JPWO2020129807A1 - Photosensitivity coloring composition, cured product, coloring spacer, and image display device - Google Patents

Abstract

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

Description

The present invention relates to a photosensitive coloring composition and the like. Specifically, for example, a photosensitive coloring composition preferably used for forming a coloring spacer or the like in a color filter of a liquid crystal display, a cured product obtained by curing the photosensitive coloring composition, a coloring spacer, and an image including the coloring spacer. Regarding display devices.
The specification of Japanese Patent Application No. 2018-236121 filed with the Japan Patent Office on December 18, 2018, the scope of claims, the entire contents of drawings and abstracts, and the documents cited in this specification, etc. Part or all of the content disclosed in the above is cited herein and incorporated as the content disclosed in the present specification.

A liquid crystal display (LCD) utilizes the property that the arrangement of liquid crystal molecules is switched by turning the voltage on and off the liquid crystal. Each member constituting the liquid crystal panel is often formed by a method using a photosensitive composition represented by photolithography. As an example, a so-called spacer, which is used to keep the distance between two substrates in a liquid crystal panel constant, can be mentioned.

Conventionally, when a transparent spacer is used for a TFT type LCD, the TFT as a switching element may malfunction due to the light transmitted through the spacer. In order to prevent this, for example, Patent Document 1 describes a method of using a spacer (colored spacer) having a light-shielding property. Further, in Patent Document 2, in order to obtain a colored spacer which can control the shape and the step while ensuring the light-shielding property and the voltage holding ratio of the liquid crystal display and has excellent adhesion to the substrate, a specific combination is provided. It has been proposed to use a colored photosensitive composition containing a pigment.

Further, since the liquid crystal panel is manufactured through a process of crimping the two substrates under high temperature and high pressure, the spacer is required to maintain the spacer function without being deformed by the high temperature and high pressure conditions at the time of crimping. NS. That is, even if it is deformed by an external pressure, mechanical properties such as a recovery rate and an elastic restoration rate are required to return to the original shape when the external pressure is removed. For example, Patent Document 3 describes that the mechanical properties at a high film thickness are enhanced by using a specific photopolymerization initiator, and Patent Document 4 uses a specific unsaturated group-containing compound. It is stated that this enhances the mechanical properties.

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

Japanese Patent Application Laid-Open No. 8-234212 International Publication No. 2013/115268 Japanese Patent Application Laid-Open No. 2015-38607 Japanese Patent Application Laid-Open No. 2005-165294 Japanese Patent Application Laid-Open No. 2018-9132

In order to suppress display defects in the liquid crystal display, it is necessary that the surface roughness of the colored spacer is low and the smoothness is excellent.
As a result of studies by the present inventors, it has been found that it is difficult to obtain a colored spacer having both surface roughness and mechanical properties with the photosensitive coloring compositions described in Patent Documents 2 and 5.

Patent Documents 3 and 4 do not describe a colored spacer, and the effect of adding a colorant to the spacer was unknown.

The present invention has been made in view of the above circumstances, and an object of the present invention is to provide a photosensitive coloring composition capable of forming a coloring spacer having excellent surface roughness and mechanical properties.

As a result of diligent studies to solve the above problems, the present inventors set the content ratio of the colorant in the total solid content within a specific range, and used a specific pigment as the colorant, and the content ratio thereof. We have found that the above-mentioned problems can be solved by setting the above-mentioned range to a specific range, and have arrived at the present invention.
That is, the present invention has the following configurations [1] to [9].

[1] A photosensitive coloring composition containing (a) a colorant, (b) an alkali-soluble resin, (c) a photopolymerization initiator, and (d) an ethylenically unsaturated compound.
The content ratio of the colorant (a) is 2 to 20% by mass in the total solid content of the photosensitive coloring composition.
The colorant (a) contains a purple pigment and
(A) A photosensitive coloring composition characterized in that the content ratio of the purple pigment in the colorant is 50% by mass or more.
[2] The purple pigment is C.I. I. Pigment Violet 29 and C.I. I. The photosensitive coloring composition according to [1], which comprises at least one selected from the group consisting of Pigment Violet 23.
[3] The photosensitive coloring composition according to [1] or [2], wherein the colorant (a) further contains an orange pigment.
[4] The photosensitive coloring according to any one of [1] to [3], wherein the content ratio of the alkali-soluble resin (b) to 100 parts by mass of the (d) ethylenically unsaturated compound is 150 parts by mass or less. Composition.
[5] The photosensitive coloring composition according to any one of [1] to [4], wherein the (c) photopolymerization initiator contains a hexaarylbiimidazole compound.
[6] The photosensitive coloring composition according to any one of [1] to [5], which is used for forming a coloring 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 cured product according to [7].
[9] An image display device including the colored spacer according to [8].

According to the present invention, a photosensitive coloring composition capable of forming a coloring spacer having excellent surface roughness and mechanical properties, a cured product, a coloring spacer composed of the photosensitive coloring composition, a coloring spacer composed of the photosensitive coloring composition, and an image display device including such a coloring spacer are provided. Can be provided.

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

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

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

Further, in the present specification, the percentage or part represented by "mass" is synonymous with the percentage or part represented by "weight".
Further, in the present specification, specific examples of pigments may be indicated by pigment numbers, but terms such as "CI Pigment Red 2" mean a color index (CI).

[Photosensitive coloring composition]
The photosensitive coloring composition of the present invention is
(A) Colorant (b) Alkaline-soluble resin (c) Photopolymerization initiator (d) Ethylene unsaturated compound is contained as an essential component, and if necessary, an adhesion improver such as a silane coupling agent and a surfactant are added. It contains other ingredients such as activators (coating improvers), pigment derivatives, photoacid generators, cross-linking agents, mercapto compounds, polymerization inhibitors, development improvers, UV absorbers, antioxidants, etc. Usually, each compounding ingredient is used in a state of being dissolved or dispersed in a solvent.

<(A) Colorant>
The photosensitive coloring composition of the present invention contains (a) a colorant. (A) By containing a colorant, it is possible to obtain an appropriate light absorption property, particularly an appropriate light shielding property when used for forming a light shielding member such as a colored spacer.
Further, in the photosensitive coloring composition of the present invention, the content ratio of (a) the colorant is 2 to 20% by mass in the total solid content. By containing (a) a specific amount of the colorant in this way, it is possible to achieve both light-shielding properties and high mechanical properties in the obtained cured product, particularly the colored spacer.

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

(A) As the colorant, a pigment or a dye may be used. Among these, it is preferable to use a pigment from the viewpoint of durability.

In the photosensitive coloring composition of the present invention, (a) the colorant contains a purple pigment, and (a) the content ratio of the purple pigment in the colorant is 50% by mass or more. By containing 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 developing solution becomes uniform during development and the surface roughness becomes good. It is considered to be. Further, since the purple pigment has a maximum absorption wavelength of the absorption peak in the vicinity of a wavelength of 500 to 600 nm in the absorption spectrum, it is effective from the viewpoint that the optical density (OD) can be easily increased by containing the purple pigment. On the other hand, since absorption of a wavelength of less than 400 nm is small, (c) there is little overlap with the absorption wavelength of the photopolymerization initiator, which is effective from the viewpoint of photocurability and sensitivity. Further, since the absorption at a wavelength of 450 nm is small, it is also effective from the viewpoint of light resistance to blue light strongly emitted from the backlight of the liquid crystal display.

As the purple pigment, C.I. I. Pigment Violet 1, 1: 1, 2, 2: 2, 3, 3: 1, 3: 3, 5, 5: 1, 14, 15, 16, 19, 23, 25, 27, 29, 31, 32, 37, 39, 42, 44, 47, 49, 50 can be mentioned. Among these, from the viewpoint of light-shielding property, C.I. I. Pigment Violet 19, 23, 29, more preferably C.I. I. Pigment Violet 23, 29 can be mentioned. On the other hand, from the viewpoint of dispersibility and light resistance, C.I. I. Pigment Violet 29 is preferably used.

(A) The content ratio of the purple pigment in the colorant is not particularly limited as long as it is 50% by mass or more, but from the viewpoint of improving the surface roughness, 55% by mass or more is preferable, 58% by mass or more is more preferable, and 60% by mass. By mass% or more is further preferable, 62% by mass or more is further preferable, and 65% by mass or more is particularly preferable. On the other hand, from the viewpoint of utilizing the optical characteristics of a colorant other than the purple pigment to widen the absorption wavelength band, 90% by mass or less is preferable, 80% by mass or less is more preferable, and 75% by mass or less is further preferable. For example, 50 to 90% by mass is preferable, 55 to 90% by mass is more preferable, 58 to 80% by mass is further preferable, 60 to 80% by mass is further preferable, 62 to 75% by mass is particularly preferable, and 65 to 75% by mass is particularly preferable. Mass% is particularly preferred.

(A) C.I. in the colorant. I. The content ratio of Pigment Violet 29 is not particularly limited, but from the viewpoint of surface roughness and light resistance factory, 50% by mass or more is preferable, 55% by mass or more is more preferable, 60% by mass or more is further preferable, and 62% by mass is used. The above is even more preferable, and 65% by mass or more is particularly preferable. On the other hand, C.I. I. From the viewpoint of utilizing the optical characteristics of a colorant other than Pigment Violet 29 and widening the absorption wavelength band, 90% by mass or less is preferable, 80% by mass or less is more preferable, and 75% by mass or less is further preferable. For example, 50 to 90% by mass is preferable, 55 to 90% by mass is more preferable, 58 to 80% by mass is further preferable, 60 to 80% by mass is further preferable, 62 to 75% by mass is particularly preferable, and 65 to 75% by mass is particularly preferable. Mass% is particularly preferred.

(A) The colorant may contain a colorant other than the purple pigment (hereinafter, abbreviated as "other colorant"). Examples of other colorants include pigments and dyes, and pigments are preferable from the viewpoint of heat resistance, and organic pigments are preferable from the viewpoint of color tone, photocurability, and sensitivity.

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

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

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

Examples of the blue pigment include C.I. I. Pigment Blue 1, 1: 2, 9, 14, 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, 16, 17, 19, 25, 27, 28, 29, 33, 35, 36, 56, 56: 1, 60, 61, 61: 1, 62, 63, 66, 67, 68, 71, 72, 73, 74, 75, 76, 78, 79 can be mentioned. Among these, from the viewpoint of light-shielding property, C.I. I. Pigment Blue 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, 16, 60, more preferably C.I. I. Pigment Blue 15: 6, 16 can be mentioned.
In terms of dispersibility and light-shielding property, C.I. I. Pigment Blue 15: 6, 16, 60 is preferably used, and when the photosensitive coloring composition is cured with ultraviolet rays, it is preferable to use a blue pigment having a low ultraviolet absorption rate, and from this viewpoint, it is preferable to use. C. I. It is more preferable to use Pigment Blue 60. On the other hand, as described in Korean Registered Patent No. 10-1840984, from the viewpoint of reliability, light-shielding property, and elastic recovery rate, C.I. I. It is preferable to use Pigment Blue 16.

Examples of the green pigment include C.I. I. Pigment Greens 1, 2, 4, 7, 8, 10, 13, 14, 15, 17, 18, 19, 26, 36, 45, 48, 50, 51, 54, 55, 58 can be mentioned. Among these, from the viewpoint of dispersibility, C.I. I. Pigment Greens 7 and 36 can be mentioned.

Examples of the brown pigment (brown pigment) include C.I. I. Pigment Brown 23, 25, 26, 28, 38, 41, 83, 93. Among these, C.I. I. Pigment Brown 26, 28, 83, 93 can be mentioned.

Among these organic coloring pigments, an orange pigment is preferable because it has an absorption band in the vicinity of a wavelength of 400 to 500 nm, which is different from the absorption band of the purple pigment.
When the orange pigment is contained, (a) the content ratio of the orange pigment in the colorant is not particularly limited, but is preferably 5% by mass or more, more preferably 10% by mass or more, further preferably 20% by mass or more, and further preferably 30% by mass. The above is particularly preferable, 50% by mass or less is preferable, 45% by mass or less is more preferable, 40% by mass or less is further preferable, and 35% by mass or less is particularly preferable. For example, 5 to 50% by mass is preferable, 10 to 45% by mass is more preferable, 20 to 40% by mass is further preferable, and 30 to 35% by mass is particularly preferable. When it is at least the lower limit value, the optical density (OD) tends to be high, and when it is at least the upper limit value, the surface roughness tends to be good.

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

Further, when the blue pigment is contained, the surface roughness tends to deteriorate. Therefore, (a) the content ratio of the blue pigment in the colorant is preferably 50% by mass or less, more preferably 40% by mass or less, and 30% by mass. % Or less is further preferable, 20% by mass or less is further preferable, 10% by mass or less is particularly preferable, and 0% by mass is most preferable.

Among the blue pigments, C.I. I. When Pigment Blue 60 is contained, the surface roughness tends to be deteriorated. Therefore, (a) C.I. I. The content ratio of Pigment Blue 60 is preferably 50% by mass or less, more preferably 40% by mass or less, further preferably 30% by mass or less, further preferably 20% by mass or less, particularly preferably 10% by mass or less, and 0% by mass. Is the most preferable.

In addition, a black pigment may be contained as another colorant. Examples of the black pigment include organic black pigments and inorganic black pigments.
The organic black pigment contains, for example, at least one 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. Examples include black pigments.

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 each independently represent 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 at least one combination selected from the group consisting of ^{R 2} and R ³ , R ³ and R ⁴ , R ⁴ and R ⁵ , R ⁷ and R ⁸ , R ⁸ and R ⁹ , and R ⁹ and R ^{10 is} They can be bonded directly to each other, or they can be bonded to each other by oxygen, sulfur, NH or NR ¹¹ bridges;
R ¹¹ and R ¹² are independently an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms, an alkenyl group having 2 to 12 carbon atoms, a cycloalkenyl group having 3 to 12 carbon atoms, or a cycloalkenyl group having 3 to 12 carbon atoms. 2-12 alkynyl groups.

The geometric isomer of the compound represented by the general formula (1) has the following core structure (however, the substituent in the structural formula is omitted), and the trans-trans isomer is probably the most stable. ..

When the compound represented by the general formula (1) is anionic, its charge is charged to any known suitable cation such as metal, organic, inorganic or metallic organic cation, specifically alkali metal or alkaline earth metal. , A transition metal, a tertiary ammonium such as primary ammonium, secondary ammonium, trialkylammonium, quaternary ammonium such as tetraalkylammonium, or a salt compensated with an organic metal complex is preferable. When the geometric isomer of the compound represented by the general formula (1) is anionic, it is preferably a similar salt.

In the substituents of the general formula (1) and their definitions, the shielding rate tends to be high, so the following is preferable. This is because the following substituents are not absorbed and are not considered to 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 independently preferably hydrogen atom, NO ₂ , OCH ₃ , OC ₂ H ₅ , bromine atom, chlorine atom, CH ₃ , C ₂ H ₅ , N (CH ₃ ) ₂ , N (CH _{3). ) (C 2 H 5),} N (C 2 H 5) 2, α- naphthyl, beta-naphthyl, SO ₃ H or SO ₃ ^- and is, more preferably a hydrogen atom or SO ₃ H.

