upper limit value, residues tend to decrease.

(Partial structure represented by general formula (IV)) When the copolymer resin (b2) has a partial structure represented by the above-mentioned general formula (I), it is also preferable that the other partial structure has the following general formula (IV) from the viewpoint of developability part of the structure represented.

[Chemical 33]

In the above formula (IV), R ⁷ represents a hydrogen atom or a methyl group.

When the copolymer resin (b2) contains a partial structure represented by the above-mentioned general formula (IV), the content ratio is not particularly limited, but is preferably 5 mol% or more, more preferably 10 mol% or more, and still more preferably It is preferably 20 mol% or more, more preferably 80 mol% or less, more preferably 70 mol% or less, and still more preferably 60 mol% or less. For example, 5 to 80 mol% is preferred, 10 to 70 mol% is more preferred, and 20 to 60 mol% is still more preferred. By setting it as above the said lower limit value, developability tends to improve, and by setting it as below the said upper limit value, surface roughness tends to improve.

On the other hand, the acid value of the copolymer resin (b2) is not particularly limited, but is preferably 10 mgKOH/g or more, more preferably 15 mgKOH/g or more, further preferably 20 mgKOH/g or more, and more preferably 150 mgKOH/g or less, more preferably 120 mgKOH/g or less, still more preferably 100 mgKOH/g or less, still more preferably 50 mgKOH/g or less. For example, 10 to 150 mgKOH/g is preferred, 10 to 120 mgKOH/g is more preferred, 15 to 100 mgKOH/g is more preferred, and 20 to 50 mgKOH/g is still more preferred. By setting it as above the said lower limit value, developability tends to improve, and by setting it as below the said upper limit value, surface roughness tends to improve.

(b2) The weight average molecular weight (Mw) of the copolymer resin is not particularly limited, but is usually 1,000 or more, preferably 2,000 or more, more preferably 4,000 or more, further preferably 6,000 or more, more preferably 7,000 or more, particularly preferably 8,000 or more, and usually 30,000 or less, preferably 20,000 or less, more preferably 15,000 or less, further preferably 10,000 or less. For example, 1000 to 20000 is preferred, 2000 to 20000 is more preferred, 4000 to 15000 is further preferred, 6000 to 15000 is still more preferred, 7000 to 10000 is particularly preferred, and 8000 to 10000 is particularly preferred. By setting it as above the said lower limit value, surface roughness tends to improve, and by setting it as below the said upper limit value, developability tends to become good.

(b2) The double bond equivalent of the copolymer resin is not particularly limited, but is preferably 500 or less, more preferably 400 or less, further preferably 350 or less, particularly preferably 300 or less, and more preferably 100 or more, more preferably 150 or more, more preferably 180 or more, especially 200 or more. For example, 100 to 500 is preferred, 150 to 400 is more preferred, 180 to 350 is further preferred, and 200 to 300 is particularly preferred. By setting the value below the upper limit, mechanical properties and surface roughness tend to be improved, and by setting it above the lower limit, storage stability tends to be improved.

Specific examples of the copolymer resin (b2) include resins described in Japanese Patent Application Laid-Open No. 8-297366 or Japanese Patent Application Laid-Open No. 2001-89533.

＜(c) Photopolymerization initiator＞ (c) Photopolymerization initiator is a component that has the function of directly absorbing light to cause decomposition reaction or hydrogen abstraction reaction, thereby generating polymerization active free radicals. If necessary, additives such as a polymerization accelerator (chain transfer agent) and a sensitizing dye can be added and used. Examples of the photopolymerization initiator include metallocene compounds including titanocene compounds described in Japanese Patent Application Laid-Open No. Sho 59-152396 and Japanese Patent Application Laid-Open No. Sho 61-151197; Hexaarylbiimidazole derivatives described in Japanese Patent Application Publication No. 2000-56118; halomethylated tetrazole derivatives, halomethyl mesostris derivatives, N- Free radical active agents such as phenylglycine and other N-aryl-α-amino acids, N-aryl-α-amino acid salts, N-aryl-α-amino acid esters, α- Aminoalkylphenone derivatives; oxime ester compounds described in Japanese Patent Application Laid-Open No. 2000-80068, Japanese Patent Application Laid-Open No. 2006-36750, etc.

As a photopolymerization initiator, from the viewpoint of improving mechanical properties and surface roughness, a hexaarylbiimidazole compound is particularly preferred.

As the hexaarylbiimidazole compound, from the viewpoint of mechanical properties, a hexaarylbiimidazole-based compound represented by the following general formula (1-1) and/or the following general formula (1-2) is preferred. Free radical initiator.

[Chemical 34]

In the above formula, R ¹ to R ³ each independently represent an alkyl group having 1 to 4 carbon atoms which may have a substituent, an alkoxy group having 1 to 4 carbon atoms which may have a substituent, or a halogen atom, l, m and n each independently represents an integer from 0 to 5.

It is not particularly limited as long as the carbon number of the alkyl group of R ¹ to R ³ is in the range of 1 to 4. From the viewpoint of mechanical properties, it is preferably 3 or less, more preferably 2 or less. The alkyl group may be chain-shaped or cyclic. Specific examples of the alkyl group include methyl, ethyl, propyl and isopropyl, of which methyl and ethyl are preferred. As the substituent that the alkyl group having 1 to 4 carbon atoms in R ¹ to R ³ may have, a group of a monovalent non-metal atomic group other than hydrogen can be used. Preferable examples include: halogen atom (-F, -Br, -Cl, -I), hydroxyl, alkoxy.

Moreover, if the carbon number of the alkoxy group of R ¹ to R ³ is in the range of 1 to 4, it is not particularly limited. From the viewpoint of increasing the taper angle, it is preferably 3 or less, and more preferably 2 or less. . The alkyl part of the alkoxy group may be chain-shaped or cyclic. Specific examples of the alkoxy group include, for example, a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, and a butoxy group. Among them, a methoxy group and an ethoxy group are preferred. Examples of substituents that the alkoxy group having 1 to 4 carbon atoms in R ¹ to R ³ may have include an alkyl group and an alkoxy group, and an alkyl group is preferred.

Moreover, the halogen atom of R ¹ to R ³ may be, for example, a chlorine atom, an iodine atom, a bromine atom, or a fluorine atom. Among them, from the viewpoint of ease of synthesis, a chlorine atom or a fluorine atom is preferred, and more preferably a chlorine atom or a fluorine atom. Preferably it is a chlorine atom. Among these, from the viewpoint of sensitivity or ease of synthesis, R ¹ to R ³ are each independently preferably a halogen atom, and more preferably a chlorine atom.

m, n, and l each independently represent an integer from 0 to 5. From the viewpoint of ease of synthesis, at least two of m, n, and l are preferably integers of 1 or more, and more preferably m, n, and l Any 2 of them are 1, and the remaining 1 is 0.

Examples of the hexaarylbimidazole compound represented by the general formula (1-1) and/or the general formula (1-2) include: 2,2'-bis(o-chlorophenyl)-4,5, 4',5'-tetraphenylbiimidazole, 2,2'-bis(o-methylphenyl)-4,5,4',5'-tetraphenylbiimidazole, 2,2'-bis(o-methylphenyl) Chlorophenyl)-4,4',5,5'-tetrakis(o,p-dichlorophenyl)biimidazole, 2,2'-bis(o,p-dichlorophenyl)-4,4',5 ,5'-tetrakis(o,p-dichlorophenyl)biimidazole, 2,2'-bis(o-chlorophenyl)-4,4',5,5'-tetrakis(p-fluorophenyl)biimidazole, 2,2'-bis(o-chlorophenyl)-4,4',5,5'-tetrakis(o,p-dibromophenyl)biimidazole, 2,2'-bis(o-bromophenyl)-4 ,4',5,5'-tetrakis(o,p-dichlorophenyl)biimidazole, 2,2'-bis(o-chlorophenyl)-4,4',5,5'-tetrakis(p-chloronaphthalene) base) biimidazole, etc. Among them, a hexaphenylbiimidazole compound is preferred, and the ortho-position of the benzene ring at the 2,2'-position bonded to the imidazole ring is substituted by a methyl group, a methoxy group, or a halogen atom. Preferably, the benzene ring bonded to the 4,4', 5,5'-position of the imidazole ring is unsubstituted or substituted with a halogen atom or a methoxy group.

As (c) the photopolymerization initiator, either a hexaarylbiimidazole compound represented by the general formula (1-1) or a hexaarylbimidazole compound represented by the general formula (1-2) can be used. , or both can be used together. In the case of combined use, the ratio is not particularly limited.

Furthermore, examples of titanocene derivatives include: dicyclopentadienyl titanium dichloride, dicyclopentadienyl titanium diphenyl, dicyclopentadienyl bis(2,3,4, 5,6-pentafluorophenyl)titanium, dicyclopentadienylbis(2,3,5,6-tetrafluorophenyl)titanium, dicyclopentadienylbis(2,4,6-trifluoro Phenyl)titanium, dicyclopentadienylbis(2,6-difluorophenyl)titanium, dicyclopentadienylbis(2,4-difluorophenyl)titanium, bis(methylcyclopentadienyl) Alkenyl)bis(2,3,4,5,6-pentafluorophenyl)titanium, bis(methylcyclopentadienyl)bis(2,6-difluorophenyl)titanium, dicyclopentadiene [2,6-difluoro-3-(pyrrol-1-yl)phenyl]titanium, etc.

In addition, examples of halomethylated ethadiazole derivatives include: 2-trichloromethyl-5-(2'-benzofuranyl)-1,3,4-ethadiazole, 2-trichloromethyl Chloromethyl-5-[β-(2'-benzofuranyl)vinyl]-1,3,4-oxadiazole, 2-trichloromethyl-5-[β-(2'-(6 ''-benzofuranyl)vinyl)]-1,3,4-ethadiazole, 2-trichloromethyl-5-furyl-1,3,4-ethadiazole, etc.

Furthermore, examples of halomethyl mesosine derivatives include: 2-(4-methoxyphenyl)-4,6-bis(trichloromethyl) mesosine, 2-(4-methyl Oxynaphthyl)-4,6-bis(trichloromethyl)strisene, 2-(4-ethoxynaphthyl)-4,6-bis(trichloromethyl)strisone, 2- (4-Ethoxycarbonylnaphthyl)-4,6-bis(trichloromethyl)trisene, etc.

Examples of α-aminoalkylphenone derivatives include: 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinylpropan-1-one, 2 -Benzyl-2-dimethylamino-1-(4-morpholinylphenyl)butan-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholine phenyl)butan-1-one, 4-dimethylaminoethylbenzoate, 4-dimethylaminoisoamylbenzoate, 4-diethylaminoacetophenone , 4-dimethylaminopropiophenone, 2-ethylhexyl-1,4-dimethylaminobenzoate, 2,5-bis(4-diethylaminobenzylidene)cyclohexan ketone, 7-diethylamino-3-(4-diethylaminobenzoyl)coumarin, 4-(diethylamino)chalcone, etc.

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

[Chemical 35]

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

The number of carbon atoms in the alkyl group in R ^21a is not particularly limited. From the viewpoint of solubility or sensitivity in a solvent, it is usually 1 or more, preferably 2 or more, and usually 20 or less, preferably 15. below, preferably below 10. For example, 1 to 20 is preferable, 1 to 15 is more preferable, 1 to 10 is still more preferable, and 2 to 10 is still more preferable. Specific examples of the alkyl group include methyl, ethyl, propyl, cyclopentylethyl, propyl, and the like. Examples of substituents that the alkyl group may have include aromatic ring groups, hydroxyl groups, carboxyl groups, halogen atoms, amino groups, amide groups, and 4-(2-methoxy-1-methyl)ethoxy- A 2-methylphenyl group or an N-acetyl-N-acetyloxyamine group is preferably unsubstituted from the viewpoint of ease of synthesis.

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

Specific examples of the aromatic ring group include phenyl, naphthyl, pyridyl, furyl, and the like. Among these, from the viewpoint of developability, phenyl or naphthyl is preferred, and more preferred is phenyl. Examples of substituents that the aromatic ring group may have include: hydroxyl group, carboxyl group, halogen atom, amine group, amide group, alkyl group, alkoxy group, a group formed by linking these substituents, etc., in terms of developability From the viewpoint of this, an alkyl group, an alkoxy group, or a linked group of these is preferred, and a linked alkoxy group is more preferred. Among these, from the viewpoint of developability, R ^21a is preferably an aromatic ring group which may have a substituent, and more preferably an aromatic ring group which has an alkoxy group linked to the substituent.

Moreover, as R ^21b , preferred examples include: optionally substituted carbazolyl group, optionally substituted 9-oxosulfanyl group group or optionally substituted diphenyl sulfide group. Among these, from the viewpoint of sensitivity, an optionally substituted carbazolyl group is preferred.

In addition, the number of carbon atoms in the alkyl group in R ^22a is not particularly limited. From the viewpoint of solubility or sensitivity in a solvent, it is usually 2 or more, preferably 3 or more, and usually 20 or less, preferably 3 or more. Preferably it is 15 or less, more preferably 10 or less, still more preferably 5 or less. For example, 2 to 20 is preferred, 2 to 15 is more preferred, 2 to 10 is still more preferred, 2 to 5 is still more preferred, and 3 to 5 is particularly preferred. Specific examples of the alkyl group include an acetyl group, a propyl group, a butyl group, and the like. Examples of substituents that the alkyl group may have include aromatic ring groups, hydroxyl groups, carboxyl groups, halogen atoms, amino groups, amide groups, and the like. From the viewpoint of ease of synthesis, unsubstituted groups are preferred.

In addition, the number of carbon atoms of the arylide group in R ^22a is not particularly limited. From the viewpoint of solubility or sensitivity in a solvent, it is usually 7 or more, preferably 8 or more, and usually 20 or less, preferably 8 or more. Preferably it is 15 or less, more preferably 12 or less, still more preferably 10 or less. For example, 7 to 20 are preferable, 7 to 15 are more preferable, 7 to 12 are still more preferable, and 8 to 12 are still more preferable. Specific examples of the arylyl group include benzyl group, naphthoyl group, and the like. Examples of substituents that the aryl group may have include a hydroxyl group, a carboxyl group, a halogen atom, an amino group, a amide group, an alkyl group, and the like. From the viewpoint of ease of synthesis, unsubstituted groups are preferred. Among these, from the viewpoint of sensitivity, R ^22a is preferably an alkyl group which may have a substituent, more preferably an unsubstituted alkyl group, and still more preferably an acetyl group.

In addition, in terms of reducing contamination of the liquid crystal layer caused by the colorant, the initiator described in Japanese Patent Application Laid-Open No. 2016-133574 can also be suitably used.

