WO2020129807A1

WO2020129807A1 - Photosensitive coloring composition, cured product, coloring spacer, and image display apparatus

Info

Publication number: WO2020129807A1
Application number: PCT/JP2019/048708
Authority: WO
Inventors: 和裕中谷; 善秀小川
Original assignee: 三菱ケミカル株式会社
Priority date: 2018-12-18
Filing date: 2019-12-12
Publication date: 2020-06-25
Also published as: TW202035467A; CN113168094A; JP7375773B2; TWI829830B; KR20210105876A; JPWO2020129807A1

Abstract

Provided is a photosensitive coloring composition capable of forming a coloring spacer having excellent mechanical properties and surface roughness. The photosensitive coloring composition according to the present invention contains a coloring agent (a), an alkali-soluble resin (b), a photoinitiator (c), and an ethylenically unsaturated compound (d), wherein the contained proportion of the coloring agent (a) is 2-20 mass% with respect to the total solid content of the photosensitive coloring composition, the coloring agent (a) contains a purple pigment, and the contained proportion of the purple pigment in the coloring agent (a) is 50 mass% or more.

Description

Photosensitive colored composition, cured product, colored spacer, and image display device

The present invention relates to a photosensitive coloring composition and the like. Specifically, for example, a photosensitive coloring composition that is preferably used for forming a colored spacer or the like in a color filter such as a liquid crystal display, a cured product and a colored spacer obtained by curing the photosensitive coloring composition, and an image including the colored spacer. Regarding display device.
Japanese Patent Application No. 2018-236121 filed with the Japan Patent Office on December 18, 2018, the description, claims, drawings and abstract of the entire contents, and references cited in this specification All or part of the content disclosed in the above is incorporated herein by reference as the disclosure content of the present specification.

Liquid crystal display (LCD) uses the property that the arrangement of liquid crystal molecules is switched by turning on and off the voltage to the liquid crystal. Many members forming the liquid crystal panel are formed by a method using a photosensitive composition, which is 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 in a TFT type LCD, the light passing through the spacer sometimes causes the TFT as a switching element to malfunction. In order to prevent this, for example, Patent Document 1 describes a method using a spacer having a light shielding property (colored spacer). Further, in Patent Document 2, a specific combination is required in order to obtain a colored spacer that can control a shape and a level difference while securing a light-shielding property and a voltage holding ratio of a liquid crystal and has excellent adhesion to a substrate. It has been proposed to use colored photosensitive compositions containing pigments.

Further, when manufacturing a liquid crystal panel, a process of press-bonding two substrates under high temperature and high pressure is performed. Therefore, the spacer is required to maintain the spacer function without being deformed by the high temperature and high pressure condition during the press bonding. It That is, mechanical properties such as a recovery rate and an elastic recovery rate are required to return to the original shape when the external pressure is removed even if the external pressure deforms. For example, Patent Document 3 describes that the mechanical properties at high film thickness can be enhanced by using a specific photopolymerization initiator, and Patent Document 4 uses a specific unsaturated group-containing compound. It is described that the mechanical properties are enhanced.

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

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

In order to suppress display defects of the liquid crystal display, it is necessary that the colored spacers have low surface roughness and excellent smoothness.
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 colored composition described in Patent Documents 2 and 5.

Patent Documents 3 and 4 have no description about colored spacers, and the effect of including a colorant in the spacers was unclear.

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 colored spacer having excellent surface roughness and mechanical properties.

The present inventors, as a result of intensive studies to solve the above problems, the total solid content, the content ratio of the colorant within a specific range, also using a specific pigment as a colorant, the content ratio It was found that the above-mentioned problems can be solved by setting the above-mentioned range to a specific range, and the present invention has been completed.
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 of the (a) colorant is 2 to 20% by mass based on the total solid content of the photosensitive coloring composition,
The (a) colorant contains a purple pigment, and
The photosensitive coloring composition, wherein the content of the purple pigment in the colorant (a) is 50% by mass or more.
[2] The purple pigment is C.I. I. Pigment Violet 29 and C.I. I. Pigment Violet 23. The photosensitive coloring composition according to [1], containing at least one selected from the group consisting of Pigment Violet 23.
[3] The photosensitive coloring composition according to [1] or [2], wherein the (a) colorant further contains an orange pigment.
[4] The photosensitive coloring according to any one of [1] to [3], wherein the content ratio of the (b) alkali-soluble resin is 150 parts by mass or less based on 100 parts by mass of the (d) ethylenically unsaturated compound. 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 for forming a colored spacer.

[7] A cured product obtained by curing the photosensitive coloring composition according to any one of [1] to [6].
[8] A colored spacer composed of the 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 colored spacer having excellent surface roughness and mechanical properties, a cured product, a colored spacer composed of the same, and an image display device including such a colored 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.
In the present invention, “(meth)acryl” means “acryl and/or methacryl”, and the same applies to “(meth)acrylate” and “(meth)acryloyl”.

The "(co)polymer" is meant to include both a homopolymer (copolymer) and a copolymer (copolymer), and "acid (anhydride)", "(anhydrous)... acid" , Both acid and its anhydride are meant to be included. 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, the term “monomer” is a term corresponding to a so-called high-molecular substance (polymer), and includes not only a narrowly defined monomer (monomer) but also a dimer, a trimer, an oligomer and the like. Is.
In the present invention, the “total solid content” means all components other than the solvent contained in the photosensitive coloring composition or the ink described below.
In the present invention, the “weight average molecular weight” refers to a polystyrene equivalent weight average molecular weight (Mw) by GPC (gel permeation chromatography).
Further, in the present invention, unless otherwise specified, the “amine value” represents an amine value in terms of effective solid content, and is a value represented by the amount of base and the equivalent amount of KOH per 1 g of solid content of the dispersant. Is. The measuring method will be described later. On the other hand, the “acid value” represents an acid value in terms of effective solid content, and is calculated by neutralization titration unless otherwise specified.

Further, in the present specification, the percentages and parts represented by “mass” have the same meanings as the percentages and parts represented by “weight”.
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) Alkali-soluble resin (c) Photopolymerization initiator (d) Ethylenically unsaturated compound is contained as an essential component, and if necessary, an adhesion improver such as a silane coupling agent and an interface. An activator (coating property improver), a pigment derivative, a photo-acid generator, a cross-linking agent, a mercapto compound, a polymerization inhibitor, a development improver, an ultraviolet absorber, an antioxidant, and other compounding ingredients, and the like. 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. By containing the (a) colorant, it is possible to obtain a suitable light-absorbing property, particularly a suitable light-shielding property when used for forming a light-shielding member such as a colored spacer.
In the photosensitive coloring composition of the present invention, the content ratio of the (a) colorant is 2 to 20% by mass based on the total solid content. By containing a specific amount of the (a) colorant in this way, it becomes possible to achieve both a light-shielding property and high mechanical properties in the obtained cured product, especially in the colored spacer.

The content ratio of the (a) colorant is not particularly limited as long as it is 2 to 20 mass% in the total solid content, but from the viewpoint of light-shielding property, 3 mass% or more is preferable, and 4 mass% or more is more preferable. It is more preferably 5% by mass or more. On the other hand, from the viewpoint of mechanical properties, it is preferably 18% by mass or less, more preferably 15% by mass or less, further preferably 12% by mass or less, further preferably 10% by mass or less, and particularly preferably 8% by mass or less. .. 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 further 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, the (a) colorant contains a purple pigment, and the content ratio of the purple pigment in the (a) colorant is 50% by mass or more. By including 50% by mass or more of the purple pigment in the colorant (a), the dispersion of the pigment in the coating film becomes uniform, so that the solubility in the developing solution during development becomes uniform and the surface roughness becomes good. It is considered to be. Further, since the violet pigment has the maximum absorption wavelength of the absorption peak in the vicinity of the wavelength of 500 to 600 nm in the absorption spectrum, it is effective in that the optical density (OD) can be easily increased by including the violet pigment. On the other hand, since absorption at a wavelength of less than 400 nm is small, there is little overlap with the absorption wavelength of the photopolymerization initiator (c), and it is effective from the viewpoint of photocurability and sensitivity. Further, since the absorption at the wavelength of 450 nm is small, it is effective from the viewpoint of light resistance to blue light strongly irradiated from the backlight of the liquid crystal display.

As a purple pigment, C.I. I. Pigment Violet 1, 1:1, 2, 2:2, 3, 3:1, 3:3, 5, 5:1, 14, 15, 16, 19, 23, 25, 27, 29, 31, 32, 37, 39, 42, 44, 47, 49, 50 can be mentioned. Of these, 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.

The content of the purple pigment in the colorant (a) 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 or more. Mass% or more is more preferable, 62 mass% or more is still more preferable, and 65 mass% or more is especially preferable. On the other hand, 90% by mass or less is preferable, 80% by mass or less is more preferable, and 75% by mass or less is still more preferable, from the viewpoint of widening the absorption wavelength band by utilizing the optical characteristics of the colorant other than the purple pigment. For example, it is preferably 50 to 90% by mass, more preferably 55 to 90% by mass, further preferably 58 to 80% by mass, further preferably 60 to 80% by mass, particularly preferably 62 to 75% by mass, and 65 to 75%. Mass% is especially preferred.

(A) C. 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, it is preferably 50% by mass or more, more preferably 55% by mass or more, further preferably 60% by mass or more, and 62% by mass. The above is more preferable, and 65% by mass or more is particularly preferable. On the other hand, C.I. I. From the viewpoint of widening the absorption wavelength band by utilizing the optical characteristics of colorants other than Pigment Violet 29, it is preferably 90% by mass or less, more preferably 80% by mass or less, and further preferably 75% by mass or less. For example, it is preferably 50 to 90% by mass, more preferably 55 to 90% by mass, further preferably 58 to 80% by mass, further preferably 60 to 80% by mass, particularly preferably 62 to 75% by mass, and 65 to 75%. Mass% is especially preferred.

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

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, and C.I. I. Pigment Yellow 138, 139, and 150 are more preferable, and C.I. I. Pigment Yellow 139 is particularly preferable.

As an orange pigment (orange pigment), C.I. I. Pigment Orange 1, 2, 5, 13, 16, 17, 19, 20, 21, 22, 23, 24, 34, 36, 38, 39, 43, 46, 48, 49, 61, 62, 64, 65, 67, 68, 69, 70, 71, 72, 73, 74, 75, 77, 78, 79. Among these, C.I. I. Pigment Orange 13, 43, 64, 72 is preferable, and when the photosensitive coloring composition is cured by ultraviolet rays, it is preferable to use an orange pigment having a low ultraviolet absorption rate. C. I. Pigment Orange 64, 72 is more preferable, and C.I. I. Pigment Orange 64 is particularly preferable.

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

Examples of blue pigments 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. Among these, C.I. I. Pigment Blue 15, 15:1, 15:2, 15:3, 15:4, 15:6, 16, 60, and more preferably C.I. I. Pigment Blue 15:6, 16 can be mentioned.
From the viewpoint of dispersibility and light shielding property, C.I. I. Pigment Blue 15:6, 16, 60, and when curing the photosensitive coloring composition with ultraviolet rays, it is preferable to use a blue pigment having a low ultraviolet absorption rate. 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. Pigment Blue 16 is preferably used.

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

As the brown pigment (brown pigment), C.I. I. Pigment Brown 23, 25, 26, 28, 38, 41, 83, 93. Among these, from the viewpoint of achieving both near-infrared transparency and light-shielding properties, C.I. I. Pigment Brown 26, 28, 83, 93.

Among these organic color pigments, the orange pigment is preferable because it has an absorption band near a wavelength of 400 to 500 nm, which is different from the absorption band of the purple pigment.
When an orange pigment is included, the content of the orange pigment in the (a) 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 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 mass% is preferable, 10 to 45 mass% is more preferable, 20 to 40 mass% is further preferable, and 30 to 35 mass% is particularly preferable. When it is at least the lower limit, the optical density (OD) tends to be high, and when it is at most the upper limit, the surface roughness tends to be good.

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

Among the blue pigments, C.I. I. When CI Pigment Blue 60 is contained, the surface roughness tends to deteriorate, so that 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 most preferred.

Further, a black pigment may be included as another colorant. Examples of black pigments include organic black pigments and inorganic black pigments.
As the organic black pigment, for example, an organic compound containing at least one selected from the group consisting of a compound represented by the following formula (1), a geometrical isomer of the compound, a salt of the compound, and a salt of the geometrical isomer of the compound. Black pigments may be mentioned.

In formula (1), R ¹ and R ⁶ are each independently a hydrogen atom, CH ₃ , CF ₃ , a fluorine atom or a chlorine atom;
R ² , R ³ , R ⁴ , R ⁵ , R ⁷ , R ⁸ , R ⁹ and R ¹⁰ are each independently a hydrogen atom, a halogen atom, R ¹¹ , COOH, COOR ¹¹ , COO ⁻ , CONH ₂ , CONHR ¹¹ , CONR ¹¹ R ¹² , CN, OH, OR ¹¹ , COCR ¹¹ , OOCNH ₂ , OOCNHR ¹¹ , OOCNR ¹¹ R ¹² , NO ₂ , NH ₂ , NHR ¹¹ , NR ¹¹ R ¹² , NHCOR ¹² , NR ¹¹ COR ¹² , N= CH ₂ , N=CHR ¹¹ , N=CR ¹¹ R ¹² , SH, SR ¹¹ , SOR ¹¹ , SO ₂ R ¹¹ , SO ₃ R ¹¹ , SO ₃ H, SO ₃ ⁻ , SO ₂ NH ₂ , SO ₂ NHR ¹¹ Or SO ₂ NR ¹¹ R ¹² ;
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 , They can be bonded directly to each other or by oxygen, sulfur, NH or NR ¹¹ bridges;
R ¹¹ and R ¹² are each 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 carbon number. 2 to 12 alkynyl groups.

The geometric isomer of the compound represented by the general formula (1) has the following core structure (however, the substituents in the structural formula are 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 any known suitable cation, for example, a metal, organic, inorganic or metal organic cation, specifically, an alkali metal or an alkaline earth metal. It is preferable that the salt is compensated by a transition metal, a primary ammonium, a secondary ammonium, a tertiary ammonium such as trialkylammonium, a quaternary ammonium such as tetraalkylammonium, or an organometallic complex. Further, when the geometric isomer of the compound represented by the general formula (1) is anionic, it is preferably the same salt.

