JP7006358B2 - Photosensitive coloring composition, cured product, coloring spacer, and image display device - Google Patents

Description

The present invention relates to a photosensitive coloring composition and the like. More specifically, the present invention relates to a photosensitive coloring composition preferably used for forming a coloring spacer or the like of a liquid crystal display, a coloring spacer obtained by curing the photosensitive coloring composition, and an image display device including the coloring spacer.

A liquid crystal display (LCD) utilizes the property that the arrangement of liquid crystal molecules is switched by turning the voltage on and off the liquid crystal. On the other hand, most of the members constituting the cells of the liquid crystal display are formed by a method using a photosensitive composition typified by photolithography. This photosensitive composition is expected to be widely applied in the future because it is easy to form a fine structure and it is easy to process a large-area substrate.
In addition, LED backlights are now widely used in the mobile terminal and television industries because of their features such as high resolution, low cost, and thin form factor.

Recently, in order to support higher definition and higher brightness of color liquid crystal displays, in active matrix type liquid crystal displays, a color filter on array method (COA method) in which a color filter is provided on the TFT element substrate side has been used. A black matrix-on-array method (BOA method) in which only the black matrix is provided on the TFT element substrate side has been proposed. According to this method, it is not necessary to take an alignment margin with the active element side as compared with the case of forming a black matrix on the color filter side, so that the aperture ratio can be increased, and as a result, the brightness is increased. Can be planned. Such a black matrix structure is required to have high light-shielding properties and to suppress light leakage in the visible light region as much as possible.

In addition, with the simplification of the liquid crystal display structure and manufacturing process, so-called columnar spacers, so-called columnar spacers, and colored spacers that integrate a photo spacer and a black matrix, which are used to keep the distance between two substrates in a liquid crystal display constant, are also available. Has been developed. Various types of such colored spacers using an organic black pigment have been proposed. For example, Patent Document 1 describes that the display reliability of an LCD is improved by using a specific photopolymerization initiator. There is. Further, Patent Document 2 describes that the pattern forming property, developability and chemical resistance are excellent by using a specific phthalocyanine pigment in combination.

Japanese Unexamined Patent Publication No. 2016-167030 Korean Publication No. 10-2015-0024176

In recent years, there has been a demand for forming fine colored spacers with the advancement of high-definition liquid crystal displays and the development of mobile applications.
As a result of studies by the present inventors, when the photosensitive coloring composition described in Patent Documents 1 and 2 is used, although the light-shielding property and reliability are good, it is difficult to form a fine coloring spacer. Was found to be.
Therefore, an object of the present invention is to provide a photosensitive coloring composition having good light-shielding property and reliability and capable of forming a fine coloring spacer.

As a result of diligent studies to solve the above problems, the present inventors have found that the above problems can be solved by using a specific pigment as a colorant and further using a specific photopolymerization initiator. , Which led to the present invention.
That is, the present invention has the following configurations [1] to [8].

[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 colorant (a) is at least one selected from the group consisting of a compound represented by the following general formula (I), a geometric isomer of the compound, a salt of the compound, and a salt of the geometric isomer of the compound. Contains an organic black pigment (A1) containing
A photosensitive coloring composition, wherein the (c) photopolymerization initiator contains a photopolymerization initiator (C1) represented by the following general formula (i).

(In formula (I), R ^a1 and R ^a6 independently represent a hydrogen atom, CH ₃ , CF ₃ , a fluorine atom or a chlorine atom;
R ^a2 , R ^a3 , R ^a4 , R ^a5 , R ^a7 , R ^a8 , R ^a9 and R ^a10 are independently hydrogen atom, halogen atom, R ^a11 , COOH, COOR ^a11 , COO- ^, CONH ₂ , CONHR ^a11 . , CONR ^a11 R ^a12 , CN, OH, OR ^a11 , COCR ^a11 , OOCNH ₂ , OOCNHR ^a11 , OOCNR ^a11 R ^a12 , NO ₂ , NH ₂ , NHR ^a11 , NR ^a11 R ^a12 , NHCOR ^a12 , NR ^a11 COR ^a12 , N = CH ₂ , N = CHR ^a11 , N = CR ^a11 R ^a12 , SH, SR ^a11 , SOR ^a11 , SO ₂ R ^a11 , SO ₃ R ^a11 , SO ₃ H, SO _3- ^, SO ₂ NH ₂ , SO ₂ NHR ^{Represents a11} or SO ₂ NR ^a11 R ^a12 ;
And at least one combination selected from the group consisting of R ^a2 and R ^a3 , R ^a3 and R ^a4 , R ^a4 and R ^a5 , R ^a7 and R ^a8 , R ^a8 and R ^a9 , and R ^a9 and R ^a10 is They may bond directly to each other, or they may bond to each other by oxygen, sulfur, NH or NR ^a11 bridges;
R ^a11 and R ^a12 are independently an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms, an alkenyl group having 2 to 12 carbon atoms, a cycloalkenyl group having 3 to 12 carbon atoms, or a cycloalkenyl group having 3 to 12 carbon atoms. Represents 2-12 alkynyl groups. )

(In formula (i), R ¹ represents an alkyl group which may have a substituent or an aromatic ring group which may have a substituent.
R ² represents an alkyl group which may have a substituent or an aromatic ring group which may have a substituent.
k represents 0 or 1.
R ³ to R ⁶ each independently represent an arbitrary monovalent substituent.
l, m and o each independently represent an integer of 0 to 3. n represents 0 or 1. )

[2] The colored photosensitive composition according to [1], wherein the (a) colorant further contains (A2) an organic coloring pigment.
[3] The colored photosensitive composition according to [1] or [2], wherein the (a) colorant further contains (A3) carbon black.

[4] The photosensitive coloring composition according to any one of [1] to [3], wherein the content ratio of the colorant (a) is 10% by mass or more with respect to the total solid content.
[5] The photosensitive coloring composition according to any one of [1] to [4], which is used for forming a coloring spacer.

[6] A cured product obtained by curing the photosensitive coloring composition according to any one of [1] to [5].
[7] A colored spacer composed of the cured product according to [6].
[8] An image display device including the coloring spacer according to [7].

According to the present invention, it is possible to provide a photosensitive coloring composition having good light-shielding property and reliability and capable of forming a fine coloring spacer.

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

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

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

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

[Photosensitive coloring composition]
The photosensitive coloring composition of the present invention is
(A) Colorant (b) Alkaline-soluble resin (c) Photopolymerization initiator (d) Ethylene unsaturated compound is contained as an essential component, and if necessary, an adhesion improver such as a silane coupling agent is applied. It contains other compounding ingredients such as property improver, development improver, ultraviolet absorber, antioxidant, surfactant, pigment derivative, etc., and is usually used in a state where each compounding component is dissolved or dispersed in a solvent. Will be done.

<(A) Colorant>
The (a) colorant contained in the photosensitive coloring composition of the present invention is a component that colors the photosensitive coloring composition. (A) By containing a colorant, desired light absorption can be obtained. (A) As the colorant, a pigment or a dye may be used.

In the photosensitive coloring composition of the present invention, the (a) colorant is a compound represented by the following general formula (I) (hereinafter, may be referred to as “compound (I)”), and the geometric isomerism of the compound. An organic black pigment (A1) containing at least one selected from the group consisting of a body, a salt of the compound, and a salt of a geometric isomer of the compound (hereinafter, may be referred to as “organic black pigment (A1)”). .)including.
As described above, by including the organic black pigment (A1), high resistance, low dielectric constant and high light-shielding ratio can be realized, the decrease in the voltage retention rate of the liquid crystal is suppressed, and the absorption of ultraviolet rays is suppressed to form the shape. It is thought that it is possible to easily control the steps and steps.

In formula (I), R ^a1 and R ^a6 independently represent a hydrogen atom, CH ₃ , CF ₃ , a fluorine atom or a chlorine atom;
R ^a2 , R ^a3 , R ^a4 , R ^a5 , R ^a7 , R ^a8 , R ^a9 and R ^a10 are independently hydrogen atom, halogen atom, R ^a11 , COOH, COOR ^a11 , COO- ^, CONH ₂ , CONHR ^a11 . , CONR ^a11 R ^a12 , CN, OH, OR ^a11 , COCR ^a11 , OOCNH ₂ , OOCNHR ^a11 , OOCNR ^a11 R ^a12 , NO ₂ , NH ₂ , NHR ^a11 , NR ^a11 R ^a12 , NHCOR ^a12 , NR ^a11 COR ^a12 , N = CH ₂ , N = CHR ^a11 , N = CR ^a11 R ^a12 , SH, SR ^a11 , SOR ^a11 , SO ₂ R ^a11 , SO ₃ R ^a11 , SO ₃ H, SO _3- ^, SO ₂ NH ₂ , SO ₂ NHR ^{Represents a11} or SO ₂ NR ^a11 R ^a12 ;
And at least one combination selected from the group consisting of R ^a2 and R ^a3 , R ^a3 and R ^a4 , R ^a4 and R ^a5 , R ^a7 and R ^a8 , R ^a8 and R ^a9 , and R ^a9 and R ^a10 is They may bond directly to each other, or they may bond to each other by oxygen, sulfur, NH or NR ¹¹ bridges;
R ^a11 and R ^a12 are independently an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms, an alkenyl group having 2 to 12 carbon atoms, a cycloalkenyl group having 3 to 12 carbon atoms, or a cycloalkenyl group having 3 to 12 carbon atoms. Represents 2-12 alkynyl groups.

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

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

As for the substituent of the general formula (I), the following is preferable because the shielding rate tends to be high. This is because the following substituents are considered to be non-absorbent and do not affect the hue of the pigment.
R ^a2 , R ^a4 , R ^a5 , R ^a7 , R ^a9 and R ^a10 are each independently, preferably a hydrogen atom, a fluorine atom, or a chlorine atom, and more preferably a hydrogen atom.
R ^a3 and R ^a8 are independent, preferably hydrogen atom, NO ₂ , OCH ₃ , OC ₂ H ₅ , bromine atom, chlorine atom, CH ₃ , C ₂ H ₅ , N (CH ₃ ) ₂ , N (CH). ₃ ) (C ₂ H ₅ ), N (C ₂ H ₅ ) ₂ , α-naphthyl, β-naphthyl, SO ₃ H or SO _3- ^, more preferably a hydrogen atom or SO ₃ H.