A photopolymerization initiator may be used individually by 1 type, and may be used in combination of 2 or more types. In the photopolymerization initiator, in order to improve the sensitivity, a sensitizing pigment and a polymerization accelerator corresponding to the wavelength of the light source for image exposure can be blended as needed. Examples of sensitizing dyes include those described in Japanese Patent Application Laid-Open No. 4-221958 and Japanese Patent Application Laid-Open No. 4-219756. Pigments, coumarin pigments having a heterocyclic ring described in Japanese Patent Application Laid-Open No. 3-239703 and Japanese Patent Application Laid-Open No. 5-289335, Japanese Patent Application Laid-Open No. 3-239703, Japanese Patent Application Laid-Open No. 5-289335 The 3-ketocoumarin compound described in Japanese Patent Application Publication No. 289335, the pyrromethene pigment described in Japanese Patent Application Publication No. 6-19240, and Japanese Patent Application Publication No. 47-2528, Japanese Patent Application Publication No. 47-2528, Japanese Patent Application Publication No. Japanese Patent Publication No. 54-155292, Japanese Patent Publication No. 45-37377, Japanese Patent Publication No. 48-84183, Japanese Patent Publication No. 52-112681, Japanese Patent Publication No. 58-15503 , Japanese Patent Laid-Open No. Sho 60-88005, Japanese Patent Laid-Open No. Sho 59-56403, Japanese Patent Laid-Open No. Hei 2-69, Japanese Patent Laid-Open No. Sho 57-168088, Japanese Patent Laid-Open No. Hei 5- Pigments having a dialkylaminobenzene skeleton described in Japanese Patent Application Laid-Open No. 107761, Japanese Patent Application Laid-Open No. 5-210240, and Japanese Patent Application Publication No. 4-288818.

Among these sensitizing dyes, a sensitizing dye containing an amine group is preferred, and a compound having an amine group and a phenyl group in the same molecule is more preferred. Particularly preferred ones are 4,4'-dimethylaminobenzophenone, 4,4'-diethylaminobenzophenone, 2-aminobenzophenone, and 4-aminodiphenyl Methyl ketone, 4,4'-diaminobenzophenone, 3,3'-diaminobenzophenone, 3,4-diaminobenzophenone and other benzophenone compounds; 2- (p-Dimethylaminophenyl)benzoethazole, 2-(p-Dimethylaminophenyl)benzoethazole, 2-(p-Dimethylaminophenyl)benzo[4,5 ]benzoethazole, 2-(p-dimethylaminophenyl)benzo[6,7]benzoethazole, 2,5-bis(p-diethylaminophenyl)-1,3, 4-Ozole, 2-(p-dimethylaminophenyl)benzothiazole, 2-(p-diethylaminophenyl)benzothiazole, 2-(p-dimethylaminophenyl)benzothiazole imidazole, 2-(p-diethylaminophenyl)benzimidazole, 2,5-bis(p-diethylaminophenyl)-1,3,4-thiadiazole, (p-dimethyl Aminophenyl)pyridine, (p-diethylaminophenyl)pyridine, (p-dimethylaminophenyl)quinoline, (p-diethylaminophenyl)quinoline, (p-dimethyl Aminophenyl)pyrimidine, (p-diethylaminophenyl)pyrimidine and other compounds containing p-dialkylaminophenyl, etc. The best one is 4,4'-dialkylaminobenzophenone. In addition, one type of sensitizing dye may be used alone, or two or more types of sensitizing dyes may be used in combination.

Examples of polymerization accelerators that can be used include aromatic amines such as p-dimethylaminoethyl benzoate and 2-dimethylaminoethyl benzoate, and aliphatic amines such as n-butylamine and N-methyldiethanolamine. , the following mercapto compounds, etc. A polymerization accelerator may be used individually by 1 type, and may be used in combination of 2 or more types.

＜(d) Ethylenically unsaturated compounds＞ The photosensitive coloring composition of the present invention contains (d) an ethylenically unsaturated compound. By including (d) an ethylenically unsaturated compound, the sensitivity is improved. 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 monovalent carboxylic acids having one ethylenically unsaturated bond and polyvalent or monovalent alcohols. Ester etc.

In the present invention, it is particularly preferred to use a polyfunctional vinyl monomer having two or more ethylenically unsaturated groups per molecule. The number of ethylenically unsaturated groups in the multifunctional ethylenic monomer is not particularly limited, but is usually 2 or more, preferably 4 or more, more preferably 5 or more, and preferably 8 or less, It is better to have less than 7. For example, 2 to 8 are preferred, 4 to 8 are more preferred, 4 to 7 are still more preferred, and 5 to 7 are even more preferred. By setting the value above the lower limit, the sensitivity tends to be high, and by setting the value below the upper limit, the solubility in the solvent tends to be improved. Examples of polyfunctional vinyl monomers include: esters of aliphatic polyhydroxy compounds and unsaturated carboxylic acids; esters of aromatic polyhydroxy compounds and unsaturated carboxylic acids; Esters obtained by the esterification reaction of polyhydroxy compounds such as polyhydroxy compounds and unsaturated carboxylic acids and polycarboxylic acids.

Examples of esters of the aliphatic polyhydroxy compound and unsaturated carboxylic acid include ethylene glycol diacrylate, triethylene glycol diacrylate, trimethylolpropane triacrylate, and trimethylolethane triacrylate. Acrylic esters of aliphatic polyhydroxy compounds such as acrylate, pentaerythritol diacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, glyceryl acrylate, etc. The acrylic acid ester of these exemplary compounds is replaced with methacrylic acid ester, the same is obtained by replacing itonic acid ester, the crotonic acid ester is replaced with crotonic acid, or the methyl ester is replaced with methacrylic acid ester. Maleic acid esters derived from esters of acid, etc.

Examples of esters of aromatic polyhydroxy compounds and unsaturated carboxylic acids include hydroquinone diacrylate, hydroquinone dimethacrylate, resorcin diacrylate, and resorcin dimethacrylate. Acrylic acid esters and methacrylic acid esters of aromatic polyhydroxy compounds such as pyrogallol acrylate and pyrogallol triacrylate.

The ester obtained by the esterification reaction of a polycarboxylic acid and an unsaturated carboxylic acid with a polyhydroxy compound is not necessarily a single substance. If specific representative examples are given, acrylic acid, phthalic acid, and the condensate of ethylene glycol; the condensate of acrylic acid, maleic acid, and diethylene glycol; the condensate of methacrylic acid, terephthalic acid, and pentaerythritol; acrylic acid, adipic acid, butylene glycol, and glycerin The condensate, etc.

In addition, as examples of the polyfunctional vinyl monomer used in the present invention, more useful examples include reacting a polyisocyanate compound with a hydroxyl-containing (meth)acrylate, or reacting a polyisocyanate compound with a polyol and (Meth)acrylic urethanes obtained by reacting hydroxyl-containing (meth)acrylates; such as addition reactants of multivalent epoxy compounds and (meth)acrylic acid hydroxyester or (meth)acrylic acid Epoxy acrylates; acrylamides such as ethyl bisacrylamide; allyl esters such as diallyl phthalate; vinyl-containing compounds such as divinyl phthalate, etc.

Examples of the (meth)acrylic urethanes 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 (Made by Kyoeisha Chemical Co., Ltd. (manufactured by Japan Synthetic Chemical Industry Co., Ltd.), UV-1700B, UV-7600B, UV-7605B, UV-7630B, UV7640B (manufactured by Nippon Synthetic Chemical Industry Co., Ltd.), etc.

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

＜(e) Solvent＞ The photosensitive coloring composition of the present invention may contain (e) solvent. By including the solvent (e), the pigment can be dispersed in the solvent, and coating tends to become easier. The photosensitive coloring composition of the present invention usually contains (a) colorant, (b) alkali-soluble resin, (c) photopolymerization initiator, and (d) ethylenically unsaturated compound dissolved or dispersed in a solvent, and Use with other ingredients as needed. Among the solvents, organic solvents are preferred from the viewpoint of dispersibility or coating properties.

Among the organic solvents, from the viewpoint of coatability, an organic solvent with a boiling point in the range of 100 to 300°C is preferred, and an organic solvent with a boiling point in the range of 120 to 280°C is more preferred. Furthermore, the boiling point referred to here refers to the boiling point at a pressure of 1013.25 hPa, and the same applies to the boiling point below.

Examples of such organic solvents include the following. Such as 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 third-butyl ether, Ethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol mono-n-butyl ether, methoxymethylpentanol, dipropylene glycol monoethyl ether, dipropylene glycol monomethyl ether, 3-methoxybutanol, Diol monoalkyl ethers such as 3-methyl-3-methoxybutanol, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, and tripropylene glycol methyl ether; Such as ethylene glycol dimethyl ether, ethylene glycol diethyl ether, diglyme glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, dipropylene glycol dimethyl ether Diol dialkyl ethers;

Such as 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 acetate, methoxybutyl acetate, 3-methoxybutyl acetate, methoxypentyl acetate, diethylene glycol monomethyl ether acetate Ester, 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 ether Acetate, glycol alkyl ether acetate esters of 3-methyl-3-methoxybutyl acetate; Glycol diacetate esters such as ethylene glycol diacetate, 1,3-butylene glycol diacetate, and 1,6-hexanediol diacetate; Alkyl acetates such as cyclohexanediol acetate; Ethers such as amyl ether, diethyl ether, dipropyl ether, diisopropyl ether, dibutyl ether, dipyl ether, ethyl isobutyl ether, and dihexyl ether;

Such as acetone, methyl ethyl ketone, methyl amyl ketone, methyl isopropyl ketone, methyl isoamyl ketone, diisopropyl ketone, diisobutyl ketone, methyl isobutyl ketone, cyclohexan Ketones, ethyl amyl ketone, methyl butyl ketone, methyl hexyl ketone, methyl nonyl ketone, methoxymethyl pentanone; Such as ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, propylene glycol, butylene glycol, diethylene glycol, dipropylene glycol, triethylene glycol, methoxymethylpentanol, glycerol, benzyl Alcohols monomonic or polyhydric alcohols; Aliphatic hydrocarbons such as n-pentane, n-octane, diisobutylene, n-hexane, hexene, isoprene, dipentene, and dodecane; Alicyclic hydrocarbons such as cyclohexane, methylcyclohexane, methylcyclohexene, and dicyclohexane;

Aromatic hydrocarbons such as benzene, toluene, xylene, and cumene; Such as amyl formate, ethyl formate, ethyl acetate, butyl acetate, propyl acetate, amyl acetate, methyl isobutyrate, ethylene glycol acetate, ethyl propionate, propyl propionate, butyric acid Butyl ester, isobutyl butyrate, methyl isobutyrate, ethyl octanoate, butyl stearate, ethyl benzoate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, 3-Methoxypropionate methyl ester, 3-methoxyethylpropionate ethyl ester, 3-methoxypropionate propyl ester, 3-methoxypropionate butyl ester, γ-butyrolactone chain or ring esters; Alkoxycarboxylic acids such as 3-methoxypropionic acid and 3-ethoxypropionic acid; Halogenated hydrocarbons such as chlorobutane and chloropentane; Ether ketones such as methoxymethylpentanone; Such as acetonitrile, benzonitrile and other nitriles.

Examples of commercially available organic solvents that meet the above requirements include mineral spirits, Varsol#2, Apco#18 solvent, Apcothinner, Socalsolvent No.1 and No.2, Solvesso#150, Shell TS28 solvent, Carbitol, Ethyl carbitol, butyl carbitol, methyl cellosolve ("Cellosolve" is a registered trademark. The same applies below), ethyl cellosolve, ethyl cellosolve acetate, methyl cellosolve Cellosolve-based acetate, diglyme (both trade names), etc. These organic solvents may be used alone, or two or more types may be used in combination.

When the colored spacer is formed by photolithography, the organic solvent is preferably an organic solvent with a boiling point in the range of 100 to 200°C, and more preferably an organic solvent with a boiling point in the range of 120 to 170°C. .

Among the above-mentioned organic solvents, glycol alkyl ether acetates are preferred in that they have a better balance of coatability, surface tension, etc., and that the solubility of the constituent components in the composition is relatively high. In addition, glycol alkyl ether acetates may be used alone or in combination with other organic solvents. As an organic solvent used in combination, glycol monoalkyl ethers are particularly preferred. Among them, propylene glycol monomethyl ether is preferred in terms of the solubility of the constituent components in the composition. Furthermore, glycol monoalkyl ethers have high polarity. If too much is added, the pigments tend to agglomerate and the viscosity of the photosensitive coloring composition obtained subsequently increases and the storage stability tends to decrease. Therefore, in the solvent The ratio of glycol monoalkyl ethers is preferably 5% to 30% by mass, more preferably 5% to 20% by mass.

In addition, it is also preferable to use an organic solvent having a boiling point of 150° C. or higher (hereinafter sometimes referred to as a “high boiling point solvent”). By using such a high boiling point solvent together, although the photosensitive coloring composition is difficult to dry, it has the effect of preventing the uniform dispersion state of the pigment in the composition from being destroyed by rapid drying. That is, it has the effect of preventing, for example, foreign matter defects caused by precipitation and solidification of colorant or the like at the tip of the slit nozzle. In view of the high effect, among the various solvents mentioned above, diethylene glycol mono-n-butyl ether, diethylene glycol mono-n-butyl ether acetate, and diethylene glycol monoethyl ether acetate are particularly preferred. .

The content ratio of the high-boiling-point solvent in the organic solvent is preferably 3% to 50% by mass, more preferably 5% to 40% by mass, and even more preferably 5% to 30% by mass. By setting the value above the lower limit, it is possible to suppress the tendency of foreign matter defects to occur at the tip of the slit nozzle due to the precipitation and solidification of colorant, etc., and by setting the value below the above upper limit, it is possible to suppress the composition from being defective. The drying temperature slows down, suppressing the tendency of problems such as poor station time in the vacuum drying process or pore marks in pre-baking.

Furthermore, the high-boiling-point solvent with a boiling point of 150°C or above may be glycol alkyl ether acetate, or may be a glycol alkyl ether. In this case, the high-boiling-point solvent with a boiling point of 150°C or above may not be included. Solvent. Preferable high boiling point solvents include diethylene glycol mono-n-butyl ether acetate, diethylene glycol monoethyl ether acetate, dipropylene glycol methyl ether acetate, and 1,3- Butanediol diacetate, 1,6-hexanol diacetate, glycerol triacetate, etc.