In the substituents of the general formula (1) and their definitions, the following is preferable because the shielding rate tends to be high. This is because the following substituents have no absorption and are considered not 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 preferably each independently a hydrogen atom, NO ₂ , OCH ₃ , OC ₂ H ₅ , a bromine atom, a chlorine atom, CH ₃ , C ₂ H ₅ , N(CH ₃ ) ₂ , N(CH ₃ )(C ₂ H ₅ ), N(C ₂ H ₅ ) ₂ , α-naphthyl, β-naphthyl, SO ₃ H or SO ₃ ⁻ , and more preferably a hydrogen atom or SO ₃ H.

R ¹ and R ⁶ are each independently preferably a hydrogen atom, CH ₃ or CF ₃ , and more preferably a hydrogen atom.
Preferably, at least one combination selected from the group consisting of R ¹ and R ⁶ , R ² and R ⁷ , R ³ and R ⁸ , R ⁴ and R ⁹ , and R ⁵ and R ¹⁰ is the same, and more preferably 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.

Examples of the alkyl group having 1 to 12 carbon atoms include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, isobutyl group, tert-butyl group, 2-methylbutyl group, n- Pentyl group, 2-pentyl group, 3-pentyl group, 2,2-dimethylpropyl group, n-hexyl group, heptyl group, n-octyl group, 1,1,3,3-tetramethylbutyl group, 2-ethylhexyl group Group, nonyl group, decyl group, undecyl group or dodecyl group.

Examples of the cycloalkyl group having 3 to 12 carbon atoms include cyclopropyl group, cyclopropylmethyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cyclohexylmethyl group, trimethylcyclohexyl group, tsudyl group, norbornyl group, bornyl group and norcalyl group. A caryl group, a menthyl group, a norpinyl group, a pinyl group, a 1-adamantyl group or a 2-adamantyl group.

Examples of the alkenyl group having 2 to 12 carbon atoms include vinyl group, allyl group, 2-propen-2-yl group, 2-buten-1-yl group, 3-buten-1-yl group and 1,3-butadiene. -2-yl group, 2-penten-1-yl group, 3-penten-2-yl group, 2-menthyl-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-pentadien-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 includes, for example, 2-cyclobuten-1-yl group, 2-cyclopenten-1-yl group, 2-cyclohexen-1-yl group, 3-cyclohexen-1-yl group, 2 ,4-cyclohexadiene-1-yl group, 1-p-menthen-8-yl group, 4(10)-tugen-10-yl group, 2-norbornen-1-yl group, 2,5-norbornadiene-1 An -yl group, a 7,7-dimethyl-2,4-norcaradien-3-yl group or a camphenyl group.

The alkynyl group having 2 to 12 carbon atoms is, for example, 1-propyn-3-yl group, 1-butyn-4-yl group, 1-pentyn-5-yl group, 2-methyl-3-butyn-2-yl group. Group, 1,4-pentadiyn-3-yl group, 1,3-pentadiyn-5-yl group, 1-hexyn-6-yl group, cis-3-methyl-2-penten-4-yn-1-yl group Group, trans-3-methyl-2-penten-4-yn-1-yl group, 1,3-hexadiyn-5-yl group, 1-octin-8-yl group, 1-nonin-9-yl group, It is a 1-decyn-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 geometrical 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 used after being dispersed by a dispersant, a solvent and a method described later. Further, the presence of the compound represented by the general formula (2) or the sulfonic acid derivative of the geometrical isomer of the compound at the time of dispersion may improve the dispersibility and the storage stability.
In addition, as the organic black pigment, from the viewpoint of optical characteristics and reliability, the organic black pigment described in Korean Published Patent No. 10-2018-0052502 and Korean Published Patent No. 10-2018-0052864 are described. It is preferable to use the known organic black pigment.

Other organic black pigments include aniline black, cyanine black, perylene black and the like.
Further, carbon black which is an inorganic black pigment may be used. Examples of carbon black include the following carbon blacks.

Mitsubishi Chemical Corporation: MA7, MA8, MA11, MA77, MA100, MA100R, MA100S, MA220, MA230, MA600, MCF88, #5, #10, #20, #25, #30, #32, #33, #40. , #44, #45, #47, #50, #52, #55, #650, #750, #850, #900, #950, #960, #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
Degussa: Printex (registered trademark; the same applies hereinafter) 3, Printex3OP, Printex30, Printex30OP, Printex40, Printex45, Printex55, Printex60, Printex75, Printex80, Printex85, Printex90, PrintexPrintG, PrintexL, PrintexA, Printex90. 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, Monarch 280, Monarch 460, Monarch 800, Monarch 880, Monarch 900, Monarch 1000, Monarch 1100, Monarch 1300, Monarch 1400, Monarch 4630, REGAL (registered trademark, REGAL, REGAL, REGAL 15R, REGAL, REGAL (registered trademark, REGA 4; REGAL415R, REGAL250, REGAL250R, REGAL330, REGAL400R, REGAL55R0, REGAL660R, BLACK PEARLS480, PEARLS130, VULCAN (registered trademark) XC72R, ELFTEX (registered trademark)-8
Birla Corporation: RAVEN (. Registered trademark, hereinafter the same) 11, RAVEN14, RAVEN15, RAVEN16, RAVEN22, RAVEN30, RAVEN35, RAVEN40, RAVEN410, RAVEN420, RAVEN450, RAVEN500, RAVEN780, RAVEN850, RAVEN890H, RAVEN1000, RAVEN1020, RAVEN1040, RAVEN1060U , RAVEN1080U, RAVEN1170, RAVEN1190U, RAVEN1250, RAVEN1500, RAVEN2000, RAVEN2500U, RAVEN3500, RAVEN5000, RAVEN5250, RAVEN5750, RAVEN7000.

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

It is preferable that these pigments are dispersed and used so that the average particle diameter 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 diameter is the number of pigment particles.
In the photosensitive coloring composition, the average particle diameter of the pigment is a value obtained from the pigment particle diameter measured by dynamic light scattering (DLS). The particle size is measured by sufficiently diluting the photosensitive coloring composition (usually diluted to prepare a pigment concentration of about 0.005 to 0.2% by mass. However, if there is a concentration recommended by the measuring device, (According to concentration) and measured at 25°C.

In addition to the above-mentioned pigment, a dye may be used. Examples of the dyes include azo dyes, anthraquinone dyes, phthalocyanine dyes, quinoneimine dyes, quinoline dyes, nitro dyes, carbonyl dyes and methine dyes.
Examples of azo dyes 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 Red 58, C.I. I. Disperse Blue 165, C.I. I. Basic Blue 41, C.I. I. Basic Red 18, C.I. I. Mordant Red 7, C.I. I. Moldant Yellow 5, C.I. I. Moldant Black 7 and the like can be mentioned.

Examples of anthraquinone dyes 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 Red 60, C.I. I. Disperse Blue 56, C.I. I. Examples include Disperse Blue 60 and the like.
In addition, phthalocyanine dyes such as C.I. I. Pad Blue 5 and the like are quinone imine dyes such as C.I. I. Basic Blue 3, C.I. I. Basic Blue 9 and the like are quinoline dyes such as C.I. I. Solvent Yellow 33, C.I. I. Acid Yellow 3, C.I. I. Disperse Yellow 64 and the like are nitro dyes such as C.I. I. Acid Yellow 1, C.I. I. Acid Orange 3, C.I. I. Examples include Disperse Yellow 42 and the like.

<(b) Alkali-soluble resin>
The (b) 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, and examples thereof include epoxy (meth)acrylate resin, acrylic resin, carboxyl group-containing epoxy resin, and carboxyl group-containing resin. Examples thereof include urethane resins, novolac resins, polyvinylphenol resins, 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 may be used alone or in combination of two or more.

<(b1) Epoxy (meth)acrylate resin>
The (b1) epoxy (meth)acrylate 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 polybasic acid and/or its anhydride with the hydroxyl group generated by the reaction.
In addition, before reacting the polybasic acid and/or its anhydride with a hydroxyl group, after reacting a compound having two or more substituents capable of reacting with the hydroxyl group, the polybasic acid and/or its anhydride The resin obtained by reacting with is also included in the above (b1) epoxy (meth)acrylate resin.

A resin obtained by reacting a compound having a functional group capable of further reacting with a carboxyl group of the resin obtained by the above reaction is also included in the above (b1) epoxy (meth)acrylate resin.
As described above, the epoxy (meth)acrylate resin does not substantially have an epoxy group in the chemical structure and is not limited to “(meth)acrylate”, but an epoxy compound (epoxy resin) is used as a raw material. , And "(meth)acrylate" is a typical example, and thus is so named in a conventional manner.

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 a “carboxyl group-containing epoxy (meth)acrylate-based resin”.) is preferably used from the viewpoint of developability and reliability.

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

Here, the epoxy resin includes the raw material compound before forming the resin by thermosetting, and the epoxy resin can be appropriately selected and used from known epoxy resins. The epoxy resin may be a compound obtained by reacting a phenolic compound with epihalohydrin. 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 type of epoxy resin used as a raw material includes cresol novolac type epoxy resin, phenol novolac type epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin, trisphenolmethane type epoxy resin, biphenyl novolac type epoxy resin, naphthalene novolac type. Epoxy resin, epoxy resin which is a reaction product of polyaddition reaction product of dicyclopentadiene and phenol or cresol and epihalohydrin, adamantyl group-containing epoxy resin, fluorene type epoxy resin 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 applies hereinafter)-828", "jER-1001", and "jER-1002" manufactured by Mitsubishi Chemical Corporation. , “JER-1004”, “NER-1302” (epoxy equivalent 323, softening point 76° C.) manufactured by Nippon Kayaku Co., Ltd., bisphenol F type resin (for example, “jER-807” manufactured by Mitsubishi Chemical Corporation, “ jER-4004P", "jER-4005P", "jER-4007P", "NER-7406" (epoxy equivalent 350, softening point 66°C), etc. made by Nippon Kayaku Co., Ltd.), bisphenol S type epoxy resin, biphenylglycidyl ether (For example, "jER-YX4000" manufactured by Mitsubishi Chemical Co., Ltd.), phenol novolac type epoxy resin (for example, "EPPN-201" manufactured by Nippon Kayaku Co., Ltd., "jER-152", "jER-154 manufactured by Mitsubishi Chemical Co., Ltd." , "DEN-438" manufactured by Dow Chemical Co., Ltd., (o, m, p-)cresol novolac type epoxy resin (for example, "EOCN (registered trademark, the same applies hereinafter)-102S manufactured by Nippon Kayaku Co., Ltd.", "EOCN-1020", "EOCN-104S"), triglycidyl isocyanurate (for example, "TEPIC (registered trademark)" manufactured by Nissan Chemical Co., Ltd.), trisphenolmethane type epoxy resin (for example, "Nippon Kayaku Co., Ltd." EPPN (registered trademark; hereinafter the same)-501", "EPPN-502", "EPPN-503"), alicyclic epoxy resin ("Celoxide (registered trademark, hereinafter the same) 2021P" manufactured by Daicel). "Celoxide EHPE"), an epoxy resin obtained by glycidylating a phenol resin by the reaction of dicyclopentadiene and 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. as an epoxy resin represented by the following general formula (B1), and "XD-1000" manufactured by Nippon Kayaku Co., Ltd. as an epoxy resin represented by the following general formula (B2). NC-3000” and epoxy resin represented by the following general formula (B4) include “ESF-300” manufactured by Nippon Steel & Sumitomo Metal Corporation.

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

In the general formula (B2), b is an average value and represents a number from 0 to 10. R ¹²¹ represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, a phenyl group, a naphthyl group, or a biphenyl group. In addition, a plurality of R ¹²¹ 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, one or more adamantane structures are included in the molecular structure. c represents 2 or 3.

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

In the general formula (B4), p and q each independently represent an integer of 0 to 4, and R ¹⁴¹ and R ¹⁴² each independently represent an alkyl group having 1 to 4 carbon atoms or a halogen atom. 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 the epoxy resin represented by any of the general formulas (B1) to (B4).

Examples of the α,β-unsaturated monocarboxylic acid or the α,β-unsaturated monocarboxylic acid ester having a carboxyl group include (meth)acrylic acid, crotonic acid, o-, m- or p-vinylbenzoic acid, (meth ) Acrylic acid α-position haloalkyl, alkoxyl, halogen, nitro, cyano-substituted monocarboxylic acids, 2-(meth)acryloyloxyethylsuccinic acid, 2-(meth)acryloyloxyethyladipic acid, 2-( (Meth)acryloyloxyethyl phthalic acid, 2-(meth)acryloyloxyethyl hexahydrophthalic acid, 2-(meth)acryloyloxyethyl maleic acid, 2-(meth)acryloyloxypropyl succinic acid, 2-( (Meth)acryloyloxypropyl adipic acid, 2-(meth)acryloyloxypropyl tetrahydrophthalic acid, 2-(meth)acryloyloxypropyl phthalic acid, 2-(meth)acryloyloxypropyl maleic acid, 2-(meth ) Acryloyloxybutylsuccinic acid, 2-(meth)acryloyloxybutyladipic acid, 2-(meth)acryloyloxybutylhydrophthalic acid, 2-(meth)acryloyloxybutylphthalic acid, 2-(meth) Acryloyloxybutyl maleic acid, (meth)acrylic acid, a monomer obtained by adding lactones such as ε-caprolactone, β-propiolactone, γ-butyrolactone and δ-valerolactone, or hydroxyalkyl( (Meth)acrylate, pentaerythritol tri(meth)acrylate, dipentaerythritol penta(meth)acrylate added with acid (anhydride) such as (anhydrous) succinic acid, (anhydrous) phthalic acid and (anhydrous) maleic acid Examples thereof include a monomer and a (meth)acrylic acid dimer.
Of these, (meth)acrylic acid is particularly preferable in terms of surface roughness.

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 an epoxy resin, a known method can be used. 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 are 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. ..

The epoxy resin, the α,β-unsaturated monocarboxylic acid and/or the α,β-unsaturated monocarboxylic acid ester having a carboxyl group, and the esterification catalyst may each be used alone. You may use 2 or more types together.
The amount of the α,β-unsaturated monocarboxylic acid and/or the α,β-unsaturated monocarboxylic acid ester having a carboxyl group used is in the range of 0.5 to 1.2 equivalents per 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 the α,β-unsaturated monocarboxylic acid and/or α,β-unsaturated monocarboxylic acid ester having a carboxyl group to be the above lower limit or more, it is possible to suppress insufficient introduction of the unsaturated group, Subsequent reaction with the polybasic acid and/or its anhydride also tends to be satisfactory. On the other hand, when the content is not more than the above upper limit, it is possible to suppress the unreacted product of the α,β-unsaturated monocarboxylic acid and/or the α,β-unsaturated monocarboxylic acid ester having a carboxyl group, and to improve the curing property. There is a tendency that it is easy to assume.