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

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

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

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

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

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

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

The organic black pigment (A1) is preferably made from a compound represented by the following general formula (I-1) (hereinafter, may be referred to as “compound (I-1)”) and a geometric isomer of the compound. At least one selected from the group of

Specific examples of such an organic black pigment include Irgaphor (registered trademark) Black S 0100 CF (manufactured by BASF) under the trade name.
This organic black pigment is preferably dispersed and used by a dispersant, a solvent, or a method described later. Further, at the time of dispersion, the sulfonic acid derivative (sulfonic acid substituent) of the compound (I) or the sulfonic acid derivative of the geometric isomer of the compound (I), particularly the sulfonic acid derivative of the compound (I-1), or The presence of a sulfonic acid derivative of the geometric isomer of the compound (I-1) may improve dispersibility and storage stability. As the sulfonic acid derivative, for example, at least one selected from the group consisting of R ² , R ³ , R ⁴ , R ⁵ , R ⁷ , R ⁸ , R ⁹ and R ¹⁰ in the above general formula (I) is SO ₃ . The one of H is mentioned.
Further, for adjusting the chromaticity, it is preferable that the organic black pigment (A1) further contains a compound represented by the following general formula (I-2) and / or a geometric isomer of the compound.

The (a) colorant used in the present invention may contain other colorants in addition to the organic black pigment (A1). As the other colorant, it is preferable to use a pigment, and the pigment may be an organic pigment or an inorganic pigment, but from the viewpoint of high resistance and low dielectric constant, it is more preferable to use an organic pigment. In particular, it is more preferable to use an organic coloring pigment (hereinafter, may be referred to as "(A2) organic coloring pigment").

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

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

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

As the blue pigment, C.I. I. Pigment Blue 1, 1: 2, 9, 14, 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, 16, 17, 19, 25, 27, 28, 29, 33, 35, 36, 56, 56: 1, 60, 61, 61: 1, 62, 63, 66, 67, 68, 71, 72, 73, 74, 75, 76, 78, 79 can be mentioned. Among these, preferably C.I. I. Pigment Blue 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, more preferably C.I. I. Pigment Blue 15: 6 can be mentioned.
In terms of dispersibility and light-shielding property, C.I. I. Pigment Blue 15: 6, 16, 60 is preferably used, and when the photosensitive coloring composition of the present invention is cured with ultraviolet rays, it is preferable to use a blue pigment having a low ultraviolet absorption rate. From the point of view, C.I. I. It is more preferable to use Pigment Blue 60.

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

Examples of organic coloring pigments that can be used in addition to red pigments, orange pigments, blue pigments, and purple pigments include green pigments and yellow pigments.
Examples of the green pigment include C.I. I. Pigment Greens 1, 2, 4, 7, 8, 10, 13, 14, 15, 17, 18, 19, 26, 36, 45, 48, 50, 51, 54, 55, 58 can be mentioned. Among these, preferably C.I. I. Pigment Greens 7 and 36 can be mentioned.
As the yellow pigment, C.I. I. Pigment Yellow 1, 1: 1, 2, 3, 4, 5, 6, 9, 10, 12, 13, 14, 16, 17, 24, 31, 32, 34, 35, 35: 1, 36, 36: 1,37,37: 1,40,41,42,43,48,53,55,61,62,62: 1,63,65,73,74,75,81,83,87,93,94, 95, 97, 100, 101, 104, 105, 108, 109, 110, 111, 116, 117, 119, 120, 126, 127, 127: 1, 128, 129, 133, 134, 136, 138, 139, 142, 147, 148, 150, 151, 153, 154, 155, 157, 158, 159, 160, 161, 162, 163, 164, 165, 166, 167, 168, 169, 170, 172, 173, 174, 175, 176, 180, 181, 182, 183, 184, 185, 188, 189, 190, 191, 191: 1, 192, 193, 194, 195, 196, 197, 198, 199, 200, 202, 203, 204, 205, 206, 207, 208 can be mentioned. Among these, preferably C.I. I. Pigment Yellow 83, 117, 129, 138, 139, 150, 154, 155, 180, 185, more preferably C.I. I. Pigment Yellow 83, 138, 139, 150, 180 can be mentioned.

Among these pigments, it is preferable to use a combination of at least one selected from the group consisting of red pigments and orange pigments and at least one selected from the group consisting of blue pigments and purple pigments. As described above, there is a tendency that high light-shielding property can be achieved by using a specific combination of pigments.

Among these, from the viewpoint of light-shielding property and color tone, it is preferable to contain at least one of the following pigments.
Red pigment: C.I. I. Pigment Red 177, 254, 272
Orange pigment: C.I. I. Pigment Orange 43, 64, 72
Blue pigment: C.I. I. Pigment Blue 15: 6, 60
Purple pigment: C.I. I. Pigment Violet 23, 29

The color combination is not particularly limited, and examples thereof include a combination of a red pigment and a blue pigment, a combination of a blue pigment and an orange pigment, and a combination of a blue pigment and an orange pigment and a purple pigment from the viewpoint of light-shielding property. ..

Further, as the other colorants, other black colorants can be used in addition to these organic color pigments.
Among other black colorants, other organic black pigments other than those represented by the general formula (I) may be used from the viewpoint of light-shielding property and color tone. Examples of other organic black pigments include aniline black, perylene black, and cyanine black.

Further, in the present invention, an inorganic black pigment can be used. Examples of the inorganic black pigment include carbon black, acetylene black, lamp black, bone black, graphite, iron black, titanium black, and the like. Among these, carbon black (hereinafter, may be referred to as "(A3) carbon black") can be preferably used from the viewpoint of light-shielding property and image characteristics. Examples of carbon black include the following carbon blacks.

Made by Mitsubishi Chemical Corporation: MA7, MA8, MA11, MA77, MA100, MA100R, MA100S, MA220, MA230, MA600, MCF88, # 5, # 10, # 20, # 25, # 30, # 32, # 33, # 40 , # 44, # 45, # 47, # 50, # 52, # 55, # 650, # 750, # 850, # 900, # 950, # 960, # 970, # 980, # 990, # 1000, # 2200, # 2300, # 2350, # 2400, # 2600, # 2650, # 3030, # 3050, # 3150, # 3250, # 3400, # 3600, # 3750, # 3950, # 4000, # 4010, OIL7B, OIL9B , OIL11B, OIL30B, OIL31B
Made by Degusa: Printex (registered trademark; the same applies hereinafter) 3, Printex3OP, Printex30, Printex30OP, Printex40, Printex45, Printex55, Printex60, Printex75, Printex80, Printex85, Printex90, PrintexA, PrintexA. U, Printex V, SpecialBlack550, SpecialBlack350, SpecialBlack250, SpecialBlack100, SpecialBlack6, SpecialBlack5, SpecialBlack4, Color Black FW1, Color Black FW2, Color Black FW2V, Color Black FW18, Color Black FW200, Color Black S160, Color Black S170
Made by Cabot Corporation: Monarch (registered trademark; the same shall apply 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; same as REGAL). REGAL415R, REGAL250, REGAL250R, REGAL330, REGAL400R, REGAL55R0, REGAL660R, BLACK PEARLS480, PEARLS130, VULCAN (registered trademark. The same shall apply hereinafter) XC72R, ELFTEX (registered trademark) -8.
Made by Biller: RAVEN (registered trademark; the same shall apply hereinafter) 11, RAVEN14, RAVEN15, RAVEN16, RAVEN22RAVEN30, RAVEN35, RAVEN40, RAVEN410, RAVEN420, RAVEN450, RAVEN500, RAVEN780, RAVEN450, RAVEN500, RAVEN780, RAVEN810RAVEN10URA , RAVEN1170, RAVEN1190U, RAVEN1250, RAVEN1500, RAVEN2000, RAVEN2500U, RAVEN3500, RAVEN5000, RAVEN5250, RAVEN5750, RAVEN7000

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

The carbon black to be subjected to the coating treatment with the resin preferably has a total content of Na and Ca of 100 ppm or less. Carbon black is usually raw material oil or combustion oil (or gas) at the time of production, reaction stop water or granulation water, Na mixed from the reactor material of the reactor, Ca, K, Mg, Al, Fe. Etc. are contained in the order of percent. Of these, Na and Ca are generally contained in an amount of several hundred ppm or more, respectively, but by reducing these, permeation into the transparent electrode (ITO) and other electrodes is suppressed, and electricity is obtained. There is a tendency to prevent short circuits.

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

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

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

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

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

The carbon black coated with the resin in this way can be used as a light-shielding material such as a partition wall and a colored spacer according to a conventional method. It can be created by a conventional method. When such carbon black is used, there is a tendency that a high shading rate and low cost can be achieved. Further, by coating the surface of carbon black with a resin, it is possible to produce a light-shielding material such as a partition wall having high resistance and a low dielectric constant and a colored spacer.

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

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

These pigments such as (A1) organic black pigment, (A2) organic coloring pigment, and other black coloring agents have an average particle size of usually 1 μm or less, preferably 0.5 μm or less, and more preferably 0.25 μm or less. It is preferable to use them in a dispersed manner. Here, the standard of the average particle size is the number of pigment particles.
The average particle size of this pigment is a value obtained from the pigment particle size measured by dynamic light scattering (DLS). The particle size is measured by a sufficiently diluted colored photosensitive resin composition (usually diluted to prepare a pigment content of about 0.005 to 0.2% by mass. However, if the concentration recommended by the measuring device is available. , According to the concentration), and measure at 25 ° C.

<(B) Alkaline-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 is, for example, an epoxy (meth) acrylate resin, an acrylic resin, a carboxyl group-containing epoxy resin, or a carboxyl group-containing resin. Examples thereof include urethane resin, novolak resin, polyvinylphenol resin and the like, and among them, (b1) epoxy (meth) acrylate resin (b2) acrylic copolymer resin is preferably used from the viewpoint of excellent plate-making property. These can be used alone or in admixture of a plurality of types.

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

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

Examples of the (b1) epoxy (meth) acrylate-based resin used in the present invention include the following epoxy (meth) acrylate-based resin (b1-1) and / or epoxy (meth) acrylate-based resin (b1-2) (hereinafter, “carboxyl”). Group-containing epoxy (meth) acrylate-based resin ”may be referred to as“ group-containing epoxy (meth) acrylate resin ”), which is preferably used from the viewpoint of developability and reliability.

