TW202030554A - Photosensitive resin composition, method for producing patterned cured film, and patterned cured film wherein the patterned cured film has an excellent straightness and adhesion to a substrate, and has a good cross-sectional shape - Google Patents

Abstract

The present invention provides a photosensitive resin composition capable of forming a patterned cured film having excellent straightness and adhesion to a substrate and having a good cross-sectional shape, a method for producing a patterned cured film by using the photosensitive resin composition, and a patterned cured film that can be produced by the production method. In the photosensitive resin composition of the present invention that contains an alkali-soluble resin (A), a photo-polymerizable monomer (B) and a photo-polymerization initiator (C), the oxime ester compound having a nitrated specific structure containing a carbazole ring, i.e. the photo-polymerization initiator (C-I), and the photo-polymerization initiator (C-II) other than the photo-polymerization initiator (C-I) are used in combination.

Description

Photosensitive resin composition, method for producing patterned cured film, and patterned cured film

The present invention relates to a photosensitive resin composition, a method for producing a patterned cured film, and a patterned cured film.

For example, in display devices such as liquid crystal display devices, insulating films, or light-transmitting members such as spacers, or light-shielding members such as black matrixes are mostly used. This kind of member is mostly formed in the form of a patterned film. In order to form a patterned film, a photosensitive resin composition that provides a cured film by exposure is widely used. By subjecting this photosensitive resin composition to regioselective exposure and then developing it, a patterned cured film can be formed.

For example, as a photosensitive resin composition capable of forming a transparent cured film, a composition containing a resin, a polymerizable compound, a polymerization initiator of a specific structure, and a solvent is disclosed (Patent Document 1). Specifically, in the Examples of Patent Document 1, a photosensitive resin composition is disclosed, which comprises a copolymer of methacrylic acid and an acrylate having an alicyclic epoxy group, dipentaerythritol hexaacrylate, and the following formula Any one of the polymerization initiator, and containing 3-methoxy-1-butanol, propylene glycol monomethyl ether acetate, 3-ethoxy ethyl propionate, and 3-methoxy acetate Mixed solvent of butyl ester.

[先前技術文獻] [專利文獻][化1]

[Prior Art Document] [Patent Document]

[Patent Document 1] Japanese Patent Laid-Open No. 2012-58728

[The problem to be solved by the invention]

In addition, with regard to the entire photosensitive resin composition, it is often required to form a patterned cured film having excellent linearity and adhesion to a substrate, and having a good cross-sectional shape. However, when using conventionally known photosensitive resin compositions such as the photosensitive resin composition described in Patent Document 1, it is often impossible to form a pattern with excellent straightness and adhesion to the substrate, and a good cross-sectional shape. The hardened film.

The present invention was accomplished in view of the above-mentioned problems, and its object is to provide a photosensitive resin composition capable of forming a patterned cured film having excellent linearity and adhesion to a substrate, and having a good cross-sectional shape, and using the photosensitive resin composition The manufacturing method of the patterned cured film of a resin composition, and the patterned cured film which can be manufactured by this manufacturing method. [Technical means to solve the problem]

The inventors of the present invention have discovered that it is possible to nitrate a photosensitive resin composition containing an alkali-soluble resin (A), a photopolymerizable monomer (B), and a photopolymerization initiator (C). The oxime ester compound containing the specific structure of the carbazole ring, that is, the photopolymerization initiator (CI), and the photopolymerization initiator (C-II) other than the photopolymerization initiator (C-II) are used in combination to solve the above The problem is to complete the present invention. More specifically, the present invention provides the following.

(式(C1)中，X⁰¹ 係於下述式(C1-1)所表示之結構中，將鍵結於芳香族環上之氫原子中之t2＋t3個氫原子去除後之基，X⁰² 及X⁰³ 分別獨立為一價有機基，X⁰⁴ 及X⁰⁵ 分別獨立為氫原子、可具有取代基之碳原子數1以上11以下之烷基、或可具有取代基之芳基，t0～t3分別獨立為0或1，t2及t3之至少一者為1， [化3]

式(C1-1)中，X⁰⁶ 係以C-N鍵鍵結於咔唑環中之氮原子之一價有機基，t4及t5分別獨立為0或1，t4及t5之至少一者為1) 光聚合起始劑(C)之質量中之上述光聚合起始劑(C-I)之質量比率為20質量%以上95質量%以下。The first aspect of the present invention is a photosensitive resin composition comprising an alkali-soluble resin (A), a photopolymerizable monomer (B), and a photopolymerization initiator (C), and the photopolymerization is initiated The agent (C) includes the photopolymerization initiator (CI) represented by the following formula (C1) and other photopolymerization initiators (C-II) other than the photopolymerization initiator (CI), [化2]

(In formula (C1), X ⁰¹ is in the structure represented by the following formula (C1-1), the group obtained by removing t2+t3 hydrogen atoms from the hydrogen atoms bonded to the aromatic ring, X ⁰² and X ^{03 is} each independently a monovalent organic group, X ⁰⁴ and X ⁰⁵ are each independently a hydrogen atom, an optionally substituted alkyl group having 1 to 11 carbon atoms, or an optionally substituted aryl group, t0 to t3, respectively Independent is 0 or 1, at least one of t2 and t3 is 1, [化3]

In the formula (C1-1), X ⁰⁶ is a monovalent organic group bonded to the nitrogen atom in the carbazole ring by a CN bond, t4 and t5 are independently 0 or 1, and at least one of t4 and t5 is 1) The mass ratio of the photopolymerization initiator (CI) in the mass of the photopolymerization initiator (C) is 20% by mass to 95% by mass.

The second aspect of the present invention is a method for manufacturing a patterned cured film, which includes the following steps: Coating the photosensitive resin composition of the first aspect on a substrate to form a coating film; Area selective exposure of the coated film; and Develop the coated film after exposure.

The third aspect of the present invention is a patterned cured film comprising the cured product of the photosensitive resin composition of the first aspect. [Effects of Invention]

According to the present invention, it is possible to provide a photosensitive resin composition capable of forming a patterned cured film having excellent linearity and adhesion to a substrate, and a good cross-sectional shape, and a patterned cured film using the photosensitive resin composition The manufacturing method of a cured film, and the patterned cured film which can be manufactured by this manufacturing method.

≪Photosensitive resin composition≫ The photosensitive resin composition contains an alkali-soluble resin (A), a photopolymerizable monomer (B), and a photopolymerization initiator (C). The photosensitive resin composition contains a photopolymerization initiator (CI) represented by the following formula (C1) and a photopolymerization initiator (C-II) other than the photopolymerization initiator (CI) in combination, as Photopolymerization initiator (C). The mass ratio of the photopolymerization initiator (C-I) in the mass of the photopolymerization initiator (C) is 20% by mass to 95% by mass. The photosensitive resin composition contains a specific amount of photopolymerization initiator (CI) and photopolymerization initiator (C-II) in combination, and the photosensitive resin composition can be used to form straightness and adhesion to the substrate A patterned cured film with excellent performance and good cross-sectional shape.

Hereinafter, the essential or optional components contained in the photosensitive resin composition will be described.

＜Alkali-soluble resin (A)＞ The photosensitive resin composition contains alkali-soluble resin (A). There are no particular limitations on the alkali-soluble resin (A), and it can be appropriately selected from alkali-soluble resins prepared in various conventional photosensitive resin compositions. Here, in this specification, the alkali-soluble resin (A) refers to a resin having an alkali-soluble functional group (for example, a phenolic hydroxyl group, a carboxyl group, a sulfonic acid group, etc.) in the molecule.

Regarding the resin suitable as the alkali-soluble resin (A), a resin (a-1) having a Cardo structure (hereinafter, also referred to as "Cardo resin (a-1)") is mentioned. When the Cardo resin (a-1) is used as the alkali-soluble resin, it is easy to obtain a photosensitive resin composition with excellent resolution, and the photosensitive resin composition is used to easily form a cured film that is not easy to flow excessively due to heating. Therefore, it is easy to form a cured film with a good shape.

〔Resin with Cardo structure (a-1)〕 As Cardo resin (a-1), it can be used for resins that have a Cardo skeleton in their structure and have specific alkali solubility. Cardo skeleton refers to a skeleton in which a second ring structure and a third ring structure are bonded to one ring carbon atom constituting the first ring structure. Furthermore, the second cyclic structure and the third cyclic structure may be the same structure or different structures. As a representative example of the Cardo skeleton, a skeleton in which two aromatic rings (for example, a benzene ring) are bonded to the 9-position carbon atom of the chrysanthemum ring can be cited.

The Cardo resin (a-1) is not particularly limited, and conventionally known resins can be used. Among them, a resin represented by the following formula (a-1) is preferred. [化4]

In the formula (a-1), X ^a represents ^{a group} represented by the following formula (a-2). m1 represents an integer of 0 to 20. [化5]

In the above formula (a-2), R ^a1 each independently represents a hydrogen atom, a hydrocarbon group with 1 to 6 carbon atoms or a halogen atom, R ^a2 each independently represents a hydrogen atom or a methyl group, and R ^a3 each independently represents a linear or branched In the alkylene group of the chain, m2 represents 0 or 1, and Wa represents ^{a group} represented by the following formula (a-3).