Examples of the polybasic acid and/or its anhydride include maleic acid, succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, pyromellitic acid, trimellitic acid, benzophenonetetracarboxylic acid, methylhexahydrophthalic acid. Examples thereof include one or more selected from acids, endomethylenetetrahydrophthalic acid, chlorendic acid, methyltetrahydrophthalic acid, biphenyltetracarboxylic acid, and their anhydrides.

Preferably, maleic acid, succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, pyromellitic acid, trimellitic acid, biphenyltetracarboxylic acid, or their anhydrides. Particularly preferred is tetrahydrophthalic acid, biphenyltetracarboxylic acid, tetrahydrophthalic anhydride, or biphenyltetracarboxylic dianhydride.

A known method can be used for the addition reaction of the polybasic acid and/or its anhydride. The α,β-unsaturated monocarboxylic acid having an α,β-unsaturated monocarboxylic acid and/or a carboxyl group on the 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 resulting carboxyl group-containing epoxy (meth)acrylate resin is in the range of 10 to 150 mgKOH/g. More preferably, it is in the range of about 140 mgKOH/g. When it is at least the lower limit, the alkali developability tends to be good, and when it is at most the upper limit, the curing performance tends to be good.

Note that a polyhydric alcohol such as trimethylolpropane, pentaerythritol, or dipentaerythritol may be added during the addition reaction of the polybasic acid and/or its anhydride to introduce a multibranched structure.

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

As the carboxyl group-containing epoxy (meth)acrylate resin, in addition to the above-mentioned ones, Korean Published Patent No. 10-2013-0022955, Korean Registered Patent No. 10-0965189, and Japanese Patent Laid-Open No. 2005-165294 are disclosed. And those described in JP-A 2006-312704.

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, more preferably 2500 or more. And usually 10,000 or less, preferably 8000 or less, more preferably 6000 or less, further 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 more preferable, and 2500 to 4000 is particularly preferable. When it is at least the above lower limit, it tends to be possible to prevent the solubility in the developing solution from becoming too high, and when it is at most the above upper limit, the solubility in the developing solution tends to be good.

The acid value of the epoxy (meth)acrylate-based resin is not particularly limited, but is preferably 10 mgKOH/g or more, more preferably 20 mgKOH/g or more, and preferably 200 mgKOH/g or less, more preferably 150 mgKOH/g or less, 100 mgKOH/g. g or less is more preferable, and 50 mg KOH/g or less is particularly preferable. 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 at least the above lower limit, moderate development solubility tends to be obtained, and when it is at most the above upper limit, development tends to proceed too much to prevent film dissolution.

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 at most the upper limit, mechanical properties and surface roughness will tend to improve, and when it is at least the lower limit, storage stability will tend to improve.
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)

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

In formula (i), R ^a represents a hydrogen atom or a methyl group, and R ^b represents a divalent hydrocarbon group which may have a substituent. The benzene ring in formula (i) may 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 above formula (i), R ^b represents a divalent hydrocarbon group which may have a substituent.
Examples of the divalent hydrocarbon group include a divalent aliphatic group, a divalent aromatic ring group, a group in which one or more divalent aliphatic groups and one or more divalent aromatic ring groups are linked. Can be mentioned.

The divalent aliphatic group may be linear, branched, cyclic, or a combination thereof. Of these, linear ones are preferable from the viewpoint of developing solubility, while cyclic ones are preferable from the viewpoint of developing adhesion. The carbon number is usually 1 or more, preferably 3 or more, more preferably 6 or more, and preferably 20 or less, more preferably 15 or less, still more preferably 10 or less. For example, 1 to 20 is preferable, 3 to 15 is more preferable, and 6 to 10 is further preferable. When it is at least the above lower limit, development adhesion tends to be good, and when it is at most the above upper limit, curability tends to be good.

Specific examples of the divalent linear aliphatic group include methylene group, ethylene group, n-propylene group, n-butylene group, n-hexylene group, n-heptylene group and the like. Of these, a methylene group is preferable from the viewpoint of curability.
Specific examples of the divalent branched chain aliphatic group include a methyl group, an ethyl group, an n-propyl group, an iso-propyl group, and an n-butyl group as side chains in addition to the above divalent linear aliphatic group. 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 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 further preferable. When it is at least the above lower limit, development adhesion tends to be good, and when it is at most the above upper limit, 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 and an adamantane ring. To be Of these, a group obtained by removing two hydrogen atoms from an adamantane ring is preferable from the viewpoint of rigidity of the skeleton.

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; a carboxyl group and the like. From the viewpoint of ease of synthesis, it is preferably unsubstituted.

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

The aromatic hydrocarbon ring in the divalent aromatic hydrocarbon ring group may be a single ring or a condensed ring. Examples of the divalent aromatic hydrocarbon ring group include 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, which has two free valences. Examples include groups such as a triphenylene ring, an acenaphthene ring, a fluoranthene ring, and a fluorene ring.
Further, the aromatic heterocycle in the divalent aromatic heterocyclic group may be a single ring or a condensed ring. Examples of the divalent aromatic heterocyclic group include a furan ring, a benzofuran ring, a thiophene ring, a benzothiophene ring, a pyrrole ring, a pyrazole ring, an imidazole ring, an oxadiazole ring, and an indole having two free valences. Ring, carbazole ring, pyrroloimidazole ring, pyrrolopyrazole ring, pyrrolopyrrole ring, thienopyrrole ring, thienothiophene ring, furopyrrole ring, furofuran ring, thienofuran ring, benzisoxazole ring, benzisothiazole ring, benzimidazole ring, pyridine ring, Examples include groups such as a pyrazine ring, a pyridazine ring, a pyrimidine ring, a triazine ring, a quinoline ring, an isoquinoline ring, a cynoline ring, a quinoxaline ring, a phenanthridine ring, a perimidine ring, a quinazoline ring, a quinazolinone ring, and an azulene ring. Among these, a benzene ring or naphthalene ring having two free valences is preferable, and a benzene ring having two free valences is more preferable, from the viewpoint of photocurability.

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 and a propoxy group. From the viewpoint of curability, it is preferably unsubstituted.

Further, as the group in which one or more divalent aliphatic groups and one or more divalent aromatic ring groups are linked, one or more of the above divalent aliphatic groups and the above divalent aromatic Examples thereof include groups in which one or more ring groups are linked.
The number of divalent aliphatic groups is not particularly limited, but is usually 1 or more and 2 or more, usually 10 or less and 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 above lower limit, development adhesion tends to be good, and when it is at most the above upper limit, curability tends to be good.
The number of divalent aromatic ring groups is not particularly limited, but is usually 1 or more and 2 or more, usually 10 or less and 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, the curability tends to be good, and when it is at most the upper limit, the curability tends to be good.

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

As described above, the benzene ring in formula (i) may be further substituted with any substituent. Examples of the substituent include a hydroxyl group, a methyl group, a methoxy group, an ethyl group, an ethoxy group, a propyl group and a propoxy group. 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.

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 the formula (i-1), R ^a and R ^b have the same meaning as in the 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 removing one OH group from a polybasic acid or its anhydride. Examples of polybasic acids include maleic acid, succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, pyromellitic acid, trimellitic acid, benzophenonetetracarboxylic acid, methylhexahydrophthalic acid, endomethylenetetrahydrophthalic acid. Examples thereof include one or more selected from acids, chlorendic acid, methyltetrahydrophthalic acid, and biphenyltetracarboxylic acid.
Of these, from the viewpoint of patterning properties, the polybasic acid is preferably maleic acid, succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, pyromellitic acid, trimellitic acid, biphenyltetracarboxylic acid. Acids, and more preferably tetrahydrophthalic acid and biphenyltetracarboxylic acid.

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

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 is preferably 1 or more, more preferably 3 or more. Moreover, 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, the curability tends to be good, and when it is at most the upper limit, the developing solubility tends to be good.

Specific examples of epoxy (meth)acrylate resin (b1-A) are 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 is 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 above lower limit, development adhesion tends to be good, and when it is at most the above upper limit, 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, and preferably 40 or less, more preferably 30 or less, further preferably 20 or less, particularly 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, 8 to 15 is even more preferable. When it is at least the above lower limit, development adhesion tends to be good, and when it is at most the above upper limit, 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 and an adamantane ring. Of these, the adamantane ring is preferable from the viewpoint of reliability.

On the other hand, the number of rings that the aromatic ring group has is not particularly limited, but is usually 1 or more, 2 or more, preferably 3 or more, and usually 10 or less, 5 or less, and 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 further preferable, and 3 to 4 is particularly preferable. When it is at least the above lower limit, development adhesion tends to be good, and when it is at most the above upper limit, 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, even more preferably 10 or more, particularly preferably 12 or more, and preferably 40 or less, 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 further preferable, and 12 to 15 is particularly preferable. When it is at least the above lower limit, development adhesion tends to be good, and when it is at most the above upper limit, curability tends to be good.
Specific examples of the aromatic ring in the aromatic ring group, benzene ring, naphthalene ring, anthracene ring, phenanthrene ring, perylene ring, tetracene ring, pyrene ring, benzpyrene ring, chrysene ring, triphenylene ring, acenaphthene ring, fluoranthene ring, Examples thereof include a fluorene ring. Among these, a fluorene ring is preferable from the viewpoint of patterning characteristics.

Further, the divalent hydrocarbon group in the divalent hydrocarbon group having a cyclic hydrocarbon group as a side chain is not particularly limited, but for example, a divalent aliphatic group, a divalent aromatic ring group, or 1 or more. And a group in which one or more divalent aromatic ring groups are linked.

The divalent aliphatic group may be linear, branched, cyclic, or a combination thereof. Of these, linear ones are preferable from the viewpoint of compatibility, and cyclic ones are 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, and further preferably 15 or less. For example, 1 to 25 is preferable, 3 to 20 is more preferable, and 6 to 15 is further preferable. When it is at least the above lower limit, development adhesion tends to be good, and when it is at most the above upper limit, curability tends to be good.

Specific examples of the divalent linear aliphatic group include methylene group, ethylene group, n-propylene group, n-butylene group, n-hexylene group, n-heptylene group and the like. Of these, a methylene group is preferable from the viewpoint of curability.
Specific examples of the divalent branched chain aliphatic group include a methyl group, an ethyl group, an n-propyl group, an iso-propyl group, and an n-butyl group as side chains in addition to the above divalent linear aliphatic group. 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 is 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 above lower limit, development adhesion tends to be good, and when it is at most the above upper limit, 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 and an adamantane ring. To be Of these, a group obtained by removing two hydrogen atoms from an adamantane ring is preferable from the viewpoint of reliability.

Further, 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, and further preferably 15 or less. For example, 4 to 30 is preferable, 5 to 20 is more preferable, and 6 to 15 is further preferable. When it is at least the above lower limit, development adhesion tends to be good, and when it is at most the above upper limit, curability tends to be good.

The aromatic hydrocarbon ring in the divalent aromatic hydrocarbon ring group may be a single ring or a condensed ring. Examples of the divalent aromatic hydrocarbon ring group include 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, each having two free valences. Examples include groups such as a triphenylene ring, an acenaphthene ring, a fluoranthene ring, and a fluorene ring.
Further, the aromatic heterocycle in the aromatic heterocyclic group may be a single ring or a condensed ring. Examples of the divalent aromatic heterocyclic group include a furan ring, a benzofuran ring, a thiophene ring, a benzothiophene ring, a pyrrole ring, a pyrazole ring, an imidazole ring, an oxadiazole ring, and an indole having two free valences. Ring, carbazole ring, pyrroloimidazole ring, pyrrolopyrazole ring, pyrrolopyrrole ring, thienopyrrole ring, thienothiophene ring, furopyrrole ring, furofuran ring, thienofuran ring, benzisoxazole ring, benzisothiazole ring, benzimidazole ring, pyridine ring, Examples include groups such as a pyrazine ring, a pyridazine ring, a pyrimidine ring, a triazine ring, a quinoline ring, an isoquinoline ring, a cynoline ring, a quinoxaline ring, a phenanthridine ring, a perimidine ring, a quinazoline ring, a quinazolinone ring, and an azulene ring. Among the divalent aromatic ring groups, from the viewpoint of patterning characteristics, a benzene ring, a naphthalene ring or a fluorene ring having two free valences is preferable, and a fluorene ring having two free valences is more preferable.

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

Further, as the group in which one or more divalent aliphatic groups and one or more divalent aromatic ring groups are linked, one or more of the above divalent aliphatic groups and the above divalent aromatic Examples thereof include groups in which one or more ring groups are linked.
The number of divalent aliphatic groups is not particularly limited, but is usually 1 or more and 2 or more, usually 10 or less and 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 above lower limit, development adhesion tends to be good, and when it is at most the above upper limit, curability tends to be good.
The number of divalent aromatic ring groups is not particularly limited, but is usually 1 or more and 2 or more, usually 10 or less and 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 above lower limit, development adhesion tends to be good, and when it is at most the above upper limit, curability tends to be good.

Specific examples of the 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) Are listed. Among these, the group represented by the above formula (iC) is preferable from the viewpoint of reliability.

The bonding mode of the cyclic hydrocarbon group which is a side chain with respect to these divalent hydrocarbon groups is not particularly limited, but for example, one hydrogen atom of an aliphatic group or an aromatic ring group is substituted with the side chain. And a mode in which a cyclic hydrocarbon group that is a side chain is configured to include one of the carbon atoms of the aliphatic group.

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 has the same ^{meaning as} the above 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 1 or more and 2 or more, and usually 6 or less, 4 or less, and more preferably 3 or less. For example, 1 to 6 is preferable, 1 to 4 is more preferable, 1 to 3 is further preferable, and 2 to 3 is even more preferable. When it is at least the above lower limit, development adhesion tends to be good, and when it is at most the above upper limit, curability tends to be good.
The number of carbon atoms of the aliphatic ring group is usually 4 or more, preferably 6 or more, more preferably 8 or more, and preferably 40 or less, more preferably 30 or less, further preferably 20 or less, particularly 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 above lower limit, development adhesion tends to be good, and when it is at most the above upper limit, 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 and an adamantane ring. 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, preferably 3 or more, and usually 10 or less, 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 above lower limit, development adhesion tends to be good, and when it is at most the above upper limit, curability tends to be good.
Examples of the aromatic ring group include an aromatic hydrocarbon ring group and an aromatic heterocyclic group. Also, the carbon number of the aromatic ring group is usually 4 or more, preferably 5 or more, more preferably 6 or more, and , 30 or less are preferred, 20 or less are more preferred, and 15 or less are even more preferred. For example, 4 to 30 is preferable, 5 to 20 is more preferable, and 6 to 15 is further preferable. When it is at least the above lower limit, development adhesion tends to be good, and when it is at most the above upper limit, 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, a 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, a tert-butyl group, Examples thereof include an alkyl group having 1 to 5 carbon atoms such as amyl group and iso-amyl group; an alkoxy group having 1 to 5 carbon atoms such as methoxy group and ethoxy group; nitro group; cyano group; and carboxyl group. From the viewpoint of ease of synthesis, unsubstituted is preferable.