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

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

Specific examples of the epoxy resin include, for example, bisphenol A type epoxy resin (for example, "jER (registered trademark, the same shall apply hereinafter) 828", "jER1001", "jER1002", "jER1004", etc. manufactured by Mitsubishi Chemical Corporation. ), Epoxy obtained by the reaction of the alcoholic hydroxyl group of the bisphenol A type epoxy resin with epichlorohydrin (for example, "NER-1302" (epoxy equivalent 323, softening point 76 ° C.) manufactured by Nippon Kayaku Co., Ltd.), bisphenol F type resin ( For example, "jER807", "EP-4001", "EP-4002", "EP-4004", etc. manufactured by Mitsubishi Chemical Corporation), an epoxy resin obtained by the reaction of an alcoholic hydroxyl group of a bisphenol F type epoxy resin with epichlorohydrin ( For example, "NER-7406" (epoxy equivalent 350, softening point 66 ° C) manufactured by Nippon Kayaku Co., Ltd., bisphenol S type epoxy resin, biphenyl glycidyl ether (for example, "YX-4000" manufactured by Mitsubishi Chemical Corporation), phenol. Novolak type epoxy resin (for example, "EPPN-201" manufactured by Nippon Kayaku Co., Ltd., "EP-152", "EP-154" manufactured by Mitsubishi Chemical Corporation, "DEN-438" manufactured by Dow Chemical Corporation), (o , M, p-) Cresol novolak type epoxy resin (for example, "EOCN (registered trademark, the same shall apply hereinafter) -102S", "EOCN-1020", "EOCN-104S") manufactured by Nippon Kayakusha, triglycidyl isocia. Nurate (for example, "TEPIC (registered trademark)" manufactured by Nissan Chemical Corporation), Trisphenol methane type epoxy resin (for example, "EPPN (registered trademark, the same shall apply hereinafter) -501" manufactured by Nippon Kayaku Co., Ltd., "EPPN-" 502 ”,“ EPPN-503 ”), alicyclic epoxy resin (“Seroxide (registered trademark, the same shall apply hereinafter) 2021P” manufactured by Daicel Chemical Industries, Ltd., “Ceroxide EHPE”), phenol by reaction of dicyclopentadiene and phenol Epoxy resin obtained by glycidylizing a resin (for example, "EXA-7200" manufactured by DIC, "NC-7300" manufactured by Nippon Kayaku Co., Ltd.), epoxy resins represented by the following general formulas (B1) to (B4), Etc. can be preferably used. Specifically, "XD-1000" manufactured by Nippon Kayaku Co., Ltd. is used as the epoxy resin represented by the following general formula (B1), and "XD-1000" manufactured by Nippon Kayaku Co., Ltd. is used as the epoxy resin represented by the following general formula (B2). Examples of the epoxy resin represented by the following general formula (B4) include "NC-3000" and "ESF-300" manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.

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

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

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

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

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

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

Examples of the α, β-unsaturated monocarboxylic acid or α, β-unsaturated monocarboxylic acid ester having a carboxyl group include (meth) acrylic acid, crotonic acid, o-, m- or p-vinyl benzoic acid, and (meth). ) Monocarboxylic acids such as α-position haloalkyl, alkoxyl, halogen, nitro, cyano-substituted acrylic acid, 2- (meth) acryloyloxyethyl succinic acid, 2- (meth) acryloyloxyethyl adipic acid, 2- ( Meta) acryloyloxyethyl phthalic acid, 2- (meth) acryloyloxyethyl hexahydrophthalic acid, 2- (meth) acryloyloxyethyl maleic acid, 2- (meth) acryloyloxypropyl succinic acid, 2- ( Meta) acryloyloxypropyl adipic acid, 2- (meth) acryloyloxypropyltetrahydrophthalic acid, 2- (meth) acryloyloxypropylphthalic acid, 2- (meth) acryloyloxypropylmaleic acid, 2- (meth) ) Acryloyloxybutyl succinic acid, 2- (meth) acryloyloxybutyl adipic acid, 2- (meth) acryloyloxybutylhydrophthalic acid, 2- (meth) acryloyloxybutylphthalic acid, 2- (meth) Acryloyloxybutylmaleic acid (meth), a monomer obtained by adding lactones such as ε-caprolactone, β-propiolactone, γ-butyrolactone, and δ-valerolactone to acrylic acid, or hydroxyalkyl ( A monomer obtained by adding an acid (anhydrous) such as (anhydrous) succinic acid, (anhydrous) phthalic acid, and (anhydrous) maleic acid to meta) acrylate and pentaerythritol tri (meth) acrylate, (meth) acrylic acid dimer. And so on.
Of these, (meth) acrylic acid is particularly preferable from the viewpoint of sensitivity.

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

As the epoxy resin, α, β-unsaturated monocarboxylic acid, α, β-unsaturated monocarboxylic acid ester having a carboxyl group, and the esterification catalyst, one type may be used alone or two types may be used. The above may be used together.
The amount of α, β-unsaturated monocarboxylic acid or α, β-unsaturated monocarboxylic acid ester having a carboxyl group is preferably in the range of 0.5 to 1.2 equivalents with respect to 1 equivalent of the epoxy group of the epoxy resin. , More preferably in the range of 0.7 to 1.1 equivalents. By setting the amount of α, β-unsaturated monocarboxylic acid or α, β-unsaturated monocarboxylic acid ester having a carboxyl group to the above lower limit or more, it is possible to suppress the shortage of the amount of unsaturated group introduced, and the number continues to increase. Reactions with basic acids and / or their anhydrides also tend to be sufficient. On the other hand, when the value is not more than the upper limit, the residual unreacted substance of α, β-unsaturated monocarboxylic acid or α, β-unsaturated monocarboxylic acid ester having a carboxyl group can be suppressed, and the curing characteristics are good. There is a tendency for it to be easy to do.

Polybasic acid and / or its anhydrate include maleic acid, succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, pyromellitic acid, trimellitic acid, benzophenone tetracarboxylic acid and methylhexahydrophthalic acid. One or more selected from acids, endomethylenetetrahydrophthalic acid, chlorendic acid, methyltetrahydrophthalic acid, biphenyltetracarboxylic acid, and anhydrates thereof and the like can be mentioned.

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

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

A polyfunctional 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 multi-branched structure.

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

Examples of the carboxyl group-containing epoxy (meth) acrylate-based resin include those described in Korean Patent Publication No. 10-2013-0022955, in addition to the above-mentioned ones.

The polystyrene-equivalent weight average molecular weight (Mw) of the epoxy (meth) acrylate resin measured by gel permeation chromatography (GPC) is usually 1,000 or more, preferably 1,500 or more, more preferably 2,000 or more. , More preferably 3,000 or more, still more preferably 4,000 or more, particularly preferably 5,000 or more, usually 10,000 or less, preferably 8,000 or less, and more preferably 7,000 or less. When it is set to the lower limit value or more, it tends to be possible to suppress the solubility in the developing solution from becoming too high, and when it is set to the upper limit value or less, the solubility in the developing solution tends to be good.

The acid value of the epoxy (meth) acrylate resin is not particularly limited, but is preferably 10 mgKOH / g or more, more preferably 20 mgKOH / g or more, further preferably 40 mgKOH / g or more, still more preferably 50 mgKOH / g or more, and further. 200 mgKOH / g or less is preferable, 150 mgKOH / g or less is more preferable, 120 mgKOH / g or less is further preferable, and 100 mgKOH / g or less is particularly preferable. When it is set to the lower limit value or more, appropriate development solubility tends to be obtained, and when it is set to the upper limit value or less, the development tends to proceed excessively and the film dissolution can be suppressed.

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

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

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

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

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

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

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

Specific examples of the divalent linear aliphatic group include a methylene group, an ethylene group, an n-propylene group, an n-butylene group, an n-pentylene group, an n-hexylene group, an n-heptylene group and the like. Among these, a methylene group is preferable from the viewpoint of skeletal rigidity.
The divalent branched chain aliphatic group includes the above-mentioned divalent linear aliphatic group, and the side chains include a methyl group, an ethyl group, an n-propyl group, an iso-propyl group, an n-butyl group and iso. Examples thereof include structures having a-butyl group, sec-butyl group, tert-butyl group and the like.
The number of rings contained in the divalent cyclic aliphatic group is not particularly limited, but is usually 1 or more, preferably 2 or more, and usually 12 or less, preferably 10 or less. When it is at least the above lower limit value, it becomes a strong film and tends to have good substrate adhesion, and when it is at least the above upper limit value, it is easy to suppress deterioration of sensitivity and film loss during development, and resolution is achieved. There is a tendency for sex to improve. Specific examples of the divalent cyclic aliphatic group include hydrogen atoms from rings such as cyclohexane ring, cycloheptane ring, cyclodecane ring, cyclododecane ring, norbornane ring, isobornane ring, adamantane ring, cyclododecane ring, and dicyclopentadiene. The group obtained by dividing by two can be mentioned. Among these, from the viewpoint of skeletal rigidity, a group obtained by removing two hydrogen atoms from the dicyclopentadiene ring and the adamantane ring is preferable.

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

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

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

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

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

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

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

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

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

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

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

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

The polystyrene-equivalent weight average molecular weight (Mw) of the (b1-I) epoxy (meth) acrylate resin measured by gel permeation chromatography (GPC) is not particularly limited, but is preferably 1,000 or more, preferably 1,500. The above is more preferable, 2,000 or more is further preferable, 3,000 or more is further preferable, 4,000 or more is particularly preferable, 5,000 or more is most preferable, and 30,000 or less is preferable, and 20,000 or less is preferable. The following is more preferable, 10,000 or less is further preferable, and 8,000 or less is particularly preferable. When it is at least the above lower limit value, the residual film ratio of the photosensitive coloring composition tends to be good, and when it is at least the above upper limit value, the resolution tends to be good.

The acid value of the (b1-I) epoxy (meth) acrylate resin is not particularly limited, but is preferably 10 mgKOH / g or more, more preferably 20 mgKOH / g or more, further preferably 40 mgKOH / g or more, and 50 mgKOH / g or more. Even more preferably, 80 mgKOH / g or more is particularly preferable, 200 mgKOH / g or less is preferable, 150 mgKOH / g or less is more preferable, 130 mgKOH / g or less is even more preferable, and 100 mgKOH / g or less is particularly preferable. When it is set to the lower limit value or more, the development solubility tends to be improved and the resolution tends to be good, and when it is set to the upper limit value or less, the residual film ratio of the photosensitive coloring composition tends to be good. There is.

Specific examples of the (b1-I) epoxy (meth) acrylate-based resin are given below. In addition, * in the example indicates a bond.

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

Specific examples of the divalent linear aliphatic group include a methylene group, an ethylene group, an n-propylene group, an n-butylene group, an n-pentylene group, an n-hexylene group, an n-heptylene group and the like. Among these, a methylene group is preferable from the viewpoint of skeletal rigidity.
The divalent branched chain aliphatic group includes the above-mentioned divalent linear aliphatic group, and the side chains include a methyl group, an ethyl group, an n-propyl group, an iso-propyl group, an n-butyl group and iso. Examples thereof include structures having a-butyl group, sec-butyl group, tert-butyl group and the like.
The number of rings contained in the divalent cyclic aliphatic group is not particularly limited, but is usually 1 or more, preferably 2 or more, and usually 12 or less, preferably 10 or less. When it is at least the above lower limit value, it becomes a strong film and tends to have good substrate adhesion, and when it is at least the above upper limit value, it is easy to suppress deterioration of sensitivity and film loss during development, and resolution is achieved. There is a tendency for sex to improve. Specific examples of the divalent cyclic aliphatic group include hydrogen atoms from rings such as cyclohexane ring, cycloheptane ring, cyclodecane ring, cyclododecane ring, norbornane ring, isobornane ring, adamantane ring, cyclododecane ring, and dicyclopentadiene. The group obtained by dividing by two can be mentioned. Among these, from the viewpoint of skeletal rigidity, a group obtained by removing two hydrogen atoms from the dicyclopentadiene ring and the adamantane ring is preferable.