R ¹ and R ⁶ are 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, more preferably.} R ¹ is the same as ^{R 6 , R 2} is the same as ^{R 7 , R 3} is the same as ^{R 8 , R 4} is the ^{same as R 9} , and R ⁵ is the same as R ¹⁰ . It is the same.

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

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

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

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

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

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

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

Specific examples of such an organic black pigment include Irgaphor (registered trademark) Black S 0100 CF (manufactured by BASF) under the trade name.
This organic black pigment is preferably dispersed and used by a dispersant, a solvent, or a method described later. Further, if the compound represented by the general formula (2) or the sulfonic acid derivative of the geometric isomer of the compound is present at the time of dispersion, the dispersibility and storage stability may be improved.
Further, as the organic black pigment, from the viewpoint of optical properties and reliability, the organic black pigment described in Korean Publication No. 10-2018-0052502 and the Korean publication Patent No. 10-2018-0052864 are described. It is preferable to use the organic black pigments that have been used.

Further, as other organic black pigments, aniline black, cyanine black, perylene black and the like can also be mentioned.
Moreover, you may use carbon black which is an inorganic black pigment. Examples of carbon black include the following carbon blacks.

Made by Mitsubishi Chemical Corporation: MA7, MA8, MA11, MA77, MA100, MA100R, MA100S, MA220, MA230, MA600, MCF88, # 5, # 10, # 20, # 25, # 30, # 32, # 33, # 40 , # 44, # 45, # 47, # 50, # 52, # 55, # 650, # 750, # 850, # 900, # 950, # 960, # 970, # 980, # 990, # 1000, # 2200, # 2300, # 2350, # 2400, # 2600, # 2650, # 3030, # 3050, # 3150, # 3250, # 3400, # 3600, # 3750, # 3950, # 4000, # 4010, OIL7B, OIL9B , OIL11B, OIL30B, OIL31B
Made by Degusa: Printex (registered trademark, the same applies hereinafter) 3, Printex3OP, Printex30, Printex30OP, Printex40, Printex45, Printex55, Printex60, Printex75, Printex80, Printex85, Printex90, PrintexA U, Printex V, 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
Made by Cabot: Monarch (registered trademark, the same applies hereinafter) 120, Monarch280, Monarch460, Monarch800, Monarch880, Monarch900, Monarch1000, Monarch1100, Monarch1300, Monarch1400, Monarch4630, REGAL (registered trademark, the same below). REGAL415R, REGAL250, REGAL250R, REGAL330, REGAL400R, REGAL55R0, REGAL660R, BLACK PEARLS480, PEARLS130, VULCAN® XC72R, ELFTEX®-8
Made by Biller: RAVEN (registered trademark, the same applies hereinafter) 11, RAVEN14, RAVEN15, RAVEN16, RAVEN22, RAVEN30, RAVEN35, RAVEN40, RAVEN410, RAVEN420, RAVEN450, RAVEN500, RAVEN780, RAVEN850, RAVEN890H, RAVEN10 , RAVEN1080U, RAVEN1170, RAVEN1190U, RAVEN1250, RAVEN1500, RAVEN2000, RAVEN2500U, RAVEN3500, RAVEN5000, RAVEN5250, RAVEN5750, RAVEN7000

As the carbon black, one coated with a resin may be used. The use of carbon black coated with resin has the effect of improving the adhesion to the glass substrate and the volume resistance value. As the carbon black coated with the resin, for example, the carbon black described in Japanese Patent Application Laid-Open No. 09-71733 can be preferably used. Resin-coated carbon black is preferably used in terms of volume resistance and dielectric constant.

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

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

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

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

<(B1) Epoxy (meth) acrylate resin>
(B1) The epoxy (meth) acrylate-based resin is a reaction product of an epoxy resin (epoxy compound) and an α, β-unsaturated monocarboxylic acid and / or an α, β-unsaturated monocarboxylic acid ester having a carboxyl group. , A resin obtained by further reacting a hydroxyl group generated in the reaction with a polybasic acid and / or an anhydride thereof.
Further, before reacting the above-mentioned polybasic acid and / or its 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 anhydride is reacted. The resin obtained by reacting with (b1) epoxy (meth) acrylate-based resin is also included in the above-mentioned (b1) epoxy (meth) acrylate-based resin.

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

Specific examples of the (b1) epoxy (meth) acrylate-based resin used in the present invention include the following epoxy (meth) acrylate-based resin (b1-1) and / or epoxy (meth) acrylate-based resin (b1-2). (Hereinafter, it may be referred to as "carboxyl group-containing epoxy (meth) acrylate resin".) Is preferably used from the viewpoint of developability and reliability.

<Epoxy (meta) acrylate resin (b1-1)>
Obtained by adding α, β-unsaturated monocarboxylic acid and / or α, β-unsaturated monocarboxylic acid ester having a carboxyl group to an epoxy resin, and further reacting with a polybasic acid and / or its anhydride. Alkali-soluble resin.
<Epoxy (meta) acrylate resin (b1-2)>
An α, β-unsaturated monocarboxylic acid and / or an α, β-unsaturated monocarboxylic acid ester having a carboxyl group is added to the epoxy resin, and further, a polyhydric alcohol and a polybasic acid and / or an anhydride thereof are added. An alkali-soluble resin obtained by reacting.

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

Specific examples of the epoxy resin include, for example, bisphenol A type epoxy resin (for example, "jER (registered trademark, the same shall apply hereinafter) -828", "jER-1001", "jER-1002" manufactured by Mitsubishi Chemical Corporation. , "JER-1004", "NER-1302" manufactured by Nippon Kayakusha (epoxy equivalent 323, softening point 76 ° C), etc.), bisphenol F type resin (for example, "jER-1007" manufactured by Mitsubishi Chemical Corporation, " "jER-4004P", "jER-4005P", "jER-4007P", "NER-7406" manufactured by Nippon Kayakusha (epoxy equivalent 350, softening point 66 ° C), etc.), bisphenol S type epoxy resin, biphenyl glycidyl ether (For example, "jER-YX4000" manufactured by Mitsubishi Chemical Corporation), phenol novolac type epoxy resin (for example, "EPPN-201" manufactured by Nippon Kayaku Co., Ltd., "jER-152" manufactured by Mitsubishi Chemical Corporation, "jER-154" , "DEN-438" manufactured by Dow Chemical Corporation), (o, m, p-) cresol novolac type epoxy resin (for example, "EOCN (registered trademark, the same shall apply hereinafter) -102S" manufactured by Nippon Kayaku Co., Ltd., "EOCN-1020", "EOCN-104S"), triglycidyl isocyanurate (for example, "TEPIC (registered trademark)" manufactured by Nissan Chemical Corporation), trisphenol methane type epoxy resin (for example, "EOCN-1020" manufactured by Nippon Kayaku Co., Ltd.) EPPN (registered trademark, the same shall apply hereinafter) -501 "," EPPN-502 "," EPPN-503 "), alicyclic epoxy resin ("Ceroxide (registered trademark, the same shall apply hereinafter) 2021P "manufactured by Daicel Corporation," Celoxide EHPE ”), epoxy resin obtained by glycidylating a phenol resin produced by the reaction of dicyclopentadiene with phenol (for example,“ EXA-7200 ”manufactured by DIC,“ NC-7300 ”manufactured by Nippon Kayaku Co., Ltd.), the following general formula Epoxy resins represented by (B1) to (B4) and the like can be preferably used. Specifically, "XD-1000" manufactured by Nippon Kayaku Co., Ltd. is used as the epoxy resin represented by the following general formula (B1), and "XD-1000" manufactured by Nippon Kayaku Co., Ltd. is used as the epoxy resin represented by the following general formula (B2). Examples of the epoxy resin represented by the following general formula (B4) include "NC-3000" and "ESF-300" manufactured by Nippon Steel & Sumitomo Metal Corporation.

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. The plurality of R ^111s present in one molecule may be the same or different.

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. The plurality of R ^121s present in one molecule may be the same or different.

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

In the above general formulas (B3-1) and (B3-2), R ^{131 to} R ¹³⁴ and R ^{135 to} R ¹³⁷ each independently have an adamantyl group, a hydrogen atom, and a substituent which may have a substituent. It represents an alkyl group having 1 to 12 carbon atoms which may have a substituent, or a phenyl group which may have a substituent. * Represents a bond.

In the above 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 of 0 or more.

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

Examples of the α, β-unsaturated monocarboxylic acid or α, β-unsaturated monocarboxylic acid ester having a carboxyl group include (meth) acrylic acid, crotonic acid, o-, m- or p-vinylbenzoic acid, and (meth). ) Monocarboxylic acids such as α-position haloalkyl, alkoxyl, halogen, nitro, cyano-substituted acrylic acid, 2- (meth) acryloyloxyethyl succinic acid, 2- (meth) acryloyloxyethyl adipic acid, 2- ( Meta) acryloyloxyethyl phthalic acid, 2- (meth) acryloyloxyethyl hexahydrophthalic acid, 2- (meth) acryloyloxyethyl maleic acid, 2- (meth) acryloyloxypropyl succinic acid, 2-( Meta) acryloyloxypropyl adipinic acid, 2- (meth) acryloyloxypropyl tetrahydrophthalic acid, 2- (meth) acryloyloxypropyl phthalic acid, 2- (meth) acryloyloxypropyl maleic acid, 2- (meth) ) Acryloyloxybutyl succinic acid, 2- (meth) acryloyloxybutyl adipic acid, 2- (meth) acryloyloxybutyl hydrophthalic acid, 2- (meth) acryloyloxybutyl phthalic acid, 2- (meth) A monomer obtained by adding lactones such as ε-caprolactone, β-propiolactone, γ-butyrolactone, and δ-valerolactone to acryloyloxybutylmaleic acid and (meth) acrylic acid, or hydroxyalkyl ( A simple addition of acids (anhydrous) such as (anhydrous) succinic acid, (anhydrous) phthalic acid, and (anhydrous) maleic acid to meta) acrylate, pentaerythritol tri (meth) acrylate, and dipentaerythritol penta (meth) acrylate. Quantum, (meth) acrylic acid dimer and the like.
Of these, (meth) acrylic acid is particularly preferable from the viewpoint of surface roughness.

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

As the epoxy resin, α, β-unsaturated monocarboxylic acid and / or α, β-unsaturated monocarboxylic acid ester having a carboxyl group, and the esterification catalyst, one kind may be used alone. Two or more types may be used in combination.
The amount of α, β-unsaturated monocarboxylic acid and / or α, β-unsaturated monocarboxylic acid ester having a carboxyl group used is in the range of 0.5 to 1.2 equivalents with respect to 1 equivalent of the epoxy group of the epoxy resin. Is preferable, and more preferably in the range of 0.7 to 1.1 equivalents. By setting the amount of α, β-unsaturated monocarboxylic acid and / or α, β-unsaturated monocarboxylic acid ester having a carboxyl group to the above lower limit or more, the shortage of the amount of unsaturated group introduced can be suppressed. Subsequent reactions with polybasic acids and / or their anhydrides also tend to be sufficient. On the other hand, when the value is not more than the above upper limit, the residual unreacted substance of α, β-unsaturated monocarboxylic acid and / or α, β-unsaturated monocarboxylic acid ester having a carboxyl group can be suppressed, and the curing characteristics are good. There is a tendency for it to be easy to make.

Polybasic acids and / or their anhydrides include maleic acid, succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, pyromellitic acid, trimellitic acid, benzophenone tetracarboxylic acid, methylhexahydrophthalic acid. Examples thereof include one or more selected from acids, endomethylene tetrahydrophthalic acid, chlorendic acid, methyl tetrahydrophthalic acid, biphenyl tetracarboxylic acid, and anhydrides thereof.

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

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

A multi-branched structure may be introduced by adding a polyhydric alcohol such as trimethylolpropane, pentaerythritol, or dipentaerythritol during the addition reaction of the polybasic acid and / or its anhydride.

The carboxyl group-containing epoxy (meth) acrylate-based resin is usually a large amount in the reaction product of the epoxy resin and the α, β-unsaturated monocarboxylic acid and / or the α, β-unsaturated monocarboxylic acid ester having a carboxyl group. After mixing the basic acid and / or its anhydride, or in the reaction product of the epoxy resin and the α, β-unsaturated monocarboxylic acid and / or the α, β-unsaturated monocarboxylic acid ester having a carboxyl group. It is obtained by mixing a polybasic acid and / or its anhydride and a polyhydric alcohol, and then heating the mixture. In this case, the mixing order of the polybasic acid and / or its anhydride and the polyhydric alcohol is not particularly limited. Any that is present in the mixture of the reaction product of the epoxy resin and the α, β-unsaturated monocarboxylic acid and / or the α, β-unsaturated monocarboxylic acid ester having a carboxyl group and the polyhydric alcohol by heating. A polybasic acid and / or its anhydride undergoes an addition reaction with respect to the hydroxyl group of.

Examples of the carboxyl group-containing epoxy (meth) acrylate-based resin include those described above, Korean Patent Publication No. 10-2013-0022955, Korean Registered Patent No. 10-0965189, and Japanese Patent Application Laid-Open No. 2005-165294. , Japanese Patent Application Laid-Open No. 2006-312704, and the like.

The polystyrene-equivalent weight average molecular weight (Mw) of the epoxy (meth) acrylate resin measured by gel permeation chromatography (GPC) is usually 1000 or more, preferably 1500 or more, more preferably 2000 or more, and more preferably 2500 or more. It is usually 10000 or less, preferably 8000 or less, more preferably 6000 or less, still more preferably 5000 or less, and particularly preferably 4000 or less. For example, 1000 to 10000 is preferable, 1000 to 8000 is more preferable, 1500 to 6000 is further preferable, 2000 to 5000 is further preferable, and 2500 to 4000 is particularly preferable. When it is set to the lower limit value or more, the solubility in the developing solution tends to be suppressed from becoming too high, and when it is set to the upper limit value or less, the solubility in the developing solution tends to be good.

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

The 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, further preferably 500 or less, particularly preferably 400 or less, and 300 or less. Is most preferable, 100 or more is preferable, 150 or more is more preferable, 200 or more is further preferable, and 250 or more is particularly preferable. For example, 100 to 800 is preferable, 100 to 700 is more preferable, 150 to 600 is further preferable, 150 to 500 is further preferable, 200 to 400 is particularly preferable, and 250 to 300 is particularly preferable. When it is set to the upper limit value or less, the mechanical properties and the surface roughness tend to be improved, and when it is set to the lower limit value or more, the storage stability tends to be improved.
The double bond equivalent of the resin can be calculated from the following formula (x).