[化6]

In the formula (a-2), ^{Ra3 is} preferably an alkylene having 1 to 20 carbon atoms, more preferably an alkylene having 1 to 10 carbon atoms, and particularly preferably 1 or more carbon atoms Alkylene groups below 6 are most preferably ethane-1,2-diyl, propane-1,2-diyl, and propane 1,3-diyl.

Ring A in the formula (a-3) represents an aliphatic ring which may be condensed with an aromatic ring and may also have a substituent. The aliphatic ring may be an aliphatic hydrocarbon ring or an aliphatic heterocyclic ring. Examples of the aliphatic ring include monocycloalkanes, bicycloalkanes, tricycloalkanes, and tetracycloalkanes. Specifically, examples include monocyclic alkanes such as cyclopentane, cyclohexane, cycloheptane, and cyclooctane, or adamantane, nordecane, isodecane, tricyclodecane, and tetracyclododecane. The aromatic ring that can be condensed with the aliphatic ring may be an aromatic hydrocarbon ring or an aromatic heterocyclic ring, and is preferably an aromatic hydrocarbon ring. Specifically, a benzene ring and a naphthalene ring are preferable.

As a preferable example of the divalent group represented by formula (a-3), the following groups can be mentioned. [化7]

The divalent group X ^a in the formula (a-1) is introduced into the Cardo resin by reacting the tetracarboxylic dianhydride providing the residue Z ^a with the diol compound represented by the following formula (a-2a) ( a-1). [化8]

In the formula (a-2a), R ^a1 , R ^a2 , R ^a3 , and m2 are as described for the formula (a-2). Regarding the ring A in the formula (a-2a), as described for the formula (a-3).

The diol compound represented by formula (a-2a) can be produced by the following method, for example. First, if necessary, replace the hydrogen atom in the phenolic hydroxyl group of the diol compound represented by the following formula (a-2b) with the group represented by -R ^a3 -OH according to the convention, and then use epichlorohydrin or the like Glycidization is performed to obtain an epoxy compound represented by the following formula (a-2c). Then, the diol compound represented by the formula (a-2a) is obtained by reacting the epoxy compound represented by the formula (a-2c) with acrylic acid or methacrylic acid. In formula (a-2b) and formula (a-2c), R ^a1 , R ^a3 , and m2 are as described for formula (a-2). Regarding the ring A in the formula (a-2b) and the formula (a-2c), as described for the formula (a-3). In addition, the manufacturing method of the diol compound represented by Formula (a-2a) is not limited to the said method. [化9]

As a preferable example of the diol compound represented by formula (a-2b), the following diol compounds can be mentioned. [化10]

In the above formula (a-1), R ^a0 is a hydrogen atom or ^a group represented by -CO-Y ^a -COOH. Here, Y ^a represents the residue after the acid anhydride group (-CO-O-CO-) is removed from the dicarboxylic anhydride. Examples of dicarboxylic acid anhydrides include: maleic anhydride, succinic anhydride, itaconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyl endomethine Tetrahydrophthalic anhydride, chloro-bridged anhydride, methyltetrahydrophthalic anhydride, glutaric anhydride, etc.

In addition, in the above formula (a-1), Za represents ^a residue obtained by removing two acid anhydride groups from tetracarboxylic dianhydride. Examples of tetracarboxylic dianhydrides include: tetracarboxylic dianhydride, pyromellitic dianhydride, benzophenone tetracarboxylic dianhydride, and biphenyl tetracarboxylic acid represented by the following formula (a-4) Acid dianhydride, diphenyl ether tetracarboxylic dianhydride, etc. In addition, in the above formula (a-1), m represents an integer of 0 or more and 20 or less.

(式(a-4)中，R^a4 、R^a5 、及R^a6 分別獨立表示選自由氫原子、碳原子數1以上10以下之烷基及氟原子所組成之群中之1種，m3表示0以上12以下之整數)[化11]

(In formula (a-4), R ^a4 , R ^a5 , and R ^a6 each independently represent one selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 10 carbon atoms and a fluorine atom, and m3 represents Integer from 0 to 12)

The alkyl group of ^Ra4 in formula (a-4) may be an alkyl group having 1 to 10 carbon atoms. By setting the number of carbon atoms of the alkyl group to this range, the heat resistance of the obtained carboxylic acid ester can be further improved. When ^Ra4 is an alkyl group, the number of carbon atoms is preferably 1 or more and 6 or less, more preferably 1 or more and 5 or less, and more preferably 1 or more in terms of easily obtaining a Cardo resin with excellent heat resistance 4 or less, more preferably 1 or more and 3 or less. When ^Ra4 is an alkyl group, the alkyl group may be linear or branched.

Formula R ^{a4 (a4)} in the, it is easy to obtain in terms of excellent heat resistance Cardo resin, more preferably each independently a hydrogen atom or an alkyl group of 10 or less carbon atoms or more. R ^a4 in the formula (a-4) is more preferably a hydrogen atom, methyl, ethyl, n-propyl or isopropyl group, and particularly preferably a hydrogen atom or a methyl group. In terms of easy preparation of high-purity tetracarboxylic dianhydride, the plural ^Ra4 in formula (a-4) are preferably the same group.

M3 in the formula (a-4) represents an integer of 0 to 12. Since the value of m3 is 12 or less, purification of tetracarboxylic dianhydride is easy. In terms of easy purification of tetracarboxylic dianhydride, the upper limit of m3 is preferably 5, more preferably 3. In terms of the chemical stability of tetracarboxylic dianhydride, the lower limit of m3 is preferably 1, and more preferably 2. In formula (a-4), m3 is particularly preferably 2 or 3.

The alkyl group with 1 to 10 carbon atoms that can be selected as ^Ra5 and ^Ra6 in formula (a-4) is the same as the alkyl group with 1 to 10 carbon atoms that can be selected as ^Ra4 . In terms of easy purification of the tetracarboxylic dianhydride, R ^a5 and R ^{a6 are} preferably a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and particularly preferably a hydrogen atom or a methyl group. The number of carbon atoms of the alkyl group as ^Ra5 and ^Ra6 is more preferably 1 or more and 6 or less, still more preferably 1 or more and 5 or less, still more preferably 1 or more and 4 or less, and particularly preferably 1 or more and 3 or less.

As the tetracarboxylic dianhydride represented by the formula (a-4), for example, norran-2-spiro-α-cyclopentanone-α'-spiro-2"-norranan-5,5" ,6,6"-Tetracarboxylic dianhydride (alias "norman-2-spiro-2'-cyclopentanone-5'-spiro-2"-normanthane-5,5",6,6" -Tetracarboxylic dianhydride”), methylnorman-2-spiro-α-cyclopentanone-α'-spiro-2"-(methylnormangan)-5,5",6,6" -Tetracarboxylic dianhydride, norrsine-2-spiro-α-cyclohexanone-α'-spiro-2"-normanthane-5,5",6,6"-tetracarboxylic dianhydride (alias "Norphalan-2-spiro-2'-cyclohexanone-6'-spiro-2"-normantane-5,5",6,6"-tetracarboxylic dianhydride"), methylnormethane Alkyl-2-spiro-α-cyclohexanone-α'-spiro-2"-(methylnormanthane)-5,5",6,6"-tetracarboxylic dianhydride, normanthane-2- Spiro-α-cycloacetone-α'-spiro-2"-norman-5,5",6,6"-tetracarboxylic dianhydride, norman-2-spiro-α-cyclobutanone-α '-Spiro-2"-Norphine-5,5",6,6"-tetracarboxylic dianhydride, norerane-2-spiro-α-cycloheptanone-α'-spiro-2"-Nor 𦯉alkane-5,5",6,6"-tetracarboxylic dianhydride, norrsan-2-spiro-α-cyclooctanone-α'-spiro-2"-normanthane-5,5", 6,6"-Tetracarboxylic dianhydride, norrsine-2-spiro-α-cyclononanone-α'-spiro-2"-normanthane-5,5",6,6"-tetracarboxylic acid Dianhydride, nordoxane-2-spiro-α-cyclodecanone-α'-spiro-2"-nordane-5,5",6,6"-tetracarboxylic dianhydride, nordoxane-2 -Spiro-α-Cycloundecanone-α'-Spiro-2"-Norkane-5,5",6,6"-tetracarboxylic dianhydride, Normane-2-Spiro-α-Cycloten Diketone-α'-spiro-2"-norphine-5,5",6,6"-tetracarboxylic dianhydride, noranthane-2-spiro-α-cyclotridecone-α'-spiro -2"-Norkane-5,5",6,6"-tetracarboxylic dianhydride, noreran-2-spiro-α-cyclotetradecone-α'-spiro-2"-normanthane -5,5",6,6"-Tetracarboxylic dianhydride, norrsan-2-spiro-α-cyclopentadecone-α'-spiro-2"-norrsan-5,5",6 ,6"-Tetracarboxylic dianhydride, norrsine-2-spiro-α-(methylcyclopentanone)-α'-spiro-2"-norrsine-5,5",6,6"- Tetracarboxylic dianhydride, norrsine-2-spiro-α-(methylcyclohexanone)-α'-spiro-2"-normanthane-5,5",6,6"-tetracarboxylic acid two Anhydride etc.