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

The polystyrene-equivalent weight average molecular weight (Mw) of the (b1-II) epoxy (meth) acrylate resin measured by gel permeation chromatography (GPC) is not particularly limited, but is preferably 1,000 or more, preferably 2,000. The above is more preferable, 30,000 or less is preferable, 20,000 or less is more preferable, 10,000 or less is further preferable, 7,000 or less is further preferable, and 5,000 or less is particularly preferable. When the value is not less than the lower limit, the patterning characteristics tend to be good, and when the value is not more than the upper limit, a strong film is easily obtained and surface roughness is less likely to occur.

The acid value of the (b1-II) epoxy (meth) acrylate resin is not particularly limited, but is preferably 10 mgKOH / g or more, more preferably 20 mgKOH / g or more, further preferably 40 mgKOH / g or more, and more preferably 60 mgKOH / g or more. More preferably, 80 mgKOH / g or more is particularly preferable, 100 mgKOH / g or more is most preferable, 200 mgKOH / g or less is preferable, 150 mgKOH / g or less is more preferable, and 120 gKOH / g or less is further preferable. When it is at least the above lower limit value, a strong film tends to be easily obtained, and when it is at least the above upper limit value, the development solubility is improved and the resolution tends to be good.

As the epoxy (meth) acrylate-based resin, one type may be used alone, or two or more types of resins may be mixed and used.
Further, a part of the above-mentioned epoxy (meth) acrylate resin may be replaced with another binder resin and used. That is, an epoxy (meth) acrylate resin and another binder resin may be used in combination. In this case, (b) the proportion of the epoxy (meth) acrylate-based resin in the alkali-soluble resin is preferably 50% by mass or more, more preferably 60% by mass or more, and 70% by mass or more. Is more preferable, and 80% by mass or more is particularly preferable.

There is no limitation on other binder resins that can be used in combination with the epoxy (meth) acrylate resin, and the resin may be selected from the resins usually used for the photosensitive coloring composition. For example, the binder resin described in JP-A-2007-27172, JP-A-2007-316620, JP-A-2007-334290, and the like can be mentioned. In addition, each of the other binder resins may be used alone or in combination of two or more.

Further, as the (b) alkali-soluble resin, it is preferable to use (b2) an acrylic copolymer resin from the viewpoint of compatibility with pigments, dispersants and the like, and those described in JP-A-2014-137466 are preferably used. be able to.

Examples of the acrylic copolymer resin include an ethylenically unsaturated monomer having one or more carboxyl groups (hereinafter referred to as “unsaturated monomer (b2-1)”) and other copolymerizable ethylene. Examples thereof include a copolymer with a sex-unsaturated monomer (hereinafter referred to as "unsaturated monomer (b2-2)").
Examples of the unsaturated monomer (b2-1) include unsaturated monocarboxylic acids such as (meth) acrylic acid, crotonic acid, α-chloracrylic acid and succinic acid; maleic acid, maleic anhydride and fumaric acid. , Citraconic acid, anhydrous citraconic acid, unsaturated dicarboxylic acid such as mesaconic acid or its anhydride; monosuccinate [2- (meth) acryloyloxyethyl], mono-phthalic acid [2- (meth) acryloyloxyethyl]. Mono [(meth) acryloyloxyalkyl] ester of a polyvalent carboxylic acid having a valence of 2 or more; ) Acrylic; p-vinylbenzoic acid and the like can be mentioned.
These unsaturated monomers (b2-1) can be used alone or in admixture of two or more.

Examples of the unsaturated monomer (b2-2) include N-position substituted maleimides such as N-phenylmaleimide and N-cyclohexylmaleimide; styrene, α-methylstyrene, p-hydroxystyrene, and p-hydroxy-. Aromatic vinyl compounds such as α-methylstyrene, p-vinylbenzyl glycidyl ether, acenaphthylene;

Methyl (meth) acrylate, n-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, allyl (meth) acrylate, benzyl (meth) acrylate, polyethylene glucol (degree of polymerization 2) ~ 10) Methyl ether (meth) acrylate, polypropylene glucol (polymerization degree 2 to 10) Methyl ether (meth) acrylate, polyethylene glycol (polymerization degree 2 to 10) mono (meth) acrylate, polypropylene glycol (polymerization degree 2 to 10) ) Mono (meth) acrylate, cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, tricyclo [5.2.1.0 ^2,6 ] decane-8-yl (meth) acrylate, dicyclopentenyl (meth) acrylate, Gglycerol mono (meth) acrylate, 4-hydroxyphenyl (meth) acrylate, ethylene oxide-modified (meth) acrylate of paracumylphenol, glycidyl (meth) acrylate, 3,4-epoxycyclohexylmethyl (meth) acrylate, 3-[(( Meta) Acryloyloxymethyl] oxetane, 3-[(meth) acryloyloxymethyl] -3-ethyl (meth) acrylic acid esters such as oxetane;

Vinyl ethers such as cyclohexyl vinyl ether, isobornyl vinyl ether, tricyclo [5.2.1.0 ^2,6 ] decane-8-ylvinyl ether, pentacyclopentadecanyl vinyl ether, 3- (vinyloxymethyl) -3-ethyloxetane Examples thereof include macromonomers having a mono (meth) acryloyl group at the end of a polymer molecular chain such as polystyrene, polymethyl (meth) acrylate, poly-n-butyl (meth) acrylate, and polysiloxane.
These unsaturated monomers (b2-2) can be used alone or in admixture of two or more.

In the copolymer of the unsaturated monomer (b2-1) and the unsaturated monomer (b2-2), the copolymerization ratio of the unsaturated monomer (b1) in the copolymer is preferably 5. It is ~ 50% by mass, more preferably 10-40% by mass. By copolymerizing the unsaturated monomer (b2-1) in such a range, it tends to be possible to obtain a photosensitive coloring composition having excellent alkali developability and storage stability.

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

<(C) Photopolymerization initiator>
(C) The photopolymerization initiator is a component having a function of directly absorbing light, causing a decomposition reaction or a hydrogen abstraction reaction, and generating a polymerization active radical. If necessary, an additive such as a polymerization accelerator (chain transfer agent) or a sensitizing dye may be added and used.

The (c) photopolymerization initiator in the photosensitive coloring composition of the present invention is a photopolymerization initiator (C1) represented by the following general formula (i) (hereinafter referred to as “photopolymerization initiator (C1)”). There is.) Including.

In formula (i), R ¹ represents an alkyl group which may have a substituent or an aromatic ring group which may have a substituent.
R ² represents an alkyl group which may have a substituent or an aromatic ring group which may have a substituent.
k represents 0 or 1.
R ³ to R ⁶ each independently represent an arbitrary monovalent substituent.
l, m and o each independently represent an integer of 0 to 3. n represents 0 or 1.

As described above, the photopolymerization initiator (C1) represented by the general formula (i) has a benzofuran ring as the condensed heterocycle, and is mutually exclusive with the organic black pigment (A1) having the same condensed heterocycle. It has a high action and is easily adsorbed on the pigment surface, and it is considered that light can be efficiently absorbed by covering the pigment surface. Further, it is considered that the content ratio of the photopolymerization initiator in the resin component is relatively lowered by adsorbing to the pigment, and the light transmission to the deep part of the coating film is improved. It is considered that the internal curability of the coating film is improved accordingly, and the adhesion to the substrate is improved even if the pattern is fine. In addition, since it has a diphenyl sulfide skeleton, the length of the conjugated system is short, the energy of the entire molecule is high, the radical generation efficiency by thermal decomposition is high, and the polymerization reaction can be promoted, so that the surface curability can be effectively improved. It is considered that the coating film becomes difficult to dissolve in NMP and the impurities derived from the organic black pigment (A1) can be suppressed from being eluted into NMP by preventing the NMP from penetrating into the coating film.

(R ¹ )
In the formula (i), R ¹ represents an alkyl group which may have a substituent or an aromatic ring group which may have a substituent.
The alkyl group in R ¹ may be linear, branched, cyclic, or bonded to each other. The number of carbon atoms of the alkyl group is not particularly limited, but is usually 1 or more, preferably 12 or less, more preferably 6 or less, still more preferably 3 or less, and particularly preferably 2 or less. By setting the number of carbon atoms of the alkyl group to the above upper limit value or less, the sensitivity tends to be high.
Specific examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a tert-butyl group, a pentyl group, an isopentyl group, a cyclopentyl group, a hexyl group, a cyclohexyl group and the like. Among these, from the viewpoint of sensitivity, a methyl group, an ethyl group, a propyl group, or a butyl group is preferable, a methyl group or an ethyl group is more preferable, and a methyl group is further preferable.
Examples of the substituent that the alkyl group may have include an alkoxy group having 1 to 10 carbon atoms, an alkylthio group having 1 to 10 carbon atoms, a halogen atom such as F, Cl, Br, and I, a hydroxyl group, and a nitro group. From the viewpoint of solvent solubility, a methoxy group or a hydroxyl group is preferable. Further, from the viewpoint of sensitivity, it is preferably unsubstituted.

Examples of the aromatic ring group in R ¹ include an aromatic hydrocarbon ring group and an aromatic heterocyclic group. The carbon number is usually 4 or more, preferably 6 or more, preferably 12 or less, more preferably 10 or less, still more preferably 8 or less. When the number of carbon atoms of the aromatic ring group is at least the above lower limit value, the storage stability tends to be good, and when it is at least the above upper limit value, the solvent solubility tends to be good.

The aromatic hydrocarbon ring in the aromatic hydrocarbon ring group may be a monocyclic ring or a condensed ring. Examples of the aromatic hydrocarbon ring group include a benzene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring, a perylene ring, a tetracene ring, a pyrene ring, a benzpyrene ring, a chrysene ring, and a triphenylene ring, which have one free atomic value. Examples include groups such as acenaphthene ring, fluoranthene ring, and fluorene ring.
Further, the aromatic heterocycle in the aromatic heterocyclic group may be a monocyclic ring or a condensed ring. Examples of the aromatic heterocyclic group include a furan ring, a benzofuran ring, a thiophene ring, a benzothiophene ring, a pyrazole ring, a pyrazole ring, an imidazole ring, an oxadiazole ring, an indole ring, and a carbazole ring having one free atomic value. Rings, pyrrolobymidazole rings, pyrrolopyrazole rings, pyrolopyrrole rings, thienopyrrole rings, thienothiophene rings, flopyrol rings, flofran rings, thienoflan rings, benzoisoxazole rings, benzoisothiazole rings, benzoimidazole rings, pyridine rings, pyrazine rings, Examples thereof include pyridazine rings, pyrimidine rings, triazine rings, quinoline rings, isoquinoline rings, sinoline rings, quinoxalin rings, phenanthridin rings, benzimidazole rings, perimidine rings, quinazoline rings, quinazolinone rings, and azulene rings.
Among these, from the viewpoint of solvent solubility, a benzene ring or a naphthalene ring having one free valence is preferable, and a benzene ring having one free valence is more preferable.

