JP6665692B2 - Photopolymerization initiator, photosensitive resin composition, cured product, color filter, and image display device - Google Patents

Description

  The present invention relates to a photopolymerization initiator, a photosensitive resin composition, a cured product, a color filter, and an image display device. More specifically, it relates to a highly sensitive and highly soluble photopolymerization initiator and its use.

  A liquid crystal display (LCD) utilizes the property that the arrangement of liquid crystal molecules is switched by turning on / off a voltage to the liquid crystal. On the other hand, most of the members constituting the LCD cell are formed by a method using a photosensitive resin composition represented by photolithography. From the viewpoint that a microstructure is easily formed and a large-area substrate can be easily processed, application of the photosensitive composition in a wide range is expected in the future.

  A technique using an oxime ester compound as a photopolymerization initiator contained in a photosensitive resin composition used for such an application is known. For example, Patent Literature 1 describes that a photopolymerization initiator having a nitro group at the 3-position of a carbazole skeleton efficiently absorbs long-wavelength light and has high sensitivity. Patent Literature 2 describes that a carbazole-based photopolymerization initiator having a nitro group in an aryl group has high sensitivity and excellent thermal stability.

International Publication No. 2008/078678 pamphlet JP 2011-080036 A

The present inventors have studied that, when industrially producing a photosensitive resin composition, the photopolymerization initiator used therein has a high solubility in a solvent, and a high sensitivity per unit weight. The photopolymerization initiator described in Patent Literature 1 satisfies the above-mentioned physical properties and easiness of production, though it is necessary to satisfy physical properties and to be able to be easily and efficiently produced by a simple process. Has been found to be difficult.
Further, the photopolymerization initiator described in Patent Document 2 requires an oxime-forming reaction time due to the necessity of an aryl group having a nitro group, and also requires the use of a considerable amount of raw materials. It has been found that it is difficult to efficiently and easily produce it by a simple process.
The present invention has been made in view of the above circumstances, and the present invention has a high solubility in a solvent, a high sensitivity per unit weight, and a photopolymerization initiation which can be efficiently and easily produced by a simple process. It is intended to provide an agent.

The present inventors have conducted intensive studies to solve the above problems, and as a result, have found that a photopolymerization initiator having a specific chemical structure can solve the above problems, and have completed the present invention.
That is, the present invention has the following configurations [1] to [7].
[1] A photopolymerization initiator represented by the following general formula (I).

(In the general formula (I), R ¹ and R ² each independently represent an alkyl group which may have a substituent. R ³ represents an alkylene group which may have a substituent.
R ⁴ represents an alkyl group which may have a substituent.
R ⁵ represents an optionally substituted alkyl group having 5 or less carbon atoms.
R ⁶ and R ⁷ each independently represent an arbitrary substituent. m and n each independently represent 0 or 1. )

[2] The photopolymerization initiator according to [1], wherein in the general formula (I), at least one of R ¹ and R ² has a branched chain.
[3] A photosensitive resin composition containing (A) an alkali-soluble resin, (B) a compound containing an ethylenically unsaturated group, and (C) a photopolymerization initiator,
(C) The photosensitive resin composition, wherein the photopolymerization initiator contains the photopolymerization initiator according to [1] or [2].
[4] The photosensitive resin composition according to [3], further comprising (D) a coloring material.

[5] A cured product obtained by curing the photosensitive resin composition according to [3] or [4].
[6] A color filter having the cured product according to [5].
[7] An image display device having the color filter according to [6].

  According to the present invention, an object is to provide a photopolymerization initiator having high solubility in a solvent, high sensitivity per unit weight, and which can be efficiently and easily produced by a simple process.

Hereinafter, embodiments of the present invention will be specifically described, but the present invention is not limited to the following embodiments, and can be implemented with various modifications within the scope of the gist.
In the present invention, “(meth) acryl” means “acryl and / or methacryl”, and the same applies to “(meth) acrylate” and “(meth) acryloyl”.

  The “(co) polymer” means to include both a homopolymer and a copolymer, and “acid (anhydride)”, “(anhydride) ... acid” , Including both acids and anhydrides. In the present invention, the “acrylic resin” means a (co) polymer containing (meth) acrylic acid and a (co) polymer containing (meth) acrylic ester having a carboxyl group.

In the present invention, “monomer” refers to a so-called high-molecular substance (polymer).


It is a term that includes dimers, trimers, oligomers, and the like in addition to monomers (monomers) in a narrow sense.
In the present invention, "total solids" means all components other than the solvent contained in the photosensitive resin composition or the ink described below.
In the present invention, the “weight average molecular weight” refers to a weight average molecular weight (Mw) in terms of polystyrene measured by GPC (gel permeation chromatography).
In the present invention, the term “amine value” means an amine value in terms of effective solid content, unless otherwise specified, and is a value represented by the mass of KOH equivalent to the amount of base per 1 g of solid content of a dispersant. It is. The measuring method will be described later. On the other hand, the “acid value” represents an acid value in terms of effective solid content unless otherwise specified, and is calculated by neutralization titration.

  In this specification, percentages and parts represented by “mass” are synonymous with percentages and parts represented by “weight”.

Hereinafter, the present invention will be described in detail.
[Photopolymerization initiator]
The photopolymerization initiator of the present invention is represented by the following general formula (I). By having the structure of —N (—R ¹ ) —CO—R ² as in the formula (I), R ¹ and R ² can be freely changed by changing the kind of raw material at the time of production, for example, amine or acid chloride. The solubility in a solvent can be increased by selecting them appropriately according to the type of the solvent.

In the general formula (I), R ¹ and R ² each independently represent an optionally substituted alkyl group. R ³ represents an alkylene group which may have a substituent.
R ⁴ represents an alkyl group which may have a substituent.
R ⁵ represents an optionally substituted alkyl group having 5 or less carbon atoms.
R ⁶ and R ⁷ each independently represent an arbitrary substituent. m and n each independently represent 0 or 1.
In the formula (I), it is considered that when R ¹ and R ² are based on an alkyl group having a good affinity for a solvent, the solubility in the solvent is increased. Further, it is considered that the molecular weight can be suppressed by using an alkyl group as a base, and the sensitivity per unit weight is also increased.
On the other hand, in the formula (I), the reaction for introducing R ¹ and R ² can be performed quantitatively and sequentially, and the reaction can be performed in the same kiln. It is believed that it can be easily manufactured.

(For R ¹ and R ²⁾
The alkyl group for R ¹ and R ² may be linear, branched or cyclic, and has usually 1 or more, preferably 3 or more, more preferably 5 or more, and usually 20 or less, Preferably it is 10 or less.
When the content is not less than the lower limit, the solubility in a solvent tends to be good, and when the content is not more than the upper limit, the number of gram absorption systems can be increased and the sensitivity tends to be high.

Specific examples of the alkyl group for R ¹ and R ² include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, a pentyl group, an isoamyl group, and a hexyl group. , Heptyl group, octyl group, 2-ethylhexyl group, 2-hexyldecyl group, 2-octyldodecyl group, cyclohexylmethyl group, and the like.

  Among them, a straight-chain or branched alkyl group is preferable from the viewpoint of easy synthesis. Further, a branched alkyl group is particularly preferred from the viewpoint of ensuring solubility in a solvent.

The alkyl group in R ¹ and R ² may have a substituent, and the substituent may be a halogen atom such as F, Cl, Br, or I; an alkoxy group having 1 to 10 carbon atoms such as methoxy and ethoxy. Group; an aromatic hydrocarbon group having 3 to 10 carbon atoms or an aromatic heterocyclic group; Among these, an F atom is preferred. When the F atom is substituted, the solubility tends to be improved.

From the viewpoint of heat resistance and solubility, the photopolymerization initiator of the present invention preferably has at least one of R ¹ and R ^{2 in} the general formula (I) having a branched chain. When ^one of R ¹ and R ² has a branched chain, the heat resistance is improved due to the bulkiness of the skeleton, and the solubility is also improved, and the solubility is adjusted with the other group. Can be. On the other hand, when both groups R ¹ and R ² have a branched chain, the heat resistance tends to be further improved, while the rigidity of the whole molecule increases, and the solubility in a solvent is increased. Tends to decrease. From the viewpoint of achieving both high heat resistance and high solubility, it is preferable that ^one of R ¹ and R ² is a group having a branched chain.
Examples of the group having a branched chain include a group having a secondary carbon atom and a group having a tertiary carbon atom. From the viewpoint of suppressing synthesis reaction inhibition due to steric hindrance and improving solubility, It is preferably a group having a secondary carbon atom.

(For R ³⁾
The alkylene group for R ³ may be linear, branched or cyclic, and has usually 1 or more, preferably 2 or more, more preferably 3 or more, and usually 20 or less, preferably 10 or less. Or less, more preferably 8 or less, and still more preferably 5 or less. When the content is not less than the lower limit, the solubility in a solvent tends to be good, and when the content is not more than the upper limit, the number of gram absorption systems can be increased and the sensitivity tends to be high.

Specific examples of the alkylene group for R ³ include methylene, ethylene, n-propylene, iso-propylene, n-butylene, sec-butylene and the like.

  Among these, a straight-chain or branched alkylene group is preferable in terms of easy synthesis. Further, a branched alkylene group is particularly preferred from the viewpoint of ensuring solubility in a solvent.

The alkylene group for R ³ may have a substituent, and examples of the substituent include halogen atoms such as F, Cl, Br, and I; alkoxy groups having 1 to 10 carbon atoms such as methoxy and ethoxy; Examples include an aromatic hydrocarbon group or an aromatic heterocyclic group represented by Formulas 3 to 10. Among these, an F atom is preferred. When the F atom is substituted, the solubility tends to be improved.

(For R ⁴⁾
The alkyl group for R ⁴ may be any of linear, branched and cyclic, and the number of carbon atoms is usually 1 or more, and usually 20 or less, preferably 10 or less, more preferably 8 or less, and further preferably It is at most 5, more preferably at most 3, particularly preferably at most 2. When the content is not less than the lower limit, the heat resistance of the molecule tends to be improved, and when the content is not more than the upper limit, the generation of generated radicals can be improved.

Specific examples of the alkyl group for R ⁴ include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, isoamyl, hexyl, and heptyl. Group, octyl group, 2-ethylhexyl group, 2-hexyldecyl group, 2-octyldodecyl group, cyclohexylmethyl group, and the like.

  Among them, a straight-chain or branched alkyl group is preferable from the viewpoint of easy synthesis. Further, a linear alkyl group is particularly preferable from the viewpoint of reducing the radical generation energy.

The alkyl group for R ⁴ may have a substituent, and examples of the substituent include halogen atoms such as F, Cl, Br, and I; alkoxy groups having 1 to 10 carbon atoms such as methoxy and ethoxy; Examples include an aromatic hydrocarbon group or an aromatic heterocyclic group represented by Formulas 3 to 10. Among these, an F atom is preferred. When the F atom is substituted, the solubility tends to be improved.

(For R ⁵⁾
The alkyl group for R ⁵ may be any of linear, branched and cyclic, and the number of carbon atoms is usually 1 or more, usually 5 or less, preferably 4 or less, more preferably 3 or less, still more preferably 2 or less. When the content is equal to or more than the lower limit, the solubility tends to be improved, and when the content is equal to or less than the upper limit, a decrease in the melting point of the molecule tends to be suppressed.

Specific examples of the alkyl group for R ⁵ include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, a pentyl group, and an isoamyl group.

  Among them, a straight-chain or branched alkyl group is preferable from the viewpoint of easy synthesis. Further, a linear alkyl group is particularly preferable from the viewpoint of availability of raw materials and ease of reaction.

The alkyl group for R ⁴ may have a substituent, and examples of the substituent include halogen atoms such as F, Cl, Br, and I; alkoxy groups having 1 to 10 carbon atoms such as methoxy and ethoxy; Examples include an aromatic hydrocarbon group or an aromatic heterocyclic group represented by Formulas 3 to 10. Among these, an F atom is preferred. When the F atom is substituted, the solubility tends to be improved.

(For R ⁶ and R ⁷⁾
Examples of the optional substituent in R ⁶ and R ⁷ include 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; , Br, I and the like; an acyl group; an ester group; an alkyl halide; a hydroxyl group; Among these, a CN group and an acyl group are preferable, and a CN group is more preferable, from the viewpoint of electron bias in a molecule.

  Further, m and n each independently represent 0 or 1, but from the viewpoint of the balance of the electronic state of the molecule, it is preferable that one of m and n is 1 and the other is 0, and that the solubility is reduced. From the viewpoint, both m and n are preferably 0.

  Among the photopolymerization initiators represented by the general formula (I), the photopolymerization represented by the following general formula (I-1) is preferred from the viewpoints of ease of synthesis and yield, solubility and ease of radical generation. Initiators are preferred.

In Formula (I-1), R ¹ and R ² have the same meaning as in Formula (I).

[Specific examples of photopolymerization initiator]
Hereinafter, preferred specific examples of the photopolymerization initiator of the present invention are shown, but the present invention is not limited thereto.

[Method for producing photopolymerization initiator]
The method for producing the photopolymerization initiator of the present invention is not particularly limited. For example, a known method as described in WO 2008/078678 can be employed. For example, it can be manufactured by the following manufacturing method.
First, N-ethyl-3-nitrocarbazole commercially available can be used as a main raw material. After the main raw material is reacted with crotonoyl chloride by the Friedel-Crafts reaction, an amination reaction and an acylation reaction are then performed in the same kiln. The amination reaction is performed quantitatively using various commercially available primary amines, and the next acylation reaction can be performed in the same kiln without the need for post-reaction treatment. Acylation is also performed quantitatively using various commercially available acid chlorides. The compound represented by the above general formula (I) enables a variety of molecular designs by a combination of a primary amine and an acid chloride. Then, after performing an oximation reaction, an acetylation reaction is performed to obtain a desired photopolymerization initiator. By the manufacturing method using the same kiln, the kiln efficiency is increased and the manufacturing cost can be reduced.
The raw material amine or acid chloride may be either of a branched type, but a branched amine is more preferable than a branched acid chloride having a strong odor of the raw material in consideration of production. That is, it can be said that it is preferable that R ¹ on the amine side is branched.

  The photopolymerization initiator of the present invention has a high solubility in a solvent and a high sensitivity per unit weight. Therefore, as a component of the photosensitive resin composition, particularly as a component of the photosensitive resin composition for constituting each member of the liquid crystal display. It is preferably used. In the photosensitive resin composition, the photopolymerization initiator has a function of polymerizing the ethylenically unsaturated group.

[Photosensitive resin composition]
Next, the photosensitive resin composition of the present invention (hereinafter, may be referred to as “resist”) will be described.

The photosensitive resin composition of the present invention contains (A) an alkali-soluble resin, (B) a compound containing an ethylenically unsaturated group, and (C) a photopolymerization initiator, wherein the (C) photopolymerization initiator is as described above. A photopolymerization initiator represented by the general formula (I).
In addition, (D) a coloring material, (E) a surfactant, (F) a solvent, (G) other components, and the like can be appropriately combined and contained.

Hereinafter, each of these components will be described.
<Ingredients>
(A) Alkali-soluble resin The photosensitive resin composition of the present invention contains (A) an alkali-soluble resin. The (A) alkali-soluble resin used in the photosensitive resin composition of the present invention is not particularly limited as long as it is a resin that is soluble in an alkaline aqueous solution such as a developing solution. And / or a resin containing a hydroxyl group.