The weight average molecular weight of the Cardo resin (a-1) is preferably 1,000 or more and 40,000 or less, more preferably 1,500 or more and 30,000 or less, and still more preferably 2,000 or more and 10,000 or less. By setting it as the said range, good developability can be obtained, and sufficient heat resistance and mechanical strength can be obtained for the cured film formed using the photosensitive resin composition.

〔Novolac resin (a-2)〕 It is also preferable that the alkali-soluble resin (A) also contains the novolak resin (a-2) in terms of easy formation of a cured film that does not flow excessively due to heating. As the novolak resin (a-2), various novolak resins prepared in conventional photosensitive resin compositions can be used. The novolak resin (a-2) is preferably one obtained by addition condensation of an aromatic compound having a phenolic hydroxyl group (hereinafter referred to as "phenols") and aldehydes under an acid catalyst.

(Phenols) Examples of phenols used when preparing the novolak resin (a-2) include: phenol; cresols such as o-cresol, m-cresol, and p-cresol; 2,3-xylenol, 2,4 -Xylenol, 2,5-xylenol, 2,6-xylenol, 3,4-xylenol, 3,5-xylenol and other xylenols; o-ethylphenol, m-ethyl Ethyl phenols such as phenol and p-ethylphenol; 2-isopropylphenol, 3-isopropylphenol, 4-isopropylphenol, o-butylphenol, m-butylphenol, p-butylphenol, and p-butylphenol Alkylphenols such as tertiary butylphenol; trialkylphenols such as 2,3,5-trimethylphenol and 3,4,5-trimethylphenol; resorcinol, catechol, p- Polyphenols such as hydroquinone, hydroquinone monomethyl ether, pyrogallol, and phloroglucinol; alkyl resorcinol, alkyl catechol, and alkyl hydroquinone Polyphenols (any alkyl group has 1 to 4 carbon atoms); α-naphthol; β-naphthol; hydroxybiphenyl; and bisphenol A, etc. These phenols may be used alone or in combination of two or more kinds.

Among these phenols, m-cresol and p-cresol are preferred, and the combined use of m-cresol and p-cresol is more preferred. In this case, by adjusting the blending ratio of the two, it is possible to adjust various characteristics such as heat resistance of the cured film formed using the photosensitive resin composition. The blending ratio of m-cresol and p-cresol is not particularly limited, but it is preferably 3/7 or more and 8/2 or less in terms of the molar ratio of m-cresol/p-cresol. By using m-cresol and p-cresol in a ratio in this range, it is easy to obtain a photosensitive resin composition capable of forming a cured film having excellent heat resistance.

Moreover, it is also preferable that it is a novolak resin manufactured by using m-cresol and 2,3,5-trimethylphenol in combination. When this novolak resin is used, it is particularly easy to obtain a photosensitive resin composition capable of forming a cured film having excellent heat resistance. The mixing ratio of m-cresol and 2,3,5-trimethylphenol is not particularly limited, but in terms of the molar ratio of m-cresol/2,3,5-trimethylphenol, it is preferably 70/30 Above 95/5.

(Aldehydes) Examples of aldehydes used when producing the novolak resin (a-2) include formaldehyde, paraformaldehyde, furfural, benzaldehyde, nitrobenzaldehyde, and acetaldehyde. These aldehydes can be used alone or in combination of two or more kinds.

(Acid catalyst) The acid catalyst used in the production of novolac resin (a-2) includes, for example, inorganic acids such as hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, and phosphorous acid; formic acid, oxalic acid, acetic acid, diethyl sulfuric acid, and p-toluene Organic acids such as sulfonic acid; and metal salts such as zinc acetate. These acid catalysts can be used alone or in combination of two or more kinds.

(Molecular weight) Regarding the weight average molecular weight (Mw; hereafter, also referred to as "weight average molecular weight") in terms of polystyrene of the novolak resin (a-2), from the viewpoint of the heat resistance of the cured film formed using the photosensitive resin composition In other words, as the lower limit value, it is preferably 2000, more preferably 5000, particularly preferably 10000, further preferably 15000, most preferably 20000, and as the upper limit value, it is preferably 50000, more preferably 45000, and more The best is 40,000, and the best is 35,000.

As the novolak resin (a-2), at least two types of polystyrene-converted weight average molecular weights can be used in combination. By combining sizes with different weight average molecular weights, the developability of the photosensitive resin composition and the heat resistance of the cured film formed using the photosensitive resin composition can be balanced.

〔Modified epoxy resin (a-3)〕 The alkali-soluble resin (A) may also include the polybasic acid anhydride (a-3c) adduct (a-3) of the reaction product of the epoxy compound (a-3a) and the unsaturated group-containing carboxylic acid (a-3b). This adduct is also referred to as "modified epoxy resin (a-3)". Furthermore, in the specification and the scope of the patent application of this application, the compound that belongs to the above definition and does not belong to the above resin (a-1) with the Cardo structure is referred to as modified epoxy resin (a-3) .

Hereinafter, the epoxy compound (a-3a), the unsaturated group-containing carboxylic acid (a-3b), and the polybasic acid anhydride (a-3c) will be described.

＜Epoxy compound (a-3a)＞ The epoxy compound (a-3a) is not particularly limited as long as it is a compound having an epoxy group, and it may be an aromatic epoxy compound having an aromatic group or an aliphatic epoxy compound that does not contain an aromatic group. , Preferably an aromatic epoxy compound having an aromatic group. The epoxy compound (a-3a) may be a monofunctional epoxy compound or a multifunctional epoxy compound having two or more functions, and a multifunctional epoxy compound is preferred.

Specific examples of the epoxy compound (a-3a) include: bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, bisphenol AD type epoxy resin, naphthalene type Epoxy resins and biphenyl type epoxy resins and other bifunctional epoxy resins; dimer acid glycidyl esters and triglycidyl esters and other glycidyl ester type epoxy resins; tetraglycidylamino diphenylmethane, triglycidyl Glycidyl-p-aminophenol, tetraglycidyl metaxylylenediamine, and tetraglycidyl diaminomethyl cyclohexane and other glycidylamine epoxy resins; triglycidyl isocyanurate Heterocyclic epoxy resins; phloroglucinol triglycidyl ether, trihydroxybiphenyl triglycidyl ether, trihydroxyphenylmethane triglycidyl ether, glycerol triglycidyl ether, 2-[4-(2, 3-glycidoxy)phenyl]-2-[4-[1,1-bis[4-(2,3-glycidoxy)phenyl]ethyl]phenyl]propane, and 1 ,3-Bis[4-[1-[4-(2,3-epoxypropoxy)phenyl]-1-[4-[1-[4-(2,3-epoxypropoxy) Phenyl]-1-methylethyl]phenyl]ethyl]phenoxy]-2-propanol and other trifunctional epoxy resins; tetrahydroxyphenylethane tetraglycidyl ether, tetraglycidyl two Four functional epoxy resins such as benzophenone, bisresorcinol tetraglycidyl ether, and tetraglycidoxybiphenyl.

Moreover, as an epoxy compound (a-3a), the epoxy compound which has a biphenyl skeleton is preferable. The epoxy compound having a biphenyl skeleton preferably has at least one biphenyl skeleton represented by the following formula (a-3a-1) in the main chain. The epoxy compound having a biphenyl skeleton is preferably a polyfunctional epoxy compound having two or more epoxy groups. By using an epoxy compound having a biphenyl skeleton, it is easy to obtain a photosensitive resin composition capable of forming a cured film having an excellent balance between sensitivity and developability and excellent adhesion to a substrate.

(式(a-3a-1)中，R^a7 分別獨立為氫原子、碳原子數1以上12以下之烷基、鹵素原子或可具有取代基之苯基。j為1以上4以下之整數)[化12]

(In formula (a-3a-1), ^{Ra7 is} each independently a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, a halogen atom, or a phenyl group which may have a substituent. j is an integer of 1 to 4)

When ^Ra7 is an alkyl group having 1 to 12 carbon atoms, specific examples of the alkyl group include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, Second butyl, third butyl, n-pentyl, isopentyl, second pentyl, third pentyl, n-hexyl, n-heptyl, n-octyl, isooctyl, second octyl, third Octyl, n-nonyl, isononyl, n-decyl, isodecyl, n-undecyl, and n-dodecyl.