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

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

As described above, the benzene ring in formula (ii-1) may be further substituted with any substituent. Examples of the substituent include a hydroxyl group, a methyl group, a methoxy group, an ethyl group, an ethoxy group, a propyl group and a propoxy group. 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 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 has the same ^{meaning as} the above 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 is 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 further preferable. When it is at least the above lower limit, development adhesion tends to be good, and when it is at most the above upper limit, 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, and preferably 40 or less, more preferably 35 or less, and further preferably 30 or less. For example, 4 to 40 is preferable, 6 to 35 is more preferable, and 8 to 30 is further preferable. When it is at least the above lower limit, development adhesion tends to be good, and when it is at most the above upper limit, 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, preferably 3 or more, and usually 10 or less, 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 above lower limit, development adhesion tends to be good, and when it is at most the above upper limit, 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 carbon atoms, more preferably 8 or more carbon atoms. 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 further preferable, and 10 to 15 is particularly preferable. When it is at least the above lower limit, development adhesion tends to be good, and when it is at most the above upper limit, 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, a fluorene ring is preferable from the viewpoint of reliability.

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 formula (ii-2) may be further substituted with any substituent. Examples of the substituent include a hydroxyl group, a methyl group, a methoxy group, an ethyl group, an ethoxy group, a propyl group and a propoxy group. The number of substituents is not particularly limited and may be one or two or more. In addition, the two benzene rings in 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 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 have the same meaning as in the formula (ii). R ^Z represents a hydrogen atom or a polybasic acid residue. )

The polybasic acid residue means a monovalent group obtained by removing one OH group from a polybasic acid or its anhydride. Further, another OH group may be removed and shared with R ^Z in another molecule represented by the formula (ii-3), that is, a plurality of formula (ii-3 may be introduced via R ^Z. ) May be linked.
Examples of polybasic acids include maleic acid, succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, pyromellitic acid, trimellitic acid, benzophenonetetracarboxylic acid, methylhexahydrophthalic acid, endomethylenetetrahydrophthalic acid. Examples thereof include one or more selected from acids, chlorendic acid, methyltetrahydrophthalic acid, and biphenyltetracarboxylic acid.
Of these, from the viewpoint of patterning properties, the polybasic acid is preferably maleic acid, succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, pyromellitic acid, trimellitic acid, biphenyltetracarboxylic acid. Acids, and more preferably tetrahydrophthalic acid and biphenyltetracarboxylic acid.

The partial structure represented by the formula (ii-3) contained in one molecule of the epoxy (meth)acrylate resin (b1-B) may be one kind or two or more kinds, for example, R ^X is a hydrogen atom. And those having R ^Z as 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 is preferably 1 or more, more preferably 3 or more. 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, 3 to 10 is even more preferable. When it is at least the lower limit, the curability tends to be good, and when it is at most the upper limit, the developing 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 (b2) acrylic copolymer resin is not particularly limited as long as it is an acrylic copolymer resin containing a carboxyl group or a hydroxyl group, but it is preferable that the side chain has an ethylenically unsaturated group. By having an ethylenically unsaturated group, it is less likely that film loss due to an alkali developer will occur during development due to photocuring by exposure, and the surface roughness tends to be good.

(Partial structure represented by general formula (I))
(B2) When the acrylic copolymer resin has an ethylenically unsaturated group in its side chain, the partial structure containing the side chain having an ethylenically unsaturated group is not particularly limited, but the emission of radicals accompanying 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. )

Among the partial structures represented by the above 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 removing one OH group from a polybasic acid or its anhydride. Examples of polybasic acids include maleic acid, succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, pyromellitic acid, trimellitic acid, benzophenonetetracarboxylic acid, methylhexahydrophthalic acid, endomethylenetetrahydrophthalic acid. Examples thereof include one or more selected from acids, chlorendic acid, methyltetrahydrophthalic acid, and biphenyltetracarboxylic acid.
Among these, maleic acid, succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, pyromellitic acid, trimellitic acid, and biphenyltetracarboxylic acid are preferable from the viewpoint of patterning characteristics, and more preferable. Are tetrahydrophthalic acid and biphenyltetracarboxylic acid.

When the acrylic copolymer resin (b2) includes the partial structure represented by the general formula (I), the content ratio is not particularly limited, but is preferably 10 mol% or more, more preferably 30 mol% or more, and 50 mol%. The above is more preferable, 70 mol% or more is still more 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 lower limit, mechanical properties tend to be improved, and when it is at most the upper limit, residues tend to be reduced.

When the acrylic copolymer resin (b2) 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 It is more preferably at least mol%, further preferably at least 70 mol%, particularly preferably at least 80 mol%, preferably at most 98 mol%, more preferably at most 95 mol%. 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 lower limit, the alkali developability and mechanical properties tend to be good, and when it is at most the upper limit, the surface roughness is improved and the residue tends to be reduced.

(Partial structure represented by general formula (II))
When the acrylic copolymer resin (b2) contains the partial structure represented by the general formula (I), the other partial structure is 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, R ⁴ represents 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 above formula (II), R ⁴ represents an alkyl group which may have a substituent, an aromatic ring group which may have a substituent, or an alkenyl group which may have a substituent. ..
Examples of the alkyl group for R ⁴ include linear, branched or cyclic alkyl groups. The carbon number is preferably 1 or more, more preferably 3 or more, further preferably 5 or more, particularly preferably 8 or more, and preferably 20 or less, more preferably 18 or less, further preferably 16 or less, and 14 or less. Even more preferable, and 12 or less are 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 further preferable, and 8 to 12 is particularly preferable. When the content is at least the lower limit, the surface roughness tends to be improved, and when it is at most the upper limit, 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.
Further, the substituent that the alkyl group may have is 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, a carboxyl group. , An acryloyl group, a 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 for R ⁴ include a monovalent aromatic hydrocarbon ring group and a monovalent aromatic heterocyclic group. The carbon number is preferably 6 or more, more preferably 24 or less, more preferably 22 or less, further preferably 20 or less, 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 at least the lower limit, the development adhesion tends to be improved, and when it is at most the upper limit, the residue tends to be reduced.
The aromatic hydrocarbon ring in the aromatic hydrocarbon ring group may be a single ring or a condensed ring, and examples thereof include a benzene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring, a perylene ring, a tetracene ring, and a pyrene. Examples thereof include a ring, a benzpyrene ring, a chrysene ring, a triphenylene ring, an acenaphthene ring, a fluoranthene ring and a fluorene ring.
The aromatic heterocyclic group in the aromatic heterocyclic group may be a single ring or a condensed ring, and examples thereof include a furan ring, a benzofuran ring, a thiophene ring, a benzothiophene ring, a pyrrole ring and a pyrazole ring. , Imidazole ring, oxadiazole ring, indole ring, carbazole ring, pyrroloimidazole ring, pyrrolopyrazole ring, pyrrolopyrrole ring, thienopyrrole ring, thienothiophene ring, furopyrrole ring, furofuran ring, thienofuran ring, benzisoxazole ring, benzoiso Thiazole ring, benzimidazole ring, pyridine ring, pyrazine ring, pyridazine ring, pyrimidine ring, triazine ring, quinoline ring, isoquinoline ring, cynoline ring, quinoxaline ring, phenanthridine 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.
Further, the substituent which the aromatic ring group may have, 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 , An oligoethylene glycol group, a phenyl group, a carboxyl group, and the like, and a hydroxy group and an oligoethylene glycol group are preferable from the viewpoint of developability.

The alkenyl group for R ⁴ includes a linear, branched or cyclic alkenyl group. The carbon number is preferably 2 or more, more preferably 22 or less, more preferably 20 or less, further preferably 18 or less, even more 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 even more preferable, and 2 to 14 is particularly preferable. When the content is at least the lower limit, the surface roughness tends to be improved, and when it is at most the upper limit, the residue tends to be reduced.

The substituent which the alkenyl group may have includes 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 group. Examples thereof include an ethylene glycol group, a phenyl group and a carboxyl group. From the viewpoint of developability, a hydroxy group and an oligoethylene glycol group are preferable.

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 alkenyl is preferable, and an alkyl group is more preferable.

When the acrylic copolymer resin (b2) 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, and more preferably 0.5 mol% or more. 1 mol% or more is more 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 the content is at least the lower limit, the surface roughness tends to be improved, and when it is at most the upper limit, the residue tends to be reduced.

(Partial structure represented by general formula (III))
When the acrylic copolymer resin (b2) includes the partial structure represented by the general formula (I), the other partial structure represented by the general formula (III) is 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. Optionally 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 of 0 to 5.

(R ⁶ )
In the 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, a carboxyl group. Represents a halogen atom, an alkoxy group which may have a substituent, a thiol group, or an alkylsulfide group which may have a substituent.
Examples of the alkyl group for 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, preferably 20 or less, more preferably 18 or less, further preferably 16 or less, still more preferably 14 or less, and 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 further preferable, and 5 to 12 is particularly preferable. When the content is at least the lower limit, the surface roughness tends to be improved, and when it is at most the upper limit, 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. Of these, a dicyclopentanyl group or a dodecanyl group is preferable, and a dicyclopentanyl group is more preferable, from the viewpoints of developability and surface roughness.
Further, as the substituent which the alkyl group may have, methoxy group, ethoxy group, chloro group, bromo group, fluoro group, hydroxy group, amino group, epoxy group, oligoethylene glycol group, phenyl group, carboxyl group , An acryloyl group, a methacryloyl group, and the like, and a hydroxy group and an oligoethylene glycol group are preferable from the viewpoint of developability.

The alkenyl group for R ⁶ includes a linear, branched or cyclic alkenyl group. The carbon number is preferably 2 or more, more preferably 22 or less, more preferably 20 or less, further preferably 18 or less, even more 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 even more preferable, and 2 to 14 is particularly preferable. When the content is at least the lower limit, the surface roughness tends to be improved, and when it is at most the upper limit, the residue tends to be reduced.

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

Further, as the substituent which the alkynyl group may have, 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, an oligo group. Examples thereof include an ethylene glycol group, a phenyl group and a carboxyl group. From the viewpoint of developability, a hydroxy group and an oligoethylene glycol group are preferable.

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 for R ⁶ include linear, branched or cyclic alkoxy groups. The carbon number is preferably 1 or more, preferably 20 or less, more preferably 18 or less, still more preferably 16 or less, even more 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 further preferable, and 1 to 12 is particularly preferable. When the content is at least the lower limit, the surface roughness tends to be improved, and when it is at most the upper limit, the residue tends to be reduced.

Further, as the substituent which the alkoxy group may have, 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, a carboxyl group. , An acryloyl group, a 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 for R ⁶ include linear, branched or cyclic alkyl sulfide groups. The carbon number is preferably 1 or more, preferably 20 or less, more preferably 18 or less, still more preferably 16 or less, even more 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 further preferable, and 1 to 12 is particularly preferable. When the content is at least the lower limit, the surface roughness tends to be improved, and when it is at most the upper limit, the residue tends to be reduced.

Further, the substituent which the alkyl group in the alkyl sulfide group may have is 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, phenyl. Group, a carboxyl group, an acryloyl group, a methacryloyl group, and the like, and a hydroxy group and an oligoethylene glycol group are preferable from the viewpoint of developability.

Thus, 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, a carboxyl group, a halogen group. An atom, an alkoxy group, a hydroxyalkyl group, a thiol group, or an alkylsulfide group which may have a substituent is represented, and among these, from the viewpoint of developability, a hydroxyl group or a carboxyl group is preferable, and a carboxyl group is more preferable. preferable.

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

When the acrylic copolymer resin (b2) 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, It is more preferably 2 mol% or more. Moreover, 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 the content is at least the lower limit, the surface roughness tends to be improved, and when it is at most the upper limit, the residue tends to be reduced.

(Partial structure represented by general formula (IV))
When the acrylic copolymer resin (b2) has a partial structure represented by the general formula (I), the partial structure represented by the following general formula (IV) is included as another partial structure 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.

When the acrylic copolymer resin (b2) includes 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, more preferably 80 mol% or less, further preferably 70 mol% or less, and further preferably 60% mol or less. 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 at least the lower limit, the developability tends to be improved, and when it is at most the upper limit, 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 10 mgKOH/g or more is preferable, 15 mgKOH/g or more is more preferable, 20 mgKOH/g or more is further preferable, and 150 mgKOH/g or less is preferable. , 120 mgKOH/g or less is more preferable, 100 mgKOH/g or less is still more preferable, and 50 mgKOH/g or less is still 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 at least the lower limit, the developability tends to be improved, and when it is at most the upper limit, the surface roughness tends to be improved.

The weight average molecular weight (Mw) of the (b2) 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 7,000 or more, and particularly preferably. Is 8,000 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, 6000 to 15000 is still more preferable, 7000 to 10000 is particularly preferable, and 8000 to 10000 is particularly preferable. When it is at least the lower limit, the surface roughness tends to be improved, and when it is at most the upper limit, 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 at most the upper limit, mechanical properties and surface roughness will tend to improve, and when it is at least the lower limit, storage stability will tend to improve.

Specific examples of the (b2) acrylic copolymer resin include resins described in JP-A-8-297366 and JP-A-2001-89533.

<(c) Photopolymerization initiator>
The (c) 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 addition agent 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 a titanocene compound described in JP-A-59-152396 and JP-A-61-151197; JP-A-2000-56118. Hexaarylbiimidazole derivatives described; N-aryl-α-amino acids such as halomethylated oxadiazole derivatives, halomethyl-s-triazine derivatives, N-phenylglycine and the like described in JP-A-10-39503, N- Radical activators such as aryl-α-amino acid salts and N-aryl-α-amino acid esters, α-aminoalkylphenone derivatives; JP-A 2000-80068, JP-A 2006-36750, etc. The oxime ester compounds described and the like can be mentioned.