  Specific examples of such an alkali-soluble resin (A) include an α, β-unsaturated monocarboxylic acid having an α, β-unsaturated monocarboxylic acid and / or a carboxyl group in an ester moiety in an epoxy resin (a). Carboxyl group-containing epoxy (meth) acrylate resin synthesized by adding ester (b) and further reacting with polybasic acid anhydride (A); unsaturated carboxylic acids such as (meth) acrylic acid and maleic acid Or a hydroxyl- and / or carboxyl-containing vinyl resin obtained by polymerizing a compound in which a hydroxyl group or a carboxyl group is bonded to (meth) acrylic acid ester or the like and another vinyl compound; and polyamide, polyester, poly Ether, polyurethane, polyvinyl butyral, polyvinyl alcohol, polyvinyl pyrrolidone, Cetyl cellulose; and the like. These may be used alone or in combination of two or more.

Among these, a carboxyl group-containing epoxy (meth) acrylate resin and a carboxyl group-containing vinyl resin are preferable from the viewpoint of alkali developability and image forming properties.
Further, as a pixel application of the color filter, a vinyl resin containing an unsaturated group and a carboxyl group is preferable from the viewpoint of hue and image forming properties. For use as a black matrix, a carboxyl group-containing epoxy (meth) acrylate resin is preferably used from the viewpoint of sensitivity.

(A-1) Carboxyl group-containing epoxy (meth) acrylate resin The carboxyl group-containing epoxy (meth) acrylate resin is obtained by adding a carboxyl group to an α, β-unsaturated monocarboxylic acid and / or an ester moiety in the epoxy resin (a). Is synthesized by adding an α, β-unsaturated monocarboxylic acid ester (b) having the formula (1) and further reacting with a polybasic acid anhydride (c). Such a reaction product has substantially no epoxy group in the chemical structure and is not limited to “acrylate”. However, since epoxy resin is a raw material and “acrylate” is a typical example, It is so named according to convention.

  Examples of the epoxy resin (a) as a raw material include bisphenol A type epoxy resin (for example, “Epicoat (registered trademark; the same applies hereinafter) 828”, “Epicoat 1001”, “Epicoat 1002”, and “Epicoat” manufactured by Mitsubishi Chemical Corporation). 1004 ”), an epoxy obtained by reacting an alcoholic hydroxyl group of a bisphenol A type epoxy resin with epichlorohydrin (for example,“ NER-1302 ”(Nippon Kayaku Co., Ltd. (epoxy equivalent: 323, softening point: 76 ° C.)), bisphenol F Mold resin (for example, "Epicoat 807", "EP-4001", "EP-4002", "EP-4004", etc., manufactured by Mitsubishi Chemical Corporation), and a reaction between epichlorohydrin and an alcoholic hydroxyl group of a bisphenol F type epoxy resin. Epoxy resin (for example, “NE -7406 "(epoxy equivalent 350, softening point 66 ° C), bisphenol S type epoxy resin, biphenyl glycidyl ether (for example," YX-4000 "manufactured by Mitsubishi Chemical Corporation), phenol novolak type epoxy resin (for example, Nippon Kayaku) "EPPN-201" manufactured by Mitsubishi Chemical Corporation, "EP-152" and "EP-154" manufactured by Mitsubishi Chemical Corporation, "DEN-438" manufactured by Dow Chemical Company), (o, m, p-) cresol novolac type epoxy Resin (for example, "EOCN (registered trademark; the same applies hereinafter) -102S", "EOCN-1020", "EOCN-104S" manufactured by Nippon Kayaku), triglycidyl isocyanurate (for example, "Nissan Chemical" TEPIC (registered trademark)), trisphenol methane type epoxy resin (for example, "EPPN (registered trademark)" manufactured by Nippon Kayaku Co., Ltd. -501 "," EPN-502 "," EPPN-503 "), an alicyclic epoxy resin (" Celoxide (registered trademark; the same applies hereinafter) 2021P "," Celoxide EHPE ", manufactured by Daicel), An epoxy resin obtained by glycidylation of a phenol resin by a reaction between dicyclopentadiene and phenol (for example, “EXA-7200” manufactured by DIC, “NC-7300” manufactured by Nippon Kayaku), and the following general formulas (a1) to (a1) The epoxy resin represented by a4) can be suitably used. Specifically, “XD-1000” manufactured by Nippon Kayaku Co., Ltd. as an epoxy resin represented by the following general formula (a1), and “XD-1000” manufactured by Nippon Kayaku Co., Ltd. as an epoxy resin represented by the following general formula (a2) NC-3000 "and an epoxy resin represented by the following general formula (a4) include" ESF-300 "manufactured by Nippon Steel & Sumitomo Metal Corporation.

In the general formula (a1), b11 represents an average value and represents a number of 0 to 10. R ¹¹ 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. A plurality of R ¹¹ present in one molecule may be the same or different.

In the general formula (a2), b12 represents an average value and represents a number of 0 to 10. R ²¹ 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. A plurality of R ²¹ present in one molecule may be the same or different.

  In the above general formula (a3), X represents a linking group represented by the following general formula (a3-1) or (a3-2). However, one or more adamantane structures are included in the molecular structure. b13 represents an integer of 2 or 3.

In the general formulas (a3-1) and (a3-2), R ^{31 to} R ³⁴ and R ^{35 to} R ³⁷ each independently represent an adamantyl group which may have a substituent, a hydrogen atom, a substituent Represents an alkyl group having 1 to 12 carbon atoms which may have a phenyl group which may have a substituent. The symbol * in the formula represents the binding site in (a3).

In the general formula (a4), p and q each independently represent an integer of 0 to 4, and R ⁴¹ and R ⁴² each independently represent an alkyl group or a halogen atom. R ⁴³ and R ⁴⁴ each independently represent an alkylene group. x and y each independently represent an integer of 0 or more.
Among these, it is preferable to use the epoxy resin (a) represented by any of the general formulas (a1) to (a4).
The molecular weight of these epoxy resins (a) is usually 200 or more, preferably 300 or more, and usually 200,000 or less, preferably 100,000 or less, as the weight average molecular weight in terms of polystyrene measured by gel permeation chromatography (GPC). 000 or less.
When the amount is not less than the lower limit, the film-forming property is good, and when the amount is not more than the above-mentioned upper limit, gelation hardly occurs during the addition reaction of the α, β-unsaturated monocarboxylic acid, which is preferable in that the production is easy.

  Examples of the α, β-unsaturated monocarboxylic acid include itaconic acid, crotonic acid, cinnamic acid, acrylic acid, methacrylic acid and the like, preferably acrylic acid and methacrylic acid, and particularly acrylic acid is rich in reactivity. Therefore, it is preferable.

  Examples of the α, β-unsaturated monocarboxylic acid ester having a carboxyl group in the ester portion include 2-succinoyloxyethyl acrylate, 2-maleinoyloxyethyl acrylate, 2-phthaloyloxyethyl acrylate, 2-hexahydrophthaloyloxyethyl acrylate, 2-succinoyloxyethyl methacrylate, 2-maleinoyloxyethyl methacrylate, 2-phthaloyloxyethyl methacrylate, 2-hexahydrophthalomethacrylate Iloxyethyl, 2-succinoyloxyethyl crotonate and the like are preferred, and 2-maleinoyloxyethyl acrylate and 2-phthaloyloxyethyl acrylate are preferred. Noyloxyethyl is preferred.

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

The epoxy resin (a), the α, β-unsaturated monocarboxylic acid and / or the α, β-unsaturated monocarboxylic acid ester having a carboxyl group in the ester portion (b), and the esterification catalyst are all one type. May be used alone or as a mixture of two or more.
The amount of the α, β-unsaturated monocarboxylic acid ester and / or the α, β-unsaturated monocarboxylic acid ester having a carboxyl group in the ester portion (b) is based on 1 equivalent of the epoxy group of the raw material epoxy resin (a). The range is preferably 0.5 to 1.2 equivalents, more preferably 0.7 to 1.1 equivalents. The amount of the unsaturated group introduced can be increased by setting the amount of the α, β-unsaturated monocarboxylic acid and / or the α, β-unsaturated monocarboxylic acid ester (b) having a carboxyl group in the ester portion at or above the lower limit. Deficiency, the subsequent reaction with polybasic acid anhydride (c) becomes sufficient, and a large amount of epoxy groups tends to remain. On the other hand, by setting the amount to be used at or below the upper limit, the α, β-unsaturated monocarboxylic acid and / or α, β-unsaturated monocarboxylic acid ester having a carboxyl group in the ester portion remains as an unreacted product. Tend to be suppressed.

  a polybasic acid anhydride (a) which is further added to an epoxy resin (a) to which an α, β-unsaturated carboxylic acid and / or an α, β-unsaturated monocarboxylic acid ester (b) having a carboxyl group at an ester moiety is added; c) includes maleic anhydride, succinic anhydride, itaconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, pyromellitic anhydride, trimellitic anhydride, benzophenone tetracarboxylic dianhydride, Methylhexahydrophthalic anhydride, endmethylenetetrahydrophthalic anhydride, chlorendic anhydride, methyltetrahydrophthalic anhydride, biphenyltetracarboxylic dianhydride and the like one or two or more, preferably maleic anhydride, Succinic anhydride, itaconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, Water hexahydrophthalic acid, pyromellitic acid anhydride, a trimellitic anhydride, biphenyltetracarboxylic acid dianhydride, particularly preferred compounds are tetrahydrophthalic anhydride and biphenyltetracarboxylic acid dianhydride.

  Known methods can be used for the addition reaction of the polybasic acid anhydride (c), and α, β-unsaturated carboxylic acid and / or α, β having a carboxyl group in the ester moiety to the epoxy resin (a) can be used. -It can be obtained by continuing the reaction under the same conditions as in the addition reaction of the unsaturated monocarboxylic acid ester (b). The addition amount of the polybasic acid anhydride (c) is preferably such that the acid value of the resulting epoxy (meth) acrylate resin is in the range of 10 to 150 mg-KOH / g, and more preferably 20 to 140 mg-KOH / g. KOH / g is particularly preferred. When the resin acid value is equal to or higher than the lower limit, alkali developability tends to be improved, and when the resin acid value is equal to or lower than the upper limit, curing performance tends to be easily ensured.

In addition, at the time of the addition reaction of the polybasic acid anhydride (c), a polyfunctional alcohol such as trimethylolpropane, pentaerythritol, or dipentaerythritol may be added to introduce a multibranched structure.
(A) The weight average molecular weight in terms of polystyrene measured by GPC of the carboxyl group-containing epoxy (meth) acrylate resin used as the alkali-soluble resin is usually 1,000 or more, preferably 2,000 or more, more preferably 3,000 or more. It is usually 30,000 or less, preferably 20,000 or less, more preferably 10,000 or less, and particularly preferably 8,000 or less.
When the content is not more than the above-mentioned upper limit, the developability of the photosensitive resin composition is good, and when it is not less than the above-mentioned lower limit, it is preferable in that alkali resistance is good.

  (A) The acid value of the carboxyl group-containing epoxy (meth) acrylate resin used as the alkali-soluble resin is usually 10 mg-KOH / g or more, preferably 50 mg-KOH / g or more, more preferably 70 mg-KOH / g or more. It is more preferably at least 90 mg-KOH / g, and usually at most 200 mg-KOH / g, preferably at most 150 mg-KOH / g, more preferably at most 130 mg-KOH / g, even more preferably at most 120 mg-KOH / g. It is. When the content is equal to or more than the lower limit, alkali developability tends to be good, and when the content is equal to or less than the upper limit, curing performance tends to be easily ensured.

(A-2) Carboxyl group-containing vinyl resin Examples of the carboxyl group-containing vinyl resin include a copolymer of an unsaturated carboxylic acid and a vinyl compound.
Examples of the unsaturated carboxylic acid include (meth) acrylic acid, crotonic acid, isocrotonic acid, maleic acid, maleic anhydride, itaconic acid, and citraconic acid. These may be used alone or as a mixture of two or more.

  Examples of the vinyl compound include styrene, α-methylstyrene, hydroxystyrene, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, pentyl (meth) acrylate, and hexyl (meth) yl. A) acrylate, dodecyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, hydroxymethyl (meth) acrylate, hydroxyethyl (meth) acrylate, glycidyl (meth) acrylate, isobornyl (meth) acrylate, dicyclopentanyl (meth) Acrylate, benzyl (meth) acrylate, N, N-dimethylaminoethyl (meth) acrylate, N- (meth) acryloylmorpholine, (meth) acrylonitrile, (meth) acrylamide , N- methylol (meth) acrylamide, N, N- dimethyl (meth) acrylamide, N, N- dimethylaminoethyl (meth) acrylamide, copolymers of vinyl compounds and vinyl acetate. These may be used alone or as a mixture of two or more.

  Among them, dicyclopentanyl (meth) acrylate is preferable in that it provides a wide latitude with respect to the development time and the deterioration of the developer. Examples of such dicyclopentanyl (meth) acrylate include compounds described in, for example, JP-A-2001-89533, such as dicyclopentadiene skeleton, dicyclopentanyl skeleton, dicyclopentenyl skeleton, and dicyclopentenyloxyalkyl skeleton. (Meth) acrylate and the like.

  Among the above copolymers (carboxyl group-containing vinyl resins), styrene- (meth) acrylate- (meth) acrylic acid copolymers are preferable from the viewpoint of image shape, sensitivity, and cured film strength, and styrene 3 to A copolymer composed of 60 mol%, 10-70 mol% of (meth) acrylate, and 10-60 mol% of (meth) acrylic acid is more preferable, and styrene 5-50 mol%, (meth) acrylate 20-60 mol%, A copolymer composed of 15 to 55 mol% of (meth) acrylic acid is particularly preferred.

  Further, as the carboxyl group-containing vinyl resin, those having an ethylenically unsaturated bond in a side chain are also preferable because the film strength after curing is increased.For example, a carboxyl group-containing vinyl resin includes allyl glycidyl ether, Glycidyl (meth) acrylate, α-ethyl glycidyl (meth) acrylate, glycidyl crotonate, glycidyl isocrotonate, crotonyl glycidyl ether, monoalkyl monoglycidyl itaconate, monoalkyl monoglycidyl fumarate, monoalkyl monomaleate Aliphatic epoxy group-containing unsaturated compounds such as glycidyl ester, or 3,4-epoxycyclohexylmethyl (meth) acrylate, 2,3-epoxycyclopentylmethyl (meth) acrylate, 7,8-epoxy [g An alicyclic epoxy group-containing unsaturated compound such as cyclo [5.2.1.0] dec-2-yl] oxymethyl (meth) acrylate is used in an amount of 5 to 90 mol% of the carboxyl group of the carboxyl group-containing polymer. And preferably about 30 to 70 mol% of the reaction product. Further, allyl (meth) acrylate, 3-allyloxy-2-hydroxypropyl (meth) acrylate, cinnamyl (meth) acrylate, crotonyl (meth) acrylate, methallyl (meth) acrylate, N, N-diallyl (meth) acrylamide, and the like Compounds having two or more unsaturated groups, or vinyl (meth) acrylate, 1-chlorovinyl (meth) acrylate, 2-phenylvinyl (meth) acrylate, 1-propenyl (meth) acrylate, vinyl crotonate, vinyl A compound having two or more kinds of unsaturated groups such as (meth) acrylamide and an unsaturated carboxylic acid such as (meth) acrylic acid or further unsaturated carboxylic acid ester are combined with the former compound having an unsaturated group. 10 to 90 mol%, preferably 30 to 8 Such as the reaction product obtained by copolymerizing the like so that the mole% of.