When ^Ra7 is a halogen atom, specific examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

When ^Ra7 is a phenyl group which may have a substituent, the number of substituents on the phenyl group is not particularly limited. The number of substituents on the phenyl group is 0 or more and 5 or less, preferably 0 or 1. Examples of substituents include: alkyl groups having 1 to 4 carbon atoms, alkoxy groups having 1 to 4 carbon atoms, aliphatic acyl groups having 2 to 4 carbon atoms, halogen atoms, and cyano groups , And nitro.

(式(a-3a-2)中，R^a7 及j與式(a-3a-1)相同。k為括弧內之結構單元之平均重複數，為0以上10以下)The epoxy compound (a-3a) having a biphenyl skeleton represented by the above formula (a-3a-1) is not particularly limited, and for example, the epoxy compound represented by the following formula (a-3a-2) Compound. [化13]

(In formula (a-3a-2), ^Ra7 and j are the same as formula (a-3a-1). k is the average repeating number of structural units in parentheses, and is 0 or more and 10 or less)

(式(a-3a-3)中，k與式(a-3a-2)相同)Among the epoxy compounds represented by the formula (a-3a-2), the following formula (a-3a-3) is particularly preferred in terms of easily obtaining a photosensitive resin composition having an excellent balance of sensitivity and developability ) Represented by the compound. [化14]

(In formula (a-3a-3), k is the same as formula (a-3a-2))

(Carboxylic acid containing unsaturated group (a-3b)) When preparing the modified epoxy compound (a-3), the epoxy compound (a-3a) is reacted with the unsaturated group-containing carboxylic acid (a-3b). The unsaturated group-containing carboxylic acid (a-3b) is preferably a monocarboxylic acid containing a reactive unsaturated double bond such as an acrylic group or a methacrylic group in the molecule. Examples of such unsaturated group-containing carboxylic acids include acrylic acid, methacrylic acid, β-styryl acrylic acid, β-furfuryl acrylic acid, α-cyanocinnamic acid, and cinnamic acid. In addition, the unsaturated group-containing carboxylic acid (a-3b) can be used alone or in combination of two or more kinds.

The epoxy compound (a-3a) and the unsaturated group-containing carboxylic acid (a-3b) can be reacted by a known method. As a preferable reaction method, for example, the following method can be cited, that is, triethylamine and tertiary amines such as benzylethylamine, dodecyltrimethylammonium chloride, tetramethylammonium chloride, tetramethylammonium chloride Ethyl ammonium chloride, quaternary ammonium salts such as benzyl triethyl ammonium chloride, pyridine or triphenyl phosphine, etc. are used as catalysts to make epoxy compound (a-3a) and unsaturated group-containing carboxylic acid ( a-3b) React in an organic solvent at a reaction temperature of 50°C or higher and 150°C or higher for several hours or longer and several tens of hours or shorter.

Regarding the ratio of the two amounts used in the reaction of the epoxy compound (a-3a) and the unsaturated group-containing carboxylic acid (a-3b), the epoxy equivalent of the epoxy compound (a-3a) and the The ratio of the carboxylic acid equivalent of the saturated carboxylic acid (a-3b) is usually 1:0.5-1:2, more preferably 1:0.8-1:1.25, and particularly preferably 1:0.9-1: 1.1. If the ratio of the use amount of epoxy compound (a-3a) to the use amount of unsaturated group-containing carboxylic acid (a-3b) is 1:0.5 to 1:2 based on the above equivalent ratio, the crosslinking efficiency will be improved The tendency is better.

(Polyacid anhydride (a-3c)) The polybasic acid anhydride (a-3c) is an anhydride of a carboxylic acid having two or more carboxyl groups. The polybasic acid anhydride (a-3c) is not particularly limited, and examples include maleic anhydride, succinic anhydride, itaconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, and hexahydrophthalic anhydride. Formic anhydride, methylhexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, trimellitic anhydride, pyromellitic dianhydride, benzophenonetetracarboxylic dianhydride, 3-methylhexa Hydrophthalic anhydride, 4-methylhexahydrophthalic anhydride, 3-ethylhexahydrophthalic anhydride, 4-ethylhexahydrophthalic anhydride, tetrahydrophthalic anhydride , 3-methyltetrahydrophthalic anhydride, 4-methyltetrahydrophthalic anhydride, 3-ethyltetrahydrophthalic anhydride, 4-ethyltetrahydrophthalic anhydride, The compound represented by the formula (a-3c-1) and the compound represented by the following formula (a-3c-2) are described. Moreover, polybasic acid anhydride (a-3c) can be used individually or in combination of 2 or more types.

(式(a-3c-2)中，R^a8 表示碳原子數1以上10以下之可具有取代基之伸烷基)[化15]

(In the formula (a-3c-2), R ^a8 represents an alkylene group having 1 to 10 carbon atoms that may have a substituent)

The polybasic acid anhydride (a-3c) is preferably a compound having two or more benzene rings in terms of easily obtaining a photosensitive resin composition having an excellent balance between sensitivity and developability. Moreover, the polybasic acid anhydride (a-3c) more preferably contains at least one of the compound represented by the above formula (a-3c-1) and the compound represented by the above formula (a-3c-2).

The method of reacting the epoxy compound (a-3a) with the unsaturated group-containing carboxylic acid (a-3b) and then reacting the polybasic acid anhydride (a-3c) can be appropriately selected from known methods. In addition, the usage ratio is based on the molar number of the OH group in the component after the reaction between the epoxy compound (a-3a) and the unsaturated group-containing carboxylic acid (a-3b) and the acid anhydride group of the polybasic acid anhydride (a-3c) The equivalent ratio is usually 1:1 to 1:0.1, preferably 1:0.8 to 1:0.2. By setting it as the said range, it becomes easy to obtain the photosensitive resin composition with good developability.

In addition, the acid value of the modified epoxy resin (a-3) is preferably 10 mgKOH/g or more and 150 mgKOH/g or less, and more preferably 70 mgKOH/g or more and 110 mgKOH/g or less in terms of resin solid content. By setting the acid value of the resin to 10 mgKOH/g or more, sufficient solubility to the developer can be obtained. Moreover, by setting the acid value of 150 mgKOH/g or less, sufficient curability can be obtained and the surface can be improved. Good sex.

In addition, the weight average molecular weight of the modified epoxy resin (a-3) is preferably 1,000 or more and 40,000 or less, more preferably 2,000 or more and 30,000 or less. With a weight average molecular weight of 1000 or more, it is easy to form a cured film with excellent heat resistance and strength. In addition, by being 40,000 or less, it is easy to obtain a photosensitive resin composition exhibiting sufficient solubility in the developer.

〔Acrylic resin (a-4)〕 Moreover, acrylic resin (a-4) is also preferable as a component which comprises alkali-soluble resin (A). As the acrylic resin (a-4), a structural unit derived from (meth)acrylic acid and/or a structural unit derived from other monomers such as (meth)acrylate can be used. (Meth)acrylic acid is acrylic acid or methacrylic acid. The (meth)acrylate is represented by the following formula (a-4-1) and is not particularly limited as long as it does not interfere with the purpose of the present invention.

[化16]

In the above formula (a-4-1), R ^a9 is a hydrogen atom or a methyl group, and R ^a10 is a monovalent organic group. The organic group may include a bond or substituent other than a hydrocarbon group such as a hetero atom in the organic group. In addition, the organic group may be any of linear, branched, and cyclic.

Substituents other than the hydrocarbon group in the organic group of ^Ra10 are not particularly limited as long as they do not impair the effect of the present invention. Examples include halogen atoms, hydroxyl groups, mercapto groups, thio groups, cyano groups, isocyano groups, and cyanic acid. Group, isocyanate group, thiocyanate group, isothiocyanate group, silyl group, silanol group, alkoxy group, alkoxycarbonyl group, aminomethanyl group, aminothiomethanyl group, nitro group, nitroso group Group, carboxyl group, carboxylate group, acyl group, acyloxy group, sulfinic acid group, sulfo group, sulfonate group, phosphine group, phosphinyl group, phosphonic acid group, phosphinyl group, hydroxyimine group, alkyl Base ether group, alkyl sulfide group, aryl ether group, aryl sulfide group, amine group (-NH ₂ , -NHR, -NRR': R and R'each independently represent a hydrocarbon group), etc. The hydrogen atom contained in the above substituent may be substituted by a hydrocarbon group. Moreover, the hydrocarbon group contained in the said substituent may be any of linear, branched, and cyclic.

In addition, the organic group as R ^a10 may have Bingxi Xi group, Bing Xixi methyl group, an epoxy group, an oxetanyl group and other reactive functional groups. Acrylic acid groups such as acryloxy group or methacryloxy group having unsaturated double bonds and the like can be obtained, for example, by combining an unsaturated carboxylic acid such as acrylic acid or methacrylic acid with an acrylic resin containing a structural unit having an epoxy group ( At least a part of the epoxy group in a-4) is produced by reacting.