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

(B1) The chemical structure of the epoxy (meth) acrylate-based resin is not particularly limited, but from the viewpoint of curability, the epoxy (meth) acrylate-based resin (b1-A) having a partial structure represented by the following general formula (i). ) (Hereinafter, it may be abbreviated as "epoxy (meth) acrylate resin (b1-A)") or an epoxy (meth) acrylate resin having a partial structure represented by the following general formula (ii). b1-B) (hereinafter, may be abbreviated as "epoxy (meth) acrylate-based resin (b1-B)") is preferable. Further, from the viewpoint of reliability, an epoxy (meth) acrylate-based resin (b1-B) is more preferable.

In formula (i), Ra ^{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 be further substituted with any substituent. * Represents a bond.

In formula (ii), ^{each 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. * Represents a bond.

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

Examples of the divalent aliphatic group include linear, branched chain, cyclic, and a combination thereof. Among these, a linear one is preferable from the viewpoint of development solubility, while 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, preferably 20 or less, more preferably 15 or less, still more preferably 10 or less. For example, 1 to 20 is preferable, 3 to 15 is more preferable, and 6 to 10 is even more preferable. When it is at least the lower limit value, the development adhesion tends to be good, and when it is at least the upper limit value, the curability tends to be good.

Specific examples of the divalent linear aliphatic group include a methylene group, an ethylene group, an n-propylene group, an n-butylene group, an n-hexylene group, an n-heptylene group and the like. Among these, a methylene group is preferable from the viewpoint of curability.
Specific examples of the divalent branched chain aliphatic group include the above-mentioned divalent linear aliphatic group and methyl group, ethyl group, n-propyl group, iso-propyl group and n-butyl as side chains. Examples thereof include a structure having a group, an iso-butyl group, a sec-butyl group, a tert-butyl group and the like.
The number of rings contained in the divalent cyclic aliphatic group is not particularly limited, but is usually preferably 1 or more and 2 or more, and usually 10 or less and 5 or less. For example, 1 to 10 is preferable, 1 to 5 is more preferable, and 2 to 5 is even more preferable. When it is at least the lower limit value, the development adhesion tends to be good, and when it is at least the upper limit value, the curability tends to be good. Specific examples of the divalent cyclic aliphatic group include a group obtained by removing two hydrogen atoms from a ring such as a cyclohexane ring, a cycloheptane ring, a cyclodecane ring, a cyclododecane ring, a norbornane ring, an isobornane ring, or an adamantane ring. Be done. Among these, from the viewpoint of skeletal rigidity, a group obtained by removing two hydrogen atoms from the adamantane ring is preferable.

Examples of the substituent that the divalent aliphatic group may have include 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; and a carboxyl group. From the viewpoint of ease of synthesis, it is preferably unsubstituted.

Examples of the divalent aromatic ring group include a divalent aromatic hydrocarbon ring group and a divalent aromatic heterocyclic group. The carbon number is usually 4 or more, preferably 5 or more, more preferably 6 or more, preferably 20 or less, more preferably 15 or less, still more preferably 10 or less. For example, 4 to 20 is preferable, 5 to 15 is more preferable, and 6 to 10 is even more preferable. When it is at least the lower limit value, the development adhesion tends to be good, and when it is at least the upper limit value, the curability tends to be good.

The aromatic hydrocarbon ring in the divalent aromatic hydrocarbon ring group may be a monocyclic ring or a condensed ring. Examples of the divalent aromatic hydrocarbon ring group include a benzene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring, a perylene ring, a tetracene ring, a pyrene ring, a benzpyrene ring, and a chrysene ring, which have two free valences. Examples include groups such as a triphenylene ring, an acenaphthene ring, a fluorene ring, and a fluorene ring.
The aromatic heterocycle in the divalent aromatic heterocyclic group may be a monocyclic ring or a condensed ring. Examples of the divalent aromatic heterocyclic group include a furan ring, a benzofuran ring, a thiophene ring, a benzothiophene ring, a pyrazole ring, a pyrazole ring, an imidazole ring, an oxadiazole ring, and an indole having two free atomic valences. Rings, carbazole rings, pyroloymidazole rings, pyrrolopyrazole rings, pyrolopyrrole rings, thienopyrol rings, thienothiophene rings, flopyrol rings, flofuran rings, thienofran rings, benzoisoxazole rings, benzoisothiazole rings, benzoimidazole rings, pyridine rings, Examples thereof include groups such as a pyrazine ring, a pyridazine ring, a pyrimidine ring, a triazine ring, a quinoline ring, an isoquinoline ring, a sinoline ring, a quinoxaline ring, a phenanthridin ring, a perimidine ring, a quinazolin ring, a quinazolinone ring, and an azulene ring. Among these, from the viewpoint of photocurability, a benzene ring or a naphthalene ring having two free valences is preferable, and a benzene ring having two free valences is more preferable.

Examples of the substituent that the divalent aromatic ring group may have include a hydroxyl group, a methyl group, a methoxy group, an ethyl group, an ethoxy group, a propyl group, a propoxy group and the like. From the viewpoint of curability, no substitution is preferable.

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

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

As described above, the benzene ring in the formula (i) may be further substituted with an arbitrary substituent. Examples of the substituent include a hydroxyl group, a methyl group, a methoxy group, an ethyl group, an ethoxy group, a propyl group, a propoxy group and the like. The number of substituents is not particularly limited, and may be one or two or more.
From the viewpoint of curability, it is preferably unsubstituted.

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

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

The polybasic acid residue means a monovalent group obtained by subtracting one OH group from the polybasic acid or its anhydride. Polybasic acids include maleic acid, succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, pyromellitic acid, trimellitic acid, benzophenone tetracarboxylic acid, methylhexahydrophthalic acid, endomethylenetetrahydrophthalic acid. One or more selected from acid, chlorendic acid, methyltetrahydrophthalic acid and biphenyltetracarboxylic acid can be mentioned.
Among these, from the viewpoint of patterning characteristics, the polybasic acid is preferably maleic acid, succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, pyromellitic acid, trimellitic acid, biphenyltetracarboxylic acid. It is an acid, more preferably a tetrahydrophthalic acid or a biphenyltetracarboxylic acid.

The partial structure represented by the above formula (i-1) contained in one molecule of the epoxy (meth) acrylate-based resin (b1-A) may be one kind or two or more kinds, for example, ^RX is a hydrogen atom. and that of, and may be mixed those R ^X is a polybasic acid residue.

The number of partial structures represented by the formula (i) contained in one molecule of the epoxy (meth) acrylate resin (b1-A) is not particularly limited, but 1 or more is preferable, and 3 or more is more preferable. , 20 or less is preferable, and 15 or less is more preferable. For example, 1 to 20 is preferable, and 3 to 15 is more preferable. When it is at least the lower limit value, the curability tends to be good, and when it is at least the upper limit value, the development solubility tends to be good.

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

(R ^d )
In the formula (ii), R ^d represents a divalent hydrocarbon group having a cyclic hydrocarbon group as a side chain.
Examples of the cyclic hydrocarbon group include an aliphatic ring group and an aromatic ring group.

The number of rings contained in the aliphatic ring group is not particularly limited, but is usually preferably 1 or more and 2 or more, and usually 10 or less, 5 or less is preferable, and 3 or less is more preferable. For example, 1 to 10 is preferable, 1 to 5 is more preferable, 1 to 3 is further preferable, and 2 to 3 is even more preferable. When it is at least the lower limit value, the development adhesion tends to be good, and when it is at least the upper limit value, the curability tends to be good.
The carbon number of the aliphatic ring group is usually 4 or more, preferably 6 or more, more preferably 8 or more, preferably 40 or less, more preferably 30 or less, further preferably 20 or less, and particularly preferably 15 or less. preferable. For example, 4 to 40 is preferable, 4 to 30 is more preferable, 6 to 20 is more preferable, 6 to 15 is further preferable, and 8 to 15 is even more preferable. When it is at least the lower limit value, the development adhesion tends to be good, and when it is at least the upper limit value, the curability tends to be good.
Specific examples of the aliphatic ring in the aliphatic ring group include a cyclohexane ring, a cycloheptane ring, a cyclodecane ring, a cyclododecane ring, a norbornane ring, an isobornane ring, an adamantane ring and the like. Among these, the adamantane ring is preferable from the viewpoint of reliability.

On the other hand, the number of rings contained in the aromatic ring group is not particularly limited, but is usually 1 or more, 2 or more, more preferably 3 or more, and usually 10 or less, 5 or less, more preferably 4 or less. For example, 1 to 10 is preferable, 1 to 5 is more preferable, 1 to 4 is further preferable, 2 to 4 is more preferable, and 3 to 4 is particularly preferable. When it is at least the lower limit value, the development adhesion tends to be good, and when it is at least the upper limit value, the curability tends to be good.
Examples of the aromatic ring group include an aromatic hydrocarbon ring group and an aromatic heterocyclic group. The carbon number of the aromatic ring group is usually 4 or more, preferably 6 or more, more preferably 8 or more, further preferably 10 or more, particularly preferably 12 or more, and preferably 40 or less, preferably 30 or less. More preferably, 20 or less is further preferable, and 15 or less is particularly preferable. For example, 4 to 40 is preferable, 6 to 30 is more preferable, 8 to 20 is further preferable, 10 to 15 is more preferable, and 12 to 15 is particularly preferable. When it is at least the lower limit value, the development adhesion tends to be good, and when it is at least the upper limit value, the curability tends to be good.
Specific examples of the aromatic ring in the aromatic ring group include a benzene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring, a perylene ring, a tetracene ring, a pyrene ring, a benzpyrene ring, a chrysene ring, a triphenylene ring, an acenaphthene ring, and a fluoranthene ring. Examples include a fluorene ring. Among these, a fluorene ring is preferable from the viewpoint of patterning characteristics.

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

Examples of the divalent aliphatic group include linear, branched chain, cyclic, and a combination thereof. Among these, a linear one is preferable from the viewpoint of compatibility, while a cyclic one is preferable from the viewpoint of reliability. The carbon number is usually 1 or more, preferably 3 or more, more preferably 6 or more, preferably 25 or less, more preferably 20 or less, still more preferably 15 or less. For example, 1 to 25 is preferable, 3 to 20 is more preferable, and 6 to 15 is even more preferable. When it is at least the lower limit value, the development adhesion tends to be good, and when it is at least the upper limit value, the curability tends to be good.

Specific examples of the divalent linear aliphatic group include a methylene group, an ethylene group, an n-propylene group, an n-butylene group, an n-hexylene group, an n-heptylene group and the like. Among these, a methylene group is preferable from the viewpoint of curability.
Specific examples of the divalent branched chain aliphatic group include the above-mentioned divalent linear aliphatic group and methyl group, ethyl group, n-propyl group, iso-propyl group and n-butyl as side chains. Examples thereof include a structure having a group, an iso-butyl group, a sec-butyl group, a tert-butyl group and the like.
The number of rings contained in the divalent cyclic aliphatic group is not particularly limited, but is usually preferably 1 or more and 2 or more, and usually 10 or less and 5 or less, more preferably 3 or less. For example, 1 to 10 is preferable, 1 to 5 is more preferable, 1 to 3 is further preferable, and 2 to 3 is even more preferable. When it is at least the lower limit value, the development adhesion tends to be good, and when it is at least the upper limit value, the curability tends to be good. Specific examples of the divalent cyclic aliphatic group include a group obtained by removing two hydrogen atoms from a ring such as a cyclohexane ring, a cycloheptane ring, a cyclodecane ring, a cyclododecane ring, a norbornane ring, an isobornane ring, or an adamantane ring. Be done. Among these, from the viewpoint of reliability, a group obtained by removing two hydrogen atoms from the adamantane ring is preferable.

Examples of the substituent that the divalent aliphatic group may have include 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; and a carboxyl group. From the viewpoint of ease of synthesis, it is preferably unsubstituted.

Examples of the divalent aromatic ring group include a divalent aromatic hydrocarbon ring group and a divalent aromatic heterocyclic group. The carbon number is usually 4 or more, preferably 5 or more, more preferably 6 or more, preferably 30 or less, more preferably 20 or less, still more preferably 15 or less. For example, 4 to 30, more preferably 5 to 20, and even more preferably 6 to 15. When it is at least the lower limit value, the development adhesion tends to be good, and when it is at least the upper limit value, the curability tends to be good.

The aromatic hydrocarbon ring in the divalent aromatic hydrocarbon ring group may be a monocyclic ring or a condensed ring. Examples of the divalent aromatic hydrocarbon ring group include a benzene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring, a perylene ring, a tetracene ring, a pyrene ring, a benzpyrene ring, and a chrysene ring, which have two free valences. Examples include groups such as a triphenylene ring, an acenaphthene ring, a fluorene ring, and a fluorene ring.
Further, the aromatic heterocycle in the aromatic heterocyclic group may be a monocyclic ring or a condensed ring. Examples of the divalent aromatic heterocyclic group include a furan ring, a benzofuran ring, a thiophene ring, a benzothiophene ring, a pyrazole ring, a pyrazole ring, an imidazole ring, an oxadiazole ring, and an indole having two free atomic valences. Rings, carbazole rings, pyroloymidazole rings, pyrrolopyrazole rings, pyrolopyrrole rings, thienopyrol rings, thienothiophene rings, flopyrol rings, flofuran rings, thienofran rings, benzoisoxazole rings, benzoisothiazole rings, benzoimidazole rings, pyridine rings, Examples thereof include groups such as a pyrazine ring, a pyridazine ring, a pyrimidine ring, a triazine ring, a quinoline ring, an isoquinoline ring, a sinoline ring, a quinoxaline ring, a phenanthridin ring, a perimidine ring, a quinazolin ring, a quinazolinone ring, and an azulene ring. Among the divalent aromatic ring groups, a benzene ring, a naphthalene ring or a fluorene ring having two free valences is preferable, and a fluorene ring having two free valences is more preferable, from the viewpoint of patterning characteristics.

Examples of the substituent that the divalent aromatic ring group may have include a hydroxyl group, a methyl group, a methoxy group, an ethyl group, an ethoxy group, a propyl group, a propoxy group and the like. From the viewpoint of development solubility and moisture absorption resistance, no substitution is preferable.

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

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

The bonding mode of the cyclic hydrocarbon group, which is a side chain, is not particularly limited with respect to these divalent hydrocarbon groups. For example, one hydrogen atom of an aliphatic group or an aromatic ring group is replaced with the side chain. Examples thereof include the above-mentioned embodiment and the embodiment in which a cyclic hydrocarbon group as a side chain is formed including one of the carbon atoms of the aliphatic group.

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

In the formula (ii-1), R ^c is synonymous with the formula (ii). R ^α represents a monovalent cyclic hydrocarbon group which may have a substituent. n is an integer of 1 or more. * Represents a bond. The benzene ring in formula (ii-1) may be further substituted with any substituent.