As the photopolymerization initiator, a hexaarylbiimidazole compound is particularly preferable from the viewpoint of improving mechanical properties and 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 each independently an alkyl group having 1 to 4 carbon atoms which may have a substituent, an alkoxy group having 1 to 4 carbon atoms which may have a substituent, or halogen. Represents an atom, and l, m and n each independently represent an integer of 0-5.

The carbon number of the alkyl group of R ¹ to R ³ is not particularly limited as long as it is within 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-shaped or cyclic. Specific examples of the alkyl group include, for example, 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 that the alkyl group having 1 to 4 carbon atoms of R ¹ to R ³ may have, a monovalent non-metal atomic group group other than hydrogen is used, and a preferable example thereof is a halogen atom (- F, —Br, —Cl, —I), a hydroxyl group and an alkoxy group.

Further, the number of carbon atoms of the alkoxy group of R ¹ to R ³ is not particularly limited as long as it is within the range of 1 to 4, but from the viewpoint of increasing the taper angle, it is preferably 3 or less, more preferably 2 or less. The alkyl group portion of the alkoxy group may be linear 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 which the alkoxy group having 1 to 4 carbon atoms represented by R ¹ to R ³ may have include an alkyl group and an alkoxy group, and an alkyl group is preferable.

The halogen atom represented by R ¹ to R ³ includes, for example, a chlorine atom, an iodine atom, a bromine atom, and a fluorine atom. Among them, a chlorine atom or a fluorine atom is preferable, and a chlorine atom is more preferable, from the viewpoint of easy synthesis. preferable.
Among these, from the viewpoint of sensitivity and ease of synthesis, R ¹ to R ³ are preferably each independently a halogen atom, and more preferably a chlorine atom.

m, n and l each independently represent an integer of 0 to 5, but from the viewpoint of ease of synthesis, at least two of m, n and l are preferably integers of 1 or more, and m, n and l It is more preferable that any two of them are 1 and the other one 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. Among them, 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 substituted 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.

As the photopolymerization initiator (c), 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. , And both may be used together. When used in combination, the ratio is not particularly limited.

Examples of titanocene derivatives include dicyclopentadienyl titanium dichloride, dicyclopentadienyl titanium bisphenyl, dicyclopentadienyl titanium bis(2,3,4,5,6-pentafluorophenyl), and dicyclopentadiene. Dienyl titanium bis(2,3,5,6-tetrafluorophenyl), dicyclopentadienyl titanium bis(2,4,6-trifluorophenyl), dicyclopentadienyl titanium di(2,6-difluoro) Phenyl), dicyclopentadienyl titanium di(2,4-difluorophenyl), di(methylcyclopentadienyl) titanium bis(2,3,4,5,6-pentafluorophenyl), di(methylcyclopenta) Examples thereof include dienyl)titanium bis(2,6-difluorophenyl) and dicyclopentadienyltitanium [2,6-difluoro-3-(pyrrol-1-yl)phenyl].

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

Further, 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.

Further, examples of α-aminoalkylphenone derivatives include 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one and 2-benzyl-2-dimethylamino-1-(4 -Morpholinophenyl)butan-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butan-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- Examples 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 an arbitrary substituent containing an aromatic ring.
R ^22a represents an alkanoyl group which may have a substituent or an aryloyl group which may have a substituent.
n represents an integer of 0 or 1.

The carbon number of the alkyl group in R ^21a is not particularly limited, but is usually 1 or more, preferably 2 or more, and usually 20 or less, preferably 15 or less, more preferably 10 or less from the viewpoint of solubility in a solvent and sensitivity. 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.
The substituent which the alkyl group may have is an aromatic ring group, a hydroxyl group, a carboxyl group, a halogen atom, an amino group, an amide group, 4-(2-methoxy-1-methyl)ethoxy-2-methylphenyl. Group or N-acetyl-N-acetoxyamino group, and the like, and is preferably unsubstituted from the viewpoint of ease of synthesis.

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

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

Further, R ^21b is preferably an optionally substituted carbazolyl group, an optionally substituted thioxanthonyl group or an optionally substituted diphenyl sulfide group. Among these, an optionally substituted carbazolyl group is preferable from the viewpoint of sensitivity.

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

The carbon number of the aryloyl group in R ^22a is not particularly limited, but is usually 7 or more, preferably 8 or more, and usually 20 or less, preferably 15 or less, more preferably from the viewpoint of solubility in a solvent and sensitivity. 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 aryloyl group include a benzoyl group and a naphthoyl group.
Examples of the substituent that the aryloyl group may have include a hydroxyl group, a carboxyl group, a halogen atom, an amino group, an amide group, and an alkyl group, and from the viewpoint of ease 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.

In addition, the initiator described in Japanese Patent Laid-Open No. 2016-133574 is also preferably used from the viewpoint that the contamination of the liquid crystal layer by the colorant is reduced.

The photopolymerization initiator may be used alone or in combination of two or more kinds.
If necessary, the photopolymerization initiator may be blended with a sensitizing dye or a polymerization accelerator depending on the wavelength of the image exposure light source for the purpose of increasing the sensitivity. Examples of the sensitizing dyes include xanthene dyes described in JP-A-4-221958 and JP-A-4-219756, JP-A-3-239703, and JP-A-5-289335. Coumarin dyes having a heterocycle described in JP-A-3-239703, 3-ketocoumarin compounds described in JP-A-5-289335, and pyrromethene described in JP-A-6-19240. Dyes, etc., JP-A-47-2528, JP-A-54-155292, JP-B-45-37377, JP-A-48-84183, and JP-A- Japanese Unexamined Patent Publication No. 52-112681, Japanese Unexamined Patent Publication No. 58-15503, Japanese Unexamined Patent Publication No. 60-88005, Japanese Unexamined Patent Publication No. 59-56403, Japanese Unexamined Patent Publication No. 2-69. And a dialkylaminobenzene skeleton described in Japanese Patent Application Laid-Open No. 57-168088, 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. Examples thereof include dyes.

Among these sensitizing dyes, preferred are sensitizing dyes containing an amino group, 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. Benzophenone compounds such as 3,4-diaminobenzophenone; 2-(p-dimethylaminophenyl)benzoxazole, 2-(p-diethylaminophenyl)benzoxazole, 2-(p-dimethylaminophenyl)benzo[4,5 ] Benzoxazole, 2-(p-dimethylaminophenyl)benzo[6,7]benzoxazole, 2,5-bis(p-diethylaminophenyl)-1,3,4-oxazole, 2-(p-dimethylaminophenyl) ) Benzothiazole, 2-(p-diethylaminophenyl)benzothiazole, 2-(p-dimethylaminophenyl)benzimidazole, 2-(p-diethylaminophenyl)benzimidazole, 2,5-bis(p-diethylaminophenyl)- 1,3,4-thiadiazole, (p-dimethylaminophenyl)pyridine, (p-diethylaminophenyl)pyridine, (p-dimethylaminophenyl)quinoline, (p-diethylaminophenyl)quinoline, (p-dimethylaminophenyl)pyrimidine , P-dialkylaminophenyl group-containing compounds such as (p-diethylaminophenyl)pyrimidine and the like. The most preferred of these is 4,4′-dialkylaminobenzophenone.
The sensitizing dyes may be used alone or in combination of two or more.

Examples of the polymerization accelerator include aromatic amines such as ethyl p-dimethylaminobenzoate and 2-dimethylaminoethyl benzoate, aliphatic amines such as n-butylamine and N-methyldiethanolamine, and mercapto compounds described below. To be The polymerization accelerators may be used alone or in combination of two or more.

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

In the present invention, it is particularly preferable 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 It is 8 or less, more preferably 7 or less. For example, 2 to 8 are preferred, 4 to 8 are more preferred, 4 to 7 are still more preferred, and 5 to 7 are even more preferred. When it is at least the lower limit value, the sensitivity tends to be high, and when it is at most the upper limit value, the solubility in a solvent tends to be improved.
Examples of the polyfunctional ethylenic monomer include, for example, an ester of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid; an ester of an aromatic polyhydroxy compound and an unsaturated carboxylic acid; an aliphatic polyhydroxy compound, an aromatic polyhydroxy compound. Examples thereof include esters obtained by the esterification reaction of a polyvalent hydroxy compound such as a hydroxy compound with an unsaturated carboxylic acid and a polybasic carboxylic acid.

As the ester of the aliphatic polyhydroxy compound and the unsaturated carboxylic acid, ethylene glycol diacrylate, triethylene glycol diacrylate, trimethylolpropane triacrylate, trimethylolethane triacrylate, pentaerythritol diacrylate, 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 obtained by replacing the acrylates of these exemplified compounds with methacrylates. Similarly, itaconic acid ester replaced with itaconate, crotonic acid ester replaced with clonate, maleic acid ester replaced with maleate, and the like can be mentioned.

Examples of the ester of an aromatic polyhydroxy compound and an unsaturated carboxylic acid include an acrylic ester and a methacrylic ester of an aromatic polyhydroxy compound such as hydroquinone diacrylate, hydroquinone dimethacrylate, resorcin diacrylate, resorcin dimethacrylate, and pyrogallol triacrylate. Etc.

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

Other examples of the polyfunctional ethylenic monomer used in the present invention include reacting a polyisocyanate compound with a hydroxyl group-containing (meth)acrylic acid ester or a polyisocyanate compound with a polyol and a hydroxyl group-containing (meth)acrylic acid ester. Urethane (meth)acrylates obtained; epoxy acrylates such as addition reaction products of polyvalent epoxy compounds with 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 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.

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

<(e) Solvent>
The photosensitive coloring composition of the present invention may contain (e) a solvent. (E) By including the solvent, the pigment can be dispersed in the solvent and the coating tends to be easy.
The photosensitive coloring composition of the present invention is usually used (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, organic solvents are 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 mentioned here means the boiling point at a pressure of 1013.25 hPa, and the same applies to the following boiling points.

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 Ether, diethylene glycol monoethyl ether, diethylene glycol mono-n-butyl ether, methoxymethyl pentanol, dipropylene glycol monoethyl ether, dipropylene glycol monomethyl ether, 3-methoxybutanol, 3-methyl-3-methoxybutanol, triethylene glycol monomethyl Glycol monoalkyl ethers such as ether, triethylene glycol monoethyl ether, tripropylene glycol methyl ether;
Glycol dialkyl ethers such as ethylene glycol dimethyl ether, ethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, dipropylene glycol dimethyl ether;

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

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

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

Commercially available organic solvents corresponding to the above include mineral spirits, balsol #2, Apco #18 solvent, Apco thinner, socal solvent No. 1 and No. 1 2, Solvesso #150, Shell TS28 solvent, carbitol, ethyl carbitol, butyl carbitol, methyl cellosolve (“cellosolve” is a registered trademark; the same applies hereinafter), ethyl cellosolve, ethyl cellosolve acetate, methyl cellosolve acetate, diglyme (any of them). Product name) etc.
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 is preferably an organic solvent having a boiling point of 100 to 200°C, more preferably 120 to 170°C.

Among the above organic solvents, glycol alkyl ether acetates are preferable because they have a good balance of coating properties, surface tension and the like, and have relatively high solubility of the constituent components in the composition.
The glycol alkyl ether acetates may be used alone or in combination with other organic solvents. As the organic solvent used in combination, glycol monoalkyl ethers are particularly preferable. Of these, propylene glycol monomethyl ether is particularly preferred because of the solubility of the constituents in the composition. Incidentally, glycol monoalkyl ethers have high polarity, and if the addition amount is too large, the pigment tends to aggregate, and the storage stability such as the viscosity of the photosensitive coloring composition obtained later 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.

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

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 the lower limit value or more, for example, there is a tendency that it is possible to prevent the colorant or the like from depositing and solidifying at the tip of the slit nozzle to cause foreign matter defects, and by setting the upper limit value or less, the drying temperature of the composition. It tends to be able to suppress the delay of the cycle time, and to suppress problems such as tact failure in the vacuum drying process and pin marks of prebaking.

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 may be contained separately. It doesn't matter.
Preferred high boiling point solvents include, for example, among the above-mentioned various solvents, diethylene glycol mono-n-butyl ether acetate, diethylene glycol monoethyl ether acetate, dipropylene glycol methyl ether acetate, 1,3-butylene glycol diacetate, 1,6-hexanol diacetate. Examples thereof include acetate and triacetin.

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

As the polymer dispersant, for example, a urethane dispersant, an acrylic dispersant, a polyethyleneimine dispersant, a polyallylamine dispersant, a dispersant comprising a monomer having an amino group and a macromonomer, polyoxyethylene alkyl ether. Examples thereof include a system dispersant, a polyoxyethylene diester dispersant, a polyether phosphoric acid dispersant, a polyester phosphoric acid dispersant, a sorbitan aliphatic ester dispersant, and an aliphatic modified polyester dispersant.

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

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

Examples of the urethane-based and acrylic-based polymer dispersants include DISPERBYK160 to 166, 182 series (all are urethane-based), DISPERBYK2000, 2001, BYK-LPN21116 and the like (all are acrylic-based) (all of which are manufactured by Big Chemie). ..
To specifically exemplify a preferable chemical structure as the urethane polymer dispersant, for example, a polyisocyanate compound, a compound having one or two hydroxyl groups in the molecule and a number average molecular weight of 300 to 10,000, and the same molecule Examples thereof include a dispersion resin having a weight average molecular weight of 1,000 to 200,000 obtained by reacting active hydrogen with a compound having a tertiary amino group. By treating these with a quaternizing agent such as benzyl chloride, all or part of the tertiary amino group can be converted to a quaternary ammonium base.

Examples of the above polyisocyanate compound include paraphenylene diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 4,4′-diphenylmethane diisocyanate, naphthalene-1,5-diisocyanate and tolidine diisocyanate. Aromatic diisocyanates, hexamethylene diisocyanates, lysine methyl ester diisocyanates, 2,4,4-trimethylhexamethylene diisocyanates, aliphatic diisocyanates such as dimer acid diisocyanates, isophorone diisocyanates, 4,4′-methylenebis(cyclohexyl isocyanate), ω,ω Aliphatic diisocyanates such as'-diisocyanate dimethylcyclohexane, xylylene diisocyanate, α,α,α',α'-tetramethyl xylylene diisocyanate, etc., aliphatic diisocyanates having aromatic rings, lysine ester triisocyanate, 1,6, 11-undecane triisocyanate, 1,8-diisocyanate-4-isocyanatomethyl octane, 1,3,6-hexamethylene triisocyanate, bicycloheptane triisocyanate, tris(isocyanatophenylmethane), tris(isocyanatophenyl)thiophosphate, etc. Examples thereof include triisocyanates, trimers thereof, water adducts, and polyol adducts thereof. Preferred as the polyisocyanate are trimers of organic diisocyanates, and most preferred are trimers of tolylene diisocyanate and trimers of isophorone diisocyanate. These may be used alone or in combination of two or more.