R ^{a10 is} preferably an alkyl group, an aryl group, an aralkyl group, or a heterocyclic group, and these groups may be substituted with a halogen atom, a hydroxyl group, an alkyl group, or a heterocyclic group. In addition, when these groups include alkylene moieties, the alkylene moieties may be interrupted by ether bonds, thioether bonds, and ester bonds.

When the alkyl group is linear or branched, the number of carbon atoms is preferably 1 or more and 20 or less, more preferably 1 or more and 15 or less, and particularly preferably 1 or more and 10 or less. Examples of preferable alkyl groups include: methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, second butyl, tertiary butyl, n-pentyl, isopentyl , Second pentyl, third pentyl, n-hexyl, n-heptyl, n-octyl, isooctyl, second octyl, third octyl, n-nonyl, isononyl, n-decyl, isodecyl Base etc.

When the alkyl group contains an alicyclic group or an alicyclic group, the preferred alicyclic group contained in the alkyl group includes monocyclic alicyclic groups such as cyclopentyl and cyclohexyl Formula group; or polycyclic alicyclic group such as adamantyl group, nor 𦯉 group, iso 𦯉 group, tricyclononyl, tricyclodecyl, and tetracyclododecyl.

In the case where the compound represented by the formula (a-4-1) has a chain-like group having an epoxy group as R ^a10 , specific examples of the compound represented by the formula (a-4-1) include: (A Base) glycidyl acrylate, 2-methyl glycidyl (meth)acrylate, 3,4-epoxybutyl (meth)acrylate, 6,7-epoxyheptyl (meth)acrylate, etc. Base) epoxy alkyl acrylates.

In addition, the compound represented by the formula (a-4-1) may be an alicyclic epoxy group-containing (meth)acrylate. The alicyclic group constituting the alicyclic epoxy group may be monocyclic or polycyclic. Examples of monocyclic alicyclic groups include cyclopentyl and cyclohexyl. In addition, examples of polycyclic alicyclic groups include nordoxy, isooxy, tricyclononyl, tricyclodecyl, tetracyclododecyl, and the like.

As a specific example when the compound represented by the formula (a-4-1) is an alicyclic epoxy group-containing (meth)acrylate, for example, the following formulas (a-4-1a) to ( a-4-1o) the compound represented. Among them, in order to make the developability moderate, the compound represented by the following formula (a-4-1a) to (a-4-1e) is preferable, and the following formula (a-4-1a) is more preferable ~(a-4-1c) The compound represented.

[化17]

[化18]

[化19]

In the above formula, R ^a20 represents a hydrogen atom or a methyl group, R ^a21 represents a divalent saturated aliphatic hydrocarbon group with 1 to 6 carbon atoms, R ^a22 represents a divalent hydrocarbon group with 1 to 10 carbon atoms, and t represents 0 or more An integer below 10. R ^{a21 is} preferably a linear or branched alkylene group, such as methylene, ethylene, propylene, tetramethylene, ethylethylene, pentamethylene, hexamethylene base. As R ^a22 , for example, methylene, ethylene, propylene, tetramethylene, ethylethylene, pentamethylene, hexamethylene, phenylene, cyclohexylene, -CH are preferred. ₂ -Ph-CH ₂ -. Ph represents phenylene.

In addition, the acrylic resin (a-4) may be obtained by polymerizing a monomer other than (meth)acrylate. Examples of such monomers include (meth)acrylamides, unsaturated carboxylic acids, allyl compounds, vinyl ethers, vinyl esters, and styrenes. These monomers can be used alone or in combination of two or more kinds.

Examples of (meth)acrylamides include (meth)acrylamide, N-alkyl (meth)acrylamide, N-aryl(meth)acrylamide, N,N-di Alkyl(meth)acrylamide, N,N-aryl(meth)acrylamide, N-methyl-N-phenyl(meth)acrylamide, N-hydroxyethyl-N-methyl Group (meth)acrylamide and the like.

Examples of unsaturated carboxylic acids include monocarboxylic acids such as crotonic acid; dicarboxylic acids such as maleic acid, fumaric acid, citraconic acid, mesaconic acid, and itaconic acid; these dicarboxylic acids The acid anhydride and so on.

Examples of allyl compounds include allyl acetate, allyl hexanoate, allyl octoate, allyl laurate, allyl palmitate, allyl stearate, allyl benzoate, Allyl esters such as allyl acetate and allyl lactate; allyloxyethanol, etc.

Examples of vinyl ethers include hexyl vinyl ether, octyl vinyl ether, decyl vinyl ether, ethylhexyl vinyl ether, methoxyethyl vinyl ether, ethoxyethyl vinyl ether, chloroethyl vinyl ether, 1-methyl-2,2-dimethyl propyl vinyl ether, 2-ethylbutyl vinyl ether, hydroxyethyl vinyl ether, diethylene glycol vinyl ether, dimethylamino ethyl vinyl ether, two Ethylamino ethyl vinyl ether, butylamino ethyl vinyl ether, benzyl vinyl ether, tetrahydrofurfuryl vinyl ether and other alkyl vinyl ethers; vinyl phenyl ether, vinyl tolyl ether, vinyl chloride Vinyl aryl ethers such as phenyl ether, vinyl-2,4-dichlorophenyl ether, vinyl naphthyl ether, vinyl anthryl ether, etc.

Examples of vinyl esters include: vinyl butyrate, vinyl isobutyrate, trimethyl vinyl acetate, diethyl vinyl acetate, vinyl valerate, vinyl caproate, vinyl chloroacetate, dichloro Vinyl acetate, methoxy vinyl acetate, butoxy vinyl acetate, phenyl vinyl acetate, vinyl acetyl acetate, vinyl lactate, vinyl β-phenyl butyrate, vinyl benzoate, salicylic acid Vinyl acid, vinyl chlorobenzoate, vinyl tetrachlorobenzoate, vinyl naphthoate, etc.

Examples of styrenes include: styrene; methyl styrene, dimethyl styrene, trimethyl styrene, ethyl styrene, diethyl styrene, isopropyl styrene, butyl styrene, Hexylstyrene, cyclohexylstyrene, decylstyrene, benzylstyrene, chloromethylstyrene, trifluoromethylstyrene, ethoxymethylstyrene, acetoxymethylstyrene, etc. Alkoxystyrenes such as methoxystyrene, 4-methoxy-3-methylstyrene, and dimethoxystyrene; chlorostyrene, dichlorostyrene, trichlorostyrene, Tetrachlorostyrene, Pentachlorostyrene, Bromostyrene, Dibromostyrene, Iodostyrene, Fluorostyrene, Trifluorostyrene, 2-Bromo-4-trifluoromethylstyrene, 4-Fluoro-3 -Halogenated styrenes such as trifluoromethyl styrene, etc.

The amount of structural units derived from (meth)acrylic acid and the amount of structural units derived from other monomers in the acrylic resin (a-4) are not particularly limited within a range that does not hinder the purpose of the present invention. The amount of the structural unit derived from (meth)acrylic acid in the acrylic resin (a-4) relative to the mass of the acrylic resin (a-4) is preferably 5% by mass or more and 50% by mass or less, more preferably 10% by mass or more and 30% by mass or less.

When the acrylic resin (a-4) has a structural unit having an unsaturated double bond, the amount of the structural unit having an unsaturated double bond in the acrylic resin (a-4) is preferably 1% by mass or more. Mass% or less, more preferably 1 mass% or more and 30 mass% or more, and particularly preferably 1 mass% or more and 20 mass% or less. Acrylic resin (a-4) contains structural units with unsaturated double bonds in the above-mentioned range, and the acrylic resin is introduced into the crosslinking reaction in the resist film to achieve homogenization. It is effective to improve the heat resistance and mechanical properties of materials.

The weight average molecular weight of the acrylic resin (a-4) is preferably 2,000 or more and 50,000 or less, more preferably 3,000 or more and 30,000 or less. By setting it as the said range, there exists a tendency for the film formation ability of a photosensitive resin composition to be easily balanced with the developability after exposure.

The content of the alkali-soluble resin (A) is preferably 20% by mass or more and 85% by mass or less relative to the mass of the photosensitive resin composition after removing the mass of the following organic solvent (S) (total solid content). Preferably it is 25 mass% or more and 75 mass% or less. By being in the above range, it is easy to obtain a photosensitive resin composition having excellent developability.

＜Photopolymerizable monomer (B)＞ As the photopolymerizable monomer (B), a monomer having an ethylenically unsaturated group can be preferably used. Monofunctional monomers and multifunctional monomers are included in the monomers having ethylenic unsaturated groups.