＜(f) Dispersant＞ The photosensitive coloring composition of the present invention may contain a dispersant (f) in order to finely disperse the colorant (a) and stabilize the dispersion state. (f) The dispersant is preferably a polymer dispersant having a functional group, and further, in terms of dispersion stability, it is preferably a polymer dispersant having a carboxyl group; a phosphate group; a sulfonic acid group; or a base thereof; first grade , secondary or tertiary amine groups; quaternary ammonium salt groups; polymer dispersants derived from functional groups such as pyridine, pyrimidine, pyridine and other nitrogen-containing heterocyclic groups. Especially from the viewpoint of dispersing the pigment with a small amount of dispersant, it is particularly preferred to have primary, secondary or tertiary amine groups; quaternary ammonium salt groups; those derived from pyridine, pyrimidine, pyridine, etc. It is a polymer dispersant for basic functional groups such as nitrogen-containing heterocyclic groups.

Examples of the polymer dispersant include urethane dispersants, acrylic dispersants, polyethyleneimine dispersants, polyallylamine dispersants, and monomers containing amine groups. Dispersants of monomers and macromonomers, polyoxyethylene alkyl ether dispersants, polyoxyethylene diester dispersants, polyether phosphate dispersants, polyester phosphate dispersants, sorbitan aliphatic ester dispersants Dispersants, aliphatic modified polyester dispersants, etc.

Specific examples of such dispersants include trade names: EFKA (registered trademark, manufactured by BASF Corporation), DISPERBYK (registered trademark, manufactured by BYK-Chemie Corporation), Disparlon (registered trademark, manufactured by Kusumoto Chemical Co., Ltd.), SOLSPERSE (registered trademark, manufactured by Kusumoto Chemical Co., Ltd.) Registered trademarks: Lubrizol Co., Ltd.), KP (manufactured by Shin-Etsu Chemical Industry Co., Ltd.), Polyflow (manufactured by Kyeisha Chemical Co., Ltd.), Ajisper (registered trademark: Ajinomoto Co., Ltd.), etc. One type of these polymer dispersants may be used alone, or two or more types may be used in combination.

The weight average molecular weight (Mw) of the polymer dispersant is usually 700 or more, preferably 1,000 or more, and usually 100,000 or less, preferably 50,000 or less. For example, 700 to 100,000 is preferred, 700 to 50,000 is more preferred, and 1,000 to 50,000 is still more preferred. Among them, from the viewpoint of the dispersibility of the pigment, (f) the dispersant is preferably a urethane-based polymer dispersant and/or an acrylic-based polymer dispersant having a functional group, and is particularly preferred. Contains acrylic polymer dispersant. In terms of dispersibility and storage properties, a polymer dispersant having a basic functional group and a polyester bond and/or a polyether bond is preferred.

Examples of urethane-based and acrylic-based polymer dispersants include: DISPERBYK160 to 166, 182 series (all urethane-based), DISPERBYK2000, 2001, BYK-LPN21116, etc. (all acrylic-based) ) (the above are all manufactured by BYK-Chemie). When specifically exemplifying a preferable chemical structure as a urethane-based polymer dispersant, for example, a polyisocyanate compound having one or two hydroxyl groups in the molecule and a number average molecular weight of 300 to 10,000 can be exemplified. Compounds, and dispersion resins with a weight average molecular weight of 1,000 to 200,000 obtained by reacting compounds with active hydrogen and tertiary amine groups in the same molecule, etc. By treating these with a quaternary agent such as benzyl chloride, all or part of the tertiary amine groups can be converted into quaternary ammonium salt groups.

Examples of the polyisocyanate compound include terephthalene diisocyanate, 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, 4,4'-diphenylmethane diisocyanate, and naphthalene-1,5- Diisocyanates, benzidine diisocyanate and other aromatic diisocyanates, hexamethylene diisocyanate, lysine methyl ester diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, dimer acid diisocyanate Aliphatic diisocyanates such as isophorone diisocyanate, 4,4'-methylene bis(cyclohexyl isocyanate), ω,ω'-diisocyanate, dimethylcyclohexane and other aliphatic diisocyanates, benzene diisocyanate, etc. Methyl diisocyanate, α,α,α',α'-tetramethylxylylene diisocyanate and other aliphatic diisocyanates with aromatic rings, lysate triisocyanate, 1,6,11-undecane Triisocyanate, 1,8-diisocyanate-4-isocyanatomethyloctane, 1,3,6-hexamethylene triisocyanate, dicycloheptane triisocyanate, triphenylmethane triisocyanate), triphenyl thiophosphoric acid Triisocyanates such as triisocyanate, their trimers, water adducts, and polyol adducts, etc. As the polyisocyanate, a terpolymer of organic diisocyanate is preferred, and a terpolymer of toluene diisocyanate and isophorone diisocyanate is most preferred. One type of these may be used alone, or two or more types may be used in combination.

An example of a method for producing an isocyanate terpolymer is as follows: using an appropriate trimerization catalyst such as tertiary amines, phosphines, alkoxides, metal oxides, carboxylates, etc. Polyisocyanates undergo partial trimerization of isocyanate groups. After the trimerization is stopped by adding catalyst poison, unreacted polyisocyanate is removed through solvent extraction and thin film distillation to obtain the target isocyanurate-containing ester. Based on polyisocyanate.

Examples of compounds having one or two hydroxyl groups in the same molecule and a number average molecular weight of 300 to 10,000 include polyether diol, polyester diol, polycarbonate diol, polyolefin diol, and the like. Compounds in which the single terminal hydroxyl group is alkoxylated with an alkyl group having 1 to 25 carbon atoms, and mixtures of two or more of these compounds. Examples of the polyether diol include polyether diol, polyether ester diol, and mixtures of two or more of these. Examples of the polyether glycol include those obtained by homopolymerizing or copolymerizing alkylene oxide, such as polyethylene glycol, polypropylene glycol, polyethylene glycol propylene glycol, polyoxytetramethylene glycol, and polyoxyhexamethylene glycol. Glycol, polyoxyoctamethylene glycol and mixtures of two or more of these.

Examples of the polyetherester diol include those obtained by reacting an ether group-containing diol or a mixture with other diols and a dicarboxylic acid or anhydride thereof, or by reacting an alkylene oxide with a polyester diol. For example, poly(polyoxytetramethylene) adipate, etc. As the polyether glycol, the most preferred ones are polyethylene glycol, polypropylene glycol, polyoxytetramethylene glycol, or compounds in which the single terminal hydroxyl group is alkoxylated with an alkyl group having 1 to 25 carbon atoms. compound.

Examples of the polyester diol include dicarboxylic acids (succinic acid, glutaric acid, adipic acid, sebacic acid, fumaric acid, maleic acid, phthalic acid, etc.) or the Acid anhydrides, and glycols (ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, 1,2-butanediol, 1,3-butanediol, 1,4- Butanediol, 2,3-butanediol, 3-methyl-1,5-pentanediol, 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-hexanediol, 2-methyl-2,4-pentanediol Alcohol, 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 Those obtained by the condensation polymerization of aromatic diols such as glycols, xylylene glycol, bishydroxyethoxybenzene, N-alkyl dialkanolamines such as N-methyldiethanolamine, etc., such as polyethylene adipate ester, polybutylene adipate, polyhexylene adipate, polyethylene adipate/propylene adipate, etc.; or use the above glycols or monohydric alcohols with 1 to 25 carbon atoms as the starting material Polylactone diol or polylactone monool obtained from the agent, such as polycaprolactone diol, polymethylvalerolactone and mixtures of two or more of these. As the polyester diol, polycaprolactone diol or polycaprolactone using an alcohol having 1 to 25 carbon atoms as a initiator is optimal.

Examples of the polycarbonate diol include poly(1,6-hexylene)carbonate, poly(3-methyl-1,5-pentylene)carbonate, and the like. Examples of the polyolefin diol include : Polybutadiene glycol, hydrogenated polybutadiene glycol, hydrogenated polyisoprene glycol, etc. One type of these may be used alone, or two or more types may be used in combination.

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

The compound having an active hydrogen and a tertiary amine group in the same molecule used in the present invention will be described. Examples of the active hydrogen, that is, a hydrogen atom directly bonded to an oxygen atom, a nitrogen atom, or a sulfur atom include hydrogen atoms in functional groups such as a hydroxyl group, an amine group, and a thiol group. Among them, an amine group is preferred, especially an amine group. It is the hydrogen atom of the primary amine group.

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. Examples of compounds having active hydrogen and tertiary amine groups in the same molecule include: N,N-dimethyl-1,3-propanediamine, N,N-diethyl-1, 3-propanediamine, N,N-dipropyl-1,3-propanediamine, N,N-dibutyl-1,3-propanediamine, N,N-dimethylethylenediamine, N ,N-diethylethylenediamine, N,N-dipropylethylenediamine, N,N-dibutylethylenediamine, N,N-dimethyl-1,4-butanediamine, N, N-diethyl-1,4-butanediamine, N,N-dipropyl-1,4-butanediamine, N,N-dibutyl-1,4-butanediamine, etc.

In addition, when the tertiary amino group is a nitrogen-containing heterocyclic structure, the nitrogen-containing heterocyclic ring may, for example, include pyrazole ring, imidazole ring, triazole ring, tetrazole ring, indole ring, carbazole ring, Indazole ring, benzimidazole ring, benzotriazole ring, benzothezole ring, benzothiazole ring, benzothiadiazole ring and other nitrogen-containing 5-membered heterocyclic rings; pyridine ring, pyridine ring, pyrimidine ring, Nitrogen-containing 6-membered heterocyclic rings such as trisulfide ring, quinoline ring, acridine ring, and isoquinoline ring. Among these nitrogen-containing heterocycles, the preferred one is an imidazole ring or a triazole ring.

Specific examples of these compounds having an imidazole ring and an amino group include: 1-(3-aminopropyl)imidazole, histidine, 2-aminoimidazole, 1-(2-aminoethyl) base) imidazole, etc. Furthermore, specific examples of compounds having a triazole ring and an amino group include: 3-amino-1,2,4-triazole, 5-(2-amino-5-chlorophenyl)- 3-Phenyl-1H-1,2,4-triazole, 4-amino-4H-1,2,4-triazole-3,5-diol, 3-amino-5-phenyl-1H -1,3,4-triazole, 5-amino-1,4-diphenyl-1,2,3-triazole, 3-amino-1-benzyl-1H-2,4-triazole wait. Among them, N,N-dimethyl-1,3-propanediamine, N,N-diethyl-1,3-propanediamine, 1-(3-aminopropyl)imidazole, 3 -Amino-1,2,4-triazole. One type of these may be used alone, or two or more types may be used in combination.

A preferable blending ratio of raw materials for producing a urethane-based polymer dispersant is a compound with a number average molecular weight of 300 to 10,000 having 1 or 2 hydroxyl groups in the same molecule relative to 100 parts by mass of the polyisocyanate compound. It is 10 to 200 parts by mass, preferably 20 to 190 parts by mass, and more preferably 30 to 180 parts by mass. The compound having active hydrogen and tertiary amine group in the same molecule is 0.2 to 25 parts by mass, preferably 0.3～24 parts by mass.

The urethane polymer dispersant is produced according to a known method for producing polyurethane resin. As solvents during production, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclopentanone, cyclohexanone, and isophorone can usually be used; ethyl acetate, butyl acetate, acetic acid solvents, etc. Esters such as cellulose agents; hydrocarbons such as benzene, toluene, xylene, and hexane; some alcohols such as diacetone alcohol, isopropyl alcohol, second butyl alcohol, and third butyl alcohol; chlorides such as methylene chloride and chloroform; Ethers such as tetrahydrofuran and diethyl ether; aprotic polar solvents such as dimethylformamide, N-methylpyrrolidone, and dimethylstyrene. One type of these may be used alone, or two or more types may be used in combination.

In the above production, a urethanization reaction catalyst can usually be used. Examples of the catalyst include tin-based catalysts such as dibutyltin dilaurate, dioctyltin dilaurate, dibutyltin dioctoate, and stannous octoate; iron-based catalysts such as iron acetyl acetonate and ferric chloride; triethyl Tertiary amines such as amine, triethylenediamine, etc. These may be used individually by 1 type, and may be used in combination of 2 or more types.

The amount of the compound having active hydrogen and tertiary amine group in the same molecule is preferably controlled to be in the range of 1 to 100 mgKOH/g based on 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 in mg of KOH corresponding to the acid value through neutralization titration of a basic amine group with an acid. By setting it as above the said lower limit value, the dispersion ability tends to become good, and by setting it as below the said upper limit value, there exists a tendency which tends to suppress the fall of developability easily.

Furthermore, in the case where the isocyanate group remains in the polymer dispersant during the above reaction, if the isocyanate group is further converted into other functional groups using an alcohol or an amine compound, the stability of the product over time will be improved, and therefore it is relatively good. The weight average molecular weight (Mw) of the urethane polymer dispersant is usually 1,000 to 200,000, preferably 2,000 to 100,000, more preferably 3,000 to 50,000. By setting it to the above-mentioned lower limit value or more, the dispersibility and dispersion stability tend to become good, and by setting it below the said upper limit value, there is a tendency to easily suppress the decrease in solubility or dispersibility.

As the acrylic polymer dispersant, it is preferable to use an unsaturated group-containing monomer having a functional group (the so-called functional group referred to here is the above-mentioned functional group as a functional group contained in the polymer dispersant), and an unsaturated group. Random copolymers, graft copolymers, and block copolymers of unsaturated monomers with functional groups. 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)acryloxyethylsuccinic acid, and 2-(meth)acryloxyethylphthalate. Dicarboxylic acid, 2-(meth)acryloxyethylhexahydrophthalic acid, acrylic acid dimer and other unsaturated monomers with carboxyl groups, dimethylaminoethyl (meth)acrylate, (meth)acrylate Specific examples include unsaturated monomers having tertiary amine groups and quaternary ammonium salt groups, such as diethylaminoethyl acrylate and their quaternary compounds. One type of these may be used alone, or two or more types may be used in combination.

Examples of the unsaturated group-containing monomer having no functional group include: (methyl)acrylate, ethyl(meth)acrylate, propyl(meth)acrylate, isopropyl(meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, tert-butyl (meth)acrylate, benzyl (meth)acrylate, phenyl (meth)acrylate, cyclo(meth)acrylate Hexyl ester, phenoxyethyl (meth)acrylate, phenoxymethyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, isoester (meth)acrylate, tricyclodecane (Meth)acrylate, tetrahydrofurfuryl (meth)acrylate, N-vinylpyrrolidone, styrene and its derivatives, α-methylstyrene, N-cyclohexylmaleimide , N-phenylmaleimide, N-benzylmaleimide and other N-substituted maleimides, acrylonitrile, vinyl acetate and poly(meth)acrylic acid methyl Ester macromonomer, polystyrene macromonomer, poly(meth)acrylate macromonomer, polyethylene glycol macromonomer, polypropylene glycol macromonomer, polycaprolactone macromonomer, etc. Monomer etc. One type of these may be used alone, or two or more types may be used in combination.