Substituents that the aromatic ring group may have include an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an alkylthio group having 1 to 10 carbon atoms, F, Cl, Br, and I. Examples thereof include halogen atoms such as, hydroxyl groups and nitro groups, and methoxy groups or hydroxyl groups are preferable from the viewpoint of solvent solubility. Further, from the viewpoint of sensitivity, it is preferably unsubstituted.

Among these, from the viewpoint of curability, R ¹ is preferably an alkyl group which may have a substituent, more preferably an unsubstituted alkyl group, and further preferably a methyl group.

(R ² )
In the formula (i), R ² represents an alkyl group which may have a substituent or an aromatic ring group which may have a substituent.
The alkyl group in R ² may be linear, branched, cyclic, or bonded thereof, but is preferably linear or branched from the viewpoint of solvent solubility, and the branched is more preferable. preferable.
The number of carbon atoms of the alkyl group is not particularly limited, but is usually 1 or more, preferably 2 or more, more preferably 3 or more, still more preferably 4 or more, particularly preferably 5 or more, and preferably 10 or less, more preferably 8 or less. , More preferably 7 or less, and particularly preferably 6 or less. When the number of carbon atoms of the alkyl group is at least the above lower limit value, the solvent solubility tends to be good, and when it is at least the above upper limit value, the sensitivity tends to be high.
Specific examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a tert-butyl group, a pentyl group, an isopentyl group, a cyclopentyl group, a hexyl group, a cyclohexyl group and the like. Among these, from the viewpoint of solvent solubility, an isopropyl group, an isobutyl group, an isopentyl group, or a cyclopentyl group is preferable, an isobutyl group or an isopentyl group is more preferable, and an isopentyl group is further preferable.
The substituents that the alkyl group may have include an aromatic ring group having 6 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an alkylthio group having 1 to 10 carbon atoms, F, Cl, Br and I. Examples thereof include halogen atoms and hydroxyl groups such as, and an alkoxy group is preferable from the viewpoint of solvent solubility. Further, from the viewpoint of sensitivity, it is preferably unsubstituted.

Examples of the aromatic ring group in R ² include an aromatic hydrocarbon ring group and an aromatic heterocyclic group. The carbon number is usually 4 or more, preferably 6 or more, preferably 12 or less, more preferably 10 or less, still more preferably 8 or less. When the number of carbon atoms of the aromatic ring group is at least the above lower limit value, the molecule tends to be stable, and when it is at least the above upper limit value, the solvent solubility tends to be good.

The aromatic hydrocarbon ring in the aromatic hydrocarbon ring group may be a monocyclic ring or a condensed ring. Examples of the aromatic hydrocarbon ring group include a benzene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring, a perylene ring, a tetracene ring, a pyrene ring, a benzpyrene ring, a chrysene ring, and a triphenylene ring, which have one free atomic value. Examples include groups such as acenaphthene ring, fluoranthene ring, and fluorene ring.
Further, the aromatic heterocycle in the aromatic heterocyclic group may be a monocyclic ring or a condensed ring. Examples of the aromatic heterocyclic group include a furan ring, a benzofuran ring, a thiophene ring, a benzothiophene ring, a pyrazole ring, a pyrazole ring, an imidazole ring, an oxadiazole ring, an indole ring, and a carbazole ring having one free atomic value. Rings, pyrrolobymidazole rings, pyrrolopyrazole rings, pyrolopyrrole rings, thienopyrrole rings, thienothiophene rings, flopyrol rings, flofran rings, thienoflan rings, benzoisoxazole rings, benzoisothiazole rings, benzoimidazole rings, pyridine rings, pyrazine rings, Examples thereof include pyridazine rings, pyrimidine rings, triazine rings, quinoline rings, isoquinoline rings, sinoline rings, quinoxalin rings, phenanthridin rings, benzimidazole rings, perimidine rings, quinazoline rings, quinazolinone rings, and azulene rings.
Among these, from the viewpoint of curability, a benzene ring or a naphthalene ring having one free valence is preferable, and a benzene ring having one free valence is more preferable.

Substituents that the aromatic ring group may have include an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an alkylthio group having 1 to 10 carbon atoms, F, Cl, Br, and I. Examples thereof include a halogen atom such as, a hydroxyl group and a nitro group, and from the viewpoint of solvent solubility, an alkoxy group or a hydroxyl group having 1 to 3 carbon atoms is preferable. Further, from the viewpoint of sensitivity, it is preferably unsubstituted.

Among these, from the viewpoint of sensitivity, R ² is preferably an alkyl group which may have a substituent, more preferably an unsubstituted alkyl group, and further preferably an isopentyl group.

(K)
In the formula (i), k represents 0 or 1. From the viewpoint of sensitivity, k is preferably 0, while from the viewpoint of solvent solubility, k is preferably 1.

(R ³ to R ⁶ )
In the formula (i), R ³ to R ⁶ each independently represent an arbitrary monovalent substituent.
As an arbitrary monovalent substituent, an alkyl group having 1 to 10 carbon atoms such as a methyl group and an ethyl group; an alkoxy group having 1 to 10 carbon atoms such as a methoxy group and an ethoxy group; F, Cl, Br, I and the like. Halogen atom; acyl group with 1 to 10 carbon atoms; alkyl ester group with 1 to 10 carbon atoms; alkoxycarbonyl group with 1 to 10 carbon atoms; alkyl halide with 1 to 10 carbon atoms; fragrance with 4 to 10 carbon atoms Examples thereof include a group ring group; an amino group; an aminoalkyl group having 1 to 10 carbon atoms; a hydroxyl group; a nitro group; a CN group and the like. Among these, a methyl group and a methoxy group are preferable, and a methyl group is more preferable, from the viewpoint of solvent solubility.
In R ³ , R ⁴ and R ⁶ , when l, m and o are 2 or more, a plurality of R ³ , R ⁴ and R ⁶ may be bonded to each other to form a ring. The ring may be an aliphatic ring or an aromatic ring.

(L, m, n, o)
In the formula (i), l, m and o each independently represent an integer of 0 to 3, and n represents 0 or 1.
From the viewpoint of sensitivity, l, m and o are preferably 0 or 1 independently, and more preferably 0. Further, from the viewpoint of sensitivity, n is preferably 0.

The photopolymerization initiator represented by the general formula (i) is preferably a photopolymerization initiator represented by the following general formula (i-1) from the viewpoint of the balance between sensitivity and solvent solubility.

In the formula (i-1), R ¹ to R ⁶ and k to o are synonymous with the above formula (i).

The method for producing the photopolymerization initiator (C1) is not particularly limited, and for example, the method described in International Publication No. 2015/036910 can be adopted.
Further, specific examples of the photopolymerization initiator (C1) include the following.

The (c) photopolymerization initiator in the photosensitive coloring composition of the present invention may contain the photopolymerization initiator (C1) alone, or may further contain another photopolymerization initiator (C2). There may be.
Examples of the other photopolymerization initiator (C2) include metallocene compounds containing the titanosen compounds described in JP-A-59-152396 and JP-A-61-151197; and described in JP-A-2000-56118. Hexaaryl imidazole derivative of JP-A-10-39503; halomethylated oxadiazole derivative, halomethyl-s-triazine derivative; α-aminoalkylphenone derivative; JP-A-2000-80068, JP-A-2006-36750 Examples thereof include oxime ester compounds described in Japanese Patent Publication No.

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

Examples of the biimidazole derivatives include 2- (2'-chlorophenyl) -4,5-diphenylimidazole dimer and 2- (2'-chlorophenyl) -4,5-bis (3'-methoxyphenyl) imidazole. Dimeric, 2- (2'-fluorophenyl) -4,5-diphenylimidazole dimer, 2- (2'-methoxyphenyl) -4,5-diphenylimidazole dimer, (4'-methoxyphenyl) ) -4,5-Diphenylimidazole dimer and the like.

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

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

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

As the other photopolymerization initiator (C2), an oxime ester compound is particularly effective in terms of sensitivity and plate-making property, and when an alkali-soluble resin containing a phenolic hydroxyl group is used, it is disadvantageous in terms of sensitivity. Therefore, such an oxime ester-based compound having excellent sensitivity is particularly useful. Since the oxime ester compound has a structure that absorbs ultraviolet rays, a structure that transmits light energy, and a structure that generates radicals in its structure, it is highly sensitive to a small amount and stable to a thermal reaction. Therefore, it is possible to obtain a highly sensitive photosensitive coloring composition in a small amount.

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

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

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

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

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

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

The carbon number of the alkanoyl group in R ^22a is not particularly limited, but 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. Specific examples of the alkanoyl group include an acetyl group, an ethiloyl group, a propanoyl group, a butanoyl group and the like.
Examples of the substituent that the alkanoyl group may have include an aromatic ring group, a hydroxyl group, a carboxyl group, a halogen atom, an amino group, an amide group and the like, and the substituent is not substituted from the viewpoint of easiness of synthesis. Is preferable.

The carbon number of the allylloyl 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 10 or less. Specific examples of the allylloyl group include a benzoyl group and a naphthoyl group.
Examples of the substituent that the allylloyl group may have include a hydroxyl group, a carboxyl group, a halogen atom, an amino group, an amide group, an alkyl group and the like, 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.

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

The photopolymerization initiator may be used alone or in combination of two or more.
If necessary, the photopolymerization initiator may be blended with a sensitizing dye and a polymerization accelerator according to the wavelength of the image exposure light source for the purpose of increasing the sensitivity. As the sensitizing dye, the xanthene dye described in JP-A-4-221958 and JP-A-4-219756, and the coumarin having a heterocycle described in JP-A-3-239703 and JP-A-5-289335. Dyes, 3-ketocoumarin compounds described in JP-A-3-239703, JP-A-5-289335, pyrromethene dyes described in JP-A-6-19240, and others, JP-A-47-2528, Japanese Patent Laid-Open No. Kaisho 54-155292, Japanese Patent Publication No. 45-373777, JP-A-48-84183, JP-A-52-112681, JP-A-58-15503, JP-A-60-88005. Japanese Patent Laid-Open No. 59-56403, Japanese Patent Application Laid-Open No. 2-69, Japanese Patent Application Laid-Open No. 57-168888, Japanese Patent Application Laid-Open No. 5-107761, Japanese Patent Application Laid-Open No. 5-210240, Japanese Patent Application Laid-Open No. 4-288818 Examples thereof include dyes having a dialkylaminobenzene skeleton described in the publication.

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

When forming a colored spacer by a photolithography method, it is preferable to select an organic solvent having a boiling point in the range of 100 to 200 ° C. (under pressure 1013.25 hPa conditions; hereinafter, the boiling points are all the same). More preferably, it has a boiling point of 120 to 170 ° C.