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

The number of rings contained in the aliphatic ring group is not particularly limited, but is usually preferably 1 or more and 2 or more, and usually 6 or less, 4 or less is preferable, and 3 or less is more preferable. For example, 1 to 6 are preferable, 1 to 4 are more preferable, 1 to 3 are further preferable, and 2 to 3 are even more preferable. When it is at least the lower limit value, the development adhesion tends to be good, and when it is at least the upper limit value, the curability tends to be good.
The carbon number of the aliphatic ring group is usually 4 or more, preferably 6 or more, more preferably 8 or more, preferably 40 or less, more preferably 30 or less, further preferably 20 or less, and particularly preferably 15 or less. preferable. For example, 4 to 40 is preferable, 4 to 30 is more preferable, 6 to 20 is further preferable, and 8 to 15 is particularly preferable. When it is at least the lower limit value, the development adhesion tends to be good, and when it is at least the upper limit value, the curability tends to be good.
Specific examples of the aliphatic ring in the aliphatic ring group include a cyclohexane ring, a cycloheptane ring, a cyclodecane ring, a cyclododecane ring, a norbornane ring, an isobornane ring, an adamantane ring and the like. Among these, the adamantane ring is preferable from the viewpoint of compatibility.

On the other hand, the number of rings contained in the aromatic ring group is not particularly limited, but is usually 1 or more, 2 or more, more preferably 3 or more, and usually 10 or less and 5 or less. For example, 1 to 10 is preferable, 1 to 5 is more preferable, 2 to 5 is further preferable, and 3 to 5 is even more preferable. When it is at least the lower limit value, the development adhesion tends to be good, and when it is at least the upper limit value, the curability tends to be good.
Examples of the aromatic ring group include an aromatic hydrocarbon ring group and an aromatic heterocyclic group. The aromatic ring group usually has 4 or more carbon atoms, preferably 5 or more, more preferably 6 or more, and further. , 30 or less is preferable, 20 or less is more preferable, and 15 or less is further preferable. For example, 4 to 30, more preferably 5 to 20, and even more preferably 6 to 15. When it is at least the lower limit value, the development adhesion tends to be good, and when it is at least the upper limit value, the curability tends to be good.
Specific examples of the aromatic ring in the aromatic ring group include a benzene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring, a fluorene ring and the like. Among these, the fluorene ring is preferable from the viewpoint of reliability.

Examples of the substituent that the cyclic hydrocarbon group may have include a hydroxyl group, a methyl group, an ethyl group, an n-propyl group, an iso-propyl group, an n-butyl group, a sec-butyl group and a tert-butyl group. Examples thereof include an alkyl group having 1 to 5 carbon atoms such as an amyl group and an iso-amyl 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, no substitution is preferable.

Although n represents an integer of 1 or more, 2 or more is preferable, and 3 or less is preferable. For example, 1 to 3 is preferable, and 2 to 3 is more preferable. When it is at least the lower limit value, the development adhesion tends to be good, and when it is at least the upper limit value, the curability tends to be good.

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

As described above, the benzene ring in the formula (ii-1) may be further substituted with an arbitrary substituent. Examples of the substituent include a hydroxyl group, a methyl group, a methoxy group, an ethyl group, an ethoxy group, a propyl group, a propoxy group and the like. The number of substituents is not particularly limited, and may be one or two or more.
From the viewpoint of patterning characteristics, it is preferably unsubstituted.

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

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

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

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

The number of rings contained in the aliphatic ring group is not particularly limited, but is usually preferably 1 or more and 2 or more, and usually 10 or less and 5 or less. For example, 1 to 10 is preferable, 1 to 5 is more preferable, and 2 to 5 is even more preferable. When it is at least the lower limit value, the development adhesion tends to be good, and when it is at least the upper limit value, the curability tends to be good.
The carbon number of the aliphatic ring group is usually 4 or more, preferably 6 or more, more preferably 8 or more, preferably 40 or less, more preferably 35 or less, still more preferably 30 or less. For example, 4 to 40 is preferable, 6 to 35 is more preferable, and 8 to 30 is even more preferable. When it is at least the lower limit value, the development adhesion tends to be good, and when it is at least the upper limit value, the curability tends to be good.
Specific examples of the aliphatic ring in the aliphatic ring group include a cyclohexane ring, a cycloheptane ring, a cyclodecane ring, a cyclododecane ring, a norbornane ring, an isobornane ring, an adamantane ring and the like. Among these, the adamantane ring is preferable from the viewpoint of compatibility.

On the other hand, the number of rings contained in the aromatic ring group is not particularly limited, but is usually 1 or more, 2 or more, more preferably 3 or more, and usually 10 or less and 5 or less. For example, 1 to 10 is preferable, 1 to 5 is more preferable, 2 to 5 is further preferable, and 3 to 5 is even more preferable. When it is at least the lower limit value, the development adhesion tends to be good, and when it is at least the upper limit value, the curability tends to be good.
Examples of the aromatic ring group include an aromatic hydrocarbon ring group and an aromatic heterocyclic group. The aromatic ring group usually has 4 or more carbon atoms, preferably 6 or more, more preferably 8 or more, and 10 or more. The above is more preferable, 40 or less is preferable, 30 or less is more preferable, 20 or less is further preferable, and 15 or less is particularly preferable. For example, 4 to 40 is preferable, 6 to 30 is more preferable, 8 to 20 is more preferable, and 10 to 15 is particularly preferable. When it is at least the lower limit value, the development adhesion tends to be good, and when it is at least the upper limit value, the curability tends to be good.
Specific examples of the aromatic ring in the aromatic ring group include a benzene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring, a fluorene ring and the like. Among these, the fluorene ring is preferable from the viewpoint of reliability.

Examples of the substituent that the cyclic hydrocarbon group may have include a hydroxyl group, a methyl group, an ethyl group, an n-propyl group, an iso-propyl group, an n-butyl group, a sec-butyl group and a tert-butyl group. Examples thereof include an alkyl group having 1 to 5 carbon atoms such as an amyl group and an iso-amyl 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, no substitution is preferable.

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

As described above, the benzene ring in the formula (ii-2) may be further substituted with an arbitrary substituent. Examples of the substituent include a hydroxyl group, a methyl group, a methoxy group, an ethyl group, an ethoxy group, a propyl group, a propoxy group and the like. The number of substituents is not particularly limited, and may be one or two or more. Further, the two benzene rings in the formula (ii-2) may be linked via these substituents.
From the viewpoint of patterning characteristics, it is preferably unsubstituted.

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

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

In the formula (ii-3), R ^c and R ^d are synonymous with the above formula (ii). R ^Z represents a hydrogen atom or a polybasic acid residue. )

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

The partial structure represented by the above formula (ii-3) contained in one molecule of the epoxy (meth) acrylate-based resin (b1-B) may be one kind or two or more kinds, for example, ^RX is a hydrogen atom. And those in which R ^Z is a polybasic acid residue may be mixed.

The number of partial structures represented by the formula (ii) contained in one molecule of the epoxy (meth) acrylate resin (b1-B) is not particularly limited, but 1 or more is preferable, and 3 or more is more preferable. Further, 20 or less is preferable, 15 or less is more preferable, and 10 or less is further preferable. For example, 1 to 20 is preferable, 1 to 15 is more preferable, 3 to 15 is more preferable, and 3 to 10 is even more preferable. When it is at least the lower limit value, the curability tends to be good, and when it is at least the upper limit value, the development solubility tends to be good.

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

<(B2) Acrylic copolymer resin>
The acrylic copolymer resin (b2) is not particularly limited as long as it is an acrylic copolymer resin containing a carboxyl group or a hydroxyl group, but it is preferably one having an ethylenically unsaturated group in the side chain. By having an ethylenically unsaturated group, film thinning due to an alkaline developer is less likely to occur during development due to photocuring due to exposure, and the surface roughness tends to be good.

(Partial structure represented by the general formula (I))
(B2) When the acrylic 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, but radicals are released due to the flexibility of the film. From the viewpoint of ease, for example, it is preferable to have a partial structure represented by the following general formula (I).

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

Further, among the partial structures represented by the formula (I), the partial structure represented by the following general formula (I') is preferable from the viewpoint of sensitivity and alkali developability.

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 polybasic acid residue means a monovalent group obtained by subtracting one OH group from the polybasic acid or its anhydride. Polybasic acids include maleic acid, succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, pyromellitic acid, trimellitic acid, benzophenone tetracarboxylic acid, methylhexahydrophthalic acid, endomethylenetetrahydrophthalic acid. One or more selected from acid, chlorendic acid, methyltetrahydrophthalic acid and biphenyltetracarboxylic acid can be mentioned.
Among these, from the viewpoint of patterning properties, maleic acid, succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, pyromellitic acid, trimellitic acid and biphenyltetracarboxylic acid are preferable. Are tetrahydrophthalic acid and biphenyltetracarboxylic acid.

(B2) When the acrylic copolymer resin contains the partial structure represented by the general formula (I), the content ratio thereof is not particularly limited, but is preferably 10 mol% or more, more preferably 30 mol% or more, and 50 mol%. The above is further preferable, 70 mol% or more is further preferable, 80 mol% or more is particularly preferable, 98 mol% or less is preferable, and 95 mol% or less is more preferable. For example, 10 to 98 mol% is preferable, 30 to 98 mol% is more preferable, 50 to 98 mol% is further preferable, 70 to 98 mol% is further preferable, and 80 to 95 mol% is particularly preferable. When it is at least the above lower limit value, the mechanical properties tend to be improved, and when it is at least the above upper limit value, the residue tends to be reduced.

(B2) When the acrylic copolymer resin contains the partial structure represented by the general formula (I'), the content ratio thereof is not particularly limited, but is preferably 10 mol% or more, more preferably 30 mol% or more, and 50. More preferably, it is more preferably mol% or more, more preferably 70 mol% or more, particularly preferably 80 mol% or more, still more preferably 98 mol% or less, and even more preferably 95 mol% or less. For example, 10 to 98 mol% is preferable, 30 to 98 mol% is more preferable, 50 to 98 mol% is further preferable, 70 to 98 mol% is further preferable, and 80 to 95 mol% is particularly preferable. When it is at least the above lower limit value, the alkali developability and mechanical properties tend to be improved, and when it is at least the above upper limit value, the surface roughness tends to be improved and the residue tends to be reduced.

(Partial structure represented by general formula (II))
(B2) When the acrylic copolymer resin contains the partial structure represented by the general formula (I), the other partial structures are not particularly limited, but from the viewpoint of development adhesion, for example, the following general formula (II) It is also preferable to have a partial structure represented by).

In the above formula (II), R ³ represents a hydrogen atom or a methyl group, and R ⁴ is an alkyl group which may have a substituent, an aromatic ring group which may have a substituent, or a substituent. Represents an alkenyl group which may have.

(R ⁴ )
In the 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, particularly preferably 8 or more, still preferably 20 or less, more preferably 18 or less, further preferably 16 or less, and further preferably 14 or less. Even more preferably, 12 or less is particularly preferable. For example, 1 to 20 is preferable, 1 to 18 is more preferable, 3 to 16 is further preferable, 5 to 14 is more preferable, and 8 to 12 is particularly preferable. When it is at least the lower limit value, the surface roughness tends to be improved, and when it is at least the upper limit value, the residue tends to be reduced.

Specific examples of the alkyl group include a methyl group, an ethyl group, a cyclohexyl group, a dicyclopentanyl group, a dodecanyl group and the like. Among these, a dicyclopentanyl group or a dodecanyl group is preferable, and a dicyclopentanyl group is more preferable, from the viewpoint of developability.
The substituents that the alkyl group may have include a methoxy group, an ethoxy group, a chloro group, a bromo group, a fluoro group, a hydroxy group, an amino group, an epoxy group, an oligoethylene glycol group, a phenyl group and a carboxyl group. , Acryloyl group, methacryloyl group and the like, and a hydroxy group and an oligoethylene glycol group are preferable from the viewpoint of developability.

Examples of the aromatic ring group in R ⁴ include a monovalent aromatic hydrocarbon ring group and a monovalent aromatic heterocyclic group. The number of carbon atoms is preferably 6 or more, preferably 24 or less, more preferably 22 or less, further preferably 20 or less, and particularly preferably 18 or less. For example, 6 to 24 is preferable, 6 to 22 is more preferable, 6 to 20 is further preferable, and 6 to 18 is particularly preferable. When it is set to the lower limit value or more, the development adhesion tends to be improved, and when it is set to the upper limit value or less, the residue tends to be reduced.
The aromatic hydrocarbon ring in the aromatic hydrocarbon ring group may be a monocyclic ring or a fused ring, and may be, for example, a benzene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring, a perylene ring, a tetracene ring, or a pyrene. Examples thereof include a ring, a benzpyrene ring, a ttracene ring, a triphenylene ring, an acenaphthene ring, a fluorene ring, and a fluorene ring.
The aromatic heterocyclic group in the aromatic heterocyclic group may be a monocyclic ring or a fused ring, and may be, for example, a furan ring, a benzofuran ring, a thiophene ring, a benzothiophene ring, a pyrazole ring, or a pyrazole ring. , Imidazole ring, oxadiazole ring, indole ring, carbazole ring, pyroloymidazole ring, pyrrolopyrazole ring, pyrolopyrrole ring, thienopyrol ring, thienothiophene ring, flopyrol ring, flofuran ring, thienofran ring, benzoisooxazole ring, benzoiso Thiazol ring, benzoimidazole ring, pyridine ring, pyrazine ring, pyridazine ring, pyrimidine ring, triazine ring, quinoline ring, isoquinoline ring, synolin ring, quinoxaline ring, phenanthridin ring, perimidine ring, quinazoline ring, quinazolinone ring, azulene ring. And so on. Among these, a benzene ring or a naphthalene ring is preferable, and a benzene ring is more preferable, from the viewpoint of developability.
The substituents that the aromatic ring group may have include a methyl group, an ethyl group, a propyl group, a methoxy group, an ethoxy group, a chloro group, a bromo group, a fluoro group, a hydroxy group, an amino group and an epoxy group. , Oligoethylene glycol group, phenyl group, carboxyl group and the like, and from the viewpoint of developability, hydroxy group and oligoethylene glycol group are preferable.

Examples ^{of the alkenyl group in R 4} include a linear, branched chain or cyclic alkenyl group. The number of carbon atoms is preferably 2 or more, preferably 22 or less, more preferably 20 or less, further preferably 18 or less, further preferably 16 or less, and particularly preferably 14 or less. For example, 2 to 22 is preferable, 2 to 20 is more preferable, 2 to 18 is further preferable, 2 to 16 is more preferable, and 2 to 14 is particularly preferable. When it is at least the lower limit value, the surface roughness tends to be improved, and when it is at least the upper limit value, the residue tends to be reduced.

The substituents that the alkenyl group may have include a methyl group, an ethyl group, a propyl group, a methoxy group, an ethoxy group, a chloro group, a bromo group, a fluoro group, a hydroxy group, an amino group, an epoxy group and an oligo. Examples thereof include an ethylene glycol group, a phenyl group and a carboxyl group, and a hydroxy group and an oligoethylene glycol group are preferable from the viewpoint of developability.

As described above, 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. From the viewpoint of developability and film strength, an alkyl group or an alkenyl is preferable, and an alkyl group is more preferable.