  Further, the acid value of these carboxyl group-containing vinyl resins is usually 10 mg-KOH / g or more, preferably 50 mg-KOH / g or more, more preferably 70 mg-KOH / g or more, and usually 250 mg-KOH / g. / G or less, preferably 200 mg-KOH / g or less, more preferably 150 mg-KOH / g or less, and still more preferably 100 mg-KOH / g or less. When the content is equal to or more than the lower limit, alkali developability tends to be good, and when the content is equal to or less than the upper limit, curing performance tends to be easily ensured.

  Further, the weight average molecular weight of these carboxyl group-containing vinyl resins in terms of polystyrene by GPC measurement is usually 1,000 or more, preferably 3,000 or more, more preferably 5,000 or more, and further preferably 7,000 or more. And it is usually 100,000 or less, preferably 50,000 or less, more preferably 30,000 or less, still more preferably 20,000 or less, and particularly preferably 10,000 or less. When the content is not more than the above-mentioned upper limit, the developability of the photosensitive resin composition is good, and when it is not less than the above-mentioned lower limit, it is preferable in that the alkali resistance is good.

The content of the (A) alkali-soluble resin in the photosensitive resin composition of the present invention is usually at least 10% by mass, preferably at least 20% by mass, more preferably at least 30% by mass, based on the total solid content. , Usually 60% by mass or less, preferably 50% by mass or less, more preferably 40% by mass or less.
If it is not less than the lower limit, the reproducibility of the image cross-sectional shape and heat resistance tend to be good, and if it is not more than the upper limit, the sensitivity and development dissolution rate of the photosensitive resin composition tend to be good. .

(B) Ethylenically unsaturated group-containing compound As the ethylenically unsaturated group-containing compound used in the photosensitive resin composition of the present invention, a compound having one or more ethylenically unsaturated groups is used. The number of ethylenically unsaturated groups contained in the ethylenically unsaturated group-containing compound is not particularly limited, but is preferably 2 or more, more preferably 3 or more, still more preferably 4 or more, from the viewpoint of curability. The above is particularly preferred. On the other hand, from the viewpoint of image formability, the number is usually 20 or less, preferably 15 or less, more preferably 10 or less, and still more preferably 8 or less.

  Specific examples of the ethylenically unsaturated group-containing compound include esters of an aliphatic (poly) hydroxy compound with an unsaturated carboxylic acid, esters of an aromatic (poly) hydroxy compound with an unsaturated carboxylic acid, and unsaturated carboxylic acids. Esters obtained from acids, polycarboxylic acids and aliphatic polyhydroxy compounds, ethylene oxide of aromatic polyhydroxy compounds, esterification products of propylene oxide adducts with unsaturated carboxylic acids, ethylene oxide of aliphatic polyhydroxy compounds, caprolactone Ester of modified polyhydric alcohol and unsaturated carboxylic acid, reaction product of polyhydric alcohol and polyisocyanate and unsaturated carboxylic acid, styryl terminal compound, unsaturated compound containing phosphoric acid, polyepoxy and unsaturated carboxylic acid And the like.

  Among them, specific examples of the ester of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid include ethylene glycol diacrylate, triethylene glycol diacrylate, neopentyl glycol diacrylate, hexanediol diacrylate, and trimethylolpropane triacrylate. Acrylates such as acrylate, trimethylolethane triacrylate, pentaerythritol diacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, glycerol acrylate, etc. Methacrylic acid in which the acrylate of the exemplified compound is replaced with methacrylate Ether, similarly itaconic acid ester instead itaconate, maleic acid esters, and the like was replaced with crotonic acid ester or maleate was replaced crotonate.

  Examples of the ester of an aromatic polyhydroxy compound with an unsaturated carboxylic acid include unsaturated carboxylic acids and aromatic carboxylic acids such as hydroquinone, resorcinol, pyrogallol, bisphenol F, bisphenol A, and bis-1,1- (4-hydroxyphenyl) fluorene. Group polyhydroxy compounds or their reaction products with ethylene oxide adducts. Specifically, for example, bisphenol A di (meth) acrylate, bisphenol A bis [oxyethylene (meth) acrylate], bisphenol A bis [glycidyl ether (meth) acrylate] and the like.

  Representative examples of the ester obtained by the reaction of the unsaturated carboxylic acid with the polyvalent carboxylic acid and the polyvalent hydroxy compound include (meth) acrylic acid, a condensate of phthalic acid and ethylene glycol, and (meth) acrylic acid. Condensates of acid, maleic acid and diethylene glycol, condensates of (meth) acrylic acid, terephthalic acid and pentaerythritol, condensates of (meth) acrylic acid, adipic acid, butanediol and glycerin. These are not necessarily single substances but may be a mixture of a plurality of compounds having similar structures.

In addition, examples of the ethylenically unsaturated group-containing compound used in the present invention include acrylamides such as ethylene bisacrylamide; allyl esters such as diallyl phthalate; and vinyl group-containing compounds such as divinyl phthalate.
Preferred among the above-mentioned compounds containing an ethylenically unsaturated group are those having a (meth) acryloyl group, more preferably an acryloyl group. Such compounds include trimethylolpropane triacrylate, trimethylolethane triacrylate, pentaerythritol diacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate and the like. Is mentioned.

One of these ethylenically unsaturated group-containing compounds may be used alone, or two or more thereof may be used in combination.
For example, when used as a composition for forming a pixel of a black matrix or a color filter, it is preferable to use an ester of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid from the viewpoint of curability.

  The content ratio of the (B) ethylenically unsaturated group-containing compound in the photosensitive resin composition of the present invention is generally 1% by mass or more, preferably 5% by mass or more, more preferably 5% by mass, based on the total solid content. Is 10% by mass or more, usually 70% by mass or less, preferably 50% by mass or less, more preferably 30% by mass or less, and further preferably 20% by mass or less. When the ratio is not less than the lower limit, the sensitivity and the developing dissolution rate tend to be good, and when the ratio is not more than the upper limit, the reproducibility of the image sectional shape tends to be good.

(C) Photopolymerization initiator In the photosensitive resin composition of the present invention, (C) the photopolymerization initiator contains a photopolymerization initiator represented by the general formula (I). The photopolymerization initiator represented by the general formula (I) has a high solubility in a solvent and a high sensitivity per unit weight. Therefore, when the photoinitiator is used in a photosensitive resin composition, the undissolved residue in the solvent is reduced. It is considered that the compound is not removed by filtration at the time of preparation because it is not present, and that curing is performed promptly because of high sensitivity, thereby improving the film formability.

  As the photopolymerization initiator (C) used in the photosensitive resin composition of the present invention, only one type of photopolymerization initiator represented by the general formula (I) may be used, or two or more types may be used in combination. May be. If necessary, other components such as other photopolymerization initiators and sensitizing dyes can be used in combination with the photopolymerization initiator represented by the general formula (I). By using them in an appropriate combination according to the use or the like, further higher sensitivity can be expected.

  The other photopolymerization initiator that can be used in the photosensitive resin composition of the present invention is not particularly limited as long as it is a compound that polymerizes an ethylenically unsaturated group by actinic rays, and a known photopolymerization initiator is used. Agents can be used. For example, the following compounds can be mentioned.

  For example, 2- (4-methoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4-methoxynaphthyl) -4,6-bis (trichloromethyl) -s-triazine, Halomethylated triazine derivatives such as (4-ethoxynaphthyl) -4,6-bis (trichloromethyl) -s-triazine and 2- (4-ethoxycarbonylnaphthyl) -4,6-bis (trichloromethyl) -s-triazine , 2-trichloromethyl-5- (2'-benzofuryl) -1,3,4-oxadiazole, 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 Halomethylated oxadiazole derivatives such as -5-furyl-1,3,4-oxadiazole, 2- (2'-chlorophenyl) -4,5-diphenylimidazole dimer, 2- (2'-chlorophenyl) -4,5-bis (3′-methoxyphenyl) imidazole dimer, 2- (2′-fluorophenyl) -4,5-diphenylimidazole dimer, 2- (2′-methoxyphenyl) -4, Imidazole derivatives such as 5-diphenylimidazole dimer and (4'-methoxyphenyl) -4,5-diphenylimidazole dimer, and benzoin alkyl ethers such as benzoin methyl ether, benzoin phenyl ether, benzoin isobutyl ether and benzoin isopropyl ether , 2-methylanthraquinone, 2-ethylanthraquinone, Anthraquinone derivatives such as -t-butylanthraquinone, 1-chloroanthraquinone, benzuanthrone derivatives, benzophenone, Michler's ketone, 2-methylbenzophenone, 3-methylbenzophenone, 4-methylbenzophenone, 2-chlorobenzophenone, 4-bromobenzophenone, 2- Benzophenone derivatives such as carboxybenzophenone, 2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxyacetophenone, 1-hydroxycyclohexylphenyl ketone, α-hydroxy-2-methylphenylpropanone, 1-hydroxy-1- Methylethyl- (p-isopropylphenyl) ketone, 1-hydroxy-1- (p-dodecylphenyl) ketone, 2-methyl- (4 ′-(methylthio) phenyl) -2-mol Halino-1-propanone, acetophenone derivatives such as 1,1,1-trichloromethyl- (p-butylphenyl) ketone, thioxanthone, 2-ethylthioxanthone, 2-isopropylthioxanthone, 2-chlorothioxanthone, 2,4-dimethylthioxanthone Thioxanthone derivatives such as 2,4-diethylthioxanthone and 2,4-diisopropylthioxanthone, benzoic acid ester derivatives such as ethyl p-dimethylaminobenzoate and ethyl p-diethylaminobenzoate, 9-phenylacridine, 9- (p- Acridine derivatives such as methoxyphenyl) acridine, phenazine derivatives such as 9,10-dimethylbenzphenazine, bis-cyclopentadienyl-Ti-dichloride, bis-cyclopentadienyl-Ti-bis-phenyl, S-cyclopentadienyl-Ti-bis- (2,3,4,5,6-pentafluorophenyl-1-yl), bis-cyclopentadienyl-Ti-bis- (2,3,5,6 -Tetrafluorophenyl-1-yl), bis-cyclopentadienyl-Ti-bis- (2,4,6-trifluorophenyl-1-yl), bis-cyclopentadienyl-Ti-2,6- Di-fluorophenyl-1-yl, bis-cyclopentadienyl-Ti-2,4-di-fluorophenyl-1-yl, bis-methylcyclopentadienyl-Ti-bis- (2,3,4 5,6-pentafluorophenyl-1-yl), bis-methylcyclopentadienyl-Ti-bis- (2,6-di-fluorophenyl-1-yl), bis-cyclopentadienyl-Ti-2 , 6-Di-fluoro-3 (Pill-1-yl) - titanocene derivatives of 1-yl and the like, and the like.

Further, compounds described in JP-A-2000-80068 and JP-T-2004-534797 can also be used.
The content of the photopolymerization initiator represented by the general formula (I) in the photosensitive resin composition of the present invention is usually 0.1% by mass or more, preferably 0.5% by mass, based on the total solid content. % Or more, more preferably 1% or more, still more preferably 1.5% or more, and usually 50% or less, preferably 30% or less, more preferably 20% or less, and still more preferably 10% or less. % By mass or less, particularly preferably 5% by mass or less. When the amount is not less than the lower limit, the curing performance tends to be sufficient, and when the amount is not more than the upper limit, the pattern at the time of development tends to be desired.

  When the photopolymerization initiator represented by the formula (I) and another photopolymerization initiator are used in combination as the photopolymerization initiator (C), the content ratio of the photopolymerization initiator (C) is It is usually at least 0.2% by mass, preferably at least 0.5% by mass, more preferably at least 1% by mass, even more preferably at least 1.5% by mass, and usually at most 40% by mass, based on the solid content. , Preferably 30% by mass or less, more preferably 20% by mass or less, further preferably 10% by mass or less, particularly preferably 5% by mass or less. When the amount is equal to or more than the lower limit, the curing characteristics of the photopolymerization initiator represented by the general formula (I) tend to be exhibited, and when the amount is equal to or less than the upper limit, other photopolymerization initiators are used. There is a tendency that they can be used together without impairing the curing properties.

In addition to the photopolymerization initiator, a sensitizing dye may be further added to the photosensitive resin composition of the present invention. In particular, in order to cause a photopolymerization reaction in a highly light-shielding photosensitive resin composition such as a composition for a black matrix, it is preferable to add a sensitizing dye.
Examples of such sensitizing dyes include coumarin compounds having a heterocyclic ring described in JP-A-3-239703 and JP-A-5-289335, and 3-ketocoumarin described in JP-A-63-221110. Compounds, xanthene dyes described in JP-A-4-221958 and JP-A-4-219756, pyromethene dyes described in JP-A-6-19240, JP-A-47-2528, JP-A-54-219 155292, JP-A-56-166154 and JP-A-59-56403 disclose a (p-dialkylaminobenzylidene) ketone, a styryl dye, and a julolidyl group described in JP-A-6-295061. Sensitizing dyes, and diaminobenzene compounds described in JP-A-11-326624. Particularly preferred among these sensitizing dyes are amino group-containing sensitizing dyes and xanthene dyes.

(D) Coloring Material When the photosensitive resin composition of the present invention is used for forming a colored pattern such as a pixel of a color filter, a black matrix, and a black column spacer, the photosensitive resin composition of the present invention includes: It is preferable to contain a coloring material (D) in addition to the components (A) to (C) described above.

(D) The coloring material can be used without any particular limitation as long as it can be used for forming a colored pattern. For example, dyes and pigments can be used. Pigments are preferred in terms of heat resistance, light resistance and the like.
In particular, in order to form a light shielding member near a liquid crystal such as a black column spacer, it is preferable to use an organic pigment and carbon black as a pigment. In the present specification, the organic pigment is a powder containing an organic compound used for coloring as a component, and means a substance that is unnecessary for water or oil.

  As the organic pigment, various pigments such as a blue pigment, a green pigment, a red pigment, a yellow pigment, a violet pigment, an orange pigment, a brown pigment, and a black pigment can be used. As the structure, organic pigments such as azo, phthalocyanine, quinacridone, benzimidazolone, isoindolinone, dioxazine, and indanthrene can be used. Further, an inorganic pigment may be used in addition to the organic pigment. In the present specification, unless otherwise specified, the color of the pigment means a color exhibited when the photosensitive resin composition is formed by using the pigment alone as a coloring material. That is, for example, a black pigment refers to a pigment that becomes black when a photosensitive coloring composition is formed using the pigment alone as a coloring material.