Examples of monofunctional monomers include (meth)acrylamide, methylol (meth)acrylamide, methoxymethyl (meth)acrylamide, and ethoxymethyl (methyl) Acrylamide, propoxymethyl(meth)acrylamide, butoxymethoxymethyl(meth)acrylamide, N-methylol(meth)acrylamide, N-hydroxymethyl Base (meth)acrylamide, (meth)acrylic acid, fumaric acid, maleic acid, maleic anhydride, itaconic acid, itaconic anhydride, citraconic acid, anhydrous citraconic acid, Crotonic acid, 2-acrylamide-2-methylpropanesulfonic acid, tertiary butylacrylamide sulfonic acid, methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate Ester, 2-ethylhexyl (meth)acrylate, cyclohexyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, (meth)acrylic acid 2-hydroxybutyl ester, 2-phenoxy-2-hydroxypropyl (meth)acrylate, 2-(meth)acryloxy-2-hydroxypropyl phthalate, glycerol mono(methyl) Acrylate, tetrahydrofurfuryl (meth)acrylate, dimethylaminoethyl (meth)acrylate, glycidyl (meth)acrylate, 2,2,2-trifluoroethyl (meth)acrylate , (Meth)acrylic acid 2,2,3,3-tetrafluoropropyl ester, phthalic acid derivative half (meth)acrylate, etc. These monofunctional monomers can be used alone or in combination of two or more kinds.

On the other hand, as multifunctional monomers, ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, and propylene glycol di(meth)acrylate can be cited. (Meth)acrylate, polypropylene glycol di(meth)acrylate, butanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate Base) acrylate, trimethylolpropane tri(meth)acrylate, glycerol di(meth)acrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, pentaerythritol Di(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, 2,2- Bis(4-(meth)acryloyloxydiethoxyphenyl)propane, 2,2-bis(4-(meth)acryloyloxypolyethoxyphenyl)propane, (methyl) Acrylic acid 2-hydroxy-3-(meth)acryloxy propyl ester, ethylene glycol diglycidyl ether di(meth)acrylate, diethylene glycol diglycidyl ether di(meth)acrylate, ortho Diglycidyl phthalate di(meth)acrylate, glycerol triacrylate, glycerol polyglycidyl ether poly(meth)acrylate, urethane (meth)acrylate (ie, toluene diisocyanate, Trimethylhexamethylene diisocyanate, or hexamethylene diisocyanate, etc. and the reaction product of 2-hydroxyethyl (meth)acrylate), methylene bis(meth)acrylamide, (meth) Multifunctional monomers such as acrylamide methylene ether, polyol and N-methylol (meth)acrylamide condensation products, or triacrylamide formal, etc. These polyfunctional monomers can be used alone or in combination of two or more kinds.

Among the monomers having ethylenically unsaturated groups, in terms of the tendency to improve the adhesion of the photosensitive resin composition to the substrate and the strength of the photosensitive resin composition after curing, it is preferably trifunctional or higher The multifunctional monomer is more preferably a multifunctional monomer with more than 4 functions, and more preferably a multifunctional monomer with more than 5 functions.

The content in the photosensitive resin composition of the photopolymerizable monomer (B) is preferably 1 relative to the mass of the photosensitive resin composition after the mass of the following organic solvent (S) is removed (the total solid content) Mass% or more and 50 mass% or less, more preferably 5 mass% or more and 40 mass% or less. By setting it in the above range, it tends to be easy to balance sensitivity, developability, and resolution.

＜Photopolymerization initiator (C)＞ The photosensitive resin composition contains a photopolymerization initiator (CI) represented by the following formula (C1) and a photopolymerization initiator (C-II) other than the photopolymerization initiator (CI) as the photopolymerization initiator Starter (C). The mass ratio of the photopolymerization initiator (C-I) in the mass of the photopolymerization initiator (C) is 20% by mass to 95% by mass. As described above, by combining the photopolymerization initiator (CI) and the photopolymerization initiator (C-II) in an amount within the above-mentioned specific range from the photosensitive resin composition, it can be formed using the photosensitive resin composition A patterned cured film with excellent straightness and adhesion to the substrate, and a good cross-sectional shape. The mass ratio of the photopolymerization initiator (C-I) in the mass of the photopolymerization initiator (C) is more preferably 25% by mass or more and 90% by mass or less, and more preferably 30% by mass or more and 85% by mass or less.

[Photopolymerization initiator (CI)] The photopolymerization initiator (CI) is an oxime ester compound represented by the following formula (C1). [化20]

式(C1-1)中，X⁰⁶ 係以C-N鍵鍵結於咔唑環中之氮原子之一價有機基。t4及t5分別獨立為0或1，t4及t5之至少一者為1。In the formula (C1), X ⁰¹ is a group in the structure represented by the following formula (C1-1) by removing t2 + t3 hydrogen atoms from the hydrogen atoms bonded to the aromatic ring. X ⁰² and X ⁰³ are each independently a monovalent organic group. X ⁰⁴ and X ⁰⁵ are each independently a hydrogen atom, an optionally substituted alkyl group having 1 to 11 carbon atoms, or an optionally substituted aryl group. t0 to t3 are independently 0 or 1, respectively. At least one of t2 and t3 is 1. [化21]

In the formula (C1-1), X ⁰⁶ is a monovalent organic group bonded to the nitrogen atom in the carbazole ring with a CN bond. t4 and t5 are independently 0 or 1, respectively, and at least one of t4 and t5 is 1.

The X ⁰⁶ monovalent organic group may also include heteroatoms such as O, S, N, P, Si, and halogen atoms. The number of carbon atoms of the organic group of X ⁰⁶ is not particularly limited. The number of carbon atoms of the organic group of X ^{06 is} , for example, preferably 1 or more and 50 or less, more preferably 1 or more and 30 or less, and particularly preferably 1 or more and 20 or less.

Preferable examples of the organic group as X ⁰⁶ include: alkyl, alkenyl, alkynyl, aliphatic cyclic hydrocarbon group, aryl, aliphatic heterocyclic group, heteroaryl, aliphatic acyl, aromatic醯基, and combinations of these bases. As a preferable example of the combination of these groups, an aralkyl group, a cycloalkylalkyl group, etc. are mentioned.

When the organic group as X ⁰⁶ is an alkyl group, an alkenyl group, or an alkynyl group, these groups may be linear or branched. When the organic group as X ⁰⁶ is an aliphatic acyl group, the part other than the carbonyl group in the aliphatic acyl group may be linear, branched, cyclic, or these structures的组合。 The combination.

The organic group as X ⁰⁶ may have a substituent. Examples of substituents that may be possessed as the organic group of X ⁰⁶ include: alkyl groups with 1 to 20 carbon atoms, alkoxy groups with 1 to 20 carbon atoms, and rings with 3 to 10 carbon atoms. Alkyl groups, cycloalkoxy groups with 3 to 10 carbon atoms, saturated aliphatic acyl groups with 2 to 20 carbon atoms, alkoxycarbonyl groups with 2 to 20 carbon atoms, and 2 to 20 carbon atoms The saturated aliphatic acyloxy group, the phenyl group which may have a substituent, the phenoxy group which may have a substituent group, the thiophenyl group which may have a substituent group, the benzyl group which may have a substituent group, the benzene which may have a substituent group An oxycarbonyl group, a benzyloxy group that may have a substituent, a phenylalkyl group that may have a substituent and a phenylalkyl group having 7 to 20 carbon atoms, a naphthyl group that may have a substituent, a naphthyloxy group that may have a substituent, The naphthyl group which may have a substituent, the naphthyloxycarbonyl group which may have a substituent, the naphthyloxycarbonyl group which may have a substituent, the naphthylalkyl group with a carbon number of 11 to 20 which may have a substituent, Substituent heterocyclic group, optionally substituted heterocyclic carbonyl group, amino group, amino group substituted by one or two organic groups, linolin-1-yl, piper-1-yl, halogen , Nitro, and cyano, etc.

^Among the above groups of X ⁰⁶ , an alkyl group, an aryl group, and an aralkyl group are preferable in terms of the ease of synthesis and acquisition of the photopolymerization initiator (CI).

Specific examples when X ⁰⁶ is an alkyl group include: methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, second butyl, tertiary butyl, n-pentyl Base, neopentyl, isopentyl, second pentyl, third pentyl, n-hexyl, n-heptyl, n-octyl, 2-ethylhexyl, n-nonyl, n-decyl, n-undecyl , N-dodecyl, n-tridecyl, n-tetradecyl, n-pentadecyl, n-hexadecyl, n-heptadecyl, n-octadecyl, n-nonadecyl, and N-eicosyl.

Preferable examples when X ⁰⁶ is an aryl group include phenyl, naphth-1-yl, naphth-2-yl, 2-biphenyl, 3-biphenyl, and 4-biphenyl .

Preferred examples when X ⁰⁶ is an aralkyl group include benzyl, phenethyl, 3-phenyl-n-propyl, 4-phenyl-n-butyl, naphth-1-ylmethyl , And naphth-2-ylmethyl.

Among the specific examples of X ⁰⁶ described above, methyl, ethyl, phenyl, naphth-1-yl, and naphth-2-yl are preferred, and ethyl and phenyl are more preferred.