(B2) When the acrylic copolymer resin contains the partial structure represented by the general formula (II), the content ratio thereof is not particularly limited, but is preferably 0.1 mol% or more, more preferably 0.5 mol% or more. Preferably, 1 mol% or more is further preferable, 70 mol% or less is preferable, 50 mol% or less is more preferable, 30 mol% or less is further preferable, and 10 mol% or less is particularly preferable. For example, 0.1 to 70 mol% is preferable, 0.1 to 50 mol% is more preferable, 0.5 to 30 mol% is further preferable, and 1 to 10 mol% is particularly preferable. When it is at least the lower limit value, the surface roughness tends to be improved, and when it is at least the upper limit value, the residue tends to be reduced.

(Partial structure represented by general formula (III))
(B2) When the acrylic copolymer resin contains the partial structure represented by the general formula (I), the other partial structure contained is represented by the following general formula (III) from the viewpoint of heat resistance and film strength. It is preferable that a partial structure is included.

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

(R ⁶ )
In the above formula (III), R ⁶ is 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, or a carboxyl group. , Halogen atom, an alkoxy group which may have a substituent, a thiol group, or an alkyl sulfide group which may have a substituent.
Examples ^{of the alkyl group in R 6} 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, still preferably 20 or less, more preferably 18 or less, further preferably 16 or less, further preferably 14 or less, and even more preferably 12 or less. Is particularly preferable. For example, 1 to 20 is preferable, 3 to 18 is more preferable, 3 to 16 is further preferable, 5 to 14 is more preferable, and 5 to 12 is particularly preferable. When it is at least the lower limit value, the surface roughness tends to be improved, and when it is at least the upper limit value, the residue tends to be reduced.

Specific examples of the alkyl group include a methyl group, an ethyl group, a cyclohexyl group, a dicyclopentanyl group, a dodecanyl group and the like. Among these, a dicyclopentanyl group or a dodecanyl group is preferable, and a dicyclopentanyl group is more preferable, from the viewpoint of developability and surface roughness.
The substituents that the alkyl group may have include a methoxy group, an ethoxy group, a chloro group, a bromo group, a fluoro group, a hydroxy group, an amino group, an epoxy group, an oligoethylene glycol group, a phenyl group and a carboxyl group. , Acryloyl group, methacryloyl group and the like, and a hydroxy group and an oligoethylene glycol group are preferable from the viewpoint of developability.

Examples ^{of the alkenyl group in R 6} include a linear, branched chain or cyclic alkenyl group. The number of carbon atoms is preferably 2 or more, preferably 22 or less, more preferably 20 or less, further preferably 18 or less, further preferably 16 or less, and particularly preferably 14 or less. For example, 2 to 22 is preferable, 2 to 20 is more preferable, 2 to 18 is further preferable, 2 to 16 is more preferable, and 2 to 14 is particularly preferable. When it is at least the lower limit value, the surface roughness tends to be improved, and when it is at least the upper limit value, the residue tends to be reduced.

The substituents that the alkenyl group may have include a methyl group, an ethyl group, a propyl group, a methoxy group, an ethoxy group, a chloro group, a bromo group, a fluoro group, a hydroxy group, an amino group, an epoxy group and an oligo. Examples thereof include an ethylene glycol group, a phenyl group and a carboxyl group, and a hydroxy group and an oligoethylene glycol group are preferable from the viewpoint of developability.

Examples of the alkynyl group in R ⁶ include a linear, branched or cyclic alkynyl group. The number of carbon atoms is preferably 2 or more, preferably 22 or less, more preferably 20 or less, further preferably 18 or less, further preferably 16 or less, and particularly preferably 14 or less. For example, 2 to 22 is preferable, 2 to 20 is more preferable, 2 to 18 is further preferable, 2 to 16 is more preferable, and 2 to 14 is particularly preferable. When it is at least the lower limit value, the surface roughness tends to be improved, and when it is at least the upper limit value, the residue tends to be reduced.

The substituents that the alkynyl group may have include a methyl group, an ethyl group, a propyl group, a methoxy group, an ethoxy group, a chloro group, a bromo group, a fluoro group, a hydroxy group, an amino group, an epoxy group and an oligo. Examples thereof include an ethylene glycol group, a phenyl group and a carboxyl group, and a hydroxy group and an oligoethylene glycol group are preferable from the viewpoint of developability.

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

Examples ^{of the alkoxy group in R 6} include a linear, branched chain or cyclic alkoxy group. The number of carbon atoms is preferably 1 or more, preferably 20 or less, more preferably 18 or less, further preferably 16 or less, further preferably 14 or less, and particularly preferably 12 or less. For example, 1 to 20 is preferable, 1 to 18 is more preferable, 1 to 16 is further preferable, 1 to 14 is more preferable, and 1 to 12 is particularly preferable. When it is at least the lower limit value, the surface roughness tends to be improved, and when it is at least the upper limit value, the residue tends to be reduced.

The substituents that the alcoholic group may have include a methoxy group, an ethoxy group, a chloro group, a bromo group, a fluoro group, a hydroxy group, an amino group, an epoxy group, an oligoethylene glycol group, a phenyl group and a carboxyl group. , Acryloyl group, methacryloyl group and the like, and a hydroxy group and an oligoethylene glycol group are preferable from the viewpoint of developability.

Examples of the alkyl sulfide group in R ⁶ include linear, branched or cyclic alkyl sulfide groups. The number of carbon atoms is preferably 1 or more, preferably 20 or less, more preferably 18 or less, further preferably 16 or less, further preferably 14 or less, and particularly preferably 12 or less. For example, 1 to 20 is preferable, 1 to 18 is more preferable, 1 to 16 is further preferable, 1 to 14 is more preferable, and 1 to 12 is particularly preferable. When it is at least the lower limit value, the surface roughness tends to be improved, and when it is at least the upper limit value, the residue tends to be reduced.

The substituents that the alkyl group in the alkyl sulfide group may have include a methoxy group, an ethoxy group, a chloro group, a bromo group, a fluoro group, a hydroxy group, an amino group, an epoxy group, an oligoethylene glycol group and a phenyl group. Examples thereof include a group, a carboxyl group, an acryloyl group and a methacryloyl group, and a hydroxy group and an oligoethylene glycol group are preferable from the viewpoint of developability.

As described above, R ⁶ has 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, and a halogen. It represents an alkylsulfide group which may have an atom, an alkoxy group, a hydroxyalkyl group, a thiol group, or a substituent. Among these, a hydroxyl group or a carboxyl group is preferable, and a carboxyl group is more preferable, from the viewpoint of developability. preferable.

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

(B2) When the acrylic copolymer resin contains the partial structure represented by the general formula (III), the content ratio thereof is not particularly limited, but is preferably 0.5 mol% or more, more preferably 1 mol% or more. 2 mol% or more is more preferable. Further, 50 mol% or less is preferable, 30 mol% or less is more preferable, 20 mol% or less is further preferable, and 10 mol% or less is more preferable. For example, 0.5 to 50 mol% is preferable, 1 to 30 mol% is more preferable, 1 to 20 mol% is further preferable, and 2 to 10 mol% is more preferable. When it is at least the lower limit value, the surface roughness tends to be improved, and when it is at least the upper limit value, the residue tends to be reduced.

(Partial structure represented by general formula (IV))
(B2) When the acrylic copolymer resin has the partial structure represented by the general formula (I), as the other partial structure contained, the partial structure represented by the following general formula (IV) is used from the viewpoint of developability. It is also preferable to have.

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

(B2) When the acrylic copolymer resin contains the partial structure represented by the general formula (IV), the content ratio thereof is not particularly limited, but is preferably 5 mol% or more, more preferably 10 mol% or more, and 20 mol. % Or more is more preferable, 80 mol% or less is preferable, 70 mol% or less is more preferable, and 60% mol or less is further preferable. For example, 5 to 80 mol% is preferable, 10 to 70 mol% is more preferable, and 20 to 60% mol is further preferable. When it is set to the lower limit value or more, the developability tends to be improved, and when it is set to the upper limit value or less, the surface roughness tends to be improved.

On the other hand, the acid value of the (b2) acrylic copolymer resin 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 preferably 150 mgKOH / g or less. , 120 mgKOH / g or less is more preferable, 100 mgKOH / g or less is further preferable, and 50 mgKOH / g or less is even more preferable. For example, 10 to 150 mgKOH / g is preferable, 10 to 120 mgKOH / g is more preferable, 15 to 100 mgKOH / g is further preferable, and 20 to 50 mgKOH / g is even more preferable. When it is set to the lower limit value or more, the developability tends to be improved, and when it is set to the upper limit value or less, the surface roughness tends to be improved.

(B2) The weight average molecular weight (Mw) of the acrylic copolymer resin is not particularly limited, but is usually 1000 or more, preferably 2000 or more, more preferably 4000 or more, still more preferably 6000 or more, still more preferably 7000 or more, particularly preferably. Is 8000 or more, and is usually 30,000 or less, preferably 20,000 or less, more preferably 15,000 or less, still more preferably 10,000 or less. For example, 1000 to 20000 is preferable, 2000 to 20000 is more preferable, 4000 to 15000 is further preferable, 60000 to 15000 is further preferable, 70000 to 10000 is particularly preferable, and 800 to 10000 is particularly preferable. When it is at least the lower limit value, the surface roughness tends to be improved, and when it is at least the upper limit value, the developability tends to be good.

(B2) The double bond equivalent of the acrylic 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 preferably 100 or more, 150 or more. Is more preferable, 180 or more is further preferable, and 200 or more is particularly preferable. For example, 100 to 500 is preferable, 150 to 400 is more preferable, 180 to 350 is further preferable, and 200 to 300 is particularly preferable. When it is set to the upper limit value or less, the mechanical properties and surface roughness tend to be improved, and when it is set to the lower limit value or more, the storage stability tends to be improved.

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

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

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

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

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

The ^{number of carbon atoms of the alkyl groups of R 1 to} R ³ is not particularly limited as long as it is in the range of 1 to 4, but from the viewpoint of mechanical properties, it is preferably 3 or less, more preferably 2 or less. The alkyl group may be chain-like or cyclic. Specific examples of the alkyl group include a methyl group, an ethyl group, a propyl group and an isopropyl group, and among them, a methyl group and an ethyl group are preferable. As the ^{substituent which the alkyl group having 1 to 4 carbon atoms of R 1 to} R ³ may have, a group of a monovalent non-metal atomic group excluding hydrogen is used, and a halogen atom (-) is a preferable example. Examples thereof include F, -Br, -Cl, -I), a hydroxyl group and an alkoxy group.

The ^{number of carbon atoms of the alkoxy groups of R 1 to} R ³ is not particularly limited as long as it is within the range of 1 to 4, but is preferably 3 or less, more preferably 2 or less, from the viewpoint of increasing the taper angle. The alkyl group portion of the alkoxy group may be chain-like or cyclic. Specific examples of the alkoxy group include, for example, a methoxy group, an ethoxy group, a propoxy group, an isopropyloxy group, and a butoxy group, and among them, a methoxy group and an ethoxy group are preferable. Examples of the substituent that the alkoxy group having 1 to 4 carbon atoms of R ^{1 to R 3} may have include an alkyl group and an alkoxy group, and an alkyl group is preferable.

Examples of the halogen atoms of R ^{1 to} R ³ include chlorine atom, iodine atom, bromine atom, and fluorine atom. Among them, chlorine atom or fluorine atom is preferable, and chlorine atom is more preferable from the viewpoint of easiness of synthesis. preferable.
Among these, from the viewpoint of sensitivity and ease of synthesis, R ^{1 to} R ³ are preferably halogen atoms independently, and more preferably chlorine atoms.

Although m, n and l each independently represent an integer of 0 to 5, from the viewpoint of ease of synthesis, it is preferable that at least two of m, n and l are integers of 1 or more, and m, n and l. It is more preferable that any two of them are 1 and the remaining 1 is 0.

Examples of the hexaarylbiimidazole 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-chlorophenyl) -4, 4', 5,5'-tetra (o, p-dichlorophenyl) biimidazole, 2,2'-bis (o, p-dichlorophenyl) -4,4', 5,5'-tetra (o, p-dichlorophenyl) ) Biimidazole, 2,2'-bis (o-chlorophenyl) -4,4', 5,5'-tetra (p-fluorophenyl) biimidazole, 2,2'-bis (o-chlorophenyl) -4, 4', 5,5'-tetra (o, p-dibromophenyl) biimidazole, 2,2'-bis (o-bromophenyl) -4,4', 5,5'-tetra (o, p-dichlorophenyl) ) Biimidazole, 2,2'-bis (o-chlorophenyl) -4,4', 5,5'-tetra (p-chloronaphthyl) biimidazole and the like. Of these, a hexaphenylbiimidazole compound is preferable, and a compound in which the o-position of the benzene ring bonded to the 2,2'-position on the imidazole ring is replaced with a methyl group, a methoxy group, or a halogen atom is more preferable. It is preferable that the benzene ring bonded to the 4,4', 5,5'-position on the imidazole ring is unsubstituted or substituted with a halogen atom or a methoxy group.

(C) As the photopolymerization initiator, either a hexaarylbiimidazole compound represented by the general formula (1-1) or a hexaarylbiimidazole compound represented by the general formula (1-2) may be used. , Both may be used together. When used in combination, the ratio is not particularly limited.

Examples of titanosen derivatives include dicyclopentadienyl titanium dichloride, dicyclopentadienyl titanium bisphenyl, dicyclopentadienyl titanium bis (2,3,4,5,6-pentafluorophenyl), and dicyclopenta. Dienyltitanium bis (2,3,5,6-tetrafluorophenyl), dicyclopentadienyltitanium bis (2,4,6-trifluorophenyl), dicyclopentadienyltitanium di (2,6-difluorophenyl) Phenyl), dicyclopentadienyl titanium di (2,4-difluorophenyl), di (methylcyclopentadienyl) titanium bis (2,3,4,5,6-pentafluorophenyl), di (methylcyclopenta) Dienyl) Titanium bis (2,6-difluorophenyl), dicyclopentadienyl titanium [2,6-difluoro-3- (pyrrole-1-yl) phenyl] and the like can be mentioned.

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

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

Examples of α-aminoalkylphenone derivatives include 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropane-1-one and 2-benzyl-2-dimethylamino-1- (4). -Morphorinophenyl) butane-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butane-1-one, 4-dimethylaminoethylbenzoate, 4-dimethylaminoisoamyl Benzoate, 4-diethylaminoacetophenone, 4-dimethylaminopropiophenone, 2-ethylhexyl-1,4-dimethylaminobenzoate, 2,5-bis (4-diethylaminobenzal) cyclohexanone, 7-diethylamino-3-3 Examples thereof include (4-diethylaminobenzoyl) coumarin and 4- (diethylamino) chalcone.