Hereinafter, specific examples of the pigment that can be used in the present invention are shown by pigment numbers. In addition, terms such as “CI Pigment Red 2” listed below mean a color index (CI).
Red pigments include C.I. I. Pigment Red 1, 2, 3, 4, 5, 6, 7, 8, 9, 12, 14, 15, 16, 17, 21, 22, 23, 31, 32, 37, 38, 41, 47, 48, 48: 1, 48: 2, 48: 3, 48: 4, 49, 49: 1, 49: 2, 50: 1, 52: 1, 52: 2, 53, 53: 1, 53: 2, 53: 3, 57, 57: 1, 57: 2, 58: 4, 60, 63, 63: 1, 63: 2, 64, 64: 1, 68, 69, 81, 81: 1, 81: 2, 81: 3, 81: 4, 83, 88, 90: 1, 101, 101: 1, 104, 108, 108: 1, 109, 112, 113, 114, 122, 123, 144, 146, 147, 149, 151, 166, 168, 169, 170, 172, 173, 174, 175, 176, 177, 178, 17 , 181, 184, 185, 187, 188, 190, 193, 194, 200, 202, 206, 207, 208, 209, 210, 214, 216, 220, 221, 224, 230, 231, 232, 233, 235 , 236, 237, 238, 239, 242, 243, 245, 247, 249, 250, 251, 253, 254, 255, 256, 257, 258, 259, 260, 262, 263, 264, 265, 266, 267 , 268, 269, 270, 271, 272, 273, 274, 275, 276. Among them, C.I. I. Pigment Red 48: 1, 122, 168, 177, 202, 206, 207, 209, 224, 242, 254, more preferably C.I. I. Pigment Red 177, 209, 224, and 254. In addition, C.I. I. Pigment Red 177, 254, and 272 are preferred. When the photosensitive resin composition of the present invention is cured with ultraviolet light, it is preferable to use a red pigment having a low ultraviolet absorptivity. Is C. I. Pigment Red 254, 272 is more preferably used.

  Blue pigments include C.I. I. Pigment Blue 1, 1: 2, 9, 14, 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, 16, 17, 19, 25, 27, 28, 29, 33, 35, 36, 56, 56: 1, 60, 61, 61: 1, 62, 63, 66, 67, 68, 71, 72, 73, 74, 75, 76, 78, 79. Among them, C.I. I. Pigment Blue 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, and more preferably C.I. I. Pigment Blue 15: 6. In addition, C.I. I. Pigment Blue 15: 6, 16, and 60 are preferably used. When the photosensitive resin composition of the present invention is cured with ultraviolet light, a blue pigment having a low ultraviolet absorption rate is preferably used. From the viewpoint, C.I. I. Pigment Blue 60 is more preferably used.

Green pigments include C.I. I. Pigment Green 1, 2, 4, 7, 8, 10, 13, 14, 15, 17, 18, 19, 26, 36, 45, 48, 50, 51, 54, 55. Among them, C.I. I. Pigment Green 7 and 36.
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, 17 , 174, 175, 176, 180, 181, 182, 183, 184, 185, 188, 189, 190, 191, 191: 1, 192, 193, 194, 195, 196, 197, 198, 199, 200, 202 , 203, 204, 205, 206, 207, 208. Among them, C.I. I. Pigment Yellow 83, 117, 129, 138, 139, 150, 154, 155, 180, 185, and more preferably C.I. I. Pigment Yellow 83, 138, 139, 150, and 180.

  Examples of orange (orange) pigments 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. Among them, C.I. I. Pigment Orange 38 and 71. In addition, C.I. I. Pigment Orange 43, 64, and 72 are preferably used. When the photosensitive resin composition of the present invention is cured with ultraviolet light, it is preferable to use an orange pigment having a low ultraviolet absorptivity. Is C. I. Pigment Orange 64, 72 is more preferable.

  Examples of purple pigments include C.I. I. Pigment Violet 1, 1: 1, 2: 2: 2, 3: 1, 3: 3, 5, 5: 1, 14, 15, 16, 19, 23, 25, 27, 29, 31, 32, 37, 39, 42, 44, 47, 49, and 50. Among them, C.I. I. Pigment Violet 19, 23, more preferably C.I. I. Pigment Violet 23. In addition, C.I. I. Pigment Violet 23 or 29 is preferably used. When the photosensitive resin composition of the present invention is cured with ultraviolet light, it is preferable to use a purple pigment having a low ultraviolet absorptivity. . I. Pigment Violet 29 is more preferably used.

  Examples of the black pigment include a black organic pigment having the following chemical structure, aniline black, cyanine black, perylene black and the like.

Among these, it is preferable that the organic pigment contains at least one or more of the following pigments.
Blue: color index pigment blue 60 or 15: 6
Red: Color index pigment red 177, 254, or 272
Purple: Color index pigment violet 23 or 29
Orange: color index pigment orange 43, 64 or 72

  In the case of using pigments of different colors in combination, the combination of colors is not particularly limited, but from the viewpoint of light shielding properties, for example, a combination of a red pigment and a blue pigment, or a combination of a blue pigment, an orange pigment, and a violet pigment And the like.

Further, a dye may be used instead of the organic pigment, and a dye may be used in addition to the organic pigment. Examples of the dye that can be used as a coloring material include an azo dye, an anthraquinone dye, a phthalocyanine dye, a quinone imine dye, a quinoline dye, a nitro dye, a carbonyl dye, and a methine dye.
Examples of azo dyes include C.I. I. Acid Yellow 11, C.I. I. Acid orange 7, C.I. I. Acid Red 37, C.I. I. Acid Red 180, C.I. I. Acid Blue 29, C.I. I. Direct Red 28, C.I. I. Direct Red 83, C.I. I. Direct Yellow 12, C.I. I. Direct Orange 26, C.I. I. Direct Green 28, C.I. I. Direct Green 59, C.I. I. Reactive Yellow 2, C.I. I. Reactive Red 17, C.I. I. Reactive Red 120, C.I. I. Reactive Black 5, C.I. I. Disperse Orange 5, C.I. I. Disperse thread 58, C.I. I. Disperse Blue 165, C.I. I. Basic Blue 41, C.I. I. Basic Red 18, C.I. I. Mordant Red 7, C.I. I. Mordant Yellow 5, C.I. I. Mordant Black 7 and the like.

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 Red 60, C.I. I. Disperse Blue 56, C.I. I. Disperse Blue 60 and the like.
Other phthalocyanine dyes include, for example, C.I. I. Pad Blue 5 and the like include quinone imine dyes such as C.I. I. Basic Blue 3, C.I. I. Basic Blue 9 and the like include quinoline dyes such as C.I. I. Solvent Yellow 33, C.I. I. Acid Yellow 3, C.I. I. Disperse Yellow 64 and the like include, for example, C.I. I. Acid Yellow 1, C.I. I. Acid Orange 3, C.I. I. Disperse Yellow 42 and the like.

  As described above, it is preferable that the coloring material (D) contains an organic pigment and carbon black. Carbon black is preferably used from the viewpoints of light blocking ratio and image characteristics. Examples of the 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
Degussa: Printex3, Printex3OP, Printex30, Printex30OP, Printex40, Printex45, Printex55, Printex60, Printex75, Printex80, Printex85, Printex90, PrintexA, Printex, Printex, Printex, Printex, Printex, Printex, Printex, Printex, Printex, Printex, Printex L SpecialBlack350, SpecialBlack250, SpecialBlack100, SpecialBlack6, SpecialBlack5, SpecialBlack4, Color Black FW1, Color Black FW2, Color Black FW2V, Color Black FW18, Color Black FW18, Color Black FW200, Color Black S160, Color Black S170
Cabot Corporation: Monarch120, Monarch280, Monarch460, Monarch800, Monarch880, Monarch900, Monarch1000, Monarch1100, Monarch1300, Monarch1400, Monarch4630, REGAL99, REGAL99R, REGAL415, REGAL415R, REGAL250, REGAL250R, REGAL330, REGAL400R, REGAL55R0, REGAL660R, BLACK PEARLS480, PEARLS130 , VULCAN XC72R, ELFTEX-8
Colombian Carbon Co .: RAVEN11, RAVEN14, RAVEN15, RAVEN16, RAVEN22RAVEN30, RAVEN35, RAVEN40, RAVE410, RAVE420, RAVE450, RAVE500, RAVE780, RAVE850, RAVE890H, RAVE1000, RAVE50, RAVE10, RAVE10, RAVE10, RAVE10, RAVE10, RAVE10, RAVE10, RAVE10, RAVE10, RAVE50, RAVE10, RAVE10, RAVE10, RAVE10, RAVE10, RAVE10, RAVE10, RAVE10, RAVE10, RAVE10, RAVE10, RAVE10, RAVE10, RAVE10, RAVE10, RAVE10, RAVE10, RAVE50 , RAVEN2000, RAVEN2500U, RAVEN3500, RAVEN5000, RAVEN5250, RAVEN5750, RAVEN7000

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

  It is preferable that the total content of Na and Ca is 100 ppm or less as the carbon black subjected to the coating treatment with the resin. Carbon black is usually made of raw material oil or combustion oil (or gas) at the time of production, reaction stop water or granulation water, Na mixed from furnace materials of a reaction furnace, or the like, and Ca, K, Mg, Al, Fe. The ash having a composition of, for example, is contained in the order of percent. Of these, each of Na and Ca generally contains several hundred ppm or more, but by reducing these, permeation to the transparent electrode (ITO) and other electrodes is suppressed, and Tends to prevent a short circuit.

  As a method of reducing the content of these ash contents including Na and Ca, a material having a minimum of these contents is carefully selected as a raw material oil, a fuel oil (or a gas) and a reaction stop water in producing carbon black. This is possible by minimizing the amount of addition of an alkali substance for adjusting the structure. As another method, there is a method in which carbon black produced from a furnace is washed with water, hydrochloric acid or the like to dissolve and remove Na and Ca.

  Specifically, after carbon black is mixed and dispersed in water, hydrochloric acid, or aqueous hydrogen peroxide, when a solvent that is hardly soluble in water is added, the carbon black moves to the solvent side and is completely separated from water. At the same time, most of Na and Ca present in the carbon black are dissolved and removed in water or acid. In order to reduce the total amount of Na and Ca to 100 ppm or less, there are cases where the raw material is carefully selected and the carbon black production process alone or the water or acid dissolving method alone can be used. The total amount of Na and Ca can be easily reduced to 100 ppm or less.

  Further, the resin-coated carbon black is preferably a so-called acidic carbon black having a pH of 6 or less. Since the dispersion diameter in water (agglomerate diameter) is reduced, it is possible to coat even fine units, which is preferable. Further, the average particle diameter is preferably 40 nm or less, and the absorption amount of dibutyl phthalate (DBP) is preferably 140 ml / 100 g or less. When the content is within the above range, a coating film having good light-shielding properties tends to be obtained. The average particle diameter means a number average particle diameter. A particle image analysis that photographs several tens of thousands of photographs taken at a magnification of tens of thousands by electron microscope observation, and measures about 2000 to 3000 particles of these photographs by an image processing apparatus. Means the equivalent circle diameter determined by

  The method for preparing the carbon black coated with the resin is not particularly limited. For example, after appropriately adjusting the blending amounts of the carbon black and the resin, After mixing and stirring a resin solution obtained by mixing and heating and dissolving the resin and a solvent such as cyclohexanone, toluene and xylene, and a suspension obtained by mixing carbon black and water, carbon black and water are separated. 1. A method in which a composition obtained by removing water, heating and kneading is formed into a sheet, pulverized, and then dried; A method of mixing and stirring the resin solution and the suspension prepared in the same manner as above to granulate the carbon black and the resin, and then separating and heating the obtained granules to remove the remaining solvent and water; 3. A carboxylic acid such as maleic acid or fumaric acid is dissolved in the solvent exemplified above, carbon black is added, mixed and dried, and after removing the solvent to obtain a carboxylic acid-impregnated carbon black, a resin is added thereto. 3. dry blending method; A reactive group-containing monomer component and water constituting the resin to be coated are stirred at high speed to prepare a suspension, and after the polymerization, the suspension is cooled to obtain a reactive group-containing resin from the polymer suspension. A method in which carbon black is added and kneaded to react the carbon black with the reactive group (graft the carbon black), cool and pulverize, or the like can be adopted.

The type of resin to be coated is not particularly limited, but synthetic resins are generally used, and a resin having a benzene ring in the structure has a stronger function as an amphoteric surfactant. It is preferable from the viewpoints of properties and dispersion stability.
Specific synthetic resins include thermosetting resins such as phenolic resins, melamine resins, xylene resins, diallyl phthalate resins, glyptal resins, epoxy resins, alkylbenzene resins, polystyrene, polycarbonate, polyethylene terephthalate, polybutylene terephthalate, and modified polyphenylene. Thermoplastic resins such as oxide, polysulfone, polyparaphenylene terephthalamide, polyamideimide, polyimide, polyaminobismaleimide, polyethersulfopolyphenylene sulfone, polyarylate, and polyetheretherketone can be used. The amount of the resin coated on the carbon black is preferably 1 to 30% by mass based on the total amount of the carbon black and the resin, and when the amount is not less than the lower limit, the coating tends to be sufficient. On the other hand, when the content is equal to or less than the upper limit value, there is a tendency that adhesion between the resins can be prevented and the dispersibility can be improved.

  The carbon black coated with the resin in this manner can be used as a light shielding material for a colored spacer according to a conventional method, and a color filter including the colored spacer as a component can be prepared by a conventional method. When such a carbon black is used, a colored spacer having a high light blocking ratio and a low surface reflectance tends to be achieved at low cost. It is also assumed that coating the surface of the carbon black with a resin also serves to seal Ca and Na in the carbon black.

  In the photosensitive resin composition of the present invention, the content of the coloring material (d) is usually 10% by mass or more, preferably 20% by mass or more, and more preferably 30% by mass or more based on the total solid content. Is more preferably 35% by mass or more, and is usually preferably 70% by mass or less, more preferably 60% by mass or less, even more preferably 50% by mass or less, It is particularly preferred that the content be 45% by mass or less. When the content ratio of (d) the coloring material is equal to or more than the lower limit, the light absorbing effect of the (d) coloring material tends to be sufficiently obtained. Tends to be good.

(E) Surfactant The photosensitive resin composition of the present invention may have a nonionic property, an anionic property, or the like, for the purpose of improving applicability as a coating solution of the composition and developing property of the photosensitive resin composition layer. It may contain a cationic or amphoteric surfactant, or a fluorine-based or silicone-based surfactant.
Examples of the nonionic surfactant include polyoxyethylene alkyl ethers, polyoxyethylene polyoxypropylene alkyl ethers, polyoxyethylene alkyl phenyl ethers, polyoxyethylene alkyl esters, polyoxyethylene fatty acid esters, Glycerin fatty acid esters, polyoxyethylene glycerin fatty acid esters, pentaerythrit fatty acid esters, polyoxyethylene pentaerythrit fatty acid esters, sorbitan fatty acid esters, polyoxyethylene sorbitan fatty acid esters, sorbite fatty acid esters, polyoxy And ethylene sorbite fatty acid esters. Examples of these commercially available products include polyoxyethylene surfactants such as "Emulgen 104P" and "Emulgen A60" manufactured by Kao Corporation.

  Examples of the anionic surfactant include alkyl sulfonates, alkyl benzene sulfonates, alkyl naphthalene sulfonates, polyoxyethylene alkyl ether sulfonates, alkyl sulfates, alkyl sulfates, and higher alcohol sulfates. Ester salts, aliphatic alcohol sulfates, polyoxyethylene alkyl ether sulfates, polyoxyethylene alkyl phenyl ether sulfates, alkyl phosphates, polyoxyethylene alkyl ether phosphates, polyoxyethylene alkyl phenyl ether phosphates, specialty Polymeric surfactants and the like can be mentioned. Among them, special polymer surfactants are preferable, and special polycarboxylic acid polymer surfactants are more preferable.