X ⁰¹ is not particularly limited as long as it is a group obtained by removing t2+t3 hydrogen atoms from the hydrogen atoms bonded to the aromatic ring in the structure represented by the above formula (C1-1). The group represented by the above formula (C1-1) is preferably a monovalent or divalent group represented by the following formulas (C1-1a) to (C1-1c). [化22]

In formula (C1-1a) to formula (C1-c), t4, t5, and X ^{06 are the} same as formula (C1-1). X ⁰⁷ is a divalent organic group bonded to the nitrogen atom in the carbazole ring by CN bond. X ⁰⁷ is a divalent organic group containing an aromatic ring. Among the two bonding bonds that X ⁰⁷ has, the other bonding bond that bonds to the carbazole ring in formula (C1-1a) and formula (C1-1c) is bonded to X ⁰⁷ Aromatic ring. In addition, X ⁰⁷ corresponds to a divalent group obtained by removing one hydrogen atom bonded to the aromatic ring from the monovalent organic group including the aromatic ring as X ⁰⁶ described above.

Taking the formula (C1-1a) as an example, a preferable specific example of X ⁰⁷ is described below. The divalent group equivalent to X ⁰⁷ in the following structure is also preferably used as X ⁰⁷ in formula (C1-1c). [化23]

In formulas (C1-1a) to (C1-1c), the bonding position of the nitro group on the carbazole ring is not particularly limited. In terms of ease of synthesis and acquisition of the compound represented by formula (C1), etc., as the group represented by formula (C1-1a), the group represented by (C1-1b), and formula (C1-1c) Preferable examples of the group represented include the group represented by the formula (C1-1aa), the group represented by the formula (C1-1ba), and the group represented by the formula (C1-1ca), respectively. [化24]

In formula (C1), X ⁰² and X ⁰³ are each independently a monovalent organic group. Examples of preferable organic groups for X ⁰² and X ⁰³ include alkyl groups, alkoxy groups, cycloalkyl groups, cycloalkoxy groups, saturated aliphatic acyl groups, alkoxycarbonyl groups, and saturated aliphatic acyloxy groups. Group, optionally substituted phenyl group, optionally substituted phenoxy group, optionally substituted benzyl group, optionally substituted phenoxycarbonyl group, optionally substituted benzyloxy group, Phenylalkyl which may have substituents, naphthyl which may have substituents, naphthyloxy which may have substituents, naphthyloxy which may have substituents, naphthyloxycarbonyl which may have substituents, which may be substituted The naphthyloxy group of the group, the naphthylalkyl group which may have a substituent, the heterocyclic group which may have a substituent, the heterocyclic carbonyl group which may have a substituent, the amine group substituted by one or two organic groups, 𠰌line-1-yl, piper-1-yl, etc.

When X ⁰² and X ⁰³ are alkyl groups, the number of carbon atoms of the alkyl group is preferably 1 or more and 20 or less, more preferably 1 or more and 6 or less. When X ⁰² and X ⁰³ are alkyl groups, they may be linear or branched. Specific examples when X ⁰² and X ⁰³ are alkyl groups include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, second butyl, and tertiary butyl. , N-pentyl, isopentyl, second pentyl, third pentyl, n-hexyl, n-heptyl, n-octyl, isooctyl, second octyl, third octyl, n-nonyl, isononyl Base, n-decyl, and isodecyl, etc. When X ⁰² and X ⁰³ are alkyl groups, the alkyl groups may also include ether bonds (-O-) in the carbon chain. Examples of alkyl groups having ether bonds in the carbon chain include: methoxyethyl, ethoxyethyl, methoxyethoxyethyl, ethoxyethoxyethyl, and propoxy Ethoxyethyl, and methoxypropyl, etc.

When X ⁰² and X ⁰³ are alkoxy groups, the number of carbon atoms of the alkoxy group is preferably 1 or more and 20 or less, more preferably 1 or more and 6 or less. When X ⁰² and X ⁰³ are alkoxy groups, they may be linear or branched. Specific examples when X ⁰² and X ⁰³ are alkoxy groups include: methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, second Butoxy, tertiary butoxy, n-pentyloxy, isopentyloxy, second pentyloxy, third pentyloxy, n-hexyloxy, n-heptyloxy, n-octyloxy, isooctyloxy , The second octyloxy group, the third octyloxy group, n-nonyloxy group, isononyloxy group, n-decyloxy group, and isodecyloxy group. When X ⁰² and X ⁰³ are alkoxy groups, the alkoxy group may also include an ether bond (-O-) in the carbon chain. Examples of alkoxy groups having ether bonds in the carbon chain include: methoxyethoxy, ethoxyethoxy, methoxyethoxyethoxy, and ethoxyethoxyethoxy Group, propoxyethoxyethoxy, and methoxypropoxy, etc.

When X ⁰² and X ⁰³ are cycloalkyl or cycloalkoxy, the number of carbon atoms of the cycloalkyl or cycloalkoxy is preferably 3 or more and 10 or less, more preferably 3 or more and 6 or less. Specific examples when X ⁰² and X ⁰³ are cycloalkyl groups include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, and cyclooctyl. Specific examples when X ⁰² and X ⁰³ are cycloalkoxy groups include cyclopropoxy, cyclobutoxy, cyclopentyloxy, cyclohexyloxy, cycloheptyloxy, and cyclooctyloxy Base etc.

When X ⁰² and X ⁰³ are saturated aliphatic acyl groups or saturated aliphatic acyloxy groups, the number of carbon atoms of the saturated aliphatic acyl groups or saturated aliphatic acyloxy groups is preferably from 2 to 21, more preferably 2 above 7 below. Specific examples when R ^c7 is a saturated aliphatic aliphatic group include: acetyl group, propionyl group, n-butyryl group, 2-methylpropionyl group, n-pentanyl group, 2,2-dimethyl Propyl, n-hexyl, n-heptanyl, n-octyl, n-nonanyloxy, n-decanoyl, n-undecanoyl, n-dodecanoyl, n-tridecanoyl, n-decyl Four-carbon acyl group, pentadecyl acyl group, and hexadecyl acyl group, etc. Specific examples when X ⁰² and X ⁰³ are saturated aliphatic oxy groups include: acetoxy, acetoxy, n-butoxy, 2-methylacetoxy, n-pentyl Acetyloxy, 2,2-dimethylacetoxy, n-hexyloxy, n-heptanoyloxy, n-octyloxy, n-nonanoyloxy, n-decanoyloxy, n-undecanoyloxy Oxy, n-dodecanoyloxy, n-tridecanoyloxy, n-tetradecanoyloxy, n-pentadecanoyloxy, and n-hexadecanoyloxy.

When X ⁰² and X ⁰³ are alkoxycarbonyl groups, the number of carbon atoms of the alkoxycarbonyl group is preferably 2 or more and 20 or less, more preferably 2 or more and 7 or less. Specific examples when X ⁰² and X ⁰³ are alkoxycarbonyl groups include: methoxycarbonyl, ethoxycarbonyl, n-propoxycarbonyl, isopropoxycarbonyl, n-butoxycarbonyl, iso Butoxycarbonyl, second butoxycarbonyl, third butoxycarbonyl, n-pentoxycarbonyl, isopentoxycarbonyl, second pentoxycarbonyl, third pentoxycarbonyl, n-hexoxycarbonyl, N-heptyloxycarbonyl, n-octyloxycarbonyl, isooctyloxycarbonyl, second octyloxycarbonyl, third octyloxycarbonyl, n-nonyloxycarbonyl, isononyloxycarbonyl, n-decyloxycarbonyl, And isodecyloxycarbonyl and so on.

When X ⁰² and X ⁰³ are phenylalkyl groups, the number of carbon atoms of the phenylalkyl group is preferably 7 or more and 20 or less, more preferably 7 or more and 10 or less. When X ⁰² and X ⁰³ are naphthyl alkyl groups, the number of carbon atoms of the naphthyl alkyl group is preferably 11 or more and 20 or less, more preferably 11 or more and 14 or less. Specific examples when X ⁰² and X ⁰³ are phenylalkyl groups include benzyl, 2-phenylethyl, 3-phenylpropyl, and 4-phenylbutyl. Specific examples when X ⁰² and X ⁰³ are naphthylalkyl groups include α-naphthylmethyl, β-naphthylmethyl, 2-(α-naphthyl)ethyl, and 2-( β-naphthyl) ethyl. When X ⁰² and X ⁰³ are phenylalkyl or naphthylalkyl, R ^c7 may further have a substituent on the phenyl or naphthyl group.

When X ⁰² and X ⁰³ are heterocyclic groups, the heterocyclic group is a five-membered or six-membered monocyclic ring containing more than one N, S, O, or the monocyclic rings are condensed with each other or the monocyclic ring and benzene ring From the heterocyclic group. When the heterocyclic group is a condensed ring, the number of monocyclic rings constituting the condensed ring is set to 3 or less. The heterocyclic group may be an aromatic group (heteroaryl group) or a non-aromatic group. Examples of the heterocyclic ring constituting the heterocyclic group include furan, thiophene, pyrrole, oxazole, isooxazole, thiazole, thiadiazole, isothiazole, imidazole, pyrazole, triazole, pyridine, pyridine, pyrimidine, Da, benzofuran, benzothiophene, indole, isoindole, indole, benzimidazole, benzotriazole, benzoxazole, benzothiazole, carbazole, purine, quinoline, isoquine Phytoline, quinazoline, phthaloline, quinazoline, quinoline, piperidine, piperidine, tetrahydropyran, tetrahydrofuran, etc. When R ^c7 is a heterocyclic group, the heterocyclic group may further have a substituent.