As a method for producing a trimer of isocyanate, the above-mentioned polyisocyanates are prepared by using a suitable trimerization catalyst such as tertiary amines, phosphines, alkoxides, metal oxides, carboxylates, etc. A method in which the desired isocyanurate group-containing polyisocyanate is obtained by removing unreacted polyisocyanate by solvent extraction and thin-film distillation after stopping the trimerization by adding a catalyst poison, is carried out.

As the 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 has a carbon number of 1 to 10 Examples thereof include those alkoxylated with 25 alkyl groups and mixtures of two or more of these.
Examples of polyether glycols include polyether diols, polyether ester diols, and mixtures of two or more thereof. As the polyether diol, those obtained by homopolymerizing or copolymerizing alkylene oxide, for example, polyethylene glycol, polypropylene glycol, polyethylene-propylene glycol, polyoxytetramethylene glycol, polyoxyhexamethylene glycol, polyoxyoctamethylene glycol and those And a mixture of two or more thereof.

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

As the 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, 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 Aliphatic glycols such as 1,5-hexanediol, 1,8-octamethylene glycol, 2-methyl-1,8-octamethylene glycol and 1,9-nonanediol, alicyclic glycols such as bishydroxymethylcyclohexane, xylyl Polyglycene adipate, polybutylene adipate, polyhexamethylene adipate obtained by polycondensation of ren glycol, aromatic glycols such as bishydroxyethoxybenzene, N-alkyl dialkanol amines such as N-methyldiethanolamine, etc. , Polyethylene/propylene adipate, or the like, or polylactone diols or polylactone monools obtained by using the above diols or monohydric alcohols having 1 to 25 carbon atoms as an initiator, for example, polycaprolactone glycol, polymethylvalerolactone and the like. Mixtures of two or more may be mentioned. The most preferable polyester glycol is polycaprolactone glycol or polycaprolactone having an alcohol having 1 to 25 carbon atoms as an initiator.

Polycarbonate glycols include poly(1,6-hexylene)carbonate and poly(3-methyl-1,5-pentylene)carbonate. Polyolefin glycols include polybutadiene glycol, hydrogenated polybutadiene glycol and hydrogenated polyisoprene glycol. Are listed.
These may be used alone or in combination of two or more.

The number average molecular weight of the compound having one or two hydroxyl groups in the same molecule is usually 300 to 10000, preferably 500 to 6000, and more preferably 1000 to 4000.

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

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, or a heterocyclic structure, more specifically, an imidazole ring or a triazole ring.
Examples of such compounds having active hydrogen and a tertiary amino group in the same molecule include N,N-dimethyl-1,3-propanediamine, N,N-diethyl-1,3-propanediamine, N , N-dipropyl-1,3-propanediamine, N,N-dibutyl-1,3-propanediamine, N,N-dimethylethylenediamine, N,N-diethylethylenediamine, N,N-dipropylethylenediamine, N,N -Dibutylethylenediamine, N,N-dimethyl-1,4-butanediamine, N,N-diethyl-1,4-butanediamine, N,N-dipropyl-1,4-butanediamine, N,N-dibutyl-1 , 4-butanediamine and the like.

When the tertiary amino group has a nitrogen-containing heterocyclic structure, examples of the nitrogen-containing heterocycle include a pyrazole ring, an imidazole ring, a triazole ring, a tetrazole ring, an indole ring, a carbazole ring, an indazole ring, a benzimidazole ring and benzo. 5-membered nitrogen-containing hetero ring such as triazole ring, benzoxazole ring, benzothiazole ring and benzothiadiazole ring, 6-membered nitrogen-containing hetero ring such as pyridine ring, pyridazine ring, pyrimidine ring, triazine ring, quinoline ring, acridine ring and isoquinoline ring A ring is included. Preferred among these nitrogen-containing heterocycles are imidazole rings and triazole rings.

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 and 3-amino-1,2,4-triazole are preferable.
These may be used alone or in combination of two or more.

A preferable mixing ratio of raw materials for producing the urethane-based polymer dispersant is 10-200 with respect to 100 parts by mass of the polyisocyanate compound, a compound having one or two hydroxyl groups in the same molecule and having a number average molecular weight of 300 to 10,000. 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 a compound having active hydrogen and a tertiary amino group in the same molecule. It is a mass part.

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

-Urethanization reaction catalyst is usually used in the above production. Examples of the catalyst include tin-based compounds such as dibutyltin dilaurate, dioctyltin dilaurate, dibutyltin dioctoate and stannas octoate; iron-based compounds such as iron acetylacetonate and ferric chloride; and triethylamine and triethylenediamine. Examples include primary amines. These may be used alone or in combination of two or more.

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

When the isocyanate group remains in the polymer dispersant by the above reaction, it is preferable to further convert the isocyanate group into another functional group with an alcohol or an amino compound because the stability of the product with time increases.
The weight average molecular weight (Mw) of the urethane polymer dispersant is usually 1,000 to 200,000, preferably 2,000 to 100,000, and more preferably 3,000 to 50,000. When it is at least the above lower limit, dispersibility and dispersion stability will tend to be good, and when it is at most the above upper limit, deterioration of solubility and dispersibility will tend to be suppressed.

As the acrylic polymer dispersant, an unsaturated group-containing monomer having a functional group (the functional group here is the functional group described above as the functional group contained in the polymer dispersant), It is preferable to use 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 a known method.

Examples of the unsaturated group-containing monomer having a functional group include (meth)acrylic acid, 2-(meth)acryloyloxyethylsuccinic acid, 2-(meth)acryloyloxyethylphthalic acid, and 2-(meth)acryloyl Unsaturated monomers having a carboxyl group such as loyloxyethyl hexahydrophthalic acid and acrylic acid dimer, dimethylaminoethyl (meth)acrylate, diethylaminoethyl (meth)acrylate and tertiary amino groups such as quaternary compounds thereof, Specific examples include unsaturated monomers having a quaternary ammonium salt group. These may be used alone or in combination of two or more.

Examples of the unsaturated group-containing monomer having no functional group include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl ( (Meth)acrylate, t-butyl(meth)acrylate, benzyl(meth)acrylate, phenyl(meth)acrylate, cyclohexyl(meth)acrylate, phenoxyethyl(meth)acrylate, phenoxymethyl(meth)acrylate, 2-ethylhexyl(meth) Acrylate, isobornyl (meth)acrylate, 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, poly-2-hydroxyethyl (meth)acrylate macromonomers, polyethylene glycol macromonomers, polypropylene glycol macromonomers, poly Examples thereof include macromonomers such as caprolactone macromonomers. These may be used alone or in combination of two or more.

The acrylic polymer dispersant is particularly preferably an AB or BABB block copolymer consisting of an A block having a functional group and a B block having no functional group. In this case, A In the block, in addition to the partial structure derived from the unsaturated group-containing monomer containing the functional group, a partial structure derived from the unsaturated group-containing monomer containing no functional group may be contained. May be contained in the A block in any form of random copolymerization or block copolymerization. The content of the partial structure containing no functional group in the A block is 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 which does not contain the above functional group, but one B block contains partial structures derived from two or more kinds of monomers. Alternatively, these may be contained in the B block in any mode of random copolymerization or block copolymerization.
The AB or BAB block copolymer is prepared, for example, by the following living polymerization method.
The living polymerization method includes an anionic living polymerization method, a cationic living polymerization method, and a radical living polymerization method. Among them, the anionic living polymerization method has an anion as a polymerization active species, and is represented by the following scheme, for example.

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 each an integer of 1 or more.

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

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 R ^a is a hydrogen atom or 1 the valence of the organic radical, the R ^b are different hydrogen atom or a monovalent organic group and R ^a.

When synthesizing this acrylic polymer dispersant, Japanese Patent Laid-Open No. 9-62002 or P. Lutz, P. Masson et al, Polym. Bull. 12, 79 (1984), B. C. Anderson, G.M. D. Andrews et al, Macromolecules, 14, 1601 (1981), K.M. Hatada, 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, Journal of Polymer Science, 46, 189 (1989), M. Kuroki, T. Aida, J. Am. Chem. Sic, 109, 4737 (1987), Takuzo Aida, Shohei Inoue, Synthetic Organic Chemistry, 43, 300 (1985), D.M. Y. Sogoh, W. R. Known methods 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, and particularly preferably 5/95 to 60/40 (mass ratio). By setting it within this range, the balance between dispersibility and storage stability can be secured. Tend.
Further, the amount of the quaternary ammonium salt group in 1 g of the AB block copolymer or BAB block copolymer that can be used in the present invention is usually preferably 0.1 to 10 mmol. Within the range, good dispersibility tends to be ensured.

Incidentally, such a block copolymer may usually contain an amino group generated in the production process, but its amine value is about 1 to 100 mgKOH/g, and from the viewpoint of dispersibility, It is 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, and further 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 the block copolymer is represented by the mass of KOH equivalent to the amount of the base per 1 g of the solid content excluding the solvent in the sample of the dispersant, and is measured by the following method.
Precisely weigh 0.5-1.5 g of the dispersant sample in a 100 mL beaker and dissolve with 50 mL acetic acid. Using an automatic titrator equipped with a pH electrode, this solution is subjected to neutralization titration with 0.1 mol/L HClO ₄ acetic acid solution. Using the inflection point of the titration pH curve as the end point of titration, the amine value is calculated by the following formula.

Amine value [mgKOH/g]=(561×V)/(W×S)
[However, W: Dispersant sample weight [g], V: Titration amount [mL] at the end point of titration, S: Solid content concentration [mass%] of the dispersant sample. ]
Although the acid value of this block copolymer depends on the presence and type of the acidic group which is the source of the acid value, it is generally preferable that the acid value is 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 salt group 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 optionally substituted aralkyl group, 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, and preferably 10 or less, 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. Among these, a methyl group, an ethyl group, a propyl group, and a butyl group. A group, a pentyl group, or a hexyl group is preferable, and a methyl group, an ethyl group, a propyl group, or a butyl group is more preferable. Further, it may be linear or branched. It may also contain a cyclic structure such as a cyclohexyl group or a cyclohexylmethyl group.

The number of carbon atoms of the optionally substituted aryl group in R ³¹ to R ³³ of the above formula (i) is not particularly limited, but is usually 6 or more, and preferably 16 or less, 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. Among these, a phenyl group, a methylphenyl group, an ethylphenyl group , A dimethylphenyl group, or a diethylphenyl group, and more preferably a phenyl group, a methylphenyl group, or an 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, and preferably 16 or less, 12 The following is more preferable. For example, 7 to 16 are preferable, and 7 to 12 are 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. Among these, a phenylmethyl group, a phenylethyl group A group, a phenylpropyl group, or a phenylbutyl group is preferable, and a phenylmethyl group or a phenylethyl group is more preferable.

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

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

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. 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. it 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. You can 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. it can.

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

The substituent which 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 is a halogen atom, an alkoxy group, Examples thereof include benzoyl group and hydroxyl group.

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

The content ratio of the repeating unit represented by the formula (i) is not particularly limited, but from the viewpoint of dispersibility, it is represented by the content ratio of the repeating unit represented by the formula (i) and the formula (ii). 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 of repeating units. , Preferably 5 mol% or more, more preferably 10 mol% or more, further preferably 20 mol% or more, particularly preferably 30 mol% or more.

Further, the content ratio of the repeating unit represented by the formula (i) in all the repeating units of the polymer dispersant is not particularly limited, but from the viewpoint of dispersibility, it is preferably 1 mol% or more, and 5 mol% or more. 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 formula (ii) in all repeating units of the polymer dispersant is not particularly limited, but from the viewpoint of dispersibility, it is preferably 5 mol% or more, and 10 mol% or more. More preferably, 15 mol% or more 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.

In addition, 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 may be said that it has ".

In the 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, and 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. Among these, a methyl group, an ethyl group, a propyl group, and a butyl group. A group, a pentyl group, or a hexyl group is preferable, and a methyl group, an ethyl group, a propyl group, or a butyl group is more preferable. Further, it may be linear or branched. It may also 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, 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 further preferable.

The content of the repeating unit represented by the formula (iii) in all 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. Within the above range, compatibility with a binder component such as a solvent and dispersion stability tend to be compatible.

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

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. Among these, a methyl group, an ethyl group, a propyl group, and a butyl group. A group, a pentyl group, or a hexyl group is preferable, and a methyl group, an ethyl group, a propyl group, or a butyl group is more preferable. Further, it may be linear or branched. It may also 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, and is preferably 16 or less, more preferably 12 or less, and 8 The following are more preferable. For example, 6 to 16 is preferable, 6 to 12 is more preferable, and 6 to 8 is further 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. Among these, a phenyl group, a methylphenyl group, an ethylphenyl group , A dimethylphenyl group, or a diethylphenyl group, and more preferably a phenyl group, a methylphenyl group, or an 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, and preferably 16 or less, and 12 or less. More preferably, it is more preferably 10 or less. For example, 7 to 16 are preferable, 7 to 12 are more preferable, and 7 to 10 are further 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. Among these, a phenylmethyl group, a phenylethyl group, a phenylpropyl group, or a phenyl group. It is preferably a butyl group, and 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 which 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 aralkyl group may have include a chain alkyl group, a halogen atom and an alkoxy group. The chain alkyl group represented by R ³⁸ includes both straight chain and branched chain groups.

From the viewpoint of dispersibility, the content of the repeating unit represented by the formula (iv) in all repeating units of the polymer dispersant is preferably 30 mol% or more, more preferably 40 mol% or more, and 50 It is more preferably at least mol%, preferably at most 80 mol%, more preferably at most 70 mol%. 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 include styrene-based monomers such as styrene and α-methylstyrene; (meth)acrylate-based monomers such as (meth)acrylic acid chloride; (meth)acrylamide, N- (Meth)acrylamide-based monomers such as methylol acrylamide; vinyl acetate; acrylonitrile; allyl glycidyl ether, crotonic acid glycidyl ether; and N-methacryloylmorpholine.