Commercial products can be used as such anionic surfactants. For example, for alkyl sulfate salts, "Emal 10" manufactured by Kao Corporation, and for alkyl naphthalene sulfonates, "Perex NB-L" manufactured by Kao Corporation Examples of special polymer surfactants include “Homogenol L-18” and “Homogenol L-100” manufactured by Kao Corporation.
Examples of the cationic surfactant include quaternary ammonium salts, imidazoline derivatives, and amine salts. Examples of the amphoteric surfactant include betaine-type compounds, imidazolium salts, imidazolines, and amino acids. Is mentioned. Of these, quaternary ammonium salts are preferred, and stearyltrimethylammonium salts are more preferred. Examples of commercially available products include "Acetamine 24" manufactured by Kao Corporation for alkylamine salts, and "Coatamine 24P" and "Coatamine 86W" manufactured by Kao Corporation for quaternary ammonium salts. On the other hand, as the fluorinated surfactant, a compound having a fluoroalkyl or fluoroalkylene group at at least one of terminal, main chain, and side chain is preferable.

  Specifically, for example, 1,1,2,2-tetrafluorooctyl (1,1,2,2-tetrafluoropropyl) ether, 1,1,2,2-tetrafluorooctylhexyl ether, octaethylene glycol Di (1,1,2,2-tetrafluorobutyl) ether, hexaethylene glycol di (1,1,2,2,3,3-hexafluoropentyl) ether, octapropylene glycol di (1,1,2,2 2-tetrafluorobutyl) ether, hexapropylene glycol di (1,1,2,2,3,3-hexafluoropentyl) ether, sodium perfluorododecylsulfonate, 1,1,2,2,8,8, Examples include 9,9,10,10-decafluorododecane, 1,1,2,2,3,3-hexafluorodecane, and the like.

  These commercial products include "BM-1000" and "BM-1100" manufactured by BM Chemie, "MegaFac F142D", "MegaFac F172", "MegaFac F173", and "MegaFac F173" manufactured by Dainippon Ink and Chemicals, Inc. "Fac F183", "Mega Fac F470", "Mega Fac F475", "FC430" and "FC4432" manufactured by Sumitomo 3M, "DFX-18" manufactured by Neos, and the like.

  Examples of the silicone surfactant include “Toray Silicone DC3PA”, “SH7PA”, “DC11PA”, “SH21PA”, “SH28PA”, “SH29PA”, and “SH29PA” manufactured by Dow Corning Toray. "SH30PA", "SH8400", "FZ2122", "TSF-4440", "TSF-4300", "TSF-4445", "TSF-444 (4) (5) (6) (7) 6), "TSF-4460", "TSF-4452", "KP341" manufactured by Silicone, "BYK323", "BYK330" manufactured by BYK-Chemie.

Among these surfactants, a fluorine-based surfactant and a silicone-based surfactant are preferable from the viewpoint of uniformity of the coating film thickness.
The surfactant may be a combination of two or more kinds. Silicone surfactant / fluorine surfactant, silicone surfactant / special polymer surfactant, fluorine surfactant / special polymer surfactant And combinations of agents. Among them, silicone surfactant / fluorine surfactant is preferable.

  In this combination of silicone-based surfactant / fluorine-based surfactant, for example, "TSF4460" manufactured by GE Toshiba Silicones / "DFX-18" manufactured by Neos, "BYK-300" or "BYK-330" manufactured by BYK Chemie. / "S-393" manufactured by Seimi Chemical Co., Ltd., "KP340" manufactured by Shin-Etsu Silicone Co., Ltd. "F-478" or "F-475" manufactured by Dainippon Ink Co., Ltd. "SH7PA" manufactured by Dow Corning Toray Co., Ltd. DS-401 ", Dow Corning Toray" FZ2122 "/ Sumitomo 3M" FC4432 ", Nippon Unicar" L-77 "/ Sumitomo 3M" FC4430 "and the like.

  When the photosensitive resin composition of the present invention contains a surfactant, the content of the surfactant in the photosensitive resin composition is usually 0.001% by mass or more, preferably 0% by mass, based on the total solid content. 0.01% by mass or more, more preferably 0.05% by mass or more, and usually 10% by mass or less, preferably 5% by mass or less, more preferably 1% by mass or less. When the content ratio of the surfactant is equal to or more than the lower limit, the smoothness of the coating film and the uniformity tend to be easily expressed, and when the content is equal to or less than the upper limit, the smoothness and uniformity of the coated film are expressed. It tends to be easy to suppress deterioration of other characteristics.

(F) Solvent The photosensitive resin composition of the present invention is usually blended with (A) an alkali-soluble resin, (B) a compound containing an ethylenically unsaturated group, and (C) a photopolymerization initiator, if necessary. The (D) coloring material, (E) surfactant and (G) other optional components described below are used in a state of being dissolved or dispersed in (F) solvent.
As the solvent (F), a solvent capable of dissolving or dispersing each component constituting the composition and having a boiling point in the range of 100 to 200 ° C is preferably selected. More preferably, it has a boiling point of 120 to 170 ° C. The boiling point here means the boiling point at a pressure of 1013.25 hPa.

  Examples of such a solvent include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol-t-butyl ether, and diethylene glycol monomethyl. Glycol mono such as ether, diethylene glycol monoethyl ether, methoxymethyl pentanol, propylene glycol monoethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monomethyl ether, 3-methyl-3-methoxybutanol, and tripropylene glycol methyl ether Alkyl ethers; ethylene glycol Glycol dimethyl ether, ethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether, glycol dialkyl ethers such as diethylene glycol dibutyl ether; ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate Glycol, such as propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, methoxybutyl acetate, methoxypentyl acetate, dipropylene glycol monomethyl ether acetate, and 3-methyl-3-methoxybutyl acetate. Ethers such as diethyl ether, dipropyl ether, diisopropyl ether, butyl ether, diamyl ether, ethyl isobutyl ether, dihexyl ether; acetone, methyl ethyl ketone, methyl amyl ketone, methyl isopropyl ketone, methyl isoamyl ketone, diisobutyl Ketones such as ketone, methyl isobutyl ketone, cyclohexanone, ethyl amyl ketone, methyl butyl ketone, methyl hexyl ketone, methyl nonyl ketone; ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, propylene glycol, diethylene glycol, dipropylene Monohydric or polyhydric alcohols such as glycol, glycerin; n-pentane; Aliphatic hydrocarbons such as n-octane, diisobutylene, n-hexane, hexene, isoprene, dipentene, dodecane; alicyclic hydrocarbons such as cyclohexane, methylcyclohexane, methylcyclohexene, bicyclohexyl; benzene, toluene , Xylene, aromatic hydrocarbons such as cumene; amyl formate, ethyl formate, ethyl acetate, butyl acetate, propyl acetate, amyl acetate, ethylene glycol acetate, ethyl propionate, propyl propionate, butyl butyrate, Isobutyl butyrate, methyl isobutyrate, ethyl caprylate, butyl stearate, ethyl benzoate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate Linear or cyclic esters such as propyl 3-methoxypropionate, butyl 3-methoxypropionate and γ-butyrolactone; alkoxycarboxylic acids such as 3-methoxypropionic acid and 3-ethoxypropionic acid; butyl chloride, amyl Halogenated hydrocarbons such as chloride; ether ketones such as methoxymethylpentanone; nitriles such as acetonitrile and benzonitrile;

Among the various solvents described above, from the viewpoints of volatility, stability, and solubility of each component, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monoethyl acetate Propyl ether acetate, methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, methyl isopropyl ketone, methyl isoamyl ketone, diisobutyl ketone, methyl isobutyl ketone, cyclohexanone, butyl acetate, propyl acetate, amyl acetate, ethylene glycol acetate, ethylpro Pionate, propyl propionate, butyl butyrate, isobutyl butyrate, methyl isobutyrate, ethyl caprylate, butyl Tearate, ethyl benzoate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, propyl 3-methoxypropionate, butyl 3-methoxypropionate, γ-butyrolactone Propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, methyl isopropyl ketone, methyl isobutyl ketone, cyclohexanone, butyl acetate, propyl acetate , Amyl acetate, ethylene glycol acetate, ethyl propionate, propyl propionate, 3-ethoxypropion Methyl acetate, ethyl 3-ethoxypropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, propyl 3-methoxypropionate, butyl 3-methoxypropionate, and γ-butyrolactone are more preferred. One of these solvents may be used alone, or two or more thereof may be used in combination.
The photosensitive resin composition of the present invention is prepared by using the solvent (e) such that the solid content concentration is usually 5 to 50% by mass, preferably 10 to 30% by mass.

(G) Other Components Other components that can be contained in the photosensitive resin composition of the present invention are described in detail below.
(G-1) Pigment dispersant When the composition of the present invention contains a pigment or the like as the (F) coloring material, it is important for quality stability to finely disperse the coloring material and stabilize the dispersion state. Therefore, it is desirable to add a pigment dispersant.

  As the pigment dispersant, a polymer dispersant having a functional group is preferable, and further, from the viewpoint of dispersion stability, a carboxyl group; a phosphoric acid group; a sulfonic acid group; or a base thereof; a primary, secondary, or tertiary amino acid Groups; quaternary ammonium bases; and polymer dispersants having a functional group such as a group derived from a nitrogen-containing heterocycle such as pyridine, pyrimidine and pyrazine are preferred. Among them, 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 and pyrazine is particularly preferred. By using such a polymer dispersant having a basic functional group, the dispersibility when carbon black is used as a coloring material can be improved, and a high light-shielding property tends to be achieved.

  Examples of the polymer dispersant include a urethane dispersant, an acrylic dispersant, a polyethyleneimine dispersant, a polyallylamine dispersant, a dispersant comprising a monomer having an amino group and a macromonomer, and a polyoxyethylene alkyl ether dispersant. Dispersants, polyoxyethylene diester dispersants, polyether phosphate dispersants, polyester phosphate dispersants, sorbitan aliphatic ester dispersants, aliphatic modified polyester dispersants, and the like can be given.

Specific examples of such dispersants include EFKA (registered trademark, manufactured by EFKA Chemicals, Inc. (EFKA)), Disperbyk (registered trademark, manufactured by BIC Chemie), and Disparon (registered trademark, Kusumoto Chemicals) under trade names. ), SOLSPERSE (registered trademark, manufactured by Lubrizol Corporation), KP (manufactured by Shin-Etsu Chemical Co., Ltd.), Polyflow or Floren (registered trademark, manufactured by Kyoeisha Chemical Co., Ltd.), Ajispar (registered trademark, manufactured by Ajinomoto Fine Techno Co., Ltd.) )).
One of these polymer dispersants may be used alone, or two or more thereof may be used in combination.

  Among these, from the viewpoint of adhesion and linearity when carbon black is used as a coloring material, it is particularly preferable to include a urethane polymer dispersant having a basic functional group and / or an acrylic polymer dispersant. preferable. In particular, a urethane polymer dispersant is preferable in terms of adhesiveness. From the viewpoint of dispersibility and storage stability, a polymer dispersant having a basic functional group and having a polyester and / or polyether bond is preferred.

The weight average molecular weight (Mw) of the polymer dispersant is usually at least 700, preferably at least 1,000, and usually at most 100,000, preferably at most 50,000, more preferably at most 30,000. When the content is not more than the upper limit, even when the pigment concentration is high, the alkali developability tends to be good.
Examples of the urethane-based and acrylic-based polymer dispersants include Disperbyk 160 to 167 and 182 series (all are urethane-based), Disperbyk 2000, 2001, and the like (all are acrylic-based) (all of which are manufactured by Big Chemie). Dispersbyk 167 and 182 are particularly preferred urethane polymer dispersants having a basic functional group and having a polyester and / or polyether bond and having a weight average molecular weight of 30,000 or less.
In addition to the above, as a polymer dispersant having a basic functional group, a block copolymer, a graft copolymer, and the like described in JP-A-2009-14927 and the like can also be used.

  When the photosensitive resin composition of the present invention contains (G-1) a pigment dispersant, the content thereof is not particularly limited, but is preferably 1% by mass based on the total solid content of the photosensitive resin composition. The above, more preferably 3% by mass or more, still more preferably 5% by mass or more, particularly preferably 8% by mass or more, preferably 40% by mass or less, more preferably 30% by mass or less, further more preferably It is at most 20% by mass, particularly preferably at most 15% by mass. The color tone of the pigment tends to be the same concentration as the pigment alone by being equal to or greater than the lower limit, and the light reaching the initiator by light absorption by the pigment is not insufficient by being equal to or less than the upper limit. Tend to be.

(G-2) Thermal Crosslinking Agent When the photosensitive resin composition of the present invention is used as an interlayer insulating film, the composition contains a thermal crosslinking agent for the purpose of improving heat resistance and chemical resistance of the film after heat curing. Is also good. As the thermal crosslinking agent, a known thermal crosslinking agent can be used as long as it undergoes a crosslinking reaction by hard baking after image formation by exposure and development. Specifically, the following may be mentioned, and these may be used alone or in combination of two or more.

(G-2-1) Compound having an epoxy group in the molecule As the compound having an epoxy group in the molecule used in the present embodiment, for example, a monohydroxy compound or a polyhydroxy compound is reacted with epichlorohydrin. (Poly) glycidyl ether compound, polyglycidyl ester compound obtained by reacting (poly) carboxylic acid compound with epichlorohydrin, and (poly) glycidylamine compound obtained by reacting (poly) amine compound with epichlorohydrin And the like, compounds ranging from low molecular weight to high molecular weight.

(G-2-2) Nitrogen-containing heat crosslinkable compound Examples of the nitrogen-containing heat crosslinkable compound include melamine, benzoguanamine, glycoluril, or a compound obtained by reacting urea with formalin, or an alkyl-modified compound thereof. .
Specifically, as an example of a compound obtained by allowing formalin to act on melamine or an alkyl-modified product thereof, "Symel" (registered trademark) 300, 301, 303, 350, 736, 738, 370, 771 manufactured by Cytec Industries, Inc. , 325, 327, 703, 701, 266, 267, 285, 232, 235, 238, 1141, 272, 254, 202, 1156, 1158, "Nikarac" (registered trademark) E-2151, Sanwa Chemical Co., Ltd., MW -100LM, MX-750LM, and the like.

Examples of a compound obtained by allowing formalin to act on benzoguanamine or an alkyl-modified product thereof include "Cymel" (registered trademark) 1123, 1125, and 1128.
Examples of a compound obtained by reacting glycoluril with formalin or an alkyl-modified product thereof include "Symel" (registered trademark) 1170, 1171, 1174, 1172, "Niclac" (registered trademark) MX-270, and the like. Can be.

Examples of a compound obtained by reacting urea with formalin or an alkyl-modified product thereof include "UFR" (registered trademark) 65, 300 and "Niclac" (registered trademark) MX-290 manufactured by Cytec Industries. be able to.
As the (G-2) thermal crosslinking agent in the present invention, a compound having a —N (CH 2 OR) 2 group (wherein, R represents an alkyl group or a hydrogen atom) in the molecule is preferable. A compound obtained by reacting urea or melamine with formalin or an alkyl-modified compound thereof is particularly preferred.