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

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

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

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

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

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

The carbon number of the alkanoyl group in R ^22a is not particularly limited, but from the viewpoint of solubility in a solvent and sensitivity, it is usually 2 or more, preferably 3 or more, and usually 20 or less, preferably 15 or less, more preferably. It is 10 or less, more preferably 5 or less. For example, 2 to 20 is preferable, 2 to 15 is more preferable, 2 to 10 is further preferable, 2 to 5 is more preferable, and 3 to 5 is particularly preferable. Specific examples of the alkanoyl group include an acetyl group, a propanoyl group, a butanoyl group and the like.
Examples of the substituent that the alkanoyl group may have include an aromatic ring group, a hydroxyl group, a carboxyl group, a halogen atom, an amino group, an amide group, and the like, and from the viewpoint of easiness of synthesis, the substituent should be unsubstituted. Is preferable.

The ^{number of carbon atoms of the allylloyl group in R 22a} is not particularly limited, but from the viewpoint of solubility in a solvent and sensitivity, it is usually 7 or more, preferably 8 or more, and usually 20 or less, preferably 15 or less, more preferably. It is 12 or less, more preferably 10 or less. For example, 7 to 20 is preferable, 7 to 15 is more preferable, 7 to 12 is further preferable, and 8 to 12 is even more preferable. Specific examples of the allylloyl group include a benzoyl group and a naphthoyl group.
Examples of the substituent that the allylloyl group may have include a hydroxyl group, a carboxyl group, a halogen atom, an amino group, an amide group, an alkyl group and the like, and from the viewpoint of easiness of synthesis, it is preferably unsubstituted. ..
Among these, from the viewpoint of sensitivity, R ^22a is preferably an alkanoyl group which may have a substituent, more preferably an unsubstituted alkanoyl group, and further preferably an acetyl group.

Further, the initiator described in Japanese Patent Application Laid-Open No. 2016-133574 is also preferably used from the viewpoint of reducing contamination of the liquid crystal layer by the colorant.

As the photopolymerization initiator, one type may be used alone, or two or more types may be used in combination.
If necessary, the photopolymerization initiator may be blended with a sensitizing dye and a polymerization accelerator according to the wavelength of the image exposure light source for the purpose of increasing the sensitivity. Examples of the sensitizing dye include the xanthene dyes described in Japanese Patent Application Laid-Open No. 4-221958, Japanese Patent Application Laid-Open No. 4-219756, Japanese Patent Application Laid-Open No. 3-239703, and Japanese Patent Application Laid-Open No. 5-289335. The coumarin dye having a heterocycle described in Japanese Patent Application Laid-Open No. 3-239703, 3-Ketokumarin compound described in Japanese Patent Application Laid-Open No. 5-289335, and pyromethene described in Japanese Patent Application Laid-Open No. 6-19240. Dyes and others, Japanese Patent Application Laid-Open No. 47-2528, Japanese Japanese Patent Application Laid-Open No. 54-155292, Japanese Patent Application Publication No. 45-373777, Japanese Patent Application Laid-Open No. 48-84183, Japanese Patent Application Laid-Open No. Japanese Patent Application Laid-Open No. 52-112681, Japanese Patent Application Laid-Open No. 58-15503, Japanese Patent Application Laid-Open No. 60-88805, Japanese Patent Application Laid-Open No. 59-56403, Japanese Patent Application Laid-Open No. 2-69 It has a dialkylaminobenzene skeleton described in Japanese Patent Application Laid-Open No. 57-168808, Japanese Patent Application Laid-Open No. 5-107761, Japanese Patent Application Laid-Open No. 5-210240, and Japanese Patent Application Laid-Open No. 4-288818. Pigments and the like can be mentioned.

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

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

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

In the present invention, it is particularly desirable to use a polyfunctional ethylenic monomer having two or more ethylenically unsaturated groups in one molecule. The number of ethylenically unsaturated groups contained in the polyfunctional ethylenic monomer is not particularly limited, but is usually 2 or more, preferably 4 or more, more preferably 5 or more, and preferably 5 or more. The number is 8 or less, more preferably 7 or less. For example, 2 to 8 are preferable, 4 to 8 are more preferable, 4 to 7 are even more preferable, and 5 to 7 are even more preferable. When it is set to the lower limit value or more, the sensitivity tends to be high, and when it is set to the upper limit value or less, the solubility in a solvent tends to be improved.
Examples of polyfunctional ethylenic monomers include, for example, an ester of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid; an ester of an aromatic polyhydroxy compound and an unsaturated carboxylic acid; an aliphatic polyhydroxy compound, an aromatic poly. Examples thereof include an ester obtained by an esterification reaction of a polyvalent hydroxy compound such as a hydroxy compound with an unsaturated carboxylic acid and a polybasic carboxylic acid.

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

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

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

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

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

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

<(E) Solvent>
The photosensitive coloring composition of the present invention may contain (e) a solvent. (E) By containing a solvent, the pigment can be dispersed in the solvent, and the application tends to be easy.
The photosensitive coloring composition of the present invention is usually used with (a) a colorant, (b) an alkali-soluble resin, (c) a photopolymerization initiator, and (d) an ethylenically unsaturated compound, and if necessary. Other compounding ingredients are used in a state of being dissolved or dispersed in a solvent. Among the solvents, an organic solvent is preferable from the viewpoint of dispersibility and coatability.

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

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

Ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol mono-n-butyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, propylene glycol monobutyl ether acetate, methoxybutyl Acetate, 3-methoxybutyl acetate, methoxypentyl acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol mono-n-butyl ether acetate, dipropylene glycol monomethyl ether acetate, triethylene glycol monomethyl ether acetate, triethylene glycol monoethyl Glycolalkyl ether acetates such as ether acetate, 3-methyl-3-methoxybutyl acetate;
Glycol diacetates such as ethylene glycol diacetate, 1,3-butylene glycol diacetate, 1,6-hexanol diacetate;
Alkyl acetates such as cyclohexanol acetate;
Ethers such as amyl ether, diethyl ether, dipropyl ether, diisopropyl ether, dibutyl ether, diamil ether, ethyl isobutyl ether, dihexyl ether;

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

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

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

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

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

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

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

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

<(F) Dispersant>
The photosensitive coloring composition of the present invention may contain (f) a dispersant for the purpose of (a) finely dispersing the colorant and stabilizing the dispersed state thereof.
(F) As the dispersant, a polymer dispersant having a functional group is preferable, and further, from the viewpoint of dispersion stability, a carboxyl group; a phosphoric acid group; a sulfonic acid group; or these bases; a primary, secondary or tertiary. A polymer dispersant having a functional group such as an amino group; a quaternary ammonium base; a group derived from a nitrogen-containing heterocycle such as pyridine, pyrimidine, or pyrazine is preferable. Among them, in particular, a polymer dispersant having a basic functional group such as a primary, secondary or tertiary amino group; a quaternary ammonium base; a group derived from a nitrogen-containing heterocycle such as pyridine, pyrimidine, or pyrazine, etc. disperses the pigment. It is particularly preferable from the viewpoint that it can be dispersed with a small amount of dispersant.

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

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

The weight average molecular weight (Mw) of the polymer dispersant is usually 700 or more, preferably 1000 or more, and usually 100,000 or less, preferably 50,000 or less. For example, 700 to 100,000 is preferable, 700 to 50,000 is more preferable, and 1,000 to 50,000 is even more preferable.
Of these, from the viewpoint of pigment dispersibility, the dispersant (f) preferably contains a urethane-based polymer dispersant having a functional group and / or an acrylic polymer dispersant, and the acrylic polymer dispersant is used. It is particularly preferable to include it.
Further, from the viewpoint of dispersibility and storage stability, a polymer dispersant having a basic functional group and having a polyester bond and / or a polyether bond is preferable.

Examples of urethane-based and acrylic-based polymer dispersants include DISPERBYK 160 to 166, 182 series (all urethane-based), DISPERBYK2000, 2001, BYK-LPN21116 and the like (all are acrylic-based) (all manufactured by Big Chemie). ..
To specifically exemplify a preferable chemical structure as a urethane-based polymer dispersant, for example, a polyisocyanate compound and a compound having one or two hydroxyl groups in the molecule and having a number average molecular weight of 300 to 10,000 are contained in the same molecule. Examples thereof include a dispersed resin having a weight average molecular weight of 1000 to 200,000, which is obtained by reacting an active hydrogen with a compound having a tertiary amino group. By treating these with a quaternary agent such as benzyl chloride, all or a part of the tertiary amino group can be converted into a quaternary ammonium base.

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

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

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

The polyether ester diol is obtained by reacting an ether group-containing diol or a mixture with other glycols with a dicarboxylic acid or an anhydride thereof, or reacting a polyester glycol with an alkylene oxide, for example, poly (poly). Oxytetramethylene) adipate and the like. The most preferable polyether glycol is polyethylene glycol, polypropylene glycol, polyoxytetramethylene glycol, or a compound in which one terminal hydroxyl group of these compounds is alkoxylated with an alkyl group having 1 to 25 carbon atoms.

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

Polycarbonate glycol includes poly (1,6-hexylene) carbonate, poly (3-methyl-1,5-pentylene) carbonate and the like, and polyolefin glycol includes polybutadiene glycol, hydrogenated polybutadiene glycol, hydrogenated polyisoprene glycol and the like. Can be mentioned.
One of these may be used alone, or two or more thereof 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 10000, preferably 500 to 6000, and more preferably 1000 to 4000.

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

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

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

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

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

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

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

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

When the isocyanate group remains in the polymer dispersant by the above reaction, it is preferable to convert the isocyanate group into another functional group with an alcohol or an amino compound because the stability of the product with time becomes high.
The weight average molecular weight (Mw) of the urethane-based polymer dispersant is usually 1000 to 20000, preferably 2000 to 100,000, and more preferably 3000 to 50000. When it is at least the lower limit value, the dispersibility and dispersion stability tend to be good, and when it is at least the upper limit value, it tends to be easy to suppress a decrease in solubility and dispersibility.

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

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

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

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

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

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

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

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

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

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

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

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

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

In the above formula (i), R ^{31 to} R ³³ each independently have a hydrogen atom, an alkyl group which may have a substituent, an aryl group which may have a substituent, or a substituent. It is an aralkyl group which may be present, and ^{two or more of R 31 to} R ³³ may be bonded to each other to form a cyclic structure. R ³⁴ is a hydrogen atom or a methyl group. X is a divalent linking group and Y ^- is a counter anion.

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

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

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

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

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

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

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

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

The substituents that the alkyl group, aralkyl group or aryl group in R ^{31 to} R ³³ of the above formula (i) and R ³⁵ and R ^{36 of the above formula (ii) may have include a halogen atom and an alkoxy group.} Benzoyl groups, hydroxyl groups and the like can be mentioned.

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

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

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

Further, the content ratio of the repeating unit represented by the above formula (ii) to all the repeating units of the polymer dispersant is not particularly limited, but from the viewpoint of dispersibility, 5 mol% or more is preferable, and 10 mol% or more is preferable. More preferably, 15 mol% or more is further preferable, 20 mol% or more is particularly preferable, 60 mol% or less is preferable, 40 mol% or less is more preferable, 30 mol% or less is further preferable, and 25 mol% or less is particularly preferable. preferable. For example, 5 to 60 mol% is preferable, 10 to 40 mol% is more preferable, 15 to 30 mol% is further preferable, and 20 to 25 mol% is particularly preferable.

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

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

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

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

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

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

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

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

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

^{The number of carbon atoms of the aralkyl group which may have a substituent in R 38} of the above formula (iv) is not particularly limited, but is usually 7 or more, preferably 16 or less, and preferably 12 or less. More preferably, it is more preferably 10 or less. For example, 7 to 16 is preferable, 7 to 12 is more preferable, and 7 to 10 is even more preferable. Specific examples of the aralkyl group include a phenylmethyl group, a phenylethyl group, a phenylpropyl group, a phenylbutyl group, a phenylisopropyl group and the like, and among these, a phenylmethyl group, a phenylethyl group, a phenylpropyl group, or a phenyl group. It is preferably a butyl group, more preferably a phenylmethyl group or a phenylethyl group.

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

Further, the content ratio of the repeating unit represented by the above formula (iv) in all the repeating units of the polymer dispersant is preferably 30 mol% or more, more preferably 40 mol% or more, and more preferably 50, from the viewpoint of dispersibility. More preferably, it is more than mol%, more preferably 80 mol% or less, and more preferably 70 mol% or less. For example, 30 to 80 mol% is preferable, 40 to 80 mol% is more preferable, and 50 to 70 mol% or more is further preferable.

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

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

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

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

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

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

<Other ingredients of the photosensitive coloring composition>
In addition to the above-mentioned components, the photosensitive coloring composition of the present invention includes adhesion improvers such as silane coupling agents, surfactants (coatability improvers), pigment derivatives, photoacid generators, cross-linking agents, and mercapto compounds. , Polymerization inhibitors, development improvers, ultraviolet absorbers, antioxidants and other additives can be appropriately added.

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

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

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

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

As the surfactant, for example, various kinds such as anionic type, cationic type, nonionic type, amphoteric surfactant and the like can be used. Among them, it is preferable to use a nonionic surfactant because it is unlikely to adversely affect various properties, and among them, a fluorine-based or silicon-based surfactant is effective in terms of coatability.
Examples of such surfactants include TSF4460 (manufactured by Momentive Performance Materials), DFX-18 (manufactured by Neos), BYK-300, BYK-325, BYK-330 (manufactured by Big Chemie), and KP340. (Manufactured by Shin-Etsu Silicone Co., Ltd.), Mega Fvck (registered trademark, the same shall apply hereinafter) F-470, Mega Fvck F-475, Mega Fvck F-478, Mega Fvck F-554, Mega Fvck F-559 (manufactured by DIC), SH7PA (manufactured by Toray Dow Corning Co., Ltd.), DS-401 (manufactured by Daikin Co., Ltd.), L-77 (manufactured by Nippon Unicar Co., Ltd.), FC4430 (manufactured by 3M Co., Ltd.) and the like can be mentioned.
As the surfactant, one type may be used, or two or more types may be used in combination in any combination and ratio.

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

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

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

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

In formula (6), R ⁶¹ represents -NR ⁶⁶ R ⁶⁷ groups or an aryl group having 6 to 12 carbon atoms, and when R ⁶¹ is -NR ⁶⁶ R ⁶⁷ groups, R ⁶² , R ⁶³ , R ⁶⁴ , R ^65. , R ⁶⁶ and R ⁶⁷ represent CH ₂ OR ⁶⁸ groups, 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 _{is −CH 2} OR ^68. Representing a group, ^{the rest of R 62} , R ⁶³ , R ⁶⁴ , R ⁶⁵ , R ⁶⁶ and R ⁶⁷ _{represent hydrogen or -CH 2} OR ⁶⁸ groups independently of each other, where R ⁶⁸ is a hydrogen atom or 1 to 4 carbon atoms. Represents the alkyl group of.
Here, the aryl group having 6 to 12 carbon atoms is typically a phenyl group, a 1-naphthyl group or a 2-naphthyl group, and these phenyl groups and naphthyl groups include an alkyl group, an alkoxy group, a halogen atom and the like. Substituents may be attached. The alkyl group and the alkoxy group can each have about 1 to 6 carbon atoms. Among the above, the alkyl group represented by R ⁶⁸ is preferably a methyl group or an ethyl group, particularly a methyl group.