The acrylic polymer dispersant is particularly preferably an A-B or B-A-B block copolymer including an A block having a functional group and a B block having no functional group. In this case, in the A block, in addition to those derived from the above In addition to the partial structure of the unsaturated group-containing monomer containing functional groups, and may include partial structures derived from the above-mentioned unsaturated group-containing monomers containing no functional groups, these may be randomly copolymerized in the A block or Any form of block copolymerization is included. Moreover, the content ratio of the partial structure containing no functional group in the A block is usually 80 mass % or less, preferably 50 mass % or less, and further preferably 30 mass % or less.

The B block contains partial structures derived from the above-mentioned unsaturated group-containing monomers without functional groups. One B block may contain partial structures derived from two or more types of monomers. These may be included in the The B block is contained in any form of random copolymerization or block copolymerization. The A-B or B-A-B block copolymer is prepared, for example, by a living polymerization method as shown below. Among the living polymerization methods, there are anionic living polymerization method, cationic living polymerization method, and radical living polymerization method. Among them, regarding the anionic living polymerization method, the polymerization active species is anion, which is represented by the following flowchart, for example.

[Chemical 36]

In the above process, 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 respectively integers above 1.

Regarding the free radical living polymerization method, the polymerization active species is a free radical, and is represented by the following scheme, for example.

[Chemical 37]

In the above process, Ar ¹ is a monovalent organic group, Ar ² is a monovalent organic group different from Ar ¹ , j and k are respectively integers above 1, R ^a is a hydrogen atom or a monovalent organic group, and R ^b is Different from the hydrogen atom or monovalent organic group of R ^a .

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

The acrylic polymer dispersant that can be used in the present invention can be an A-B block copolymer or a B-A-B block copolymer. The A block/B block ratio constituting the copolymer is preferably 1/99 to 80. /20, particularly preferably 5/95 to 60/40 (mass ratio). By setting it within this range, a balance between dispersibility and storage stability tends to be ensured. In addition, the amount of the quaternary ammonium salt group in 1 g of the A-B block copolymer and B-A-B block copolymer that can be used in the present invention is usually 0.1 to 10 mmol. By setting it within this range, there is Can ensure good dispersion tendency.

Furthermore, such block copolymers often contain amine groups generated during the manufacturing process. The amine value is about 1 to 100 mgKOH/g. From the viewpoint of dispersion, 10 is preferred. mgKOH/g or more, more preferably 30 mgKOH/g or more, further preferably 50 mgKOH/g or more, and preferably 90 mgKOH/g or less, more preferably 80 mgKOH/g or less, still more preferably 75 mgKOH /g or less. For example, 10 to 90 mgKOH/g is preferred, 30 to 80 mgKOH/g is more preferred, and 50 to 75 mgKOH/g is still more preferred. Here, the amine value of dispersants such as block copolymers is expressed by the mass of KOH equivalent to the amount of alkali per 1 g of solid components other than solvent in the dispersant sample, and is expressed by the following method to measure. Accurately weigh 0.5 to 1.5 g of the dispersant sample and place it in a 100 mL beaker, and dissolve it with 50 mL of acetic acid. Use an automatic titration device equipped with a pH value electrode to neutralize and titrate the solution with 0.1 mol/L HClO ₄ acetic acid solution. Set the inflection point of the titration pH curve as the titration end point, and calculate the amine value by the following formula.

Amine value [mgKOH/g]=(561×V)/(W×S) [Wherein, W: represents the weighed amount of the dispersant sample [g], V: represents the titration amount at the titration end point [mL], S: represents the solid content concentration of the dispersant sample [mass %]] In addition, the acid value of the block copolymer also depends on the presence and type of the acidic group that forms the basis of the acid value. Generally, it is preferably lower, usually 10 mgKOH/g or less, and its weight average molecular weight (Mw) is relatively low. The preferred range is 1,000 to 100,000. By setting it within the above range, good dispersibility tends to be ensured.

When the acrylic polymer dispersant has a quaternary ammonium salt group as a functional group, the specific structure of the acrylic polymer dispersant is not particularly limited. From the viewpoint of dispersion, it is preferred to have the following formula The repeating unit represented by (i) (hereinafter, may be referred to as "repeating unit (i)").

[Chemical 38]

In the above formula (i), R ³¹ to R ³³ are each independently a hydrogen atom, an alkyl group which may have a substituent, an aryl group which may have a substituent, or an aralkyl group which may have a substituent, and R ³¹ to R ³³ Two or more of them can bond with each other to form a cyclic structure. R ³⁴ is a hydrogen atom or a methyl group. X is a divalent linking group, and Y ^- is a counter anion.

The carbon number of the optionally substituted alkyl group among R ³¹ to R ³³ in the above formula (i) is not particularly limited, but is usually 1 or more, preferably 10 or less, and more preferably 6 or less. For example, 1 to 10 are preferred, and 1 to 6 are more preferred. Specific examples of the alkyl group include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, and the like. Among these, methyl, ethyl, and propyl are preferred. group, butyl, pentyl, or hexyl, more preferably methyl, ethyl, propyl, or butyl. Moreover, it may be either linear or branched. Furthermore, cyclic structures such as cyclohexyl group and cyclohexylmethyl group may be included.

The carbon number of the aryl group which may have a substituent among R ³¹ to R ³³ in the above formula (i) is not particularly limited, but is usually 6 or more, preferably 16 or less, and more preferably 12 or less. For example, 6 to 16 are preferred, and 6 to 12 are more preferred. Specific examples of the aryl group include phenyl, methylphenyl, ethylphenyl, dimethylphenyl, diethylphenyl, naphthyl, and anthracenyl. Among these, preferred It is phenyl, methylphenyl, ethylphenyl, dimethylphenyl or diethylphenyl, more preferably phenyl, methylphenyl or ethylphenyl.

The carbon number of the optionally substituted aralkyl group among R ³¹ to R ³³ in the above formula (i) is not particularly limited, but is usually 7 or more, preferably 16 or less, and more preferably 12 or less. For example, 7 to 16 are preferred, and 7 to 12 are more preferred. Specific examples of the aralkyl group include phenylmethyl (benzyl), phenylethyl (phenylethyl), phenylpropyl, phenylbutyl, phenylisopropyl, etc. Among them, phenylmethyl, phenylethyl, phenylpropyl, or phenylbutyl is preferred, and phenylmethyl or phenylethyl is more preferred.

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

In addition, when the acrylic polymer dispersant has a tertiary amine as a functional group, from the viewpoint of dispersibility, it is preferable to have a repeating unit represented by the following formula (ii) (hereinafter, sometimes referred to as is "repeating unit (ii)").

[Chemical 39]

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

In addition, 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 used. Similarly, as the aryl group which may have a substituent in R ³⁵ and R ³⁶ of the above formula (ii), those exemplified as R ³¹ to R ³³ of the above formula (i) are preferably used. In addition, 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 used.

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

Examples of substituents that the alkyl group, aralkyl group or aryl group in R ³¹ to R ³³ in the above formula (i) and R ³⁵ and R ³⁶ in the above formula (ii) may have include: halogen atom, alkoxy base, benzyl group, hydroxyl group, etc.

In the above formulas (i) and (ii), examples of the divalent linking groups X and Z include an alkylene group having 1 to 10 carbon atoms, an aryl group having 6 to 12 carbon atoms, and -CONH-R. ⁴³ -yl, -COOR ⁴⁴ -yl [wherein R ⁴³ and R ⁴⁴ are a single bond, an alkylene group with 1 to 10 carbon atoms, or an ether group (alkoxyalkyl group with 2 to 10 carbon atoms)], etc., Preferred is -COO-R ⁴⁴ - group. In addition, in the above formula (i), examples of Y ^- as the counter anion include Cl ^- , Br ^- , I ^- , ClO ₄ ^- , BF ₄ ^- , CH ₃ COO ^- , PF ₆ ^- , etc.

The content ratio of the repeating unit represented by the above formula (i) is not particularly limited. From the viewpoint of dispersibility, the content ratio of the repeating unit represented by the above formula (i) is different from that represented by the above formula (ii). The total content ratio of the repeating units is preferably 60 mol% or less, more preferably 50 mol% or less, further preferably 40 mol% or less, particularly preferably 35 mol% or less, and more preferably 5 mol% or more, more preferably 10 mol% or more, further preferably 20 mol% or more, especially 30 mol% or more.

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

In addition, 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 from the viewpoint of dispersibility, it is preferably 5 mol% or more, more preferably It is preferably 10 mol% or more, more preferably 15 mol% or more, especially 20 mol% or more, and preferably 60 mol% or less, more preferably 40 mol% or less, still more preferably It is 30 mol% or less, and it is especially preferable that it is 25 mol% or less. For example, it is preferably 5 to 60 mol%, more preferably 10 to 40 mol%, further preferably 15 to 30 mol%, and particularly preferably 20 to 25 mol%.

Furthermore, from the viewpoint of improving compatibility with binder components such as solvents and improving dispersion stability, the polymer dispersant preferably has a repeating unit represented by the following formula (iii) (hereinafter, sometimes referred to as " Repeating unit (iii)").

[Chemical 40]

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

The carbon number of the optionally substituted alkyl group in R ⁴¹ of the above formula (iii) is not particularly limited, but is usually 1 or more, preferably 2 or more, and preferably 10 or less, more preferably 6 or less. For example, 1 to 10 are preferred, 1 to 6 are more preferred, and 2 to 6 are even more preferred. Specific examples of the alkyl group include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, and the like. Among these, methyl, ethyl, and propyl are preferred. group, butyl, pentyl, or hexyl, more preferably methyl, ethyl, propyl, or butyl. Moreover, it may be either linear or branched. Furthermore, cyclic structures such as cyclohexyl group and cyclohexylmethyl group may be included.

Furthermore, n in the above formula (iii) is preferably 1 or more, more preferably 2 or more, and more preferably 10 or less from the viewpoint of compatibility and dispersibility with binder components such as solvents. More preferably, it is less than 5. For example, 1 to 10 are preferable, 1 to 5 are more preferable, and 2 to 5 are still more preferable.

In addition, the content ratio of the repeating unit represented by the above formula (iii) in the total repeating units of the polymer dispersant is not particularly limited, but is preferably 1 mol% or more, more preferably 2 mol% or more. Furthermore, it is preferably 4 mol% or more, further preferably 30 mol% or less, more preferably 20 mol% or less, still more preferably 10 mol% or less. For example, it is preferably 1 to 30 mol%, more preferably 2 to 20 mol%, and still more preferably 4 to 10 mol%. Within the above range, there is a tendency to achieve both compatibility with binder components such as solvents and dispersion stability.

In addition, from the viewpoint of improving the compatibility of the dispersant with binder components such as solvents and improving the dispersion stability, the polymer dispersant preferably has a repeating unit represented by the following formula (iv) (hereinafter sometimes referred to as is "repeating unit (iv)").

[Chemical 41]

In the above formula (iv), R ³⁸ represents 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 carbon number of the alkyl group which may have a substituent in R ³⁸ of the above formula (iv) is not particularly limited, but is usually 1 or more, preferably 2 or more, more preferably 4 or more, and preferably 10 or less. More preferably, it is 8 or less. For example, 1 to 10 are preferable, 1 to 8 are more preferable, 2 to 8 are still more preferable, and 4 to 8 are still more preferable. Specific examples of the alkyl group include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, and the like. Among these, methyl, ethyl, and propyl are preferred. group, butyl, pentyl, or hexyl, more preferably methyl, ethyl, propyl, or butyl. Moreover, it may be either linear or branched. Furthermore, cyclic structures such as cyclohexyl group and cyclohexylmethyl group may be included.

The carbon number of the aryl group which may have a substituent in R ³⁸ of the above formula (iv) is not particularly limited, but is usually 6 or more, preferably 16 or less, more preferably 12 or less, still more preferably 8 or less. . For example, 6 to 16 are preferred, 6 to 12 are more preferred, and 6 to 8 are still more preferred. Specific examples of the aryl group include phenyl, methylphenyl, ethylphenyl, dimethylphenyl, diethylphenyl, naphthyl, and anthracenyl. Among these, preferred It is phenyl, methylphenyl, ethylphenyl, dimethylphenyl or diethylphenyl, more preferably phenyl, methylphenyl or ethylphenyl.

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, more preferably 12 or less, still more preferably 10 the following. For example, 7 to 16 are preferred, 7 to 12 are more preferred, and 7 to 10 are still more preferred. Specific examples of the aralkyl group include phenylmethyl, phenylethyl, phenylpropyl, phenylbutyl, and phenylisopropyl. Among these, phenylmethyl is preferred. base, phenylethyl, phenylpropyl, or phenylbutyl, more preferably phenylmethyl or phenylethyl.

Among them, 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 substituents that the alkyl group in R ³⁸ may have include a halogen atom, an alkoxy group, and the like. In addition, examples of substituents that the aryl group or aralkyl group may have include chain alkyl groups, halogen atoms, alkoxy groups, and the like. Furthermore, the chain alkyl group represented by R ³⁸ includes both linear and branched chains.

In addition, the content ratio of the repeating unit represented by the above formula (iv) in the total repeating units of the polymer dispersant is preferably 30 mol% or more, and more preferably 40 mol% from the viewpoint of dispersion. Mol% or more, more preferably 50 mol% or more, and preferably 80 mol% or less, more preferably 70 mol% or less. For example, it is preferably 30 to 80 mol%, more preferably 40 to 80 mol%, and still more preferably 50 to 70 mol% or more.

The polymer dispersant may have repeating units other than repeating unit (i), repeating unit (ii), repeating unit (iii) and repeating unit (iv). Examples of such repeating units include styrene-based monomers such as styrene and α-methylstyrene; (meth)acrylate-based monomers such as (meth)acrylic acid chloride; ) Acrylamide, N-hydroxymethylacrylamide and other (meth)acrylamide-based monomers; vinyl acetate; acrylonitrile; allyl glycidyl ether, crotonic acid glycidyl ether; N-methyl Repeating unit of monomers such as acryloyl 𠰌line.

From the viewpoint of further improving dispersion, the polymer dispersant is preferably one that has an A block having repeating units (i) and repeating units (ii), and one that does not have repeating units (i) and repeating units (ii). B block block copolymer. The block copolymer is preferably an A-B block copolymer or a B-A-B block copolymer. By introducing not only quaternary ammonium salt groups but also tertiary amine groups into the A block, the dispersing ability of the dispersant tends to be significantly improved unexpectedly. Moreover, it is preferable that the B block has a repeating unit (iii), and it is more preferable that it has a repeating unit (iv).