  When the photosensitive resin composition of the present invention contains (G-2) a nitrogen-containing thermally crosslinkable compound as a thermal crosslinking agent, the content ratio of the nitrogen-containing thermally crosslinkable compound in the composition is based on the total solid content. On the other hand, it is usually at most 40% by mass, preferably at most 30% by mass, more preferably at most 20% by mass. When the content is equal to or less than the upper limit, a decrease in the residual film ratio during development and a decrease in resolution tend to be suppressed.

(G-3) Adhesion Aid The photosensitive resin composition of the present invention may contain an adhesion aid for the purpose of improving the adhesion to the substrate. Examples of the adhesion assistant include a silane coupling agent. More specifically, for example, trimethoxysilylbenzoic acid, γ-methacryloxypropyltrimethoxysilane, vinyltriacetoxysilane, vinyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-isocyanatopropyltriethoxy Silane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane and the like. These silane coupling agents may be used alone or in combination of two or more.

  In addition, the silane coupling agent has not only a function as an adhesion assistant but also a function of giving appropriate heat melting (thermal fluidity) to the protective film in heat treatment and improving flatness. Examples of the silane coupling agent blended for such a purpose include a silane coupling agent having an epoxy group. More specifically, for example, γ-glycoxypropylmethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane and the like can be mentioned.

  When the adhesion aid is used, the content of the adhesion aid (G-3) is usually 0.1% by mass or more, and usually 20% by mass, based on the total solid content of the photosensitive resin composition. Or less, preferably 10% by mass or less.

(G-4) Curing Agent When the photosensitive resin composition of the present invention contains (G-2) a thermal cross-linking agent, a curing agent can be further contained for adjusting the curing time and the curing temperature. . Thereby, the curing conditions when the photosensitive resin composition of the present invention is used can be more appropriately selected.

  Such a curing agent is not particularly limited as long as the required function is not impaired, and includes, for example, a benzoic acid compound, a polycarboxylic acid (anhydride), and a polycarboxylic acid (anhydride). Examples include a polymer, a thermal acid generator, an amine compound, a polyamine compound, and a block carboxylic acid. In particular, when the epoxy group-containing compound is contained as a thermal crosslinking agent, it is preferable to use a thermosetting agent.

  One of these curing agents may be used alone, or two or more thereof may be used in combination. Among the curing agents, polycarboxylic acid copolymers and benzoic acid compounds are excellent in improving the adhesion to the support, and monosulfonium salts are excellent in improving the hardness. In particular, a benzoic acid compound is preferable because it has excellent thermosetting properties, high light transmittance, and a low effect of color change due to heat.

  When the photosensitive resin composition of the present invention contains a (G-4) curing agent, the content of the (G-4) curing agent in the photosensitive resin composition is usually 0.05 to the total solid content. It is at least 0.1% by mass, preferably at least 0.1% by mass, usually at most 20% by mass, preferably at most 10% by mass. When the content is not less than the lower limit, the adhesion to the support (substrate) and the hardness tend to be good, and when the content is not more than the upper limit, an increase in the thermal weight loss tends to be suppressed.

(G-5) Thermal Polymerization Inhibitor The photosensitive resin composition of the present invention includes, for example, an optionally substituted o-hydroxybenzophenone, hydroquinone, p-methoxyphenol, 2,6-di-t- A thermal polymerization inhibitor such as butyl-p-cresol can be contained. The content ratio of these (G-5) thermal polymerization inhibitors is usually 10% by mass or less, preferably 2% by mass or less based on the total solids.

(G-6) Plasticizer The photosensitive resin composition of the present invention contains (G-6) a plasticizer such as dioctyl phthalate, didodecyl phthalate, and tricresyl phosphate in an amount of 40% by mass based on the total solid content. It may be contained at a ratio of preferably 20% by mass or less.

(G-7) Polymerization accelerator Further, a polymerization accelerator can be added to the photosensitive resin composition of the present invention, if necessary. Specific examples of the polymerization accelerator include, for example, esters of amino acids such as N-phenylglycine or zwitterionic compounds thereof, 2-mercaptobenzothiazole, 2-mercaptobenzimidazole, 2-mercaptobenzoxazole, 3-mercapto-1, Mercapto group-containing such as 2,4-triazole, 2-mercapto-4 (3H) -quinazoline, β-mercaptonaphthalene, ethylene glycol dithiopropionate, trimethylolpropane tristhiopropionate, and pentaerythritol tetrakisthiopropionate. Compounds, polyfunctional thiol compounds such as hexanedithiol, trimethylolpropane tristhioglyconate, pentaerythritol tetrakisthiopropionate, N, N-dialkylaminobenzoate, N Derivatives such as phenylglycine or its ammonium salt or sodium salt, phenylalanine, or salts such as its ammonium and sodium salts, amino acids or derivatives thereof and the like having an aromatic ring such as derivatives of esters.

  When the photosensitive resin composition of the present invention contains (G-7) a polymerization accelerator, its content is preferably 20% by mass or less, and preferably 1 to 10% by mass, based on the total solid content. Is more preferable.

(G-8) Ultraviolet absorber (G-8) An ultraviolet absorber can be added to the photosensitive resin composition of the present invention, if necessary. The ultraviolet absorber controls the photocuring speed when the film of the photosensitive resin composition of the present invention formed on the substrate is exposed by absorbing a specific wavelength of a light source used for exposure by the ultraviolet absorber. It is added for the purpose of doing. By adding an ultraviolet absorber, effects such as improving the pattern shape after exposure and development and eliminating residues remaining in the non-exposed areas after development are obtained.

  As the ultraviolet absorber, for example, a compound having an absorption maximum between 250 nm and 400 nm can be used. More specifically, for example, Sumisorb 130 (manufactured by Sumitomo Chemical Co., Ltd.), EVERSORB10, EVERSORB11, EVERSORB12 (manufactured by Taiwan Eiko Chemical Industry Co., Ltd.), Tomisorb 800 (manufactured by API Corporation), SEESORB100, SEESORB101, SEESORB103S, SEESORB102, SEESORB102 And benzophenone compounds such as SEESORB105, SEESORB106, SEESORB107, and SEESORB151 (manufactured by Cipro Kasei); Sumisorb 200, Sumisorb 250, Sumisorb 300, Smisorb 340, Sumisorb 350 (manufactured by Sumitomo Chemical), JF77, JF78, JF79, JF80, JF80 Jouhoku Chemical Industry Co., Ltd.), TINUVIN PS, TINUVIN99-2 TINUVIN109, TINUVIN384-2, TINUVIN900, TINUVIN928, TINUVIN1130 (manufactured by Ciba Specialty Chemicals, Inc.), EVERSORB70, EVERSORB71, EVERSORB72, EVERSORB73, EVERSORB74, EVERSORB75, EVERSORB76, EVERSORB234, EVERSORB77, EVERSORB78, EVERSORB80, EVERSORB81 (Taiwan Yongguang Chemical Industry Co., Ltd. Manufactured by Tomisorb 100, Tomisorb 600 (manufactured by API Corporation), SEESORB701, SEESORB702, SEESORB703, SEESORB704, SEESORB706, SEESORB707, SEESORB7 Benzotriazole compounds such as 09 (manufactured by Cipro Kasei); benzoate compounds such as Sumisorb 400 (manufactured by Sumitomo Chemical) and phenyl salicylate; hydroxy such as TINUVIN400, TINUVIN405, TINUVIN460, TINUVIN477DW, TINUVIN479 (manufactured by Ciba Specialty Chemicals). A phenyltriazine compound and the like can be mentioned. Among them, benzotriazole compounds and hydroxyphenyltriazine compounds are preferable, and benzotriazole compounds are particularly preferable.

  When these ultraviolet absorbers are contained, their content is generally 0.01% by mass to 15% by mass, preferably 0.05% by mass to 10% by mass, based on the total solid content of the photosensitive resin composition. % Or less. When the amount is equal to or more than the lower limit, effects such as improvement of the pattern shape and / or the elimination of the residue tend to be easily obtained, and when the amount is equal to or less than the upper limit, a decrease in sensitivity and / or a decrease in remaining film ratio is suppressed. Tend to be able to.

<Method for producing photosensitive resin composition>
The photosensitive resin composition of the present invention is produced according to a conventional method.
Usually, it is preferable that the colorant (D) is previously subjected to dispersion treatment using a paint conditioner, a sand grinder, a ball mill, a roll mill, a stone mill, a jet mill, a homogenizer, or the like. Since the colorant (D) is finely divided by the dispersion treatment, the coating characteristics of the resist are improved.

The dispersing treatment is usually preferably performed in a system in which (D) a colorant, (F) a solvent, and (G) a dispersant as other components and a part or all of (A) an alkali-soluble resin are used in combination ( Hereinafter, the mixture to be subjected to the dispersion treatment and the composition obtained by the treatment may be referred to as “ink” or “pigment dispersion liquid”). In particular, it is preferable to use a polymer dispersant as a dispersant as the other component of (G) because the obtained ink and resist are prevented from thickening over time (excellent in dispersion stability).
As described above, in the step of producing a resist, it is preferable to produce a pigment dispersion containing at least a (D) coloring material, (F) a solvent, and (G) at least a dispersant as another component. As the (D) coloring material, the (F) solvent, and the (G) dispersant as other components that can be used in the pigment dispersion, those described as those that can be used in the photosensitive resin composition, respectively, can be used. It can be preferably adopted.

When a dispersion treatment is performed on a liquid containing all components to be mixed with the photosensitive resin composition, a highly reactive component may be denatured due to heat generated during the dispersion treatment. Therefore, it is preferable to perform the dispersion treatment in a system containing a polymer dispersant.
When the colorant (D) is dispersed by a sand grinder, glass beads or zirconia beads having a particle diameter of about 0.1 to 8 mm are preferably used. The dispersing conditions are generally such that the temperature is from 0 ° C to 100 ° C, preferably from room temperature to 80 ° C. The dispersion time is appropriately adjusted because the appropriate time varies depending on the composition of the liquid, the size of the dispersion processing apparatus, and the like. Controlling the gloss of the ink so that the 20-degree specular gloss (JIS Z8741) of the resist falls within the range of 50 to 300 is a measure of dispersion. When the glossiness of the resist is low, the dispersion treatment is not sufficient, and coarse pigment (coloring material) particles often remain, and the developability, adhesion, resolution, and the like may be insufficient. . Further, when the dispersion treatment is performed until the gloss value exceeds the above range, the pigment is crushed and a large number of ultrafine particles are generated, so that the dispersion stability tends to be impaired.

The dispersed particle size of the pigment dispersed in the ink is usually from 0.03 to 0.3 μm, and is measured by a dynamic light scattering method or the like.
Next, the ink obtained by the dispersion treatment and the other components contained in the resist are mixed to form a uniform solution. In the resist manufacturing process, fine dust is often mixed in the liquid, and if they are mixed, a uniform film tends not to be obtained, so the obtained resist should be filtered using a filter or the like. desirable.

[Cured product (How to use photosensitive resin composition)]
The cured product of the present invention is obtained by curing the photosensitive resin composition of the present invention.
The photosensitive resin composition of the present invention is suitably used, for example, for image forming applications for producing various members such as a liquid crystal display device, and a cured product obtained by curing the photosensitive resin composition is used as the various members. be able to. That is, it is suitably used for forming various cured products provided in a liquid crystal display device such as a pixel in a color filter, a black matrix, a photo spacer, and a rib (liquid crystal alignment control projection).

  Hereinafter, these will be described more specifically.

<Production method of color filter>
Next, a method for producing a color filter using the photosensitive resin composition of the present invention will be described. In the following, a case where the photosensitive resin composition of the present invention is used for forming a pixel and a black matrix will be described as an example. Liquid crystal alignment control projections) can also be used.

In the following description, an example will be described in which the photosensitive resin composition of the present invention is used for forming pixels (RGB) and a black matrix (BM) in a color filter.
In order to manufacture a color filter, first, after coating and drying the photosensitive resin composition of the present invention on a transparent substrate, the coated film is exposed and developed by various exposure methods as described above, The resin BM is formed by heat curing or light curing according to the conditions. Further, the same operation is repeated for each of the three colors RGB to form pixels and form color filters.

{1} Transparent substrate The transparent substrate used here is a transparent substrate for a color filter, and its material is not particularly limited. For example, polyester such as polyethylene terephthalate, polypropylene, polyolefin such as polyethylene, polycarbonate, etc. And thermoplastic resin sheets such as polymethyl methacrylate and polysulfone, thermosetting plastic sheets such as epoxy resin, polyester resin and poly (meth) acrylic resin, and various glass plates. Particularly, a glass plate and a heat-resistant plastic sheet are preferably used from the viewpoint of heat resistance. Such a transparent substrate may be subjected to a corona discharge treatment, an ozone treatment, a thin film treatment of various polymers such as a silane coupling agent or a urethane polymer, etc. in advance to improve physical properties such as surface adhesiveness. .

{2} Coating and drying process The coating method of the photosensitive resin composition on the transparent substrate is not particularly limited, but is usually performed using a coating device such as a spinner, a wire bar, a flow coater, a die coater, a roll coater, and a spray. Will be In the drying after the application, a hot plate, an IR oven, a convection oven, or the like, or a combination thereof can be used. Preferred drying conditions are 20 to 150 ° C., and the drying time is 10 seconds to 60 minutes. The thickness of the resin BM after coating and drying is preferably in the range of 0.1 to 2 μm, preferably 0.1 to 1.5 μm, and more preferably 0.1 to 1 μm. The resin BM formed from the photosensitive resin composition of the present invention preferably has an optical density of 3.0 or more at a film thickness of 1 μm from the viewpoint of light shielding properties. Further, it is advantageous that the 20-degree gloss value of the BM is 100 to 200 as an index of the dispersion state of solids such as pigments.

{3} Exposure and development process The light source used for exposure is, for example, a lamp light source such as a xenon lamp, a halogen lamp, a tungsten lamp, a high-pressure mercury lamp, an ultra-high-pressure mercury lamp, a metal halide lamp, a medium-pressure mercury lamp, a low-pressure mercury lamp, an argon ion laser, and a YAG laser. A laser light source such as a laser, an excimer laser, and a nitrogen laser is exemplified. When only the wavelength of the specific irradiation light is used, an optical filter can be used.

  The developer used for the development treatment is not particularly limited as long as it is a solvent capable of dissolving the unexposed resist film. For example, organic solvents such as acetone, methylene chloride, trichlene, and cyclohexanone can be used. However, since many organic solvents have environmental pollution, harm to the human body, and danger of fire, it is preferable to use an alkali developing solution having no such danger.

Examples of such an alkaline developer include inorganic alkali agents such as sodium carbonate, potassium carbonate, sodium silicate, potassium silicate, sodium hydroxide, and potassium hydroxide, or diethanolamine, triethanolamine, and tetraalkylammonium hydroxide salts. And an aqueous solution containing an organic alkaline agent.
If necessary, the alkali developer may contain a surfactant, a water-soluble organic solvent, a low-molecular compound having a hydroxyl group or a carboxyl group, or the like. In particular, a surfactant is preferably added because many of them have an effect of improving the developing property, the resolution and the background stain. For example, as a surfactant for a developer, an anionic surfactant having a sodium naphthalenesulfonate group, a sodium benzenesulfonate group, a nonionic surfactant having a polyalkyleneoxy group, a cation having a tetraalkylammonium group Surfactants and the like.