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

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

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

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

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

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

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

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

Examples of the urethane-based and acrylic polymer dispersants include DISPERBYK 160 to 166, 182 series (all urethane-based), DISPERBYK2000, 2001, LPN21116 and the like (all acrylic-based) (all manufactured by Big Chemie).
To specifically exemplify a preferable chemical structure as a urethane-based polymer dispersant, for example, it is the same as a polyisocyanate compound and a compound having one or two hydroxyl groups in the molecule and having a number average molecular weight of 300 to 10,000. Examples thereof include a dispersed resin having a weight average molecular weight of 1,000 to 200,000, which is obtained by reacting an active hydrogen with a compound having a tertiary amino group in the molecule. By treating these with a quaternary agent such as benzyl chloride, all or part of the tertiary amino group can be converted into a quaternary ammonium base.

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

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

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

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

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

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

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

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

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

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

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

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

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

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

The amount of the compound having active hydrogen and a tertiary amino group in the same molecule is preferably controlled in the range of 1 to 100 mgKOH / g in terms of the amine value after the reaction. More preferably, it is in the range of 5 to 95 mgKOH / g. The amine value is a value expressed by the number of mg of KOH corresponding to the acid value by neutralizing and titrating the basic amino group with an acid. When the value is not less than the lower limit, the dispersibility tends to be good, and when the value is not more than the upper limit, the decrease in developability tends to be suppressed.

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

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

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

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

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

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

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

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

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

In synthesizing this acrylic polymer dispersant, JP-A-9-62002 and P.I. Lutz, P.M. Masson et al, Polym. Bull. 12, 79 (1984), B.I. C. Anderson, G.M. D. Andrews et al, Macromolecules, 14, 1601 (1981), K. et al. Hatada, K.K. Ute, et al, Polym. J. 17, 977 (1985), 18, 1037 (1986), Koichi Right Hand, Koichi Hatada, Polymer Processing, 36, 366 (1987), Toshinobu Higashimura, Mitsuo Sawamoto, Polymer Papers, 46, 189 (1989), M. Kuroki, T.K. Aida, J.M. Am. Chem. Sic, 109, 4737 (1987), Takuzo Aida, Shohei Inoue, Synthetic Organic Chemistry, 43, 300 (1985), D.I. Y. Sogoh, W. R. A known method described in Hertler et al, Macromolecules, 20, 1473 (1987) and the like can be adopted.

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

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

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

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

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

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

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

The number of carbon atoms of the aralkyl group which may have a substituent in R ³¹ to R ³³ of the above formula (i) is not particularly limited, but is usually 7 or more, preferably 16 or less, and 12 The following is more preferable. Specific examples of the aralkyl group include a phenylmethylene group, a phenylethylene group, a phenylpropylene group, a phenylbutylene group, a phenylisopropylene group and the like, among which a phenylmethylene group, a phenylethylene group, a phenylpropylene group, or a phenylpropylene group. It is preferably a phenylbutylene group, more preferably a phenylmethylene group or a phenylethylene group.

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

The carbon number of the aralkyl group which may have a substituent in R ³⁸ of the above formula (iv) is not particularly limited, but is usually 7 or more, preferably 16 or less, and preferably 12 or less. More preferably, it is more preferably 10 or less. Specific examples of the aralkyl group include a phenylmethylene group, a phenylethylene group, a phenylpropylene group, a phenylbutylene group, a phenylisopropylene group and the like, among which a phenylmethylene group, a phenylethylene group, a phenylpropylene group, or a phenylpropylene group. It is preferably a phenylbutylene group, more preferably a phenylmethylene group or a phenylethylene 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 phenylmethylene group.
Examples of the substituent that the alkyl group may have in R ³⁸ include a halogen atom and an alkoxy group. Further, examples of the substituent that the aryl group or the aralkyl group may have include a chain-like alkyl group, a halogen atom, an alkoxy group and the like. Further, the chain-like alkyl group represented by R ³⁸ includes both a linear chain and a branched chain.

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

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

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

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

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

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

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

<Other ingredients of the photosensitive coloring composition>
In addition to the above-mentioned components, the photosensitive coloring composition of the present invention includes adhesion improvers such as silane coupling agents, coatability improvers, development improvers, ultraviolet absorbers, antioxidants, surfactants, and pigment derivatives. Additives such as these 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 silane coupling agent, various types such as epoxy type, (meth) acrylic type, and amino type can be used alone or in combination of two or more.

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

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

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

As the surfactant, for example, various kinds such as anionic type, cationic type, nonionic type and amphoteric surfactant can be used. Of these, nonionic surfactants are preferable because they are less likely to adversely affect various properties, and fluorine-based and silicon-based surfactants are particularly effective in terms of coatability.
Examples of such a surfactant include TSF4460 (manufactured by GE Toshiba Silicone Co., Ltd.), DFX-18 (manufactured by Neos Co., Ltd.), BYK-300, BYK-325, BYK-330 (manufactured by BIC Chemie Co., Ltd.), KP340 (Shinetsu Silicone Co., Ltd.). F-470, F-475, F-478, F-559 (DIC), SH7PA (Torre Silicone), DS-401 (Daikin), L-77 (Nippon Unicar) ), FC4430 (manufactured by Sumitomo 3M) and the like.
As the surfactant, one type may be used, or two or more types may be used in combination in any combination and ratio.

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

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

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

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

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

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

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

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

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

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

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

Types of mercapto compounds include 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, 2-mercaptobenzoimidazole, hexanedithiol, decandithiol, 1,4-dimethylmercaptobenzene, butanediol bisthiopropionate, butanediol bis. Thioglycolate, Ethylene Glycol Bisthioglycolate, Trimethylol Propantristhioglycolate, Butanediol Bisthiopropionate, Trimethylol Propanistristhiopropionate, Trimethylol Propanistristhioglycolate, Pentaerythritol Tetrakissthiopropio Nate, pentaerythritol tetrakisthioglycolate, trishydroxyethyltristhiopropionate, ethylene glycol bis (3-mercaptobutyrate), butanediol bis (3-mercaptobutyrate), 1,4-bis (3-mercaptobutyrate) Liloxy) butane, trimethylolpropanthris (3-mercaptobutyrate), pentaerythritol tetrakis (3-mercaptobutyrate), pentaerythritol tris (3-mercaptobutyrate), ethylene glycol bis (3-mercaptoisobutyrate) , Butanediolbis (3-mercaptoisobutyrate), trimethylolpropanetris (3-mercaptoisobutyrate), 1,3,5-tris (3-mercaptobutyloxyethyl) -1,3,5-triazine- Examples thereof include a mercapto compound having a heterocycle such as 2,4,6 (1H, 3H, 5H) -trione, an aliphatic polyfunctional mercapto compound, and the like. These can be used alone or in admixture of two or more.

<Amount of ingredients in the photosensitive coloring composition>
In the photosensitive coloring composition of the present invention, the content ratio of (a) the colorant is preferably 10% by mass or more, preferably 15% by mass or more, based on the total solid content in the photosensitive coloring composition. Is more preferably 20% by mass or more, further preferably 25% by mass or more, particularly preferably 30% by mass or more, and usually preferably 90% by mass or less. , 80% by mass or less, more preferably 70% by mass or less, further preferably 60% by mass or less, particularly preferably 50% by mass or less, and 40% by mass or less. Is most preferable. (A) When the content ratio of the colorant is at least the above lower limit value, a sufficient optical density (OD) tends to be obtained, and when it is at least the above upper limit value, sufficient image forming property can be obtained. Tend.

The content ratio of the organic black pigment (A1) to the total solid content of the photosensitive coloring composition is preferably 5% by mass or more, preferably 10% by mass or more, based on the total solid content in the photosensitive coloring composition. Is more preferably 20% by mass or more, further preferably 25% by mass or more, particularly preferably 30% by mass or more, and preferably 90% by mass or less. It is more preferably 80% by mass or less, further preferably 70% by mass or less, further preferably 60% by mass or less, particularly preferably 50% by mass or less, and 40% by mass or less. Most preferably. When it is at least the above lower limit value, sufficient optical density (OD) and desired pattern forming property tend to be compatible, and when it is at least the above upper limit value, sufficient image forming property tends to be obtained.

The content ratio of the organic black pigment (A1) in the total colorant contained in the photosensitive coloring composition is preferably 1% by mass or more, more preferably 10% by mass or more, and more preferably 20% by mass or more. It is more preferably 100% by mass or less, more preferably 90% by mass or less, further preferably 80% by mass or less, still more preferably 70% by mass or less. , 60% by mass or less is particularly preferable. When it is at least the above lower limit value, sufficient optical density (OD) tends to be obtained, and when it is at least the above upper limit value, sufficient image formability tends to be obtained.

(B) The content ratio of the alkali-soluble resin is usually 5% by mass or more, preferably 10% by mass or more, more preferably 20% by mass or more, still more preferably 30 with respect to the total solid content of the photosensitive coloring composition of the present invention. By mass or more, particularly preferably 35% by mass or more, usually 90% by mass or less, preferably 80% by mass or less, more preferably 70% by mass or less, still more preferably 60% by mass or less, still more preferably 50% by mass. Hereinafter, it is particularly preferably 45% by mass or less. (B) By setting the content ratio of the alkali-soluble resin to the lower limit value or more, there is a tendency that development defects caused by a decrease in the solubility of the unexposed portion in the developing solution can be suppressed. Further, by setting the value to the upper limit or less, there is a tendency that the decrease in adhesion caused by the high permeability of the developing solution to the exposed portion can be suppressed.

(C) The content ratio of the photopolymerization initiator is usually 0.1% by mass or more, preferably 1% by mass or more, more preferably 2% by mass or more, and further, with respect to the total solid content of the photosensitive coloring composition of the present invention. It is preferably 3% by mass or more, usually 20% by mass or less, preferably 15% by mass or less, more preferably 10% by mass or less, still more preferably 8% by mass or less, and particularly preferably 6% by mass or less. (C) When the content ratio of the photopolymerization initiator is at least the lower limit value, the curability tends to be good, and when it is at least the upper limit value, development defects tend to be suppressed.

The content ratio of the photopolymerization initiator (C1) is usually 0.1% by mass or more, preferably 1% by mass or more, more preferably 2% by mass or more, and further, with respect to the total solid content of the photosensitive coloring composition of the present invention. It is preferably 3% by mass or more, usually 20% by mass or less, preferably 15% by mass or less, more preferably 10% by mass or less, still more preferably 8% by mass or less, and particularly preferably 6% by mass or less. When it is set to the lower limit value or more, the curability tends to be good, and when it is set to the upper limit value or less, development defects tend to be suppressed.