In the A block, the repeating unit (i) and the repeating unit (ii) can be contained in any form of random copolymerization or block copolymerization. In addition, the repeating unit (i) and the repeating unit (ii) may each contain two or more types in one A block. In this case, each repeating unit may be randomly copolymerized or block copolymerized in the A block. Contains any form.

In addition, repeating units other than repeating unit (i) and repeating unit (ii) may be contained in the A block. Examples of such repeating units include repeating units derived from the above-mentioned (meth)acrylate monomers. Unit etc. The content ratio of repeating units other than repeating unit (i) and repeating unit (ii) in the A block is preferably 0 to 50 mol%, more preferably 0 to 20 mol%, and the repeating unit is preferably not Contained in the A block.

Repeating units other than repeating units (iii) and (iv) may be contained in the B block. Examples of such repeating units include styrene-based monomers such as styrene and α-methylstyrene; (Meth)acrylamide-based monomers such as (meth)acrylyl chloride; (meth)acrylamide-based monomers such as (meth)acrylamide and N-hydroxymethylacrylamide; vinyl acetate; Acrylonitrile; allyl glycidyl ether, crotonic acid glycidyl ether; repeating unit of N-methacrylyl noline and other monomers. The content of repeating units other than repeating unit (iii) and repeating unit (iv) in the B block is preferably 0 to 50 mol%, more preferably 0 to 20 mol%, and the repeating unit is preferably free of in the B block.

In addition, from the viewpoint of improving dispersion stability, the (f) dispersant is preferably used in combination with the following pigment derivative.

＜Other ingredients of the photosensitive coloring composition＞ In the photosensitive coloring composition of the present invention, in addition to the above-mentioned components, adhesion improving agents such as silane coupling agents, surfactants (coatability improving agents), pigment derivatives, photoacid generators, crosslinking agents, etc. can be suitably blended. additives such as agents, sulfhydryl compounds, polymerization inhibitors, development improvers, ultraviolet absorbers, and antioxidants.

(1) Close contact enhancer The photosensitive coloring composition of the present invention may contain an adhesion improving agent in order to improve the adhesion with the substrate. As the close contact improving agent, silane coupling agents, phosphate group-containing compounds, etc. are preferred. As the type of silane coupling agent, one of various types such as epoxy type, (meth)acrylic type, and amino type may be used alone, or two or more types may be mixed and used.

Preferred silane coupling agents include (meth)acrylates such as 3-methacryloxypropylmethyldimethoxysilane and 3-methacryloxypropyltrimethoxysilane. Dihydryloxysilanes; 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethyl Epoxysilanes such as oxysilanes and 3-glycidoxypropyltriethoxysilane; ureidosilanes such as 3-ureidopropyltriethoxysilane; 3-isocyanatepropyltriethoxysilane Silane coupling agents such as isocyanate silanes, especially epoxy silanes. As the phosphate group-containing compound, a (meth)acrylyl group-containing phosphate ester is preferred, and one represented by the following general formula (g1), (g2) or (g3) is preferred.

[Chemical 42]

In the above general formulas (g1), (g2) and (g3), R ⁵¹ represents a hydrogen atom or a methyl group, l and l' are integers from 1 to 10, and m is 1, 2 or 3. These phosphate 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, various surfactants such as anionic, cationic, nonionic, and amphoteric surfactants can be used. Among them, it is preferable to use nonionic surfactants in terms of low possibility of adversely affecting various properties. Among them, fluorine-based or silicon-based surfactants are more effective in terms of coatability. Examples of such surfactants include TSF4460 (manufactured by Momentive Performance Materials), DFX-18 (manufactured by NEOS), BYK-300, BYK-325, BYK-330 (manufactured by BYK-Chemie), and KP340 (manufactured by Shin-Etsu Silicones Co., Ltd.), MEGAFAC (registered trademark, the same below) F-470, MEGAFAC F-475, MEGAFAC F-478, MEGAFAC F-554, MEGAFAC F-559 (manufactured by DIC Corporation), SH7PA (Dow Corning Toray Co., Ltd.), DS-401 (Daikin Co., Ltd.), L-77 (Nippon Unicar Co., Ltd.), FC4430 (3M Co., Ltd.), etc. In addition, one type of surfactant may be used, and two or more types of surfactants may be used in combination in any combination and ratio.

(3)Pigment derivatives The photosensitive coloring composition of the present invention may contain a pigment derivative as a dispersion aid in order to improve dispersibility and storage properties. Examples of pigment derivatives include azo-based, phthalocyanine-based, quinacridone-based, benzimidazolone-based, quinphthalone-based, isoindolinone-based, bistriol-based, anthraquinone-based, and indene-based pigments. Derivatives such as anthracene series, perylene series, iconone series, diketopyrrolopyrrole series, diketopyrrolide series, etc., among which the phthalocyanine series and quinophthalone series are preferred. Examples of substituents of the pigment derivative include sulfonic acid group, sulfonamide group and its quaternary salt, phthalimide methyl group, dialkylaminoalkyl group, hydroxyl group, carboxyl group, and amide group. Those bonded to the pigment skeleton directly or via alkyl groups, aryl groups, heterocyclic groups, etc. are preferably sulfonic acid groups. In addition, these substituents may substitute multiple substituents on one pigment skeleton.

Specific examples of the pigment derivatives include: phthalocyanine sulfonic acid derivatives, quinphthalone sulfonic acid derivatives, anthraquinone sulfonic acid derivatives, quinacridone sulfonic acid derivatives, pyrrolopyrrole di Sulfonic acid derivatives of ketone, sulfonic acid derivatives of dimethacin, etc. One type of these may be used alone, or two or more types may be used in combination.

(4) Photoacid generator The so-called photoacid generator is a compound that can generate an acid using ultraviolet rays, and a cross-linking reaction is carried out by the action of the acid generated during exposure, for example, by the presence of a cross-linking agent such as a melamine compound. Among the photoacid generators, those with greater solubility in solvents, particularly those with greater solubility in solvents used for photosensitive coloring compositions, are preferably exemplified by diphenylphosphonium and xylene. Base iodide, phenyl (p-anisyl) iodide, bis (m-nitrophenyl) iodide, bis (p-tert-butylphenyl) iodide, bis (p-chlorophenyl) iodide, bis (n-dodecyl) ) chloride or bromide of diaryl sulfonium, such as p-isobutylphenyl (p-tolyl) sulfonium, p-isopropylphenyl (p-tolyl) sulfonium or other diarylsulfonium, or triphenylsulfonium or other triarylsulfonium, Or boron fluoride salt, hexafluorophosphate, hexafluoroarsenate, aromatic sulfonate, tetrakis(pentafluorophenyl)borate ester salt, etc. or diphenylbenzoyl methylsulfonium (n-butyl) Triphenylate and other sulfonium organoboron complexes, or 2-methyl-4,6-bis(trichloromethyl)trisulfate, 2-(4-methoxyphenyl)-4,6- Bis(trichloromethyl)trifluoroethylene and other bistrifluoroethylene compounds, but are not limited thereto.

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

[Chemical 43]

In formula (6), R ⁶¹ represents a -NR ⁶⁶ R ⁶⁷ group or an aryl group having 6 to 12 carbon atoms. When R ⁶¹ is a -NR ⁶⁶ R ⁶⁷ group, R ⁶² , R ⁶³ , R ⁶⁴ , and R ⁶⁵ , one of R ⁶⁶ and R ⁶⁷ represents a CH ₂ OR ⁶⁸ group, and when R ⁶¹ is an aryl group having 6 to 12 carbon atoms, one of R ⁶² , R ⁶³ , R ⁶⁴ and R ⁶⁵ represents -CH ₂ OR ⁶⁸ group, the rest of R ⁶² , R ⁶³ , R ⁶⁴ , R ⁶⁵ , R ⁶⁶ and R ⁶⁷ independently represent hydrogen or -CH ₂ OR ⁶⁸ group, R ⁶⁸ represents a hydrogen atom or an alkane with 1 to 4 carbon atoms. base. Here, the aryl group having 6 to 12 carbon atoms is typically a phenyl group, 1-naphthyl group or 2-naphthyl group, and the phenyl group or naphthyl group may be substituted by an alkyl group, an alkoxy group, a halogen atom, etc. base. The alkyl group and the alkoxy group may each have about 1 to 6 carbon atoms. Among the above, the alkyl group represented by R ⁶⁸ is preferably methyl or ethyl, especially methyl.

The melamine-based compounds conforming to the general formula (6), that is, the compounds of the following general formula (6-1), include hexamethylolmelamine, pentamethylolmelamine, tetramethylolmelamine, and hexamethoxymethyl Melamine, pentamethoxymethylmelamine, tetramethoxymethylmelamine, hexaethoxymethylmelamine, etc.

[Chemical 44]

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 represents a -CH ₂ OR ⁶⁸ group, and the rest of R ⁶² , R ⁶³ , R ⁶⁴ , R ⁶⁵ , R ⁶⁶ and R ⁶⁷ independently represent a hydrogen atom or a -CH ₂ OR ⁶⁸ group, where R ⁶⁸ represents a hydrogen atom or alkyl.

Moreover, among the guanamine-based compounds conforming to the general formula (6), that is, the compounds in which R ⁶¹ in the general formula (6) is an aryl group, tetrahydroxymethylbenzoguanamine, tetramethoxymethylbenzo Guanamine, trimethoxymethylbenzoguanamine, tetraethoxymethylbenzoguanamine, etc.

Furthermore, a cross-linking agent having a hydroxymethyl or hydroxymethyl alkyl ether group can also be used. Examples are given below. 2,6-bis(hydroxymethyl)-4-methylphenol, 4-tert-butyl-2,6-bis(hydroxymethyl)phenol, 5-ethyl-1,3-bis(hydroxymethyl) Perhydro-1,3,5-tris-2-one (commonly known as N-ethyl dihydroxymethyl tris-one) or its dimethyl ether form, dimethylol trimethylene urea or its dimethyl ether form , 3,5-bis(hydroxymethyl)perhydro-1,3,5-dihydroxymethylglyoxal-4-one (commonly known as dihydroxymethylfurfural) or its dimethyl ether, tetrahydroxymethylglyoxal Dialkyl urea or its tetramethyl ether.

In addition, these cross-linking agents may be used individually by 1 type, and may be used in combination of 2 or more types. The amount when using a crosslinking agent 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 compounds In addition, in order to improve the hardenability and surface roughness of the surface of the cured product, a mercapto compound may be added as a polymerization accelerator. Examples of the mercapto compound include mercapto group-containing compounds having an aromatic ring and aliphatic mercapto group-containing compounds.

As the mercapto group-containing compound having an aromatic ring, a compound represented by the following general formula (1-3) can be suitably used from the viewpoint of photocurability.

[Chemical 45]

In formula (1-3), Z represents -O-, -S- or -NH-, and R ⁶¹ , R ⁶² , R ⁶³ , and R ⁶⁴ each independently represent a hydrogen atom or a monovalent substituent. Among these, from the viewpoint of photohardenability, Z is preferably -S- or -NH-, and more preferably -NH-. Furthermore, from the viewpoint of photohardenability, R ⁶¹ , R ⁶² , R ⁶³ , and R ⁶⁴ are preferably each independently a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or an alkoxy group having 1 to 4 carbon atoms. More preferably, it is a hydrogen atom.

Specific examples include: 2-mercaptobenzothiazole, 2-mercaptobenzimidazole, 2-mercaptobenzoethazole, 3-mercapto-1,2,4-triazole, 2-mercapto-4(3H )-Quazoline, β-mercaptonaphthalene, 1,4-dimethylmercaptobenzene and other mercapto group-containing compounds with aromatic rings. From the viewpoint of the cone angle, 2-mercaptobenzothiazole, 2 -Mercaptobenzimidazole.

On the other hand, as the aliphatic mercapto group-containing compound, from the viewpoint of photocurability, hexanedithiol, decanedithiol, or those represented by the following general formula (1-4) can be suitably used. compound.

[Chemical 46]

In formula (1-4), m represents an integer from 0 to 4, and n represents an integer from 2 to 4. R ⁷¹ and R ⁷² each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. X represents n valence basis.

In the above general formula (1-4), m is preferably 1 or 2 from the viewpoint of photocurability. Moreover, from the viewpoint of photohardenability, n is preferably 3 or 4, more preferably 4. In addition, the alkyl groups of R ⁷¹ and R ⁷² are preferably those having 1 to 3 carbon atoms from the viewpoint of photocurability. From the viewpoint of photohardenability, at least one of R ⁷¹ and R ⁷² is preferred. For example, R ⁷² is a hydrogen atom. In this case, R ⁷¹ is preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. .

When n is 2, from the viewpoint of photocurability, X is preferably an alkylene group having 1 to 6 carbon atoms which may have an ether bond and/or a branch part. From the viewpoint of photohardenability, an alkylene group having 1 to 6 carbon atoms is more preferred, and an alkylene group having 4 carbon atoms is even more preferred.

When n is 3, from the viewpoint of photohardenability, X preferably has a structure represented by the following general formula (1-5) or (1-6).

[Chemical 47]

In formula (1-5), R ⁷³ represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a hydroxymethyl group. Among R ⁷³ , from the viewpoint of photocurability, ethyl group is preferred.

[Chemical 48]

In formula (1-6), R ⁷⁴ represents an alkylene group having 1 to 4 carbon atoms. Among R ⁷⁴ , from the viewpoint of photocurability, ethylidene is preferred.

On the other hand, when n is 4, X preferably has a structure represented by the following general formula (1-7).

[Chemical 49]

Specific examples include butanediol bis(3-mercaptopropionate), butylene glycol bismercaptoacetate, ethylene glycol bis(3-mercaptopropionate), and ethylene glycol bismercaptoacetate. , Trimethylolpropane Tris(3-Mercaptopropionate), Trimethylolpropane Trimercaptoacetate, Trihydroxyethyl Trithiopropionate, Pentaerythritol Tetrakis(3-Mercaptopropionate), Pentaerythritol Tris(3-mercaptobutyrate), butylene glycol bis(3-mercaptobutyrate), ethylene glycol bis(3-mercaptobutyrate), trimethylolpropane tris(3-mercaptobutyrate) , Pentaerythritol tetrakis (3-mercaptobutyrate), pentaerythritol tris (3-mercaptobutyrate), 1,3,5-tris(3-mercaptobutoxyethyl)-1,3,5-tris𠯤- 2,4,6(1H,3H,5H)-triketone, etc.