The development processing method is not particularly limited, but is usually performed at a development temperature of 10 to 50 ° C, preferably 15 to 45 ° C, by a method such as immersion development, spray development, brush development, or ultrasonic development.
As described above, the application, drying, exposure, and development of the photosensitive resin composition are repeatedly performed for each of the three colors BM and RGB to produce a color filter. The photosensitive resin composition of the present invention can be used for the formation of BM and the formation of RGB three-color pixels.

  In the case where a pixel of a color filter is formed using the photosensitive resin composition of the present invention, exposure and development are performed without providing an oxygen barrier layer of polyvinyl alcohol or the like because of extremely high sensitivity and high resolution. To form an image.

<Other uses>
The photosensitive resin composition of the present invention can be used for forming photo spacers, ribs (liquid crystal alignment control projections), and the like, in addition to the BM and RGB three color pixels of the color filter as described above. Hereinafter, this usage pattern will be described.

<Photo spacer applications>
The photospacer is formed by applying the photosensitive resin composition of the present invention to a substrate, drying, exposing, developing, and thermosetting. In forming the photo spacer, the photosensitive resin composition of the present invention is applied to a substrate. The coating method can be performed by a conventionally known method, for example, a spinner method, a wire bar method, a flow coating method, a die coating method, a roll coating method, a spray coating method, or the like. Above all, according to the die coating method, the use amount of the coating liquid (photosensitive resin composition) is greatly reduced, and there is no influence of mist or the like attached at the time of coating by the spin coating method, and the generation of foreign substances is suppressed. It is preferable from a comprehensive point of view.

The coating amount is adjusted so as to be in a range of usually 0.5 to 10 μm, preferably 1 to 8 μm, particularly preferably 1 to 5 μm as a dry film thickness. 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 in the height of the spacer is large, an uneven defect will occur in the liquid crystal panel.
In addition, as a coating method other than the above, for example, the photosensitive resin composition of the present invention may be supplied on a substrate in a pattern by an inkjet method or a printing method.

  The drying of the photosensitive resin composition after the application is preferably performed using a hot plate, an IR oven, a convection oven, or the like. Further, a reduced pressure drying method in which drying is performed in a reduced pressure chamber without increasing the temperature may be combined. Drying conditions can be appropriately selected according to the type of the solvent component, the performance of the dryer used, and the like. Drying conditions are usually selected at a temperature of 40 to 100 ° C. for 15 seconds to 5 minutes, and preferably at a temperature of 50 to 90 ° C., depending on the type of the solvent component, the performance of the dryer used, and the like. It is selected in the range of 30 seconds to 3 minutes.

  Exposure is performed by overlaying a negative mask pattern on the coating film of the photosensitive resin composition, and irradiating an ultraviolet or visible light source through the mask pattern. The composition may be cured in a pattern by a scanning exposure method using laser light. The light source used for the above exposure is not particularly limited. As the light source, for example, a lamp light source such as a xenon lamp, a halogen lamp, a tungsten lamp, a high-pressure mercury lamp, an ultra-high-pressure mercury lamp, a metal halide lamp, a medium-pressure mercury lamp, a low-pressure mercury lamp, a carbon arc, a fluorescent lamp, an argon ion laser, a YAG laser, Laser light sources such as an excimer laser, a nitrogen laser, a helium cadmium laser, a blue-violet semiconductor laser, and a near-infrared semiconductor laser are exemplified. When irradiating with light of a specific wavelength, an optical filter can be used.

  After the above exposure, an image pattern can be formed on the substrate by development using an aqueous solution containing an alkaline compound and a surfactant or an organic solvent. The aqueous solution may further contain an organic solvent, a buffer, a complexing agent, a dye or a pigment. Examples of the alkaline compound include sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium carbonate, potassium carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, 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), choline and the like. Machine alkaline compounds. These alkaline compounds may be a mixture of two or more.

  Examples of the surfactant include nonionic surfactants such as polyoxyethylene alkyl ethers, polyoxyethylene alkyl aryl ethers, polyoxyethylene alkyl esters, sorbitan alkyl esters, and monoglyceride alkyl esters, and alkylbenzene sulfonic acid. Examples include anionic surfactants such as salts, alkyl naphthalene sulfonates, alkyl sulfates, alkyl sulfonates, sulfosuccinate salts, and amphoteric surfactants such as alkyl betaines and amino acids.

  Examples of the organic solvent include isopropyl alcohol, benzyl alcohol, ethyl cellosolve, butyl cellosolve, phenyl cellosolve, propylene glycol, diacetone alcohol, and the like. The organic solvent can be used alone or in combination with the aqueous solution. The substrate after the development is preferably subjected to a heat curing treatment. In this case, the temperature of the thermosetting treatment is selected in the range of 100 to 280C, preferably in the range of 150 to 250C, and the time is selected in the range of 5 to 60 minutes.

<Rib (liquid crystal alignment control projection) application>
The ribs (liquid crystal alignment control projections) are projections formed on a transparent electrode in order to improve the viewing angle of the liquid crystal display device. Is used to orient the liquid crystal in multiple directions.
In order to form a rib with the photosensitive resin composition of the present invention, first, the photosensitive resin composition of the present invention is formed on a transparent substrate having a thickness of usually 0.1 to 2 mm formed by depositing ITO on a color filter. Coating is performed using a coating device such as a spinner, a wire bar, a flow coater, a die coater, a roll coater, and a spray. The coating thickness of the composition is usually 0.5 to 5 μm. After drying the coating film made of the composition, the coating film is exposed by various exposure methods as described above. After exposure, an image is formed by removing an unexposed (uncured) portion by development. Usually, images obtained after development are required to have fine line reproducibility in a width of 5 to 20 μm, and there is a tendency that higher definition fine line reproducibility is required from the demand for high-quality displays. In order to stably reproduce high-definition fine lines, the cross-sectional shape of the fine line image after development is preferably a rectangular shape in which the contrast between the non-image portion and the image portion is clear. The rectangular shape is preferable because a development margin such as a development time, a development solution elapse, and a physical stimulus of a development shower is widened.

When the photosensitive resin composition of the present invention is used, the image after development usually has a cross-sectional shape close to a rectangular shape. It is preferable to carry out a heat treatment in order to make this into an arch shape required for the shape of the rib. The temperature of the heat treatment is usually at least 150 ° C, preferably at least 180 ° C, more preferably at least 200 ° C, usually at most 400 ° C, preferably at most 300 ° C, more preferably at most 280 ° C. The time of the heat treatment is usually 10 minutes or more, preferably 15 minutes or more, more preferably 20 minutes or more, usually 120 minutes or less, preferably 60 minutes or less, and more preferably 40 minutes or less. By performing the heat treatment under such conditions, the rectangular cross-sectional shape is transformed into an arch shape, and a rib having a width of 0.5 to 20 μm and a height of 0.2 to 5 μm is formed.
The range of the deformation during heating can be adjusted by appropriately adjusting the composition of the photosensitive resin composition and the heating conditions. Specifically, a contact angle (W1) formed from the side surface of the thin line image (having a rectangular cross section) and the substrate surface before heating, and a contact angle formed from the side surface of the fine line image and the substrate surface after the heat treatment. When (W2) is compared, W1 / W2 is usually 1.2 or more, preferably 1.3 or more, more preferably 1.5 or more, usually 10 or less, preferably 8 or less. The higher the heating temperature or the longer the heating time, the larger the deformation ratio tends to be. On the contrary, the lower the heating temperature or the shorter the heating time, the lower the deformation ratio.

<Application for batch formation>
Further, the photosensitive resin composition of the present invention can also be used for a method of simultaneously forming cured products having different heights and shapes with the same material (batch forming method).
As the cured product here, for example, in addition to the above-mentioned photospacer and rib, a sub-photospacer (a photospacer having a pattern height slightly lower than that of a normal photospacer), an overcoat (protective film) and the like can be mentioned. . Examples of the combination of the cured products having different heights and shapes include, for example, a combination of a photospacer and a sub-photospacer, a photospacer and a rib, a photospacer and an overcoat, and the photosensitive resin composition of the present invention simultaneously uses these. It can also be used for a collective formation method.

  The methods such as coating, drying, exposure, development, and heat curing used in the batch formation method are the same as those described in the above-described method for forming the photo spacer and the rib, but in the exposure step, the amount of transmitted light is plural. It is preferable to use a halftone mask or the like having a plurality of openings adjusted to the types. By using a halftone mask and adjusting the exposure amount to be suitable for each cured product, cured products having different heights and shapes can be formed simultaneously. Further, it is also possible to collectively form cured products having different heights and shapes by curing the composition in a pattern by a scanning exposure method using a laser beam.

[Color filter]
The color filter of the present invention includes the cured product of the present invention as described above, for example, on a glass substrate as a transparent substrate, a black matrix, red, green, blue pixel coloring layer, and an overcoat layer Are laminated, a spacer is formed, and then an alignment film is formed. As the alignment film, a resin film such as polyimide is preferable.

[Image display device]
An image display device of the present invention has the above-described color filter. The image display device is not particularly limited as long as it displays an image or a video, and examples thereof include a liquid crystal display device and an organic EL (Electro Luminesence) display described later.

[Liquid crystal display]
The liquid crystal display device of the present invention is manufactured by using the above-described cured product of the present invention, and is not particularly limited in the order of forming or forming positions of the color pixels and the black matrix.
For example, a black matrix is provided on a TFT element substrate, red, green, and blue pixels are formed. If necessary, an overcoat layer is formed, and then a transparent image of ITO, IZO, or the like is further formed on the image. An electrode is formed and used as a part of components such as a color display and a liquid crystal display. In some applications, such as the planar alignment type driving method (IPS mode), the transparent electrode may not be formed.

  A liquid crystal display device usually forms an alignment film on a color filter, sprays spacers on the alignment film, or forms the spacer of the present invention, and then forms a liquid crystal cell by bonding to a counter substrate. The liquid crystal is injected into the liquid crystal cell and connected to the counter electrode to complete the liquid crystal cell.

Next, the present invention will be described more specifically with reference to Examples and Comparative Examples, but the present invention is not limited to the following Examples as long as the gist of the present invention is not exceeded.
<Synthesis of photopolymerization initiator>
(Example 1)
(1-1 Friedel-Crafts reaction)

  14.2 g (107 mmol) of aluminum chloride and 50 ml of 1,2-dichloroethane were placed in a 500-ml four-necked round-bottomed flask under a nitrogen atmosphere, and the mixture was stirred with a mechanical stirrer while keeping the inside of the system at 5 ° C. or lower in an ice bath. 4.9 g (47 mmol) of noyl chloride were charged. After 65 minutes, 50 ml of a 1,2-dichloroethane solution in which 8.1 g (33 mmol) of N-ethyl-3-nitrocarbazole was dissolved was slowly added dropwise, followed by stirring for 2 hours. After confirming the disappearance of the raw materials by liquid chromatography (LC), the reaction solution was added to 200 ml of crushed ice, and after the ice melted, fold-folded and filtered to collect the filtrate. After dehydration by adding sodium, folds and filtration were performed to remove sodium sulfate. Thereafter, 1,2-dichloroethane as a solvent was distilled off under reduced pressure using a rotary evaporator to recover 6.5 g of compound (1). . The yield was 63% in terms of charged mol of N-ethyl-3-nitrocarbazole as a raw material.

(1-2 Amination reaction and acylation reaction)

  Under a nitrogen atmosphere, 1.4 g (5 mmol) of compound (1), 0.8 g (11 mmol) of isobutylamine, 0.7 g (5 mmol) of potassium carbonate, and 15 ml of acetonitrile were placed in a 100-ml four-necked round-bottomed flask, and the oil was stirred using a mechanical stirrer. The mixture was heated and stirred in the bath so that the internal temperature became 50 ° C. for 25 minutes. After confirming the disappearance of the compound (1) and the formation of the compound (2) by LC, the mixture was allowed to cool, the oil bath was removed, the ice bath was replaced, and the mixture was cooled. ), 2.1 g (17 mmol) of isovaleric chloride was added dropwise, and the mixture was stirred for 40 minutes while keeping the temperature at 5 ° C. or lower. Thereafter, the reaction solution was added to the crushed ice, and the resulting precipitate was collected. Since unreacted compound (2) was confirmed by LC, it was again charged into the flask, and acetonitrile 15 ml, triethylamine 0.7 ml (5 mmol) were added. ), And 0.9 g (7 mmol) of isovaleric chloride was added dropwise at 5 ° C or lower, and the mixture was reacted for 1 hour. The disappearance of the compound (2) was confirmed by LC, and the reaction solution was added to crushed ice, and the compound (3) precipitated and solidified was recovered. The recovered compound (3) was 2.4 g, and the yield was 99% in terms of the charged mole of the compound (1) as a raw material. Amination and acylation were completed in tens of minutes, and both reacted quantitatively. Furthermore, since the reaction can be performed in the same kiln, two reactions can be easily performed.

(1-3 Oximation reaction)

Under a nitrogen atmosphere, 2.4 g (4.6 mmol) of compound (3), 0.64 g (9.2 mmol) of hydroxylamine hydrochloride, and 11 ml of N, N-dimethylformamide were placed in a 100-ml four-necked round-bottomed flask, and magnetized under nitrogen. The internal temperature was set to 80 ° C. by an oil bath using a tick stirrer, and the mixture was heated and stirred for 2 hours. After confirming by LC that the compound (3) had disappeared, the mixture was allowed to cool. The amount of hydroxylamine hydrochloride used was 2.0 equivalents relative to compound (3).
After returning to room temperature, the reaction solution was added to crushed ice, the resulting precipitate was recovered, washed with water, filtered, and air-dried at room temperature under atmospheric pressure to recover 1.6 g of compound (4). . The yield was 71% in terms of the charged mole of compound (3) as a raw material.

(1-4 acetylation reaction)

  Under a nitrogen atmosphere, 1.5 g (3 mmol) of compound (4), 15 ml of ethyl acetate, and 0.5 ml (4 mmol) of triethylamine were put into a 100-ml four-necked round-bottomed flask, and cooled and stirred at 5 ° C. or lower with a magnetic stirrer. Then, 0.7 g (9 mmol) of acetyl chloride was added, and the mixture was stirred for 3.5 hours while keeping the temperature at 5 ° C. or lower. After confirming the disappearance of the compound (4) by LC, the reaction solution was added to crushed ice to collect an organic layer, which was filtered through a paper filter through sodium sulfate, and the solvent was distilled off to recover 1.9 g of a crude product. The mixture was dissolved using 2 ml of a mixture of ethyl acetate: n-hexane = 1: 1 (volume ratio), insolubles were removed by suction filtration, the filtrate was evaporated, and column chromatography was performed using silica gel (developing solvent: acetic acid). Purification was performed with ethyl: n-hexane 1: 1 (by volume) to recover 0.55 g of compound A. The yield was 34% in terms of mol of compound (4) as a raw material.

(Example 2)
A compound was obtained in the same manner as in Example 1 except that the same amount of 2-ethylhexylamine was used in place of isobutylamine and that the same amount of propionyl chloride was used instead of isovaleric chloride in 1-2 of Example 1. B was obtained.