The content ratio of the photopolymerization initiator (C1) in the total photopolymerization initiator contained in the photosensitive coloring composition is usually 1% by mass or more, preferably 10% by mass or more, more preferably 20% by mass or more, still more preferably 50. It is mass% or more, usually 100% by mass or less, preferably 90% by mass or less, more preferably 80% by mass or less, still more preferably 70% by mass or less, and particularly preferably 60% by mass or less. When it is at least the lower limit value, the internal curability tends to be good, and when it is at least the upper limit value, the surface curability tends to be good.

(D) The content of the ethylenically unsaturated compound is usually 1% by mass or more, preferably 5% by mass or more, more preferably 10% by mass or more, still more preferably, based on the total solid content of the photosensitive coloring composition of the present invention. Is 15% by mass or more, usually 90% by mass or less, preferably 70% by mass or less, more preferably 50% by mass or less, still more preferably 30% by mass or less, and particularly preferably 20% by mass or less. When it is set to the lower limit value or more, the photocurability due to ultraviolet irradiation tends to be improved, and when it is set to the upper limit value or less, the permeability of the developing solution to the exposed portion is moderate and good image forming property is obtained. There is.
On the other hand, the content ratio of (b) alkali-soluble resin to 100 parts by mass of (d) ethylenically unsaturated compound is usually 80 parts by mass or more, preferably 100 parts by mass or more, more preferably 150 parts by mass or more, and 200 parts by mass. The above is more preferable, 250 parts by mass or more is particularly preferable, and usually 700 parts by mass or less, 500 parts by mass or less is preferable, 400 parts by mass or less is more preferable, and 300 parts by mass or less is further preferable. When it is set to the lower limit value or more, it tends to be in an appropriate melting and developing state without peeling, and when it is set to the upper limit value or less, it tends to be possible to obtain an appropriate melting time for a developer. ..

In the photosensitive coloring composition of the present invention, by using the solvent (e), the content 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 liquid is usually adjusted to be 50% by mass or less, preferably 30% by mass or less, and more preferably 25% by mass or less.

(F) The content ratio of the dispersant is usually 1% by mass or more, preferably 3% by mass or more, more preferably 5% by mass or more, and usually 30% by mass or less, based on the total solid content of the photosensitive coloring composition. 20% by mass or less is preferable, 15% by mass or less is more preferable, 10% by mass or less is further preferable, and 8% by mass or less is particularly preferable.
The content ratio of (f) dispersant to 100 parts by mass of (a) colorant is usually 5 parts by mass or more, more preferably 10 parts by mass or more, further preferably 15 parts by mass or more, and usually 50 parts by mass or less, particularly. It is preferably 30 parts by mass or less. (F) Sufficient dispersion stability tends to be obtained by setting the content ratio of the dispersant to the lower limit value or more, and by setting the content ratio to the upper limit value or less, the color density and sensitivity without reducing the ratio of other components. -There is a tendency that image formation is sufficient.

When the adhesion improver is used, the content ratio thereof is usually 0.1 to 5% by mass, preferably 0.2 to 3% by mass, and more preferably 0.4 with respect to the total solid content in the photosensitive coloring composition. ~ 2% by mass. By setting the content ratio of the adhesion improver to the lower limit value or more, the effect of improving the adhesion tends to be sufficiently obtained, and by setting the content ratio to the upper limit value or less, the sensitivity is lowered or the residue remains after development. There is a tendency to prevent it from becoming a defect.

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

<Physical characteristics of the photosensitive coloring composition>
The photosensitive coloring composition of the present invention can be suitably used for forming a coloring spacer, and from the viewpoint of being used as a coloring spacer, the one having a higher optical density (OD) per 1 μm film thickness of the coating film. Is preferable. The colored spacer alone obtained by curing the photosensitive coloring composition of the present invention is preferably 0.1 or more, more preferably 0.5 or more, still more preferably 1.0 or more. , 1.2 or more is particularly preferable. Here, the optical density (OD) is a value measured by a method described later.

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

The dispersion treatment is usually preferably carried out in a system in which (a) a colorant, a solvent, and (f) a dispersant, and (b) a part or all of an alkali-soluble resin are used in combination (hereinafter, subjected to the dispersion treatment). The mixture 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 dispersant because the thickening of the obtained ink and resist over time is suppressed (excellent in dispersion stability).
As described above, in the step of producing the resist, it is preferable to produce a pigment dispersion liquid containing at least (a) a colorant, a solvent, and (f) a dispersant. As the (a) colorant, solvent, and (f) dispersant that can be used in the pigment dispersion liquid, those described as being usable in the photosensitive coloring composition can be preferably adopted.

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

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

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

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

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

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

(2) Coloring Spacer The photosensitive coloring composition of the present invention is used for the same purpose as a known photosensitive coloring composition for a color filter, but hereinafter, when used as a coloring spacer, the photosensitive coloring composition of the present invention is used. A specific example of a method for forming a colored spacer using a sex-colored composition will be described.

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

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

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

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

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

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

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

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

As a preferred embodiment of the present invention, when 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 (intermediate transmittance opening) having a smaller average light transmittance than the opening (completely transmitted opening) is used. By this method, the difference in the average light transmittance between the intermediate transmission opening and the complete transmission opening, that is, the difference in the exposure amount causes a difference in the residual film ratio.
For example, a method of creating an intermediate transmission opening by a matrix-like light-shielding pattern having a minute polygonal light-shielding unit is known. Further, as an absorber, a method of controlling the light transmittance by a film of a material such as chromium-based, molybdenum-based, tungsten-based, or silicon-based is known.

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

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

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

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

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

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

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

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

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

The size and shape of the colored spacer of the present invention are appropriately adjusted according to the specifications of the color filter to which the colored spacer is applied, but the photosensitive coloring composition of the present invention is particularly high in the spacer and the sub-spacer by the photolithography method. It is useful for forming colored spacers with different colors at the same time, in which case the height of the spacer is usually about 2 to 7 μm, and the sub-spacer is usually about 0.2 to 1.5 μm lower than the spacer. Have.

[Color filter]
The color filter of the present invention includes the coloring spacer of the present invention as described above, for example, on a glass substrate as a transparent substrate, a black matrix, red, green, and blue pixel coloring layers, and an overcoat layer. Is manufactured by laminating and forming a colored spacer and then forming an alignment film. Alternatively, the pixel coloring layer and the coloring spacer may be formed on the liquid crystal drive side substrate, or may be formed separately on the transparent substrate and the liquid crystal drive side substrate.

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

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

<Organic black pigment>
Made by BASF, Irgaphor (registered trademark) Black S 0100 CF (having a chemical structure represented by the following formula (2))

<Alkali-soluble resin-I>
145 parts by mass of propylene glycol monomethyl ether acetate was stirred while substituting with nitrogen, and the temperature was raised to 120 ° C. To this, 10 parts by mass of styrene, 85.2 parts by mass of glycidyl methacrylate and 66 parts by mass of monomethacrylate (FA-513M manufactured by Hitachi Chemical Co., Ltd.) having a tricyclodecane skeleton were added dropwise, and 2,2'-azobis-2-methyl. 8.47 parts by mass of butyronitrile was added dropwise over 3 hours, and stirring was continued at 90 ° C. for 2 hours. Next, the inside of the reaction vessel was replaced with air, 0.7 parts by mass of trisdimethylaminomethylphenol and 0.12 parts by mass of hydroquinone were added to 43.2 parts by mass of acrylic acid, and the reaction was continued at 100 ° C. for 12 hours. Then, 56.2 parts by mass of tetrahydrophthalic anhydride (THPA) and 0.7 parts by mass of triethylamine were added, and the mixture was reacted at 100 ° C. for 3.5 hours. The weight average molecular weight Mw of the alkali-soluble resin-I thus obtained measured by GPC was about 8400, and the acid value was 80 mgKOH / g.

<Alkali-soluble resin-II>
"ZCR-1642H" manufactured by Nippon Kayaku Co., Ltd. (Mw6500, acid value 98 mgKOH / g)

<Dispersant-I>
"BYK-LPN21116" manufactured by Big Chemie (acrylic AB) consisting of an A block having a quaternary ammonium base and a tertiary amino group in the side chain and a B block having no quaternary ammonium base and a tertiary amino group. Block copolymer)

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

<Photopolymerization Initiator-I>
A compound having the following chemical structure synthesized by the method described in International Publication No. 2015/036910 was used.

<Photopolymerization Initiator-II>
IRGACURE OXE01 (compound having the following chemical structure) manufactured by BASF was used.

<Photopolymerization Initiator-III>
A compound having the following chemical structure was used.

<Photopolymerization Initiator-IV>
A compound having the following chemical structure synthesized by the method described in International Publication No. 2008/07786 was used.

<Photopolymerizable Monomer-I>
DPHA: Dipentaerythritol hexaacrylate manufactured by Nippon Kayaku Co., Ltd.

<Additive-I>
KAYAMER PM-21 (phosphate containing methacryloyl group) manufactured by Nippon Kayaku Co., Ltd.

<Additive-II>
SH6040 manufactured by Toray Dow Corning

<Surfactant-I>
DIC Megafuck F-559

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

<Preparation of Photosensitive Coloring Compositions of Examples 1 and Comparative Examples 1 to 3>
Using the pigment dispersion 1 prepared above, each component was added so that the mass ratio in the solid content was the blending ratio shown in Table 2, and PGMEA was further added so that the solid content was 19% by mass, and the mixture was stirred and dissolved. Then, each photosensitive coloring composition of Example 1 and Comparative Examples 1 to 3 was prepared. The mass part of each component of the photosensitive coloring composition in Table 2 indicates the mass of the solid content.
Next, the evaluation was performed by the following method.

<Measurement of optical density (unit OD value) per unit film thickness>
Each of the prepared photosensitive coloring compositions was applied to a glass substrate with a spin coater so that the film thickness after heat curing was 3 μm, dried under reduced pressure for 1 minute, and then dried on a hot plate at 90 ° C. for 60 seconds. A resist-coated substrate was obtained by heating and curing at 230 ° C. for 20 minutes.
The optical density (OD value) of the obtained substrate is measured by the transmission densitometer Gretag Macbeth D200-II, and the film thickness is measured by the non-contact surface / layer cross-sectional shape measurement system VertScan (R) 2.0 manufactured by Ryoka System Co., Ltd. did. Table 2 shows the optical density (unit OD value) per 1 μm film thickness. The OD value is a numerical value indicating the light-shielding ability, and the larger the value is, the higher the light-shielding property is.