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

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

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

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

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

(6) Mercapto compound It is also possible to add a mercapto compound as a polymerization accelerator and for improving the curability and surface roughness of the surface of the cured product.
Examples of the mercapto compound include a mercapto group-containing compound having an aromatic ring and an aliphatic mercapto group-containing compound.

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

In formula (1-3), Z represents -O-, -S- or -NH-, and R ⁶¹ , R ⁶² , R ⁶³ , and R ⁶⁴ each independently have a hydrogen atom or a monovalent substituent. show.
Of these, from the viewpoint of photocurability, Z is preferably -S- or -NH-, and more preferably -NH-.
From the viewpoint of photocurability, R ⁶¹ , R ⁶² , R ⁶³ , and R ⁶⁴ are each independently preferably a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or an alkoxy group having 1 to 4 carbon atoms, and a hydrogen atom. Is more preferable.

Specifically, 2-mercaptobenzothiazole, 2-mercaptobenzimidazole, 2-mercaptobenzoxazole, 3-mercapto-1,2,4-triazole, 2-mercapto-4 (3H) -quinazoline, β-mercaptonaphthalene. , 1,4-Dimethylmercaptobenzene and the like, which include mercapto group-containing compounds having an aromatic ring, and 2-mercaptobenzothiazole and 2-mercaptobenzimidazole are preferable from the viewpoint of taper angle.

On the other hand, as the aliphatic mercapto group-containing compound, hexanedithiol, decandithiol, or a compound represented by the following general formula (1-4) is preferably used from the viewpoint of photocurability.

In equation (1-4), m represents an integer of 0 to 4, and n represents an integer of 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 an n-valent group.

In the general formula (1-4), m is preferably 1 or 2 from the viewpoint of photocurability. Further, from the viewpoint of photocurability, n is preferably 3 or 4, and more preferably 4.
Further, ^{as the alkyl group of R 71} and R ⁷² , those having 1 to 3 carbon atoms are preferable from the viewpoint of photocurability. From the viewpoint of photocurability, at least one of ^{R 71} and R ^{72 , for example, R 72} is preferably a hydrogen atom, in which case R ⁷¹ is a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. It is preferable to have.

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 branched portion. From the viewpoint of photocurability, an alkylene group having 1 to 6 carbon atoms is more preferable, and an alkylene group having 4 carbon atoms is further preferable.

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

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

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

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

Specifically, butanediol bis (3-mercaptopropionate), butanediol bisthioglycolate, ethylene glycol bis (3-mercaptopropionate), ethylene glycol bisthioglycolate, trimethylpropanthris (3-). Mercaptopropionate), Trimethylol Propanetristhioglycolate, Trishydroxyethyl Tristhiopropionate, Pentaerythritol Tetrakiss (3-Mercaptopropionate), Pentaerythritol Tris (3-Mercaptopropionate), Butanediolbis (3-Mercaptobutyrate), Ethylene Glycolbis (3-Mercaptobutyrate), Trimethylol Propantris (3-Mercaptobutyrate), Pentaerythritol Tetrakiss (3-Mercaptobutyrate), Pentaerythritol Tris (3-Mercaptobutyrate) Rate), 1,3,5-tris (3-mercaptobutyloxyethyl) -1,3,5-triazine-2,4,6 (1H, 3H, 5H) -trione and the like.

Of these, trimethylolpropanthris (3-mercaptopropionate), pentaerythritol tetrakis (3-mercaptopropionate), pentaerythritoltris (3-mercaptopropionate), and trimethylolpropanthris (3-mercaptobutyrate). ), Pentaerythritol tetrakis (3-mercaptobutyrate), pentaerythritol tris (3-mercaptobutyrate), 1,3,5-tris (3-mercaptobutyloxyethyl) -1,3,5-triazine-2, 4,6 (1H, 3H, 5H) -trione is preferable, and pentaerythritol tetrakis (3-mercaptopropionate) and pentaerythritol tetrakis (3-mercaptobutyrate) are more preferable.

These can be used alone or in admixture of two or more.

Among these, from the viewpoint of photocurability, one or more selected from the group consisting of 2-mercaptobenzothiazole, 2-mercaptobenzimidazole, and 2-mercaptobenzoxazole are combined with a photopolymerization initiator to produce light. It is suitable to be used as a polymerization initiator system. For example, 2-mercaptobenzothiazole may be used, 2-mercaptobenzimidazole may be used, or 2-mercaptobenzothiazole and 2-mercaptobenzimidazole may be used in combination.
Further, from the viewpoint of photocurability, it is preferable to use one or more selected from the group consisting of pentaerythritol tetrakis (3-mercaptopropionate) and pentaerythritol tetrakis (3-mercaptobutyrate).

Further, particularly from the viewpoint of photocurability, it is preferable to use a mercapto group-containing compound having an aromatic ring and an aliphatic mercapto group-containing compound in combination. This is because by using a mask with a narrow opening width, the illuminance per unit area is lowered due to diffraction during exposure, and it is more susceptible to oxygen inhibition than when the line width is wide, and the surface curability is lowered. Because there is a tendency.

In particular, (c) when a hexaarylbiimidazole-based photopolymerization initiator is used as the photopolymerization initiator, a mercapto group-containing compound having an aromatic ring and an aliphatic mercapto group-containing compound are used in combination. Is preferable. On the other hand, when an acetophenone-based photopolymerization initiator is used, a sufficient effect tends to be obtained even when an aliphatic mercapto group-containing compound is used alone.

For example, one or more selected from the group consisting of 2-mercaptobenzothiazole, 2-mercaptobenzimidazole, and 2-mercaptobenzoxazole, and pentaerythritol tetrakis (3-mercaptopropionate), pentaerythritol tetrakis (3-mercapto). It is preferable to use one or more selected from the group consisting of (butylate) in combination with a photopolymerization initiator.

(7) Polymerization inhibitor From the viewpoint of shape control, a polymerization inhibitor may be contained.
Examples of the polymerization inhibitor include hydroquinone, hydroquinone monomethyl ether, methylhydroquinone, methoxyphenol, 2,6-di-tert-butyl-4-cresol (BHT) and the like. Among these, 2,6-di-tert-butyl-4-cresol is preferable from the viewpoint of shape control. Further, from the viewpoint of safety to the human body, hydroquinone monomethyl ether and methyl hydroquinone are preferable.
The polymerization inhibitor may contain one kind or two or more kinds. (B) When producing an alkali-soluble resin, a polymerization inhibitor may be contained in the resin, which may be used as the polymerization inhibitor of the present invention, or in addition to the polymerization inhibitor in the resin. , The same or different polymerization inhibitor may be added at the time of producing the photosensitive coloring composition.

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

(C) The content ratio of the photopolymerization initiator is not particularly limited, but is usually 0.1% by mass or more, preferably 0.5% by mass or more, more preferably 1% by mass or more, still more preferably 1 in the total solid content. It is 5.5% by mass or more, usually 15% by mass or less, preferably 10% by mass or less, more preferably 8% by mass or less, still more preferably 6% by mass or less, and particularly preferably 4% by mass or less. For example, 0.1 to 15% by mass is preferable, 0.1 to 10% by mass is more preferable, 0.5 to 8% by mass is further preferable, 1 to 6% by mass is particularly preferable, and 1.5 to 4% by mass is preferable. Is particularly preferable. (C) When the content ratio of the photopolymerization initiator is at least the above lower limit value, the photocurability tends to be improved and the surface roughness tends to be improved, and when it is at least the above upper limit value, the development solubility tends to be improved. There is.

(C) When a polymerization accelerator is used together with the photopolymerization initiator, the content ratio of the polymerization accelerator is preferably 0.05% by mass or more, usually 10% by mass, in the total solid content of the photosensitive coloring composition of the present invention. % Or less, preferably 5% by mass or less, for example, 0.05 to 10% by mass, preferably 0.05 to 5% by mass. The polymerization accelerator is usually used in a ratio of 0.1 to 50 parts by mass, preferably 0.1 to 20 parts by mass with respect to 100 parts by mass of the (c) photopolymerization initiator. By setting the content ratio of the polymerization accelerator to the lower limit value or more, the decrease in sensitivity to the exposed light tends to be suppressed, and by setting the content ratio to the upper limit value or less, the decrease in the solubility of the unexposed portion in the developing solution is suppressed. However, there is a tendency that development defects can be suppressed.

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

(D) The content ratio of the ethylenically unsaturated compound is usually 1% by mass or more, preferably 5% by mass or more, more preferably 10% by mass or more, and further, in the total solid content of the photosensitive coloring composition of the present invention. It is preferably 20% by mass or more, more preferably 30% by mass or more, particularly preferably 40% by mass or more, most preferably 50% by mass or more, and usually 80% by mass or less, preferably 70% by mass or less. It is preferably 65% by mass or less. For example, 1 to 80% by mass is preferable, 5 to 80% by mass is more preferable, 10 to 70% by mass is further preferable, 20 to 70% by mass is further preferable, 30 to 70% by mass is particularly preferable, and 40 to 65% by mass is particularly preferable. The mass% is particularly preferable, and 50 to 65% by mass or more is most preferable. (D) When the content ratio of the ethylenically unsaturated compound is at least the above lower limit value, the mechanical properties tend to be improved, and when it is at least the above upper limit value, 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 30 parts by mass or more. More preferably, 40 parts by mass or more is particularly preferable, and usually 150 parts by mass or less, 120 parts by mass or less is preferable, 100 parts by mass or less is more preferable, and 70 parts by mass or less is further preferable. For example, 10 to 150 parts by mass is preferable, 20 to 120 parts by mass is more preferable, 30 to 100 parts by mass is further preferable, and 40 to 70 parts by mass is particularly preferable. When it is at least the lower limit value, the development solubility tends to be improved, and when it is at least the upper limit value, the mechanical properties tend to be good.

By using the solvent (e), the photosensitive coloring composition of the present invention has a total solid content of usually 5% by mass or more, preferably 10% by mass or more, and more preferably 15% by mass or more. The liquid is usually adjusted to be 50% by mass or less, preferably 30% by mass or less, and more preferably 25% by mass or less. For example, 5 to 50% by mass is preferable, 10 to 30% by mass is more preferable, and 15 to 25% by mass is further preferable.

When the photosensitive coloring composition of the present invention contains (f) a dispersant, the content ratio of the (f) dispersant is usually 0.5% by mass or more in the total solid content of the photosensitive coloring composition, and is 1% by mass. % Or more is preferable, 1.5% by mass or more is more preferable, and usually 30% by mass or less, 20% by mass or less is preferable, 15% by mass or less is more preferable, 10% by mass or less is further preferable, and 5% by mass or less is preferable. Especially preferable. For example, 0.5 to 30% by mass is preferable, 0.5 to 20% by mass is more preferable, 1 to 15% by mass is further preferable, 1 to 10% by mass is further preferable, and 1.5 to 5% by mass is preferable. Especially preferable. (F) When the content ratio of the dispersant is not less than the lower limit value, the storage stability tends to be improved, and when it is not more than the upper limit value, the display reliability tends to be improved.

The content ratio of (f) dispersant to 100 parts by mass of (a) colorant is usually 5 parts by mass or more, more preferably 10 parts by mass or more, further preferably 20 parts by mass or more, and usually 50 parts by mass or less, particularly. It is 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 further preferable. (F) When the content ratio of the dispersant is not less than the lower limit value, the storage stability tends to be improved, and when it is not more than the upper limit value, the display reliability tends to be improved.

When an adhesion improver is used, the content ratio thereof is usually 0.1% by mass or more, preferably 0.2% by mass or more, more preferably 0.5% by mass or more in the total solid content of the photosensitive coloring composition. It is preferable, and usually 30% by mass or less, 20% by mass or less is preferable, 10% by mass or less is more preferable, 5% by mass or less is further preferable, and 3% by mass or less is particularly preferable. For example, 0.1 to 30% by mass is preferable, 0.2 to 20% by mass is more preferable, 0.2 to 10% by mass is further preferable, 0.5 to 5% by mass is further preferable, and 0.5 to 0.5% by mass is preferable. 3% by mass is particularly preferable. Adhesion tends to be improved by setting the content ratio of the adhesion improver to the lower limit value or more, and the residue tends to be reduced by setting the content ratio to the upper limit value or less.

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

When a mercapto compound is used, the content ratio thereof is usually 0.1% by mass or more, preferably 0.2% by mass or more, more preferably 0.5% by mass or more in the total solid content of the photosensitive coloring composition. It is preferable, and usually 30% by mass or less, 20% by mass or less is preferable, 10% by mass or less is more preferable, 5% by mass or less is further preferable, and 3% by mass or less is particularly preferable. For example, 0.1 to 30% by mass is preferable, 0.2 to 20% by mass is more preferable, 0.2 to 10% by mass is further preferable, 0.5 to 5% by mass is further preferable, and 0.5 to 0.5% by mass is preferable. 3% by mass is particularly preferable. When the content ratio of the mercapto compound is at least the above lower limit value, the photocurability tends to be improved and the surface roughness tends to be improved, and when it is at least the above upper limit value, the storage stability tends to be improved.

When a polymerization inhibitor is used, the content ratio thereof is usually 0.05% by mass or more, preferably 0.1% by mass or more, and 0.2% by mass or more in the total solid content of the photosensitive coloring composition. More preferably, it is usually 2% by mass or less, 1% by mass or less, 0.8% by mass or less is more preferable, 0.7% by mass or less is further preferable, and 0.5% by mass or less is particularly preferable. For example, 0.05 to 2% by mass is preferable, 0.05 to 1% by mass is more preferable, 0.1 to 0.8% by mass is further preferable, and 0.1 to 0.7% by mass is further preferable. 0.2 to 0.5% by mass is particularly preferable. When the content ratio of the polymerization inhibitor is not less than the lower limit value, the resolution tends to be higher, and when it is not more than the upper limit value, the curability tends to be higher.

<Physical characteristics of the photosensitive coloring composition>
The photosensitive coloring composition of the present invention can be suitably used for forming a coloring spacer, and from the viewpoint of being used as a coloring spacer, the one having a higher optical density (OD) per 1 μm of the film thickness of the coating film. Is preferable. The colored spacer alone obtained by curing the photosensitive coloring composition of the present invention is preferably 0.1 or more, more preferably 0.15 or more, still more preferably 0.2 or more. , 0.25 or more, more preferably. Here, the optical density (OD) is a value measured by a method described later.

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

The dispersion treatment is usually preferably carried out in a system in which (a) a colorant, (e) a solvent, and (f) a dispersant, and if necessary, a part or all of (b) an alkali-soluble resin are used in combination ( Hereinafter, the mixture to be subjected to the dispersion treatment and the composition obtained by the treatment may be referred to as "ink" or "pigment dispersion liquid"). In particular, it is preferable to use (f) a polymer dispersant as the dispersant because the thickening of the obtained ink and the photosensitive coloring composition with time is suppressed (excellent dispersion stability).
As described above, 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, those described as being usable in the photosensitive coloring composition are preferably used. can.