(Example 3)
Compound C was prepared in the same manner as in Example 1 except that the same amount of isopentylamine was used in place of isobutylamine and that the same amount of acetyl chloride was used instead of isovaleric chloride in 1-2 of Example 1. I got

(Example 4)
In 1-2 of Example 1, the same procedure was performed as in Example 1, except that the same amount of isopentylamine was used instead of isobutylamine and the same amount of isobutyryl chloride was used instead of isovaleric acid chloride. Compound D was obtained.

(Example 5)
A compound was prepared in the same manner as in Example 1, except that the same amount of isobutylamine was used in place of isobutylamine and that the same amount of trifluoroacetyl chloride was used instead of isovaleric chloride in 1-2 of Example 1. E was obtained.

(Comparative Example 1)

  1.4 g (11 mmol) of aluminum chloride and 10 ml of ethane dichloride were charged, and 0.8 g (5 mmol) of cinnamoyl chloride was added under ice-cooling at 5 ° C. or lower, followed by 1.0 g (4 mmol) of N-ethyl-3-nitrocarbazole. Of ethane dichloride in 8 ml was gradually added dropwise and stirred at 5 ° C. for 1 hour. After confirming the disappearance of N-ethyl-3-nitrocarbazole as a raw material by LC, the reaction solution was added to 50 ml of ice water, insolubles were filtered, 10 ml of ethane dichloride was added, and the mixture was separated to collect an organic layer. . The organic layer was washed with a saturated saline solution (10 ml × 2), a 1N-NaOH aqueous solution (10 ml × 2), and a saturated saline solution (10 ml × 2), and then dried over anhydrous magnesium sulfate and dried. After filtration, the solvent was distilled off, and 1.1 g of the target compound (i) was recovered. The yield was 69% in terms of mol of charged N-ethyl-3-nitrocarbazole as a raw material.

1.00 g (3 mmol) of compound (i), 0.5 g (7 mmol) of hydroxylamine hydrochloride, 0.8 ml (5 mmol) of triethylamine, and 5 ml of ethane dichloride were added, and the mixture was stirred at 70 ° C. for 3 hours. After confirming by LC that the compound (i) had disappeared, the mixture was allowed to cool, cooled to room temperature, and the precipitated solid was filtered and washed with isopropyl alcohol to obtain 0.6 g of the compound (ii). The yield was 57% in terms of the charged mole of compound (i).
0.6 g (1 mmol) of the compound (ii) and 1 ml (10 mmol) of triethylamine were dissolved in 10 ml of ethyl acetate, and 0.56 g (7 mmol) of acetyl chloride was added at room temperature. After stirring at room temperature for 1 hour, disappearance of compound (ii) was confirmed by LC, and then 1 ml of water was added. After liquid separation, the organic layer was washed with a saturated aqueous solution of sodium hydrogencarbonate (5 ml × 2) and a saturated saline solution (5 ml × 2), dried over anhydrous magnesium sulfate, and dried. After filtration, the solvent was distilled off, and 0.11 g of Comparative Compound 1 was recovered. The yield was 14% in terms of the charged mole of compound (ii). LCMS (ESI, posi) m / z 544 ((M + C 29 H 28 N 4 O 7)

(Reference example)
(3-1 Oxime formation)

Under a nitrogen atmosphere, 0.7 g (1 mmol) of the upper compound (5), 0.14 g (2 mmol) of hydroxylamine hydrochloride, and 8 ml of N, N-dimethylformamide were placed in a 50-ml four-necked round-bottomed flask, and a magnetic stirrer was placed under nitrogen. Using an oil bath, the internal temperature was set to 80 ° C., and the mixture was heated and stirred for 3.5 hours. Since the reaction was not completely extinguished, 0.16 g (2 mmol) of hydroxylamine hydrochloride was added, and the mixture was heated and stirred for 3 hours. Since it was confirmed by LC that the compound (5) as a raw material remained, 0.11 g (2 mmol) of hydroxylamine hydrochloride was added for 2 hours, and 0.19 g (3 mmol) of hydroxylamine hydrochloride was further added, followed by heating and stirring for 1 hour. did. Since compound (5) still showed an area% by LC of less than 14%, the reaction was continued while appropriately adding hydroxylamine hydrochloride. After a total of 0.90 g (13 mmol) of hydroxylamine hydrochloride for a total of 16 hours, the reaction was terminated after confirming by LC that the starting material (5) had disappeared. The added hydroxylamine hydrochloride was 10.4 times the reaction substrate.
After allowing to cool to room temperature, the mixture was added to ice water, the resulting precipitate was collected, washed with water, and dried under reduced pressure at a set temperature of 38 ° C. to recover 0.54 g of compound (6). The yield was 79% in terms of charged mol of compound (5) as a raw material. Since the reaction time in oximation was long and it was necessary to add a considerable amount of hydroxylamine hydrochloride, mass production was found to be difficult.

(3-2 acetylation)

  Under a nitrogen atmosphere, 0.54 g of compound (6), 5 ml of ethyl acetate, and 0.2 ml of triethylamine were put into a 50-ml four-necked round-bottomed flask, and cooled to 5 ° C. or lower with a magnetic stirrer. Was added, and the mixture was stirred for 4 hours while keeping the temperature at 5 ° C or lower. After completion of the reaction, the reaction mixture was released into ice water, the precipitate and a viscous solid were collected, and purified by column chromatography using silica gel (developing solvent: ethyl acetate: n-hexane 1: 1 (volume ratio)) to obtain Reference Compound 1 in 0%. .44 g were recovered. The yield was 76% in terms of mol of compound (6) as a raw material.

  The chemical structures of Compounds A to E and Comparative Compound 1 are described below.

  Table 1 shows the reaction conditions for oximation. Reference compound 1 of an aromatic substituent had to react for 10 hours or more of hydroxylamine hydrochloride and had to react for a long period of 16 hours. 5 has a low equivalent weight, and many react in a few hours.

Compounds A to E, Comparative Compound 1, and Reference Compound 1 were subjected to absorption maximum wavelength measurement, solubility test, thermal decomposition temperature measurement, and plate making characteristic evaluation. Table 2 summarizes the measurement results of the absorption maximum wavelength (λ _max ), solubility, and gram extinction coefficient.

<Maximum absorption wavelength measurement>
Compounds A to E, Comparative Example Compound 1, and Reference Compound 1 were each weighed, and a solution (solution concentration: 1000 ppm by mass) diluted with propylene glycol monomethyl ether acetate (hereinafter abbreviated as PGMEA) using a 100 ml volumetric flask was used. The sample was put into a quartz cell, and the absorption spectrum was measured in a wavelength range of 250 to 500 nm with a Hitachi spectrophotometer U-4100. The value of the maximum absorption wavelength (λ _max ) was read from the obtained absorption spectrum.
The method of calculating the gram extinction coefficient is as follows. When the monochromatic light having the intensity I ₀ passes through the material layer and reaches the intensity I, the absorption intensity of the material layer is the absorbance A = −log (I / I ₀ ), and the absorbance A is the thickness 1 of the solution layer. (L) and proportional to the concentration c of the solution (Beer's law). The equation established at that time is A = ε · l (ell) (cm) · c (mol / l (liter)), where ε is called the molar extinction coefficient and permeates 1 cm of a 1 mol / l (liter) solution. Absorbance. The gram extinction coefficient is a coefficient obtained by dividing ε by the molecular weight. It can be said that as this value is larger, the absorption per gram is larger. Table 2 shows the gram extinction coefficient at the absorption maximum wavelength (λ _max ).

<Solubility test>
The solubility of each compound in PGMEA was measured as follows.
Each compound was added to PGMEA until a residual amount of the solution was generated, and ultrasonic treatment was performed at 30 ° C. for 30 minutes. After standing at 5 ° C. for 24 hours, the mixture was centrifugally filtered with a 0.1 μm filter using a micro centrifuge (centrifugal force: 5200 × g). The obtained saturated solution was diluted to an appropriate concentration, and the solubility of each compound was calculated from the relationship with the previously measured extinction coefficient.

<Pyrolysis temperature measurement>
The thermal behavior of each compound was measured with TG / DTA6200 manufactured by SII under an Air atmosphere. The temperature was raised at a rate of 10 ° C./min, and the temperature was raised to 30 to 500 ° C. The pyrolysis temperature was read from the intersection of the tangents of the TG curve weight loss curves.

From Table 2, all compounds have λ _max of 365 nm or more and have a long-wavelength maximum absorption peak. Therefore, they absorb more light of 365 nm (i-line) of a high-pressure mercury lamp used for photocuring and have high sensitivity. It was suggested that Further, since the g extinction coefficient was large, it was suggested that the light absorption was large and the sensitivity was high when compared with the same mass. In particular, the compounds of Examples 1 to 5 maintain the absorption wavelength without significantly changing the electron density of the π-electron system by adopting a skeleton based on a saturated hydrocarbon as a substituent of the carbazole ring, It is also considered that the molecular weight was prevented from becoming excessively large, and the g extinction coefficient could be increased.

Further, the compounds of Examples 1 to 5 have a higher thermal decomposition temperature than the compound of Comparative Example 1. It is considered that the compounds of Examples 1 to 5 are rigid because the branched alkyl chains are bulky in the chemical structure, and the thermal decomposition temperature is high. If the thermal decomposition temperature is high, it will not be decomposed even by a heat treatment or the like in a subsequent step. If the thermal decomposition temperature is low, it may decompose during heat treatment to generate gas or cause distortion of the resist pattern, but in the compounds of Examples 1 to 5, on the other hand, such problems are suppressed. It was suggested that this could be done.
Furthermore, the compounds of Examples 1 to 5 have higher solubility in PGMEA than the compound of Comparative Example 1. It is considered that the compounds of Examples 1 to 5 have high solubility in PGMEA because their chemical structures employ a skeleton based on a saturated hydrocarbon.

<Evaluation of plate making characteristics>
The components of the photosensitive resin composition prepared for evaluating plate making characteristics are as follows.

<Alkali-soluble resin-I>
The mixture was stirred while replacing 145 parts by mass of propylene glycol monomethyl ether acetate with nitrogen, and heated to 120 ° C. 10 parts by mass of styrene, 85.2 parts by mass of glycidyl methacrylate and 66 parts by mass of monomethacrylate having a tricyclodecane skeleton (FA-513M manufactured by Hitachi Chemical Co., Ltd.) were added dropwise thereto, and 2,2′-azobis-2-methyl was added. 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, and 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. Thereafter, 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 thus obtained alkali-soluble resin-I had a weight average molecular weight Mw of about 8400 and an acid value of 80 mgKOH / g as measured by GPC.

<Alkali-soluble resin-II>
"ZCR-1642H" manufactured by Nippon Kayaku Co., Ltd. (MW = 6500, acid value = 98 mg-KOH / g)
<Alkali-soluble resin-III>
A resin obtained by reacting a reaction product of an epoxy compound having the following structure with acrylic acid with trimethylolpropane (TMP) and biphenyltetracarboxylic dianhydride (BPDA) (MW = 3500-4500, acid value = about 110 mg-KOH / g)

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

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

<Pigment derivative>
"Solsperse12000" manufactured by Lubrizol

<Solvent-I>
PGMEA: Propylene glycol monomethyl ether acetate <Solvent-II>
MB: 3-methoxybutanol <Photopolymerizable monomer-I>
DPHA: Nippon Kayaku Co., Ltd. dipentaerythritol hexaacrylate <additive-I>
KAYAMER PM-21 (methacryloyl group-containing phosphate) manufactured by Nippon Kayaku Co., Ltd.
<Surfactant-I>
Mega Fuck F-559 manufactured by DIC

<Pigment dispersion liquids-1 and 2>
The pigment, the dispersant, the dispersing aid, the alkali-soluble resin, and the solvent shown in Table 3 were mixed so as to have the mass ratio shown in Table 3. This solution was subjected to a dispersion treatment at 25 to 45 ° C. for 3 hours using a paint shaker. As the beads, zirconia beads having a diameter of 0.5 mm were used, and a mass 2.5 times that of the dispersion was added. After the dispersion, the beads and the dispersion were separated by a filter to prepare Pigment Dispersions-1 and 2. The amount of the dispersant was adjusted so that the viscosity of the obtained pigment dispersion was in the range of 6 to 8 mPa · s.

<Photosensitive resin composition>
Using the pigment dispersion prepared above, each component was added so that the ratio in the solid content became the mixing ratio in Table 4, and PGMEA was further added so that the solid content became 20% by mass, followed by stirring and dissolving. Thereafter, the solution was filtered through a 5 μm filter to prepare a photosensitive resin composition. In addition, the mass part of the photosensitive resin composition in Table 4 shows the mass of solid content. Table 4 also shows the results of plate making characteristics evaluated by the method described below.

<Plate making characteristics>
The prepared photosensitive resin composition was applied to a glass substrate by a spin coater so as to have a final film thickness of 2.2 μm, dried under reduced pressure for 1 minute, and then dried at 80 ° C. for 90 seconds on a hot plate.
This sample was image-exposed (illuminance: 30 mW / cm ² , exposure amount: 50 mJ / cm ² ) through a negative type mask having a linear pattern with an opening of 10 μm, using a high-pressure mercury lamp through a filter that cuts light of 330 nm or less. At this time, the distance between the sample and the mask was 150 μm. Thereafter, spray development was performed at a temperature of 23 ° C. using a developer having a KOH concentration of 0.04% by mass. The development time was 1.5 times the dissolution time of the unexposed part. Next, the linear pattern was cured by heating at 230 ° C. for 20 minutes. Table 3 shows the results of the line width of the linear pattern.

From Table 4, all of the linear patterns of Examples 1 to 5 have a wide line width with respect to the opening width of the mask, which indicates that compounds 1 to 5 have high sensitivity. all right.
On the other hand, in Comparative Example 1, the line width could not be evaluated because a linear pattern could not be obtained during the spray development without dissolving in a developer having a predetermined concentration. This is considered to be because the low solubility of the comparative compound 1 resulted in filtration of the prepared solution during the filtration process, resulting in a shortage of the initiator.

  In the reference example, although dissolved in the developer, the film formability was poor, and the linear pattern peeled off from the substrate during development, making it impossible to evaluate the line width. This is probably because Reference Compound 1 had low sensitivity due to the low gram extinction coefficient.

Claims (7)

A photopolymerization initiator represented by the following general formula (I).

(In the general formula (I), R ¹ and R ² each independently represent an alkyl group which may have a substituent. R ³ represents an alkylene group which may have a substituent.
R ⁴ represents an alkyl group which may have a substituent.
R ⁵ represents an optionally substituted alkyl group having 5 or less carbon atoms.
R ⁶ and R ⁷ each independently represent an arbitrary substituent. m and n each independently represent 0 or 1. ) The photopolymerization initiator according to claim 1, wherein in the general formula (I), at least one of R ¹ and R ² has a branched chain. A photosensitive resin composition containing (A) an alkali-soluble resin, (B) an ethylenically unsaturated group-containing compound, and (C) a photopolymerization initiator,
A photosensitive resin composition, wherein the (C) photopolymerization initiator contains the photopolymerization initiator according to claim 1.   The photosensitive resin composition according to claim 3, further comprising (D) a coloring material.   A cured product obtained by curing the photosensitive resin composition according to claim 3.   A color filter comprising the cured product according to claim 5.   An image display device comprising the color filter according to claim 6.