<Batch formation method of cured products with different heights>
Each photosensitive coloring composition was applied onto a glass substrate (“AN100” manufactured by AGC) using a spin coater so that the film thickness after heat curing was 3 μm. Then, it was heated and dried on a hot plate at 90 ° C. for 60 seconds to form a coating film.
For the obtained coating film, a complete permeation opening of a circular pattern having various diameters with a diameter of 5 to 50 μm (every 5 to 20 μm: 1 μm, 25 μm to 50 μm: every 5 μm) and a diameter of 5 to 50 μm (every 5 to 20 μm: 1 μm). , 25 μm to 50 μm: every 5 μm), the exposure process was performed using an exposure mask having an intermediate transmission opening of a circular pattern having various diameters. The intermediate transmission opening is a thin film of Cr oxide having a light transmittance of 10 ± 2% at a wavelength of 365 nm. The exposure gap (distance between the mask and the coated surface) was set to 200 μm. As the irradiation light, ultraviolet rays having an intensity of 32 mW / cm ² at a wavelength of 365 nm were used, and the exposure amount was 60 mJ / cm ² . In addition, ultraviolet irradiation was performed under air.

Subsequently, a developer consisting of an aqueous solution containing 0.05% by mass of potassium hydroxide and 0.08% by mass of a nonionic surfactant (“A-60” manufactured by Kao Co., Ltd.) was used, and the water pressure was 0 at 25 ° C. After shower development at 10. MPa, development was stopped with pure water and washed with a water-washing spray. The shower development time was adjusted between 10 and 120 seconds, and was 1.5 times the time for dissolving and removing the unexposed coating film.
By these operations, a pattern in which unnecessary parts were removed was obtained. The substrate on which the pattern was formed was heat-cured at 230 ° C. for 25 minutes in an oven to cure the pattern, and a substantially columnar spacer pattern was obtained.

<Evaluation of substrate adhesion>
Of the patterns corresponding to the complete transmission opening of the circular pattern of 5 to 50 μm and the intermediate transmission opening of 5 to 50 μm, the one with the smallest diameter among the patterns remaining on the substrate with good resolution, respectively. The values of the opening diameter (μm) of the corresponding masks are shown in Table 2 as the minimum adhesion. The smaller this value is, the better the substrate adhesion is. Further, when no pattern having good resolution remained on the substrate, “None” was described in Table 2. The evaluation criteria are as follows.
(Completely transparent opening)
◯: 6 μm or less Δ: 7 μm or more and 8 μm or less ×: 9 μm or more, or no pattern remains (intermediate transmission opening)
◯: 20 μm or less Δ: 25 μm or more and 30 μm or less ×: 35 μm or more, or no pattern remains

<NMP dissolution test>
The prepared photosensitive coloring composition was applied to a glass substrate with a spin coater so that the film thickness after heat curing was 3 μm, dried under reduced pressure for 1 minute, and then dried on a hot plate at 80 ° C. for 70 seconds. After undergoing the exposure and development steps, the resist-coated substrate was obtained by heating and curing at 230 ° C. for 20 minutes in an oven.

Two measurement substrates (2.5 cm × 1.0 cm square) were cut out from the prepared resist-coated substrate and immersed in a 10 mL vial containing 8 mL of N-methylpyrrolidone (NMP). Then, the NMP elution test was carried out in a state where the vial containing the measurement substrate was allowed to stand in a hot bath at 80 ° C. for 40 minutes. After allowing to stand for 40 minutes, the vial was taken out from the hot bath, and the absorbance of the NMP elution solution was measured every 1 nm in the wavelength range of 300 to 800 nm with a spectrophotometer (“UV-3100PC” manufactured by Shimadzu Corporation). A halogen lamp and a deuterium lamp (switching wavelength 360 nm) are used as a light source, and a photomal is used as a detector, and a slit width of 2 nm is a measurement condition. In the case of a liquid, the sample solution is placed in a 1 cm square quartz cell for measurement. Absorbance is a dimensionless quantity that indicates how much light intensity is attenuated when light passes through a certain object in spectroscopy, and is defined by the following equation.

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

Further, when light is incident on the sample solution and the NMP single solution from the same light source, the light intensity transmitted through the NMP single solution can be regarded as I ₀ , and the light intensity transmitted through the sample solution can be regarded as I. Therefore, (I / I ₀ ) in the above equation represents the light transmittance, and the absorbance A is a value obtained by logarithmically expressing the reciprocal of the transmittance. Absorbance A is a notation used when calculating the concentration of a substance contained in a sample solution. When the absorbance A = 0, it indicates a state in which no light is absorbed (transmittance 100%), and when the absorbance A = ∞, it indicates a state in which no light is transmitted (transmittance 0%). become. That is, the stronger the absorbance, the more resist coating film components are eluted in NMP, indicating that the NMP resistance is poor. In this evaluation standard, the NMP resistance was evaluated by the absorbance of the pigment dispersion 1 at a wavelength of 670 nm, which is strongly absorbed. The results are shown in Table 2. The evaluation criteria are as follows.
(NMP resistance evaluation criteria)
◯: Absorbance at wavelength 670 nm is 0.05 or less ×: Absorbance at wavelength 670 nm exceeds 0.05

A method of using an organic black pigment (A1) is known in order to improve the light-shielding property of the colored spacer. However, in such a method, the ultraviolet transmittance is low, the photocurability at the bottom of the pattern is weakened, and particularly a fine pattern is peeled off during development, and the substrate adhesion tends to be insufficient. In addition, impurities derived from the organic black pigment (A1) tend to elute into the liquid crystal layer, which tends to reduce the display reliability of the panel.
As is clear from Table 2, the photosensitive coloring composition of Example 1 contains an organic black pigment (A1) and a photopolymerization initiator (C1), and has a complete transmission opening and an intermediate transmission opening. It was found that the minimum adhesion value was small in both parts, good substrate adhesion was exhibited even with a slightly different pattern, and impurity elution to NMP could be suppressed, resulting in excellent NMP resistance.

The photopolymerization initiator (C1) in the photosensitive coloring composition of the present invention has a benzofuran ring of a condensed heterocycle and has a strong interaction with an organic black pigment (A1) having a similar condensed heterocycle, and has a strong interaction with the pigment surface. It is thought that light can be efficiently absorbed by covering the surface of the pigment. Further, it is considered that the content ratio of the photopolymerization initiator in the resin component is relatively low by adsorbing to the pigment, and the light transmission to the deep part of the coating film is improved. It is considered that the internal curability of the coating film is improved accordingly, and the adhesion to the substrate is improved even if the pattern is fine.
In addition, the photopolymerization initiator (C1) has a diphenyl sulfide skeleton, the length of the conjugated system is short, the energy of the entire molecule is high, the radical generation efficiency by thermal decomposition is high, and the polymerization reaction can be promoted effectively. It is considered that the surface curability can be improved. It is considered that this made it difficult for the coating film to dissolve in NMP, and by preventing the penetration of NMP into the coating film, it was possible to suppress the elution of impurities derived from the organic black pigment (A1) into NMP.

On the other hand, the photosensitive coloring compositions of Comparative Example 1 and Comparative Example 2 each contain a photopolymerization initiator-II and a photopolymerization initiator-III, both of which have a diphenyl sulfide skeleton. NMP resistance was good by improving the surface curability. However, since they do not have the benzofuran ring of the condensed heterocycle, it is considered that the internal curability of the coating film is low and the substrate adhesion is insufficient.

Further, the photosensitive coloring composition of Comparative Example 3 contains a photopolymerization initiator-IV, has high absorbency near a wavelength of 365 nm, which has a strong exposure intensity, and has high internal curability, so that the substrate adhesion is good. Met. However, since it has a carbazole skeleton instead of a diphenyl sulfide skeleton, it is in a stable state during the thermal curing treatment, and the surface curability is low due to the low radical generation efficiency by thermal decomposition, resulting in insufficient NMP resistance. Conceivable.

From the above, it was found that by using the photosensitive coloring composition of the present invention, the light-shielding property and reliability are good, and it is possible to form a fine coloring spacer.

Claims (8)

A photosensitive coloring composition containing (a) a colorant, (b) an alkali-soluble resin, (c) a photopolymerization initiator, and (d) an ethylenically unsaturated compound.
The colorant (a) is at least one selected from the group consisting of a compound represented by the following general formula (I), a geometric isomer of the compound, a salt of the compound, and a salt of the geometric isomer of the compound. Contains an organic black pigment (A1) containing
A photosensitive coloring composition, wherein the (c) photopolymerization initiator contains a photopolymerization initiator (C1) represented by the following general formula (i).

(In formula (I), R ^a1 and R ^a6 independently represent a hydrogen atom, CH ₃ , CF ₃ , a fluorine atom or a chlorine atom;
R ^a2 , R ^a3 , R ^a4 , R ^a5 , R ^a7 , R ^a8 , R ^a9 and R ^a10 are independently hydrogen atom, halogen atom, R ^a11 , COOH, COOR ^a11 , COO- ^, CONH ₂ , CONHR ^a11 . , CONR ^a11 R ^a12 , CN, OH, OR ^a11 , COCR ^a11 , OOCNH ₂ , OOCNHR ^a11 , OOCNR ^a11 R ^a12 , NO ₂ , NH ₂ , NHR ^a11 , NR ^a11 R ^a12 , NHCOR ^a12 , NR ^a11 COR ^a12 , N = CH ₂ , N = CHR ^a11 , N = CR ^a11 R ^a12 , SH, SR ^a11 , SOR ^a11 , SO ₂ R ^a11 , SO ₃ R ^a11 , SO ₃ H, SO _3- ^, SO ₂ NH ₂ , SO ₂ NHR ^{Represents a11} or SO ₂ NR ^a11 R ^a12 ;
And at least one combination selected from the group consisting of R ^a2 and R ^a3 , R ^a3 and R ^a4 , R ^a4 and R ^a5 , R ^a7 and R ^a8 , R ^a8 and R ^a9 , and R ^a9 and R ^a10 is They may bond directly to each other, or they may bond to each other by oxygen, sulfur, NH or NR ^a11 bridges;
R ^a11 and R ^a12 are independently an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms, an alkenyl group having 2 to 12 carbon atoms, a cycloalkenyl group having 3 to 12 carbon atoms, or a cycloalkenyl group having 3 to 12 carbon atoms. Represents 2-12 alkynyl groups. )

(In formula (i), R ¹ represents an alkyl group which may have a substituent or an aromatic ring group which may have a substituent.
R ² represents an alkyl group which may have a substituent or an aromatic ring group which may have a substituent.
k represents 0 or 1.
R ³ to R ⁶ each independently represent an arbitrary monovalent substituent.
l, m and o each independently represent an integer of 0 to 3. n represents 0 or 1. ) The colored photosensitive composition according to claim 1, wherein the (a) colorant further contains (A2) an organic color pigment. The colored photosensitive composition according to claim 1 or 2, wherein the (a) colorant further contains (A3) carbon black. The photosensitive coloring composition according to any one of claims 1 to 3, wherein the content ratio of the colorant (a) is 10% by mass or more with respect to the total solid content. The photosensitive coloring composition according to any one of claims 1 to 4, which is used for forming a coloring spacer. A cured product obtained by curing the photosensitive coloring composition according to any one of claims 1 to 5. A colored spacer composed of the cured product according to claim 6. An image display device including the colored spacer according to claim 7.