Among them, preferred are trimethylolpropane tris(3-mercaptopropionate), pentaerythritol tetrakis(3-mercaptopropionate), pentaerythritol tris(3-mercaptopropionate), and trimethylolpropane tris(3-mercaptopropionate). -Mercaptobutyrate), pentaerythritol tetrakis (3-mercaptobutyrate), pentaerythritol tris (3-mercaptobutyrate), 1,3,5-tris(3-mercaptobutoxyethyl)-1,3 , 5-tris-2,4,6(1H,3H,5H)-trione, more preferably pentaerythritol tetrakis (3-mercaptopropionate) and pentaerythritol tetrakis (3-mercaptobutyrate).

These can be used individually by 1 type, or in mixture of 2 or more types.

Among these, from the viewpoint of photocurability, a combination of one selected from the group consisting of 2-mercaptobenzothiazole, 2-mercaptobenzimidazole, and 2-mercaptobenzoethazole is more suitable. The above and photopolymerization initiator are used as photopolymerization initiator system. For example, 2-mercaptobenzothiazole can be used, 2-mercaptobenzimidazole can be used, or 2-mercaptobenzothiazole and 2-mercaptobenzimidazole can be used in combination. Moreover, from the viewpoint of photocurability, it is preferable to use one or more types selected from the group consisting of pentaerythritol tetrakis (3-mercaptopropionate) and pentaerythritol tetrakis (3-mercaptobutyrate).

Furthermore, especially from the viewpoint of photocurability, it is more suitable to use a mercapto group-containing compound having an aromatic ring and an aliphatic mercapto group-containing compound in combination. The reason for this is that by using a mask with a narrow opening, the illumination per unit area is reduced due to diffraction during exposure, and it is more susceptible to the influence of oxygen suppression than when the line width is thicker, resulting in surface Tendency to reduce hardenability.

Particularly when a hexaarylbiimidazole-based photopolymerization initiator is used as (c) the photopolymerization initiator, it is more suitable to use a mercapto group-containing compound having an aromatic ring and an aliphatic mercapto group-containing compound in combination. And use. On the other hand, when an acetophenone-based photopolymerization initiator is used, sufficient effects tend to be obtained even when an aliphatic mercapto group-containing compound is used alone.

For example, it is preferable to combine at least one selected from the group consisting of 2-mercaptobenzothiazole, 2-mercaptobenzimidazole, and 2-mercaptobenzoethazole, and one selected from the group consisting of pentaerythritol tetrakis(3-mercaptopropionic acid) It is used at least one of the group consisting of ester), pentaerythritol tetrakis (3-mercaptobutyrate), and a photopolymerization initiator.

(7)Polymerization inhibitor From the viewpoint of controlling the shape, a polymerization inhibitor may be contained. Examples of polymerization inhibitors include hydroquinone, hydroquinone monomethyl ether, methyl hydroquinone, methoxyphenol, and 2,6-di-tert-butyl-4-cresol (BHT )wait. Among these, from the viewpoint of shape control, 2,6-di-tert-butyl-4-cresol is preferred. Furthermore, from the viewpoint of safety to the human body, hydroquinone monomethyl ether and methyl hydroquinone are preferred. The polymerization inhibitor may contain one type or two or more types. When producing the alkali-soluble resin (b), the polymerization inhibitor may be included in the resin. This can be used as the polymerization inhibitor of the present invention, or the polymerization inhibitor can be removed from the resin when producing the photosensitive coloring composition. In addition to this, the same or different polymerization inhibitor is added.

<Amounts of ingredients in the photosensitive coloring composition> In the photosensitive coloring composition of the present invention, the content ratio of (b) alkali-soluble resin is not particularly limited, but it is usually 5 mass % or more, preferably 10 mass % or more, and more preferably 15 mass % in the total solid content. Mass % or more, more preferably 20 mass % or more, especially 25 mass % or more, and usually 80 mass % or less, preferably 70 mass % or less, more preferably 60 mass % or less, further preferably 50 mass % % by mass or less, more preferably 40 % by mass or less, still more preferably 35 % by mass or less. For example, 5 to 80 mass % is preferred, 5 to 70 mass % is more preferred, 10 to 60 mass % is still more preferred, 15 to 50 mass % is still more preferred, and 20 to 40 mass % is particularly preferred. Particularly preferred is 25 to 35% by mass. By setting the content ratio of (b) the alkali-soluble resin to not less than the above-mentioned lower limit, the development solubility tends to be improved. Furthermore, by setting it below the above-mentioned upper limit value, mechanical characteristics tend to be improved.

(c) The content ratio of the photopolymerization initiator is not particularly limited, but it is usually 0.1% by mass or more, preferably 0.5% by mass or more, more preferably 1% by mass or more, and still more preferably 1.5% by mass in the total solid content. Mass% or more, usually 15 mass% or less, preferably 10 mass% or less, more preferably 8 mass% or less, further preferably 6 mass% or less, particularly preferably 4 mass% or less. For example, 0.1 to 15 mass % is preferred, 0.1 to 10 mass % is more preferred, 0.5 to 8 mass % is more preferred, 1 to 6 mass % is particularly preferred, and 1.5 to 4 mass % is particularly preferred. By setting the content ratio of the photopolymerization initiator (c) to the above-mentioned lower limit value or more, the photocurability tends to be improved and the surface roughness is improved, and by setting the content ratio of the (c) photopolymerization initiator to the above-mentioned upper limit value or less, the development solubility is improved. tendency to improve.

When a polymerization accelerator is used together with (c) the photopolymerization initiator, the content ratio of the polymerization accelerator is preferably 0.05 mass in the total solid content of the photosensitive coloring composition of the present invention. % or more, usually 10 mass% or less, preferably 5 mass% or less, for example, 0.05 to 10 mass%, preferably 0.05 to 5 mass%. Moreover, the polymerization accelerator is usually used at a ratio of 0.1 to 50 parts by mass, preferably 0.1 to 20 parts by mass relative to 100 parts by mass of the (c) photopolymerization initiator. By setting the content ratio of the polymerization accelerator to not less than the above-mentioned lower limit, it is possible to suppress the tendency of the sensitivity to exposure light to decrease, and by setting it to not more than the above-mentioned upper limit, it is possible to suppress the development of unexposed parts. The solubility in liquid is reduced and the tendency of poor development is suppressed.

Furthermore, when a sensitizing dye is used together with (c) the photopolymerization initiator, the content ratio of the sensitizing dye in the total solid content of the photosensitive coloring composition of the present invention is preferably 0.1 mass% or more, more preferably 0.2 mass% or more, further preferably 0.3 mass% or more, and preferably 5 mass% or less, more preferably 4 mass% or less, still more preferably 3 mass% or less. For example, the content is preferably 0.1 to 5 mass%, more preferably 0.2 to 4 mass%, and still more preferably 0.3 to 3 mass%. When the value is equal to or higher than the above-mentioned lower limit, the photocurability tends to be improved and the surface roughness is improved, and when the value is equal to or less than the above-mentioned upper limit, the development solubility tends to be improved.

The content ratio of (d) the ethylenically unsaturated compound is usually 1 mass % or more, preferably 5 mass % or more, and more preferably 10 mass % in the total solid content of the photosensitive coloring composition of the present invention. or above, more preferably 20 mass% or more, more preferably 30 mass% or more, particularly preferably 40 mass% or more, most preferably 50 mass% or more, and usually 80 mass% or less, preferably 70 mass% or less, more preferably 65% by mass or less. For example, 1 to 80 mass % is preferred, 5 to 80 mass % is more preferred, 10 to 70 mass % is still more preferred, 20 to 70 mass % is still more preferred, and 30 to 70 mass % is particularly preferred. Particularly preferably, it is 40 to 65% by mass, and most preferably 50 to 65% by mass or more. By setting the content ratio of the ethylenically unsaturated compound (d) to the above lower limit value or more, the mechanical properties tend to be improved, and by setting the content ratio of the ethylenically unsaturated compound (d) to the above upper limit value or below, the development solubility tends to be improved.

On the other hand, the content ratio of (b) alkali-soluble resin to 100 parts by mass of (d) ethylenically unsaturated compound is not particularly limited, but is preferably 10 parts by mass or more, more preferably 20 parts by mass or more, and still more preferably It is 30 parts by mass or more, preferably 40 parts by mass or more, and usually 150 parts by mass or less, preferably 120 parts by mass or less, more preferably 100 parts by mass or less, and still more preferably 70 parts by mass or less. For example, 10 to 150 parts by mass is preferred, 20 to 120 parts by mass is more preferred, 30 to 100 parts by mass is further preferred, and 40 to 70 parts by mass is particularly preferred. By setting it as above the said lower limit value, the development solubility tends to improve, and by setting it as below the said upper limit value, the mechanical characteristics tend to become favorable.

Furthermore, in the photosensitive coloring composition of the present invention, by using (e) the solvent, the content ratio of the total solid content is usually 5 mass % or more, preferably 10 mass % or more, more preferably 15 mass % or more. Moreover, it is usually formulated so that it may become 50 mass % or less, Preferably it is 30 mass % or less, More preferably, it is 25 mass % or less. For example, 5 to 50 mass% is preferred, 10 to 30 mass% is more preferred, and 15 to 25 mass% is still more preferred.

When the photosensitive coloring composition of the present invention contains the (f) dispersant, the content ratio of the (f) dispersant in the total solid content of the photosensitive coloring composition is usually 0.5 mass % or more, preferably 1 mass% or more, more preferably 1.5 mass% or more, and usually 30 mass% or less, preferably 20 mass% or less, more preferably 15 mass% or less, further preferably 10 mass% or less, particularly preferably 5% by mass or less. For example, 0.5 to 30 mass% is preferred, 0.5 to 20 mass% is more preferred, 1 to 15 mass% is still more preferred, 1 to 10 mass% is still more preferred, and 1.5 to 5 mass% is particularly preferred. By setting the content ratio of the dispersing agent (f) to the above lower limit value or more, the storage stability tends to be improved, and by setting the content ratio of the dispersant (f) to the above upper limit value or less, the display reliability tends to be improved.

Moreover, the content ratio of the (f) dispersant with respect to 100 parts by mass of the (a) colorant is usually 5 parts by mass or more, more preferably 10 parts by mass or more, further preferably 20 parts by mass or more, and usually 50 parts by mass. or less, particularly preferably 40 parts by mass or less. For example, 5 to 50 parts by mass is preferable, 10 to 50 parts by mass is more preferable, and 20 to 40 parts by mass is still more preferable. By setting the content ratio of the dispersing agent (f) to the above lower limit value or more, the storage stability tends to be improved, and by setting the content ratio of the dispersant (f) to the above upper limit value or less, the display reliability tends to be improved.

When an adhesive improving agent is used, its content ratio in the total solid content of the photosensitive coloring composition is usually 0.1 mass% or more, preferably 0.2 mass% or more, more preferably 0.5 mass% or more, and, It is usually 30 mass% or less, preferably 20 mass% or less, more preferably 10 mass% or less, further preferably 5 mass% or less, particularly preferably 3 mass% or less. For example, 0.1 to 30 mass% is preferred, 0.2 to 20 mass% is more preferred, 0.2 to 10 mass% is still more preferred, 0.5 to 5 mass% is still more preferred, and 0.5 to 3 mass% is particularly preferred. By setting the content ratio of the adhesion improving agent to be equal to or greater than the above-mentioned lower limit, adhesion tends to be improved, and by being equal to or less than the above-mentioned upper limit, residues tend to be reduced.

Moreover, when a surfactant is used, its content ratio in the total solid content of the photosensitive coloring composition is usually 0.001 to 10 mass %, preferably 0.005 to 1 mass %, and further preferably 0.01 to 1 mass %. 0.5% by mass, preferably 0.03 to 0.3% by mass. By setting the content ratio of the surfactant above the above lower limit, the smoothness and uniformity of the coating film tend to be easily expressed, and by setting the content ratio below the above upper limit, the smoothness and uniformity of the coating film tend to be easily expressed. The smoothness and uniformity of the film can also inhibit the deterioration of other characteristics.

When a mercapto compound is used, its content ratio in the total solid content of the photosensitive coloring composition is usually 0.1 mass% or more, preferably 0.2 mass% or more, more preferably 0.5 mass% or more, and usually It is 30 mass % or less, preferably 20 mass % or less, more preferably 10 mass % or less, further preferably 5 mass % or less, particularly preferably 3 mass % or less. For example, 0.1 to 30 mass% is preferred, 0.2 to 20 mass% is more preferred, 0.2 to 10 mass% is still more preferred, 0.5 to 5 mass% is still more preferred, and 0.5 to 3 mass% is particularly preferred. By setting the content ratio of the mercapto compound to be not less than the above-mentioned lower limit, the photocurability tends to be improved and the surface roughness is improved, and by being not more than the above-mentioned upper limit, the storage stability tends to be improved.

When a polymerization inhibitor is used, its content ratio in the total solid content of the photosensitive coloring composition is usually 0.05 mass% or more, preferably 0.1 mass% or more, more preferably 0.2 mass% or more, and, It is usually 2 mass% or less, preferably 1 mass% or less, more preferably 0.8 mass% or less, further preferably 0.7 mass% or less, particularly preferably 0.5 mass% or less. For example, 0.05 to 2 mass% is preferred, 0.05 to 1 mass% is more preferred, 0.1 to 0.8 mass% is still more preferred, 0.1 to 0.7 mass% is still more preferred, and 0.2 to 0.5 mass% is particularly preferred. By setting the content ratio of the polymerization inhibitor to be equal to or higher than the above-mentioned lower limit, the resolution tends to be increased, and by being equal to or less than the above-mentioned upper limit, the curability tends to be increased.

＜Physical properties of photosensitive coloring composition＞ The photosensitive coloring composition of the present invention can be suitably used for forming colored spacers. From the viewpoint of being used as a colored spacer, it is preferable that the optical density (OD) per 1 μm of the film thickness of the coating film is relatively high. high. Regarding the colored spacer obtained by hardening the photosensitive coloring composition of the present invention alone, it is preferably 0.1 or more, more preferably 0.15 or more, still more preferably 0.2 or more, and even more preferably 0.25 or more. Here, the optical density (OD) is a value measured by the following method.

<Production method of photosensitive coloring composition> The photosensitive coloring composition of the present invention is produced according to conventional methods. Generally, (a) the coloring agent is preferably dispersed in advance using a paint conditioner, a sand mill, a ball mill, a roller mill, a stone mill, a jet mill, a homogenizer, or the like. The coloring agent is finely divided by the dispersion treatment (a), thereby improving the coating properties of the photosensitive coloring composition.