When the liquid containing all the components to be blended in the photosensitive coloring composition is subjected to the dispersion treatment, the highly reactive components may be denatured due to the heat generated during the dispersion treatment. Therefore, it is preferable to carry out the dispersion treatment in a system that does not contain (c) a photopolymerization initiator or (d) an ethylenically unsaturated compound.
When (a) the colorant is dispersed with a sand grinder, glass beads or zirconia beads having a particle size of about 0.1 to 8 mm are preferably used. The dispersion treatment conditions are such that the temperature is usually 0 ° C. to 100 ° C., preferably in the range of room temperature to 80 ° C. The dispersion time tends to differ depending on the composition of the liquid, the size of the dispersion treatment apparatus, and the like, and may be appropriately adjusted. The guideline for dispersion is to control the gloss of the ink so that the 20-degree mirror gloss (JIS Z8741) when the pigment dispersion liquid or the photosensitive coloring composition is applied to the substrate is in the range of 50 to 300. By setting it to the above lower limit value or more, the dispersion treatment is not sufficient and the residual coarse pigment ((a) colorant) particles can be suppressed, and the developability, adhesion, resolution and the like tend to be sufficient. .. Further, by setting the value to the upper limit or less, it is possible to prevent the pigment from being crushed and generate a large number of ultrafine particles, and there is a tendency that the dispersion stability can be improved.

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

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

[Colored spacer]
Next, the colored spacer of the present invention composed of the cured product of the present invention will be described according to the manufacturing method thereof.

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

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

(2) Coloring Spacer The photosensitive coloring composition of the present invention can be used for the same purposes as known photosensitive coloring compositions for color filters, but the formation thereof will be described below when used as a coloring spacer. The method will be explained.

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

(3) Formation of Colored Spacer [1] Method of Supplying to Substrate The photosensitive coloring composition of the present invention is usually supplied onto a support in a state of being dissolved or dispersed in a solvent. As the supply method, a conventionally known method, for example, a spinner method, a wire bar method, a flow coating method, a die coating method, a roll coating method, a spray coating method, or the like can be used. Further, it may be supplied in a pattern by an inkjet method, a printing method, or the like. Above all, according to the die coating method, the amount of the coating liquid used is significantly reduced, there is no influence of mist adhering when the spin coating method is used, and the generation of foreign substances is suppressed. Is preferable.

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

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

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

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

Drying conditions such as drying temperature and drying time can be appropriately selected according to the type of solvent component, the performance of the dryer used, and the like. Usually, it is selected in the range of 15 seconds to 5 minutes at a temperature of 40 ° C. to 130 ° C., preferably in the 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 a coating film of a photosensitive coloring composition and irradiating a light source of ultraviolet rays or visible light through the mask pattern. When exposure is performed using an exposure mask, the exposure mask may be placed close to the coating film of the photosensitive coloring composition, or the exposure mask may be placed at a position away from the coating film of the photosensitive coloring composition. The method of projecting the exposure light through the mask may also be used. Further, a scanning exposure method using a laser beam that does not use a mask pattern may be used. At this time, if necessary, in order to prevent the sensitivity of the photopolymerizable layer from being lowered by oxygen, the exposure is performed in a deoxidized atmosphere or after forming an oxygen blocking layer such as a polyvinyl alcohol layer on the photopolymerizable layer. You may do it.

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

The light source used for the above exposure is not particularly limited. Examples of the light source include lamp light sources such as xenon lamp, halogen lamp, tungsten lamp, high pressure mercury lamp, ultrahigh pressure mercury lamp, metal halide lamp, medium pressure mercury lamp, low pressure mercury lamp, carbon arc, fluorescent lamp, argon ion laser, YAG laser, etc. Examples thereof include laser light sources such as an excimer laser, a nitrogen laser, a helium cadmium laser, a blue-violet semiconductor laser, and a near-infrared semiconductor laser. An optical filter can also be used when irradiating light of a specific wavelength for use.

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

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

[4] Development method After the above exposure, an image pattern can be formed on the substrate by development using an aqueous solution of an alkaline compound or an organic solvent. The aqueous solution can further contain a surfactant, an organic solvent, a buffer, a complexing agent, a dye or a pigment.

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

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

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

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

[5] Additional Exposure and Thermosetting Treatment The substrate after development may be subjected to additional exposure by the same method as the above-mentioned exposure method, or may be subjected to thermosetting treatment, if necessary. The thermosetting treatment conditions at this time are selected in the temperature range of 100 ° C. to 280 ° C., preferably in the range of 150 ° C. to 250 ° C., and the time is selected in the range of 5 minutes to 60 minutes.

The size, shape, etc. of the colored spacer of the present invention are appropriately adjusted according to the specifications of the color filter to which the colored spacer is applied. It is useful for forming colored spacers with different colors at the same time, in which case the height of the spacer is usually about 1 to 7 μm, and the sub-spacer is usually about 0.2 to 1.5 μm lower than the spacer. Has.

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

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

<Alkali-soluble resin-I>
145 parts by mass of propylene glycol monomethyl ether acetate was stirred while substituting with nitrogen, and the temperature was raised to 120 ° C. To this, 10 parts by mass of styrene, 85 parts by mass of glycidyl methacrylate and 66 parts by mass of monomethacrylate (FA-513M manufactured by Hitachi Kasei Co., Ltd.) having a tricyclodecane skeleton were added dropwise, and 2,2'-azobis-2-methylbutyronitrile was added. 8.5 parts by mass was added dropwise over 3 hours, and stirring was continued at 90 ° C. for 2 hours. Next, the inside of the reaction vessel was changed to air, 0.7 parts by mass of trisdimethylaminomethylphenol 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. Then, 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 polystyrene-equivalent weight average molecular weight Mw measured by GPC of the alkali-soluble resin-I thus obtained was 8400, and the acid value was 80 mgKOH / g.

<Alkali-soluble resin-II>
124 parts by mass of propylene glycol monomethyl ether acetate was stirred while substituting with nitrogen, and the temperature was raised to 120 ° C. To this, 4 parts by mass of styrene, 132 parts by mass of glycidyl methacrylate and 4 parts by mass of monomethacrylate (FA-513M manufactured by Hitachi Kasei Co., Ltd.) having a tricyclodecane skeleton were added dropwise, and 2,2'-azobis-2-methylbutyronitrile was added. 7.2 parts by mass was added dropwise over 3 hours, and stirring was continued at 90 ° C. for 2 hours. Next, the inside of the reaction vessel was changed to air, 0.6 part by mass of trisdimethylaminomethylphenol and 0.12 part 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. Then, 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 polystyrene-equivalent weight average molecular weight Mw of the alkali-soluble resin-II thus obtained was 9000, the acid value was 24 mgKOH / g, and the double bond equivalent was 260 g / mol.

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

<Solvent-I>
PGMEA: Propylene Glycol Monomethyl Ether Acetate <Solvent-II>
MB: 3-Methoxybutanol

<Photopolymerization Initiator-I>
Kurokin Kasei Co., Ltd. 2,2'-bis (o-chlorophenyl) -4,5,4', 5'-tetraphenyl-1,2-biimidazole <photopolymerization initiator-II>
BASF's Irgacure® 369
<Mercapto compound>
Made by Tokyo Kasei Co., Ltd. 2-Mercaptobenzothiazole

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

<Surfactant>
DIC Mega Fvck F-554
<Additive-I>
KAYAMER® PM-21 (methacryloyl group-containing phosphate) manufactured by Nippon Kayaku Co., Ltd.
<Additive-II>
Methyl hydroquinone manufactured by Seiko Kagaku Co., Ltd.

<Preparation of pigment dispersion liquids 1 to 7>
The pigments, dispersants, alkali-soluble resins, and solvents shown in Table 1 were mixed so as to have the mass ratios shown in Table 1 to obtain a mixed solution. The blending ratio of the solvent in Table 1 also includes the amount of the solvent derived from the dispersant and the alkali-soluble resin.
This mixed solution was dispersed with a paint shaker in the range of 25 to 45 ° C. for 3 hours. As the beads, 0.5 mmφ zirconia beads were used, and a mass 2.5 times that of the dispersion was added. After the dispersion was completed, the beads and the dispersion liquid were separated by a filter to prepare pigment dispersion liquids 1 to 7.

<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, each component is added so that the ratio of the solid content of each component in the total solid content is the blending ratio shown in Table 2 or Table 3, and the content ratio of the total solid content is further increased. PGMEA was added so as to be 19% by mass, and the mixture was stirred and dissolved to prepare photosensitive coloring compositions 1 to 13. Each of the obtained photosensitive coloring compositions was evaluated by the method described later.

<Measurement of optical density per unit film thickness (unit OD value)>
The photosensitive coloring composition was applied onto a glass substrate with a spin coater so that the film thickness after heat curing was 1.5 μm, dried under reduced pressure for 1 minute, and then dried on a hot plate at 90 ° C. for 100 seconds. The obtained coating film was subjected to full-scale exposure treatment so that the exposure amount was 60 mJ / cm ^{2 using ultraviolet rays having an intensity of 40 mW / cm 2} at 365 nm without using a mask.
Subsequently, a developing solution consisting of an aqueous solution containing 0.05% by mass of potassium hydroxide and 0.08% by mass of a nonionic surfactant (“A-60” manufactured by Kao Co., Ltd.) was used, and the water pressure was 0 at 25 ° C. After shower development at .15 MPa for 100 seconds, development was stopped with pure water and washed with a water-washing spray. The substrate was heat-cured at 230 ° C. for 20 minutes in an oven to obtain a resist-cured film substrate.

The optical density (OD) of the obtained resist cured film substrate was measured with a transmission densitometer X-Rite 361T (V), and the film thickness was measured with a scanning white interference microscope VS1530 manufactured by Hitachi High Technology. The optical density per unit film thickness (unit OD value, OD / μm) was calculated from the optical density (OD) and the film thickness, and is shown in Table 4. The OD value is a numerical value indicating the light-shielding ability, and the larger the value, the higher the light-shielding property.

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

(Roughness evaluation criteria)
A: 2 nm or less B: 2 nm or more

<Evaluation of elastic recovery rate>
A glass substrate having an ITO film formed on its surface was used as the substrate, a mask having a 20 μm opening (circular opening with a diameter of 20 μm) was used at the time of exposure, and a colored spacer was used in the same manner as the resist cured film substrate except that the exposure gap was 150 μm. Got
The elastic recovery rate of the obtained colored spacer was measured by the following procedure. Using a Fisherscope H-100 (manufactured by Fisher Instruments), using a flat indenter with a measurement temperature of 23 ° C and a diameter of 50 μm, a load is applied to the colored spacer at a constant speed (5 mN / sec), and the load reaches 300 mN. After that, the load was held for 5 seconds, and then the load was unloaded at the same speed to obtain a load-displacement curve. From this load-displacement curve, the maximum displacement H [max] and the final displacement H [Last] (displacement after the load became 0 mN and held for 5 seconds) were measured. Next, the elastic recovery rate was calculated by the following formula and evaluated according to 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 criteria for elastic recovery rate)
A: 95% or more B: less than 95%

<Evaluation of light resistance>
A substrate for light resistance evaluation was obtained in the same manner as the 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 Corporation.
^{Next, the substrate was irradiated with light having a wavelength of 450 nm and an intensity of 19 mW / cm 2} for 500 hours from the film surface side in an environment of a temperature of 25 ° C. and a relative humidity of 50% RH. The absorbance of the substrate at a wavelength of 450 nm was measured in the same manner. The rate of change in absorbance at a wavelength of 450 nm was calculated by the following formula, evaluated according to the following criteria, and the results are shown in Table 5.

Rate of change in absorbance (%) = {(absorbance at 450 nm before irradiation-absorbance at 450 nm after irradiation) / absorbance at 450 nm before irradiation} x 100

(Evaluation criteria)
A: less than 20% B: 20% or more

As is clear from Examples 1 to 8 shown in Table 4, the content ratio of the colorant is 2 to 20% by mass in the total solid content, the purple pigment is contained, and the content ratio of the purple pigment in the colorant is. It can be seen that a colored spacer having excellent surface roughness and mechanical properties can be formed by using a photosensitive coloring composition having an amount of 50% by mass or more.

From the comparison between Example 1 and Comparative Example 1, it can be seen that the surface roughness is excellent when the content ratio of the purple pigment in the colorant is 50% by mass or more. It is considered that the purple pigment has high dispersibility and is uniformly dispersed in the cured film. Therefore, it is considered that the solubility at the time of development becomes uniform by containing a large amount of the purple pigment.

Further, from the comparison between Example 1 and Comparative Example 2, it can be seen that when the content ratio of the colorant is 20% by mass or less in the total solid content of the photosensitive coloring composition, the mechanical properties are good. This is because the content ratio of the alkali-soluble resin and the ethylenically unsaturated compound can be set relatively high by preventing the content ratio of the colorant from becoming too high, and the crosslink density of the obtained colored spacer becomes high. It is thought that this is because of the fact.

As is clear from the comparison with Comparative Examples 3 and 4, when the content ratio of the colorant is less than 2% by mass in the total solid content of the photosensitive coloring composition, the optical density is insufficient. Furthermore, the surface roughness is good regardless of the content ratio of the purple pigment in the colorant. Therefore, when the content ratio of the colorant is 2% by mass or more in the total solid content of the photosensitive coloring composition, the optical density becomes good, and the surface roughness depends on the type and ratio of the pigment in the colorant. It can be seen that may be insufficient.

From the comparison between Examples 1 and 5 and Comparative Example 5 shown in Table 5, it can be seen that the light resistance is excellent when the content ratio of the purple pigment in the colorant is 50% by mass or more. It is considered that the purple pigment has a low absorbance in the vicinity of the wavelength of 450 nm, and because it contains a large amount of the purple pigment, it is not easily affected by the irradiation light having a wavelength of 450 nm.

Claims (9)

A photosensitive coloring composition containing (a) a colorant, (b) an alkali-soluble resin, (c) a photopolymerization initiator, and (d) an ethylenically unsaturated compound.
The content ratio of the colorant (a) is 2 to 20% by mass in the total solid content of the photosensitive coloring composition.
The colorant (a) contains a purple pigment and
(A) A photosensitive coloring composition characterized in that the content ratio of the purple pigment in the colorant is 50% by mass or more. The purple pigment is C.I. I. Pigment Violet 29 and C.I. I. The photosensitive coloring composition according to claim 1, which comprises at least one selected from the group consisting of Pigment Violet 23. The photosensitive coloring composition according to claim 1 or 2, wherein the colorant (a) further contains an orange pigment. The photosensitive coloring composition according to any one of claims 1 to 3, wherein the content ratio of the alkali-soluble resin (b) 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 photopolymerization initiator (c) contains a hexaarylbiimidazole compound. The photosensitive coloring composition according to any one of claims 1 to 5, which is used for forming a coloring spacer. A cured product obtained by curing the photosensitive coloring composition according to any one of claims 1 to 6. A colored spacer composed of the cured product according to claim 7. An image display device including the colored spacer according to claim 8.