From the viewpoint of further improving dispersibility, the polymer dispersant is 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 preferable that the block copolymer has The block copolymer is preferably an AB block copolymer or a BAB block copolymer. Surprisingly, the dispersibility of the dispersant tends to be significantly improved by introducing not only a quaternary ammonium salt group but also a tertiary amino group into the A block. 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 form of random copolymerization and block copolymerization. Further, the repeating unit (i) and the repeating unit (ii) may each be contained in one A block in an amount of two or more, and in that case, each repeating unit is randomly copolymerized in the A block, It may be contained in any form of block copolymerization.

Further, the repeating unit (i) and a repeating unit other than 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 monomer. Examples include repeating units derived from a monomer. 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 %. 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; (Meth)acrylic acid chloride-based monomers such as (meth)acrylic acid chloride; (meth)acrylamide-based monomers such as (meth)acrylamide and N-methylolacrylamide; vinyl acetate; acrylonitrile; allyl glycidyl ether, glycidyl crotonic acid Ether; a repeating unit derived from a monomer 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 %. Most preferably, it is not contained in the block.

Further, from the viewpoint of improving dispersion stability, it is preferable to use the (f) dispersant in combination with a pigment derivative described later.

<Other compounding components of photosensitive coloring composition>
In the photosensitive coloring composition of the present invention, in addition to the above-mentioned components, an adhesion improver such as a silane coupling agent, a surfactant (coating improver), a pigment derivative, a photoacid generator, a crosslinking agent, a mercapto compound. Additives such as a polymerization inhibitor, a development improver, an ultraviolet absorber and an antioxidant 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.

Examples of preferable silane coupling agents include (meth)acryloxysilanes such as 3-methacryloxypropylmethyldimethoxysilane and 3-methacryloxypropyltrimethoxysilane, and 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane. Epoxy silanes such as 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane and 3-glycidoxypropyltriethoxysilane, ureidosilanes such as 3-ureidopropyltriethoxysilane, Isocyanate silanes such as 3-isocyanate propyl triethoxy silane may be mentioned, but silane coupling agents of epoxy silanes are particularly preferable.
As the phosphoric acid group-containing compound, (meth)acryloyl group-containing phosphates are preferable, and compounds represented by the following general formula (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 to improve coatability.

As the surfactant, various ones such as anionic, cationic, nonionic and amphoteric surfactants 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 surfactant or a silicon-based surfactant is effective in terms of coating properties.
Examples of such a surfactant include TSF4460 (manufactured by Momentive Performance Materials), DFX-18 (manufactured by Neos), BYK-300, BYK-325, BYK-330 (manufactured by Big Chemie), KP340. (Manufactured by Shin-Etsu Silicone Co., Ltd.), Megafac (registered trademark, the same applies hereinafter) F-470, Megafac F-475, Megafac F-478, Megafac F-554, Megafac F-559 (manufactured by DIC), Examples include SH7PA (manufactured by Toray Dow Corning), DS-401 (manufactured by Daikin), L-77 (manufactured by Nippon Unicar), FC4430 (manufactured by 3M), and the like.
In addition, 1 type may be used for a surfactant and 2 or more types may be used together by arbitrary combinations and ratios.

(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 storability.
Examples of pigment derivatives include azo, phthalocyanine, quinacridone, benzimidazolone, quinophthalone, isoindolinone, dioxazine, anthraquinone, indanthrene, perylene, perinone, diketopyrrolopyrrole, dioxazine. Examples thereof include derivatives such as phthalocyanine compounds and quinophthalone compounds.
As the substituent of the pigment derivative, a sulfonic acid group, a sulfonamide group and a quaternary salt thereof, a phthalimidomethyl group, a dialkylaminoalkyl group, a hydroxyl group, a carboxyl group, an amide group, etc. may be directly attached to the pigment skeleton or may be an alkyl group, an aryl group, a hetero group. Examples thereof include those bonded via a ring group and the like, and a sulfonic acid group is preferable. Further, a plurality of these substituents may be substituted on one pigment skeleton.

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

(4) Photo-acid generator The photo-acid generator is a compound capable of generating an acid by ultraviolet rays, and has a cross-linking agent such as a melamine compound due to the action of the acid generated upon exposure. The crosslinking reaction proceeds. Among such photo-acid generators, those having a large solubility in a solvent, especially a solvent used in the photosensitive coloring composition are preferable, and examples thereof include diphenyliodonium, ditolyliodonium, and 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 -Diaryl iodonium such as isopropylphenyl (p-tolyl) iodonium, or chloride, bromide, or borofluoride salt, hexafluorophosphate salt, hexafluoroarsenate salt, aromatic sulfonate of triarylsulfonium such as triphenylsulfonium , Tetrakis(pentafluorophenyl)borate salt, etc., sulfonium organoboron complexes such as diphenylphenacylsulfonium(n-butyl)triphenylborate, 2-methyl-4,6-bistrichloromethyltriazine, 2-( Examples thereof include, but are not limited to, triazine compounds such as 4-methoxyphenyl)-4,6-bistrichloromethyltriazine.

(5) Crosslinking Agent A crosslinking 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-based compounds represented by the following general formula (6).

In the formula (6), R ⁶¹ represents a —NR ⁶⁶ R ⁶⁷ group or an aryl group having 6 to 12 carbon atoms, and when R ⁶¹ is a —NR ⁶⁶ R ⁶⁷ group, R ⁶² , R ⁶³ , R ⁶⁴ , R ⁶⁵ , R ⁶⁶ and R ⁶⁷ each represent a CH ₂ OR ⁶⁸ group, and when R ⁶¹ is an aryl group having 6 to 12 carbon atoms, one of R ⁶² , R ⁶³ , R ⁶⁴ and R ⁶⁵ is —CH ₂ OR ^68. R ⁶² , R ⁶³ , R ⁶⁴ , R ⁶⁵ , R ⁶⁶ and the remaining of R ⁶⁷ each independently represent hydrogen or a —CH ₂ OR ⁶⁸ group, and R ⁶⁸ represents a hydrogen atom or a carbon number of 1 to 4 Represents an alkyl group.
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, etc. The substituent of may be bonded. The alkyl group and the alkoxy group may each have about 1 to 6 carbon atoms. Among the above, the alkyl group represented by R ⁶⁸ is preferably a methyl group or an ethyl group, and particularly preferably a methyl group.

Melamine compounds corresponding to the general formula (6), that is, compounds of the following general formula (6-1) include hexamethylolmelamine, pentamethylolmelamine, tetramethylolmelamine, hexamethoxymethylmelamine, pentamethoxymethylmelamine, tetramethoxy. Methyl melamine, hexaethoxymethyl melamine and the like are included.

In Formula (6-1), when one of R ⁶² , R ⁶³ , R ⁶⁴ , R ⁶⁵ , R ⁶⁶ and R ⁶⁷ is an aryl group, one of R ⁶² , R ⁶³ , R ⁶⁴ and R ⁶⁵ is —CH ₂ Represents an OR ⁶⁸ group, the rest of R ⁶² , R ⁶³ , R ⁶⁴ , R ⁶⁵ , R ⁶⁶ and R ⁶⁷ independently of each other represents a hydrogen atom or a —CH ₂ OR ⁶⁸ group, wherein R ⁶⁸ represents a hydrogen atom or Represents an alkyl group.

Further, the guanamine-based compound corresponding to the general formula (6), that is, the compound in which R ⁶¹ in the general formula (6) is aryl, includes tetramethylolbenzoguanamine, tetramethoxymethylbenzoguanamine, trimethoxymethylbenzoguanamine, and tetraethoxymethylbenzoguanamine. Are included.

Further, a cross-linking agent having a methylol group or a methylol alkyl ether group can 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-Triazin-2-one (commonly called N-ethyldimethyloltriazone) or its dimethyl ether compound, dimethyloltrimethylene urea or its dimethyl ether compound, 3,5-bis(hydroxymethyl)perhydro-1,3,5- Oxadiazin-4-one (commonly called dimethylolurone) or its dimethyl ether body, tetramethylol glyoxaldiurene or its tetramethyl ether body.

Note that these crosslinking agents may be used alone or in combination of two or more. The amount of the crosslinking agent used is preferably 0.1 to 15% by mass, and 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 represent a hydrogen atom or a monovalent substituent. Represent
Of these, from the viewpoint of photocurability, Z is preferably —S— or —NH—, more preferably —NH—.
From the viewpoint of photocurability, R ⁶¹ , R ⁶² , R ⁶³ , and R ⁶⁴ are each independently preferably a hydrogen atom, a C 1-4 alkyl group or a C 1-4 alkoxy group, 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 Examples thereof include mercapto group-containing compounds having an aromatic ring such as 1,4-dimethylmercaptobenzene, 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, decanedithiol, or the compound represented by the following general formula (1-4) is preferably used from the viewpoint of photocurability.

In formula (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. From the viewpoint of photocurability, n is preferably 3 or 4, and more preferably 4.
The alkyl group for R ⁷¹ and R ⁷² is preferably one having 1 to 3 carbon atoms 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, and in this 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, 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. 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, X is preferably a structure represented by the following general formula (1-5) or (1-6) from the viewpoint of photocurability.

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, X preferably 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, trimethylolpropane tris(3- Mercaptopropionate), trimethylolpropane tristhioglycolate, trishydroxyethyltristhiopropionate, pentaerythritol tetrakis(3-mercaptopropionate), pentaerythritol tris(3-mercaptopropionate), butanediol bis (3-mercaptobutyrate), ethylene glycol bis(3-mercaptobutyrate), trimethylolpropane tris(3-mercaptobutyrate), pentaerythritol tetrakis(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, trimethylolpropane tris (3-mercaptopropionate), pentaerythritol tetrakis (3-mercaptopropionate), pentaerythritol tris (3-mercaptopropionate), trimethylolpropane tris (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.

Various types of these can be used alone or in combination 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 is combined with a photopolymerization initiator to form a photopolymerization initiator. It is preferably 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.
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 when a mask with a narrow opening is used, the illuminance per unit area becomes low due to diffraction during exposure, and it is more susceptible to oxygen inhibition than when the line width is thick, and the surface curability becomes low. Because there is a tendency.

In particular, when a hexaarylbiimidazole-based photopolymerization initiator is used as the (c) photopolymerization initiator, a mercapto group-containing compound having an aromatic ring and an aliphatic mercapto group-containing compound are used in combination. Is preferred. On the other hand, when the acetophenone-based photopolymerization initiator is used, the effect tends to be sufficiently obtained even when the 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, pentaerythritol tetrakis (3-mercaptopropionate), pentaerythritol tetrakis (3-mercapto). It is preferable to use one or more selected from the group consisting of butyrate) and a photopolymerization initiator in combination.

(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 human body, hydroquinone monomethyl ether and methylhydroquinone are preferable.
The polymerization inhibitor may contain one kind or two or more kinds. (B) When an alkali-soluble resin is produced, the resin may contain a polymerization inhibitor, which may be used as the polymerization inhibitor of the present invention. The same or different polymerization inhibitor may be added during the production of the photosensitive coloring composition.

<Amount of Components in Photosensitive Coloring Composition>
In the photosensitive coloring composition of the present invention, the content ratio of the (b) alkali-soluble resin is not particularly limited, but is usually 5% by mass or more, preferably 10% by mass or more, more preferably 15% by mass or more based on the total solid content. , More preferably 20 mass% or more, particularly preferably 25 mass% or more, usually 80 mass% or less, preferably 70 mass% or less, more preferably 60 mass% or less, more preferably 50 mass% or less, even more It is preferably 40% by mass or less, and particularly preferably 35% by mass or less. For example, it is preferably 5 to 80% by mass, more preferably 5 to 70% by mass, further preferably 10 to 60% by mass, further preferably 15 to 50% by mass, particularly preferably 20 to 40% by mass, and 25 to 35% by mass. Mass% is especially preferred. When the content ratio of the alkali-soluble resin (b) is not less than the above lower limit, the developing solubility tends to be improved. Further, when the content is not more than the upper limit, the mechanical properties tend to be improved.

The content ratio of (c) 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, further preferably 1% by mass based on the total solid content. The amount is 0.5% by mass or more, usually 15% by mass or less, preferably 10% by mass or less, more preferably 8% by mass or less, further 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, 1.5 to 4% by mass. Are particularly preferred. (C) When the content ratio of the photopolymerization initiator is not less than the lower limit value, photocurability is increased, and the surface roughness tends to be improved, and when it is not more than the upper limit value, the developing solubility is 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, and 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 proportion of 0.1 to 50 parts by mass, preferably 0.1 to 20 parts by mass, relative to 100 parts by mass of the (c) photopolymerization initiator. By setting the content ratio of the polymerization accelerator to the lower limit value or more, there is a tendency that it is possible to suppress the decrease in sensitivity to exposure light, and by setting the content ratio to the upper limit value or less, it is possible to suppress the decrease in solubility in the developer of the unexposed portion. However, development failure tends to be suppressed.

When a sensitizing dye is used together with the (c) photopolymerization initiator, the content ratio of the sensitizing dye is preferably 0.1% by mass or more, based on 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 mass% is preferable, 0.2 to 4 mass% is more preferable, and 0.3 to 3 mass% is further preferable. When it is at least the above lower limit, photocurability will be enhanced and surface roughness will tend to be improved, and when it is at most the above upper limit, development solubility will tend to be improved.

The content ratio of the (d) ethylenically unsaturated compound is usually 1% by mass or more, preferably 5% by mass or more, more preferably 10% by mass or more, based on 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 mass% or less. For example, 1 to 80% by weight is preferable, 5 to 80% by weight is more preferable, 10 to 70% by weight is further preferable, 20 to 70% by weight is further preferable, 30 to 70% by weight is particularly preferable, and 40 to 65%. Mass% is particularly preferable, and 50 to 65 mass% or more is the most preferable. (D) When the content ratio of the ethylenically unsaturated compound is not less than the lower limit value, mechanical properties tend to be improved, and when it is not more than the upper limit value, the developing solubility tends to be improved. ..

On the other hand, the content ratio of the (b) alkali-soluble resin to 100 parts by mass of the (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. It is more preferably 40 parts by mass or more, particularly preferably 150 parts by mass or less, 120 parts by mass or less, more preferably 100 parts by mass or less, and further preferably 70 parts by mass or less. For example, it is preferably 10 to 150 parts by mass, more preferably 20 to 120 parts by mass, further preferably 30 to 100 parts by mass, particularly preferably 40 to 70 parts by mass. When it is at least the lower limit, the developing solubility tends to be improved, and when it is at most the upper limit, the mechanical properties tend to be good.