The dispersion treatment is usually preferably carried out in a system in which part or all of (a) colorant, (e) solvent, (f) dispersant, and optionally (b) alkali-soluble resin are used in combination (hereinafter, it may be referred to as The mixture in the dispersion process and the composition obtained in the process are called "ink" 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 photosensitive coloring composition over time is suppressed (excellent dispersion stability). In this way, in the step of producing the photosensitive coloring composition, it is preferable to produce a pigment dispersion liquid containing at least (a) a colorant, (e) a solvent, and (f) a dispersant. As the (a) colorant, (e) solvent, and (f) dispersant that can be used in the pigment dispersion liquid, those described as being usable in the photosensitive coloring composition can each be preferably used.

Furthermore, when a liquid containing all the components blended into the photosensitive coloring composition is subjected to a dispersion process, highly reactive components may be modified due to the heat generated during the dispersion process. Therefore, it is preferable to perform the dispersion treatment using a system that does not contain (c) a photopolymerization initiator or (d) an ethylenically unsaturated compound. When dispersing (a) the colorant using a sand mill, glass beads or zirconia beads with a particle size of about 0.1 to 8 mm can be preferably used. In the dispersion treatment conditions, the temperature is usually in the range of 0°C to 100°C, preferably in the range of room temperature to 80°C. Depending on the composition of the liquid and the size of the dispersion processing device, the appropriate dispersion time tends to vary, and it can be adjusted appropriately. The dispersion standard is to control the gloss of the ink so that the 20-degree specular gloss (JIS Z8741) when the pigment dispersion or photosensitive coloring composition is applied to the substrate is in the range of 50 to 300. By being equal to or above the above lower limit, it is possible to suppress the tendency that the dispersion treatment is insufficient and coarse pigment ((a) colorant) particles remain, making it easier to achieve sufficient developability, adhesion, resolution, etc. In addition, by setting it below the above upper limit, it is possible to suppress the pigment from being pulverized and generate a large number of ultrafine particles, thereby tending to improve the dispersion stability.

In addition, 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-mentioned dispersion treatment and the above-mentioned other components contained in the photosensitive coloring composition are mixed to prepare a uniform solution. In the production process of the photosensitive coloring composition, fine contaminants are often mixed into the liquid, so the obtained photosensitive coloring composition is preferably filtered using a filter or the like.

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

[Colored spacers] Next, the colored spacer of the present invention composed of the hardened material of the present invention will be described based on its manufacturing method.

(1)Support The material of the support used to form the colored spacer is not particularly limited as long as it has appropriate strength. Transparent substrates are mainly used. Examples of materials include polyester resins such as polyethylene terephthalate, polyolefin resins such as polypropylene and polyethylene, polycarbonate, polymethyl methacrylate, and polyethylene terephthalate. Thermoplastic resin sheets such as turmeric, thermosetting resin sheets such as epoxy resin, unsaturated polyester resin, poly(meth)acrylic resin, or various glasses. Among them, from the viewpoint of heat resistance, glass and heat-resistant resin are preferred. In addition, there are cases where transparent electrodes such as ITO (Indium Tin Oxide) and IZO (Indium Zinc Oxide) are formed on the surface of the substrate. In addition to transparent substrates, it can also be formed on TFT arrays.

In order to improve surface physical properties such as adhesion, the support may be subjected to corona discharge treatment, ozone treatment, film formation treatment with various resins such as silane coupling agent or urethane resin, if necessary. The thickness of the transparent substrate is usually in the range of 0.05 to 10 mm, preferably in the range of 0.1 to 7 mm. In addition, when performing thin film formation processing of various resins, the film thickness is usually in the range of 0.01 to 10 μm, preferably 0.05 to 5 μm.

(2) Colored spacers The photosensitive coloring composition of the present invention can be used for the same purposes as known photosensitive coloring compositions for color filters. When used as a coloring spacer, the formation method will be described below.

Usually, the photosensitive coloring composition is supplied in the form of a film or a pattern by a method such as coating on a support to be provided with a coloring spacer, and the solvent is dried. Then, pattern formation is performed by methods such as photolithography that performs exposure and development. Thereafter, if necessary, additional exposure or thermal hardening treatment is performed to form colored spacers on the support.

(3) Formation of colored spacers [1] Supply method to substrate The photosensitive coloring composition of the present invention is usually supplied on a support in a state of being dissolved or dispersed in a solvent. As the supply method, conventionally known methods can be used, such as spin method, wire bar coating method, flow coating method, die coating method, roller coating method, spray coating method, etc. Moreover, it can be supplied in the form of a pattern by an inkjet method, a printing method, etc. Among them, according to the die nozzle coating method, the usage amount of coating liquid can be greatly reduced, and there is no influence of mist, etc. that may adhere when using the spin coating method, and the generation of foreign matter can be suppressed. From a comprehensive point of view, it is relatively good.

The coating amount varies depending on the application. For example, in the case of colored spacers, the dry film thickness is usually 0.5 μm to 10 μm, preferably 1 μm to 9 μm, and particularly preferably 1 μm to 7 μm. Scope. Furthermore, it is important that the dry film thickness or the final height of the spacers is relatively uniform over the entire substrate. When the unevenness is large, defects such as display spots may occur in the liquid crystal panel.

Among them, when the photosensitive coloring composition of the present invention is used to form colored spacers with different heights at one time by photolithography, the heights of the colored spacers finally formed will be different.

In addition, as the substrate, a known substrate such as a glass substrate can be used. In addition, the surface of the substrate is preferably flat.

[2]Drying method The drying method after supplying the photosensitive coloring composition to the substrate is preferably a drying method using a hot plate, an IR (Infrared Radiation, infrared radiation) oven, or a convection oven. In addition, a reduced pressure drying method that performs drying in a reduced pressure chamber without raising the temperature may be combined.

Drying conditions such as drying temperature and drying time can be appropriately selected depending on the type of solvent components and the performance of the dryer used. It is usually selected within the range of 15 seconds to 5 minutes at a temperature of 40°C to 130°C, preferably within a range of 30 seconds to 3 minutes at a temperature of 50°C to 110°C.

[3]Exposure method Exposure is performed by superimposing a negative mask pattern on the coating film of the photosensitive coloring composition and irradiating a light source of ultraviolet rays or visible light through the mask pattern. When an exposure mask is used for exposure, the exposure mask can be brought close to the coating film of the photosensitive coloring composition; or the exposure mask can be placed away from the coating film of the photosensitive coloring composition. The position and method of projecting the exposure light through this exposure mask. In addition, a scanning exposure method using laser light without using a mask pattern can also be used. At this time, if necessary, in order to prevent the sensitivity of the photopolymerizable layer from decreasing due to oxygen, the exposure can be performed in a deoxidizing atmosphere, or after forming an oxygen barrier layer such as a polyvinyl alcohol layer on the photopolymerizable layer.

As a preferred aspect of the present invention, when color spacers with different heights are simultaneously formed by photolithography, for example, the following exposure mask is used, which has: a light shielding portion (light transmittance 0%); and as Among the plurality of openings, the opening has the highest average light transmittance (complete transmission opening) and the opening has a lower average light transmittance (intermediate transmission opening). With this method, the difference in average light transmittance between the intermediate transmission opening and the complete transmission opening, that is, the difference in exposure, is used to generate a difference in the remaining film rate. A method of producing a matrix light-shielding pattern using minute polygonal light-shielding units for the intermediate transmission opening is known. In addition, there is known a method of producing a film using a chromium-based, molybdenum-based, tungsten-based, silicon-based material as an absorber and controlling the light transmittance.

The light source used in the above exposure is not particularly limited. Examples of the light source include: xenon lamp, halogen lamp, tungsten lamp, high-pressure mercury lamp, ultra-high-pressure mercury lamp, metal halide lamp, medium-pressure mercury lamp, low-pressure mercury lamp, carbon arc, fluorescent lamp and other light sources; or argon ion laser , YAG laser, excimer laser, nitrogen laser, helium-cadmium laser, blue-violet semiconductor laser, near-infrared semiconductor laser and other laser light sources. Optical filters can also be used when using light of a specific wavelength.

The optical filter may be, for example, a type in which the light transmittance at the exposure wavelength can be controlled using a thin film. In this case, the material may be, for example, Cr compounds (Cr oxides, nitrides, nitrogen oxides, Fluoride, etc.), MoSi, Si, W, Al, etc.

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, and usually 300 mJ/cm ² or less, preferably 200 mJ/cm ² or less, more preferably 150 mJ/cm ² or less. In the case of a close exposure method, the distance between the exposure object and the mask pattern is usually 10 μm or more, preferably 50 μm or more, more preferably 75 μm or more, and usually 500 μm or less, preferably 500 μm or less. 400 μm or less, more preferably 300 μm or less.

[4]Developing method After the above exposure, an image pattern can be formed on the substrate by development using an aqueous solution of a basic compound or an organic solvent. The aqueous solution may further contain surfactants, organic solvents, buffers, complexing agents, dyes or pigments.

Examples of the basic compound include sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, sodium silicate, potassium silicate, sodium metasilicate, and sodium phosphate. , potassium phosphate, sodium hydrogen phosphate, potassium hydrogen phosphate, sodium dihydrogen phosphate, potassium dihydrogen phosphate, ammonium hydroxide and other inorganic alkaline compounds, or monoethanolamine, diethanolamine or triethanolamine, monomethylamine, dimethylamine or trimethylamine, monoethylamine, diethylamine or triethylamine, monopropylamine or diisopropylamine, n-butylamine, monoisopropanolamine, diisopropanolamine or triethylamine Organic alkaline compounds such as isopropanolamine, ethyleneimine, ethylenediimine, tetramethylammonium hydroxide (TMAH), choline, etc. These basic compounds may be a mixture of two or more types.

Examples of the surfactant include polyoxyethylene alkyl ethers, polyoxyethylene alkyl aryl ethers, polyoxyethylene alkyl esters, sorbitan alkyl esters, and monoglyceride alkyl esters. Nonionic surfactants such as esters; anionic surfactants such as alkyl benzene sulfonates, alkyl naphthalene sulfonates, alkyl sulfates, alkyl sulfonates, sulfosuccinate salts, etc. Surfactants; 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 for the development treatment are not particularly limited. Usually, the development temperature can be in the range of 10 to 50°C, with 15 to 45°C, especially 20 to 40°C. The development method can be immersion development, spray development, or magnetic brush. It can be performed by any method such as development method, ultrasonic development method, etc.

[5]Additional exposure and thermal hardening treatment On the developed substrate, if necessary, additional exposure can be performed by the same method as the above-mentioned exposure method, and thermal hardening treatment can also be performed. Regarding the thermal hardening treatment conditions at this time, the temperature is selected within the range of 100°C to 280°C, preferably 150°C to 250°C, and the time is selected within the range of 5 minutes to 60 minutes.

The size or shape of the colored spacer of the present invention is appropriately adjusted according to the specifications of the color filter to which it is applied. The photosensitive colored composition of the present invention is particularly suitable for the simultaneous formation of spacers and sub-spacers by photolithography. Colored spacers with different heights are useful. In this case, the height of the spacer is usually about 1 to 7 μm, and the secondary spacer usually has a height about 0.2 to 1.5 μm lower than the spacer.

[Image display device] The image display device of the present invention includes the colored spacer of the present invention. For example, by laminating the above-mentioned color filter having the colored spacer of the present invention and the liquid crystal driving side substrate to form a liquid crystal cell, and injecting liquid crystal into the formed liquid crystal cell, a device having the colored spacer of the present invention can be manufactured. An image display device of the present invention such as a liquid crystal display device. [Example]

Next, the present invention will be explained more specifically with reference to Examples and Comparative Examples. However, the present invention is not limited to the following Examples as long as the gist of the invention is not exceeded. The components of the photosensitive coloring composition used in the following Examples and Comparative Examples are as follows.

＜Alkali-soluble resin-I＞ While 145 parts by mass of propylene glycol monomethyl ether acetate was replaced with nitrogen, the mixture was stirred and heated to 120°C. 10 parts by mass of styrene, 85 parts by mass of glycidyl methacrylate, and 66 parts by mass of monomethacrylate having a tricyclodecane skeleton (FA-513M manufactured by Hitachi Chemical Co., Ltd.) were added dropwise for 3 hours. 8.5 parts by mass of 2,2'-azobis-2-methylbutyronitrile was added, 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 tris-dimethylaminomethylphenol and 0.12 parts by mass of hydroquinone were added to 43 parts by mass of acrylic acid, and the reaction was continued at 100° C. for 12 hours. Thereafter, 56 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 alkali-soluble resin-I thus obtained had a weight average molecular weight Mw measured by GPC in terms of polystyrene of 8400 and an acid value of 80 mgKOH/g.

＜Alkali-soluble resin-II＞ The mixture was stirred while replacing 124 parts by mass of propylene glycol monomethyl ether acetate with nitrogen, and the temperature was raised to 120°C. 4 parts by mass of styrene, 132 parts by mass of glycidyl methacrylate, and 4 parts by mass of monomethacrylate having a tricyclodecane skeleton (FA-513M manufactured by Hitachi Chemical Co., Ltd.) were added dropwise thereto for 3 hours. 7.2 parts by mass of 2,2'-azobis-2-methylbutyronitrile was added dropwise, and stirring was continued at 90° C. for 2 hours. Next, the inside of the reaction vessel was replaced with air, 0.6 parts by mass of tris-dimethylaminomethylphenol and 0.12 parts by mass of hydroquinone were added to 67 parts by mass of acrylic acid, and the reaction was continued at 100° C. for 12 hours. Thereafter, 15 parts by mass of tetrahydrophthalic anhydride (THPA) and 0.6 parts by mass of triethylamine were added, and the mixture was reacted at 100° C. for 3.5 hours. The alkali-soluble resin-II thus obtained had a weight average molecular weight Mw measured by GPC in terms of polystyrene of 9000, an acid value of 24 mgKOH/g, and a double bond equivalent of 260 g/mol.

＜Dispersant-I＞ "BYK-LPN21116" manufactured by BYK-Chemie (comprising an A block with a quaternary ammonium salt group and a tertiary amine group on the side chain and a B block without a quaternary ammonium salt group and a tertiary amine group) Acrylic A-B block copolymer. Amine value is 70 mgKOH/g. Acid value is 1 mgKOH/g or less). The A block of dispersant-I contains repeating units of the following formulas (1a) and (2a), and the B block contains 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.

[Chemical 50]

＜Solvent-I＞ PGMEA: propylene glycol monomethyl ether acetate ＜Solvent-II＞ MB: 3-methoxybutanol

＜Photopolymerization initiator-I＞ 2,2'-bis(o-chlorophenyl)-4,5,4',5'-tetraphenyl-1,2-biimidazole manufactured by Kurogane Chemicals Co., Ltd. ＜Photopolymerization Initiator-II＞ Irgacure (registered trademark) 369 made by BASF Corporation ＜Mercapto compound＞ 2-Mercaptobenzothiazole manufactured by Tokyo Chemical Industry Co., Ltd.