In the photosensitive coloring composition of the present invention, by using the solvent (e), the content ratio of the total solid content is usually 5% by mass or more, preferably 10% by mass or more, more preferably 15% by mass or more. Further, the solution is usually adjusted to 50% by mass or less, preferably 30% by mass or less, and more preferably 25% by mass or less. For example, 5 to 50 mass% is preferable, 10 to 30 mass% is more preferable, and 15 to 25 mass% is further preferable.

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

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

When an adhesion improver is used, its content is usually 0.1% by mass or more, preferably 0.2% by mass or more, more preferably 0.5% by mass or more, based on the total solid content of the photosensitive coloring composition. It is preferably, usually 30% by mass or less, 20% by mass or less, more preferably 10% by mass or less, further preferably 5% by mass or less, particularly preferably 3% by mass or less. 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 still more preferable, 0.5 to 5% by mass. 3% by weight is particularly preferred. When the content ratio of the adhesion improver is not less than the lower limit, the adhesion tends to be improved, and when it is not more than the upper limit, the residue tends to be reduced.

When a surfactant is used, its content is usually 0.001 to 10% by mass, preferably 0.005 to 1% by mass, and more preferably 0.01% by mass based on the total solid content of the photosensitive coloring composition. To 0.5 mass %, and most preferably 0.03 to 0.3 mass %. By setting the content ratio of the surfactant to the lower limit or more, the smoothness and uniformity of the coating film tend to be easily expressed, and by setting the content ratio of the surfactant or less to the smoothness and uniformity of the coating film. It tends to be easy and can suppress deterioration of other characteristics.

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

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

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

<Method for producing 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 previously subjected to a dispersion treatment 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 properties of the photosensitive coloring composition are improved.

Generally, the dispersion treatment is preferably performed in a system in which (a) a colorant, (e) a solvent, (f) a dispersant, and optionally (b) an alkali-soluble resin are used in combination or in part ( 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". In particular, it is preferable to use a polymer dispersant as the (f) dispersant, because the obtained ink and the photosensitive coloring composition are prevented from increasing in viscosity over time (excellent in dispersion stability).
Thus, 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 those that can be used in the photosensitive coloring composition are preferably adopted. it can.

When the dispersion treatment is performed on the liquid containing all the components to be mixed in the photosensitive coloring composition, the highly reactive component may be modified due to the heat generated during the dispersion treatment. Therefore, it is preferable to perform the dispersion treatment in a system that does not contain (c) a photopolymerization initiator or (d) an ethylenically unsaturated compound.
When the (a) colorant is dispersed with a sand grinder, glass beads or zirconia beads having a particle diameter of about 0.1 to 8 mm are preferably used. Regarding the dispersion treatment condition, the temperature is usually 0° C. to 100° C., preferably room temperature to 80° C. The dispersion time tends to vary depending on the composition of the liquid, the size of the dispersion treatment device, etc., and may be adjusted appropriately. The standard of dispersion is to control the gloss of the ink so that the 20-degree specular gloss (JIS Z8741) when the pigment dispersion or the photosensitive coloring composition is applied to the substrate is in the range of 50 to 300. When the content is at least the lower limit value, the dispersion treatment is not sufficient, and it is possible to suppress the residual of the coarse pigment ((a) colorant) particles, and it is easy to make the developability, adhesion, resolution, etc. sufficient. .. Further, when the content is not more than the upper limit, it is possible to prevent the pigment from crushing and to generate a large number of ultrafine particles, which tends to improve the dispersion stability.

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

[Cured product]
The cured product of the present invention is 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 colored spacer.

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

(1) Support The support for forming the colored spacer is not particularly limited in its material as long as it has appropriate strength. Although transparent substrates are mainly used, examples of the material include polyester resins such as polyethylene terephthalate, polyolefin resins such as polypropylene and polyethylene, thermoplastic resin sheets such as polycarbonate, polymethylmethacrylate and polysulfone, and epoxy. Examples thereof include resins, unsaturated polyester resins, thermosetting resin sheets such as poly(meth)acrylic resins, and various glasses. Among these, glass and heat resistant resin are preferable from the viewpoint of heat resistance. In addition, 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.

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

(2) Colored Spacer The photosensitive colored composition of the present invention can be used in the same applications as known photosensitive colored compositions for color filters, but in the following, when it is used as a colored spacer, its formation The method will be described.

Usually, a photosensitive coloring composition is supplied in a film form or a pattern form by a method such as coating on a support on which a coloring spacer is to be provided, and the solvent is dried. Subsequently, pattern formation is performed by a method such as a photolithography method of exposing and developing. Then, if necessary, additional exposure or heat curing 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 such as a spinner method, a wire bar method, a flow coating method, a die coating method, a roll coating method, or a spray coating method can be used. Further, it may be supplied in a pattern by an inkjet method or a printing method. Among them, according to the die coating method, the usage amount of the coating liquid is significantly reduced, there is no influence of mist attached when the spin coating method is used, and the generation of foreign matter is suppressed. Is preferred.

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

However, in the case of collectively forming colored spacers having different heights by the photolithography method using the photosensitive coloring composition of the present invention, the heights of the finally formed colored spacers are different.

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

[2] Drying Method Drying after supplying the photosensitive coloring composition onto the substrate is preferably performed by a drying method using a hot plate, an IR oven, or a convection oven. Further, it is also possible to combine a reduced pressure drying method in which drying is performed in a reduced pressure chamber without raising the temperature.

The drying conditions such as the drying temperature and the 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 at a temperature of 40° C. to 130° C. for 15 seconds to 5 minutes, preferably at a temperature of 50° C. to 110° C. for 30 seconds to 3 minutes.

[3] Exposure Method The exposure is performed by superimposing a negative mask pattern on the coating film of the photosensitive coloring composition and irradiating a light source of ultraviolet rays or visible light through the mask pattern. In the case of performing exposure using an exposure mask, a method of bringing the exposure mask close to the coating film of the photosensitive coloring composition or disposing the exposure mask at a position distant from the coating film of the photosensitive coloring composition, A method of projecting exposure light through a mask may be used. Alternatively, 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 treatment is performed in a deoxygenated atmosphere, or the exposure is performed after forming an oxygen barrier layer such as a polyvinyl alcohol layer on the photopolymerizable layer. You may

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 0%) and a plurality of openings have the highest average light transmittance. An exposure mask having an opening (completely transmissive opening) and an opening having a low average light transmittance (intermediate transmissive opening) is used. By this method, a difference in average film transmittance between the intermediate transmission opening and the complete transmission opening, that is, a difference in exposure amount causes a difference in residual film rate.
For example, a method is known in which the intermediate transmission opening is formed by a matrix light-shielding pattern having minute polygonal light-shielding units. Further, there is known a method of controlling the light transmittance by using a film of a material such as a chromium-based material, a molybdenum-based material, a tungsten-based material, or a silicon-based material as the absorber.

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

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

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.
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, and usually 500 μm or less, preferably 400 μm or less, more preferably It is 300 μm or less.

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

As the alkaline compound, sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium carbonate, potassium carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, sodium silicate, potassium silicate, sodium metasilicate, sodium phosphate, potassium phosphate. Inorganic alkaline compounds such as sodium hydrogen phosphate, potassium hydrogen phosphate, sodium dihydrogen phosphate, potassium dihydrogen phosphate and ammonium hydroxide, and mono-, di- or triethanolamine, mono-, di- or trimethylamine Organic alkalinity such as mono-, di- or triethylamine, mono- or diisopropylamine, n-butylamine, mono-, di- or triisopropanolamine, ethyleneimine, ethylenediimine, tetramethylammonium hydroxide (TMAH), choline Compounds. These alkaline compounds may be a mixture of two or more kinds.

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

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

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

[5] Additional exposure and heat curing treatment The substrate after development may be subjected to additional exposure by a method similar to the above-mentioned exposure method, if necessary, or may be subjected to heat curing treatment. The heat curing treatment conditions at this time are selected such that the temperature is in the 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 depending on the specifications of the color filter to which the colored spacer is applied, and the photosensitive colored composition of the present invention is particularly high in height of the spacer and the sub spacer by a photolithography method. It is useful for simultaneously forming colored spacers having different heights, in which case the height of the spacer is usually about 1 to 7 μm, and the height of the sub spacer is usually about 0.2 to 1.5 μm lower than that of the spacer. Have.

[Image display device]
The image display device of the present invention includes the colored spacer of the present invention.
For example, a color filter having the above-described colored spacer of the present invention and a liquid crystal driving side substrate are bonded together to form a liquid crystal cell, and liquid crystal is injected into the formed liquid crystal cell to provide the colored spacer of the present invention. 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 more specifically with reference to Examples and Comparative Examples, but the present invention is not limited to the following Examples unless it exceeds the gist.
The 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. 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 Chemical Co., Ltd.) having a tricyclodecane skeleton were added dropwise to 2,2′-azobis-2-methylbutyronitrile. 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 weight average molecular weight Mw in terms of polystyrene measured by GPC of the thus obtained alkali-soluble resin-I 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. 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 Chemical Co., Ltd.) having a tricyclodecane skeleton were added dropwise to 2,2′-azobis-2-methylbutyronitrile. 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 parts by mass of trisdimethylaminomethylphenol and 0.12 parts by mass of hydroquinone were added to 67 parts by mass of acrylic acid, and the reaction was continued at 100° C. for 12 hours. Then, 15 parts by mass of tetrahydrophthalic anhydride (THPA) and 0.6 parts by mass of triethylamine were added, and the reaction was carried out at 100° C. for 3.5 hours. The thus obtained alkali-soluble resin-II had a polystyrene-equivalent weight average molecular weight Mw measured by GPC of 9000, an acid value of 24 mgKOH/g, and a double bond equivalent of 260 g/mol.

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

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

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

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

<Surfactant>
DIC Megafac F-554
<Additive-I>
KAYAMER (registered trademark) PM-21 (methacryloyl group-containing phosphate) manufactured by Nippon Kayaku Co., Ltd.
<Additive-II>
Seiko Chemical Co., Ltd. Methylhydroquinone

<Preparation of Pigment Dispersions 1 to 7>
The pigment, the dispersant, the alkali-soluble resin, and the solvent described in Table 1 were mixed in a mass ratio shown in Table 1 to obtain a mixed solution. The blending ratio of the solvent in Table 1 includes the amounts of the dispersant and the solvent derived from the alkali-soluble resin.
This mixed solution was subjected to a dispersion treatment in the range of 25 to 45° C. for 3 hours with a paint shaker. As the beads, zirconia beads having a diameter of 0.5 mm were used, and a mass 2.5 times that of the dispersion liquid was added. After the dispersion was completed, the beads and the dispersion were separated by a filter to prepare pigment dispersions 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, the respective components were added so that the solid content ratio of the respective components in the total solid content would be the compounding ratio of Table 2 or Table 3, and the content ratio of the total solid content was further added. Was added so that the content of PGMEA was 19% by mass, and the mixture was stirred and dissolved to prepare photosensitive coloring compositions 1 to 13. Using each of the obtained photosensitive coloring compositions, evaluation was performed by the method described below.

<Measurement of optical density (unit OD value) per unit film thickness>
The photosensitive coloring composition was applied onto a glass substrate with a spin coater so that the film thickness after heat curing would be 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 the whole surface exposure treatment using an ultraviolet ray having an intensity at 365 nm of 40 mW/cm ² without using a mask so that the exposure amount was 60 mJ/cm ² .
Then, using 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 Corporation), the water pressure at 0° C. is 0. After shower development of 0.15 MPa for 100 seconds, development was stopped with pure water, and washing was performed with a water spray. The substrate was heated and 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 by a transmission densitometer X-Rite 361T (V), and the film thickness was measured by Hitachi High-Technology scanning white light interference microscope VS1530. The optical density (unit OD value, OD/μm) per unit film thickness was calculated from the optical density (OD) and film thickness, and shown in Table 4. The OD value is a numerical value indicating the light-shielding ability, and the larger the numerical value, the higher the light-shielding property.

<Roughness evaluation>
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 average surface roughness (Sa) of the surface of the obtained substrate in the range of 10 μm×10 μm was measured with 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 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 colored spacer was used in the same manner as the resist-cured film substrate except that a glass substrate having an ITO film formed on the surface was used as a substrate, a mask having a 20 μm opening (circular opening having a diameter of 20 μm) was used during exposure, and the exposure gap was 150 μm. Got
The elastic recovery rate of the obtained colored spacer was measured by the following procedure. Using Fisher Scope 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, it was held for 5 seconds, and then 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 light resistance evaluation substrate 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 Technology Co., Ltd.
Next, the substrate was irradiated with light having an intensity of 19 mW/cm ² at a wavelength of 450 nm for 500 hours 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 similarly measured. 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.

Change rate of absorbance (%)={(absorbance at 450 nm before irradiation-absorbance at 450 nm after irradiation)/absorbance at 450 nm before irradiation}×100

(Evaluation criteria)
A: less than 20% B: 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 content of the purple pigment is contained in the colorant, and the content ratio of the purple pigment in the colorant is It can be seen that it is possible to form a colored spacer having excellent surface roughness and mechanical properties by using the photosensitive coloring composition 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 since the purple pigment has high dispersibility and is uniformly dispersed in the cured film, 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 if 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 it is possible to set the content ratio of the alkali-soluble resin or the ethylenically unsaturated compound relatively high by preventing the content ratio of the colorant from becoming too high, and the crosslinking density of the obtained colored spacer becomes high. It is thought that it is because of it.

As is clear from a 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. Further, 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 based on the total solid content of the photosensitive coloring composition, the optical density is improved, and the surface roughness is increased depending on the kind and ratio of the pigment in the colorant. It can be seen that is sometimes 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 violet pigment has a low absorbance around a wavelength of 450 nm, and contains a large amount of the violet pigment, so that it is less susceptible to the irradiation light having a wavelength of 450 nm.

Claims

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 of the (a) colorant is 2 to 20% by mass based on the total solid content of the photosensitive coloring composition,
The (a) colorant contains a purple pigment, and
The photosensitive coloring composition, wherein the content of the purple pigment in the colorant (a) is 50% by mass or more.
The above-mentioned purple pigment is C.I. I. Pigment Violet 29 and C.I. I. Pigment Violet 23, The photosensitive coloring composition of Claim 1 containing at least 1 sort(s) selected from the group which consists of.
The photosensitive coloring composition according to claim 1 or 2, wherein the (a) colorant further contains an orange pigment.
The photosensitive coloring composition according to any one of claims 1 to 3, wherein the content ratio of the (b) alkali-soluble resin to 150 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 for forming a colored 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 provided with the colored spacer according to claim 8.