＜Photopolymerizable monomer＞ DPHA (dipentaerythritol hexaacrylate) manufactured by Nippon Chemical Co., Ltd.

＜Surface active agent＞ MEGAFAC F-554 manufactured by DIC Corporation ＜Additive-I＞ KAYAMER (registered trademark) PM-21 (methacrylyl-containing phosphate) manufactured by Nippon Chemical Co., Ltd. ＜Additive-II＞ Methylhydroquinone manufactured by Seiko Chemical Co., Ltd.

<Preparation of Pigment Dispersions 1 to 7> The pigments, dispersants, alkali-soluble resins, and solvents described in Table 1 were mixed so as to obtain the mass ratios described in Table 1 to obtain a mixed liquid. Furthermore, the solvent preparation ratio in Table 1 also includes the amount of the solvent derived from the dispersant and the alkali-soluble resin. The mixed liquid was dispersed using a paint shaker in the range of 25 to 45° C. for 3 hours. Use 0.5 mm Zirconia beads were used as beads, and 2.5 times the mass of the dispersion was added. After the dispersion is completed, the beads and the dispersion liquid are separated using a filter to prepare pigment dispersion liquids 1 to 7.

[Table 1] Pigment dispersion 1 Pigment dispersion 2 Pigment dispersion 3 Pigment dispersion 4 Pigment dispersion 5 Pigment dispersion 6 Pigment dispersion 7 Mixing ratio (mass parts) Pigments CI Pigment Orange 64 33 10 100 33 CI Pigment Orange 72 100 CI Pigment Violet 29 67 35 100 CI Pigment Violet 23 67 CI Pigment Blue 60 55 100 Dispersant (solid content conversion) Dispersant-I 29 20 33 20 20 20 100 Alkali-soluble resin (solid content conversion) Alkali soluble resin-I 33 33 33 33 33 33 100 Solvent Solvent-I 389 367 398 367 367 367 720 Solvent-II 97 92 100 92 92 92 180

<Preparation of photosensitive coloring compositions 1 to 13> [Examples 1 to 8 and Comparative Examples 1 to 5] Using the pigment dispersions 1 to 7 prepared above, add each component so that the ratio of the solid content of each component in the total solid content becomes the compounding ratio in Table 2 or Table 3, and further add the content ratio of the total solid content in the ratio of Table 2 or Table 3. PGMEA was added so that it may become 19 mass %, and it stirred and dissolved, and the photosensitive coloring composition 1-13 was prepared. Each of the obtained photosensitive coloring compositions was used for evaluation by the following method.

[Table 2] Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Example 7 Example 8 Composition 1 Composition 2 Composition 3 Composition 4 Composition 5 Composition 6 Composition 7 Composition 8 Mixing ratio (mass parts) Pigment dispersion 1 (solid content conversion) 9.73 16.13 24.19 Pigment dispersion 2 (solid content conversion) Pigment dispersion 3 (solid content conversion) 8.00 9.00 6.66 8.00 6.50 Pigment dispersion 4 (solid content conversion) 1.84 0.92 0.92 2.99 Pigment dispersion 5 (solid content conversion) 3.07 Pigment dispersion 6 (solid content conversion) 0.92 Pigment dispersion 7 (solid content conversion) 0.45 Alkali-soluble resin-II (solid content conversion) 27.44 24.49 20.72 27.40 27.37 27.43 27.40 27.30 Photopolymerizable monomer (solid content conversion) 58.87 55.42 51.12 58.80 58.75 58.88 58.80 58.80 Photopolymerization initiator-I (solid content conversion) 1.20 1.20 1.20 1.20 1.20 1.20 1.20 1.20 Photopolymerization initiator-II (solid content conversion) 0.63 0.63 0.63 0.63 0.63 0.63 0.63 0.63 Thiol compound (solid content conversion) 1.00 1.00 1.00 1.00 1.00 1.00 1.00 1.00 Surfactant (solid content conversion) 0.10 0.10 0.10 0.10 0.10 0.10 0.10 0.10 Additive-I (Solid content conversion) 1.00 1.00 1.00 1.00 1.00 1.00 1.00 1.00 Additive-II (Solid content conversion) 0.03 0.03 0.03 0.03 0.03 0.03 0.03 0.03 Colorant content ratio Colorant content ratio in total solid content (mass %) 6 10 15 6 6 6 6 6 Purple pigment content ratio among all colorants (mass %) 67 67 67 80 90 67 80 67

[table 3] Comparative example 1 Comparative example 2 Comparative example 3 Comparative example 4 Comparative example 5 Composition 9 Composition 10 Composition 11 Composition 12 Composition 13 Mixing ratio (mass parts) Pigment dispersion 1 (solid content conversion) 38.93 1.62 Pigment dispersion 2 (solid content conversion) 9.20 1.53 Pigment dispersion 3 (solid content conversion) Pigment dispersion 4 (solid content conversion) 9.20 Pigment dispersion 5 (solid content conversion) Pigment dispersion 6 (solid content conversion) Pigment dispersion 7 (solid content conversion) Alkali-soluble resin-II (solid content conversion) 27.61 13.70 31.25 31.28 27.61 Photopolymerizable monomer (solid content conversion) 59.23 43.40 63.17 63.23 59.23 Photopolymerization initiator-I (solid content conversion) 1.20 1.20 1.20 1.20 1.20 Photopolymerization initiator-II (solid content conversion) 0.63 0.63 0.63 0.63 0.63 Thiol compound (solid content conversion) 1.00 1.00 1.00 1.00 1.00 Surfactant (solid content conversion) 0.10 0.10 0.10 0.10 0.10 Additive-I (Solid content conversion) 1.00 1.00 1.00 1.00 1.00 Additive-II (Solid content conversion) 0.03 0.03 0.03 0.03 0.03 Colorant content ratio Colorant content ratio in total solid content (mass %) 6 twenty four 1 1 6 Purple pigment content ratio among all colorants (mass %) 35 67 67 35 0

<Measurement of optical density per unit film thickness (unit OD value)> The photosensitive coloring composition was coated on a glass substrate using a spin coater so that the film thickness after heat-hardening became 1.5 μm, and the film was reduced for 1 minute. After pressure drying, it was dried at 90° C. for 100 seconds using a hot plate. The obtained coating film was exposed to the entire surface using ultraviolet light with an intensity of 40 mW/cm ² at 365 nm and an exposure dose of 60 mJ/cm ² without using a mask. Next, using a developer containing an aqueous solution containing 0.05 mass % potassium hydroxide and 0.08 mass % nonionic surfactant ("A-60" manufactured by Kao Corporation), a water pressure of 0.15 MPa was implemented at 25°C. After spray development for 100 seconds, use pure water to stop development, and use water spray to wash. This substrate was heated and hardened in an oven at 230° C. for 20 minutes, thereby obtaining a resist cured film substrate.

The optical density (OD) of the obtained resist cured film substrate was measured with a transmission density meter 361T(V) manufactured by X-Rite Corporation, and the film thickness was measured using a scanning white interference microscope VS1530 manufactured by Hitachi High-Technologies Corporation. . Based on the optical density (OD) and film thickness, the optical density per unit film thickness (unit OD value, OD/μm) was calculated and shown in Table 4. Furthermore, the OD value represents the light-shielding ability. The larger the value, the higher the light-shielding ability.

<Evaluation of Roughness> A substrate for roughness evaluation was obtained in the same manner as the above-mentioned resist cured film substrate except that the exposure amount was 10 mJ/cm ² . The arithmetic average surface roughness (Sa) of the surface of the obtained substrate in the range of 10 μm × 10 μm was measured using a scanning white interference microscope VS1530 manufactured by Hitachi High-Technologies, and the roughness was evaluated according to the following standards. . The measurement results and evaluation results are shown in Table 4. Furthermore, the measurement mode is set to Focus mode, the magnification of the objective lens is set to 50 times, and the central wavelength of the measurement light is set to 520 nm. Sa is the volume of the part surrounded by the surface shape curved surface and the average surface divided by the measured area. The smaller the value, the higher the smoothness.

(Evaluation criteria for roughness) A: Below 2 nm B: More than 2 nm

＜Evaluation of elastic response rate＞ A glass substrate with an ITO film formed on the surface is used as the substrate, a mask with a 20 μm opening (a circular opening with a diameter of 20 μm) is used during exposure, and the exposure gap is set to 150 μm. In addition, in order to be consistent with the above resist The colored spacers are obtained in the same manner as the cured film substrate. The elastic recovery rate of the obtained colored spacer was measured in the following procedure. Use Fischerscope H-100 (manufactured by Fischer Instruments), use a flat indenter with a measuring temperature of 23°C and a diameter of 50 μm to apply a load to the colored spacer at a certain speed (5 mN/sec), and maintain 5 when the load reaches 300 mN. seconds, and then unload at the same speed to obtain the load-displacement curve. Based on this load-displacement curve, the maximum displacement H [max] and the final displacement H [Last] (the displacement after the load reaches 0 mN and is maintained for 5 seconds) are measured. Next, the elastic recovery rate was calculated based on the following equation, and evaluated based on the following criteria. The results are shown in Table 4.

Elastic recovery rate (%) = {(maximum displacement H[max]-final displacement H[Last])/maximum displacement H[max]}×100

(Evaluation basis for elastic response rate) A: More than 95% B: Less than 95%

[Table 4] Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Example 7 Example 8 Comparative example 1 Comparative example 2 Comparative example 3 Comparative example 4 Colorant content ratio Colorant content ratio in total solid content (mass %) 6 10 15 6 6 6 6 6 6 twenty four 1 1 Purple pigment content ratio among all colorants (mass %) 67 67 67 80 90 67 80 67 35 67 67 35 Evaluation results Optical density OD (/μm) 0.26 0.36 0.49 0.27 0.31 0.23 0.29 0.24 0.26 0.62 0.07 0.07 Roughness(nm) 0.8(A) 0.8(A) 0.8(A) 0.7(A) 0.7(A) 0.9(A) 1.0(A) 1.1 (A) 3.5(B) 0.9(A) 0.8(A) 1.1 (A) Flexible response rate (%) 100(A) 100(A) 97(A) 100(A) 100(A) 100(A) 100(A) 100(A) 100(A) 78(B) 100(A) 100(A)

<Evaluation of light resistance> A substrate for light resistance evaluation was obtained in the same manner as the above-mentioned resist cured film substrate. The absorbance of the obtained substrate at a wavelength of 450 nm was measured using a spectrophotometer U-3500 manufactured by Hitachi High-Technologies. Secondly, the above-mentioned substrate was irradiated from the film surface side with an intensity of 19 mW/cm ² at a wavelength of 450 nm for 500 hours in an environment with an air temperature of 25°C and a relative humidity of 50% RH. Similarly, the absorbance of the substrate at a wavelength of 450 nm was measured. The change rate of absorbance at a wavelength of 450 nm was calculated according to the following formula, and evaluated based on the following standards. The results are shown in Table 5.

Absorbance change rate (%) = {(Absorbance at 450 nm before irradiation - Absorbance at 450 nm after irradiation)/Absorbance at 450 nm before irradiation} × 100

(evaluation criteria) A: Less than 20% B: More than 20%

[table 5] Example 1 Example 5 Comparative example 5 Absorbance change rate (%) 12(A) 10(A) 36(B)

From Examples 1 to 8 shown in Table 4, it is clear that the content ratio of the colorant in the total solid content is 2 to 20% by mass. By using a purple pigment, the content ratio of the purple pigment in the colorant is More than 50% by mass of the photosensitive coloring composition can form a colored spacer with excellent surface roughness and mechanical properties.

Comparison between Example 1 and Comparative Example 1 shows that by setting the content ratio of the purple pigment in the colorant to 50 mass % or more, the surface roughness is excellent. The reason is considered to be that the purple pigment has high dispersibility and is uniformly dispersed in the cured film. Therefore, by containing a large amount of the purple pigment, the solubility during development becomes uniform.

Moreover, from the comparison between Example 1 and Comparative Example 2, it can be seen that when the content ratio of the colorant is 20 mass % or less in the total solid content of the photosensitive coloring composition, the mechanical properties become good. The reason for this is considered to be that by not making the content ratio of the colorant too high, the content ratio of the alkali-soluble resin or the ethylenically unsaturated compound can be set relatively high, and the crosslinking density of the obtained colored spacer increases.

Furthermore, it is clear from the comparison between Comparative Examples 3 and 4 that when the content ratio of the colorant in the total solid content of the photosensitive coloring composition is less than 2% by mass, the optical density is insufficient, and further, regardless of the colorant Regardless of the purple pigment content ratio, the surface roughness becomes good. Therefore, it is understood that by setting the content ratio of the colorant to 2 mass % or more in the total solid content of the photosensitive coloring composition, the optical density becomes good, and it is understood that the surface exists depending on the type and ratio of the pigment in the colorant. A situation in which the roughness becomes insufficient.

Comparison between Examples 1 and 5 and Comparative Example 5 shown in Table 5 shows that by setting the content ratio of the purple pigment in the colorant to 50 mass % or more, the light resistance is excellent. The reason is thought to be that the absorbance of purple pigments near the wavelength of 450 nm is low, and containing a large amount of purple pigments makes them less susceptible to the influence of irradiation light with a wavelength of 450 nm.

Claims (10)

A photosensitive coloring composition, characterized in that it contains (a) a colorant, (b) an alkali-soluble resin, (c) a photopolymerization initiator, and (d) an ethylenically unsaturated compound, and the above ( a) The content ratio of the coloring agent is 2 to 20% by mass in the total solid content of the photosensitive coloring composition, the coloring agent (a) above includes a purple pigment, and the C.I. Pigment Violet 29 in the coloring agent (a) above is The content ratio is 50% by mass or more. The photosensitive coloring composition according to claim 1, wherein the colorant (a) further contains an orange pigment. The photosensitive coloring composition according to claim 1, wherein the content ratio of the (b) alkali-soluble resin relative to 100 parts by mass of the (d) ethylenically unsaturated compound is 150 parts by mass or less. The photosensitive coloring composition of claim 2, wherein the content ratio of the (b) alkali-soluble resin to 100 parts by mass of the (d) ethylenically unsaturated compound is 150 parts by mass or less. The photosensitive coloring composition according to any one of claims 1 to 4, wherein the (c) photopolymerization initiator contains a hexaarylbiimidazole compound. The photosensitive coloring composition according to any one of claims 1 to 4, which is used to form a colored spacer. The photosensitive coloring composition of claim 5 is used to form a colored spacer. A cured product obtained by curing the photosensitive coloring composition according to any one of claims 1 to 7. A colored spacer composed of the hardened material according to claim 8. An image display device provided with the colored spacer according to claim 9.