In the case where X ⁰² and X ⁰³ are heterocyclic carbonyl groups, the heterocyclic group contained in the heterocyclic carbonyl group is the same as the case where X ⁰² and X ⁰³ are heterocyclic groups.

When X ⁰² and X ⁰³ are amino groups substituted with 1 or 2 organic groups, preferable examples of the organic groups include: alkyl groups with 1 to 20 carbon atoms, and 3 to 10 carbon atoms Cycloalkyl groups, saturated aliphatic acyl groups with 2 to 21 carbon atoms, substituted phenyl groups, substituted benzyl groups, substituted groups with 7 to 20 carbon atoms Phenylalkyl, optionally substituted naphthyl, optionally substituted naphthylalkyl, optionally substituted naphthylalkyl having 11 to 20 carbon atoms, heterocyclic group, and the like. The specific examples of these preferred organic groups are the same as X ⁰² and X ⁰³ . Specific examples of the amino group substituted with one or two organic groups include: methylamino, ethylamino, diethylamino, n-propylamino, di-n-propylamino, Isopropylamino, n-butylamino, di-n-butylamino, n-pentylamino, n-hexylamino, n-heptylamino, n-octylamino, n-nonylamino, n- Decylamino, phenylamino, naphthylamino, acetylamino, propionylamino, n-butyrylamino, n-pentylamino, n-hexylamino, n-heptanylamine Group, n-octylamino group, n-decanoylamino group, benzylamino group, α-naphthoylamino group, β-naphthoylamino group, etc.

Examples of the substituents when the phenyl, naphthyl, and heterocyclic groups contained in X ⁰² and X ⁰³ further have substituents include: alkyl groups with 1 to 6 carbon atoms, and 1 or more carbon atoms Alkoxy groups with 6 or less, saturated aliphatic acyl groups with 2 to 7 carbon atoms, alkoxycarbonyl groups with 2 to 7 carbon atoms, saturated aliphatic acyloxy groups with 2 to 7 carbon atoms, Monoalkylamino groups of alkyl groups with 1 to 6 carbon atoms, dialkylamino groups with alkyl groups with 1 to 6 carbon atoms, linolin-1-yl, piperidine-1-yl, halogen , Nitro, and cyano, etc.

Where the substituents are alkyl groups with 1 to 6 carbon atoms, alkoxy groups with 1 to 6 carbon atoms, saturated aliphatic aliphatic groups with 2 to 7 carbon atoms, and 2 to 7 carbon atoms Alkoxycarbonyl group, saturated aliphatic oxy group with carbon number 2 or more and 7 or less, monoalkylamino group having alkyl group with 1 or more and 6 carbon atoms, and alkyl group with 1 or more and 6 carbon atoms In the case of the dialkylamino group of the group, an ether bond (-O-) may be included in the carbon chain of the substituents.

When the phenyl, naphthyl, and heterocyclic groups contained in X ⁰² and X ⁰³ further have substituents, the number of the substituents is not limited within a range that does not hinder the purpose of the present invention, but preferably It is 1 or more and 4 or less. When the phenyl group, the naphthyl group, and the heterocyclic group contained in X ⁰² and X ⁰³ have a plurality of substituents, the plurality of substituents may be the same or different.

X ⁰² and X ^{03 are} preferably cycloalkylalkyl, phenoxyalkyl which may have a substituent on the aromatic ring, and phenylthioalkyl which may have a substituent on the aromatic ring. The substituents that the phenoxyalkyl group and the phenylthioalkyl group may have are as described above as the substituents that the phenyl group may have.

Among the organic groups, X ⁰² and X ^{03 are} preferably alkyl, cycloalkyl, optionally substituted phenyl, or cycloalkylalkyl, or phenylthioalkyl optionally substituted on the aromatic ring . The alkyl group is preferably an alkyl group having 1 to 20 carbon atoms, more preferably an alkyl group having 1 to 8 carbon atoms, particularly preferably an alkyl group having 1 to 4 carbon atoms, and most preferably methyl base. Among the phenyl groups that may have a substituent, methylphenyl is preferred, and 2-methylphenyl is more preferred. The number of carbon atoms of the cycloalkyl group contained in the cycloalkylalkyl group is preferably 5 or more and 10 or less, more preferably 5 or more and 8 or less, and particularly preferably 5 or 6. The number of carbon atoms of the alkylene group contained in the cycloalkylalkyl group is preferably 1 or more and 8 or less, more preferably 1 or more and 4 or less, and particularly preferably 2. Among cycloalkylalkyls, cyclopentylethyl is preferred. The number of carbon atoms of the alkylene group contained in the phenylthioalkyl group which may have a substituent on the aromatic ring is preferably 1 or more and 8 or less, more preferably 1 or more and 4 or less, and particularly preferably 2. Among the phenylthioalkyl groups which may have a substituent on the aromatic ring, 2-(4-chlorophenylthio)ethyl is preferred.

X ⁰² and X ^{03 are} preferably groups represented by -A ¹ -CO-OA ² . A ¹ is a divalent organic group, preferably a divalent hydrocarbon group, preferably an alkylene group. A ² is a monovalent organic group, preferably a monovalent hydrocarbon group.

When A ¹ is an alkylene group, the alkylene group may be linear or branched, and is preferably linear. When A ¹ is an alkylene group, the number of carbon atoms of the alkylene group is preferably 1 or more and 10 or less, more preferably 1 or more and 6 or less, and particularly preferably 1 or more and 4 or less.

Preferred examples of A ² include an alkyl group having 1 to 10 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, and an aromatic hydrocarbon group having 6 to 20 carbon atoms. Preferred specific examples of A ⁴ include: methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, second butyl, tertiary butyl, n-pentyl, n-hexyl , Phenyl, naphthyl, benzyl, phenethyl, α-naphthylmethyl, and β-naphthylmethyl.

Preferred specific examples of the group represented by -A ¹ -CO-OA ² include: 2-methoxycarbonylethyl, 2-ethoxycarbonylethyl, 2-n-propoxycarbonylethyl , 2-n-butoxycarbonylethyl, 2-n-pentoxycarbonylethyl, 2-n-hexoxycarbonylethyl, 2-benzyloxycarbonylethyl, 2-phenoxycarbonylethyl, 3- Methoxycarbonyl-n-propyl, 3-ethoxycarbonyl-n-propyl, 3-n-propoxycarbonyl-n-propyl, 3-n-butoxycarbonyl-n-propyl, 3-n-pentoxy Carbonyl-n-propyl, 3-n-hexyloxycarbonyl-n-propyl, 3-benzyloxycarbonyl-n-propyl, 3-phenoxycarbonyl-n-propyl, etc.

式(C1a)及(C1b)中，X⁰⁸ 及X⁰⁹ 分別為有機基。t6為0以上4以下之整數。於X⁰⁸ 與X⁰⁹ 存在於苯環上之相鄰之位置之情形時，X⁰⁸ 及X⁰⁹ 亦可相互鍵結而形成環。t7為1以上8以下之整數。t8為1以上5以下之整數。t9為0以上(t8＋3)以下之整數。X⁰¹⁰ 為有機基。In the above, X ⁰² and X ⁰³ have been described, but X ⁰² and X ^{03 are} preferably groups represented by the following formula (C1a) or (C1b). [化25]

In formulas (C1a) and (C1b), X ⁰⁸ and X ⁰⁹ are each an organic group. t6 is an integer of 0 or more and 4 or less. When X ⁰⁸ and X ⁰⁹ exist in adjacent positions on the benzene ring, X ⁰⁸ and X ⁰⁹ may also be bonded to each other to form a ring. t7 is an integer of 1 or more and 8 or less. t8 is an integer of 1 to 5. t9 is an integer of 0 or more (t8+3). X ⁰¹⁰ is an organic base.

Examples of organic groups related to X ⁰⁸ and X ⁰⁹ in formula (C1a) are the same as X ⁰² and X ⁰³ . X ^{08 is} preferably an alkyl group or a phenyl group. When X ⁰⁸ is an alkyl group, the number of carbon atoms is preferably 1 to 10, more preferably 1 to 5, particularly preferably 1 to 3, and most preferably 1. That is, X ^{08 is} most preferably a methyl group. When X ⁰⁸ and X ^{09 are} bonded to form a ring, the ring may be an aromatic ring or an aliphatic ring. Preferred examples of the group represented by the formula (C1a) and X ⁰⁸ and X ⁰⁹ form a ring include naphth-1-yl, 1,2,3,4-tetralin-5-yl, and the like. In the above formula (C1a), t6 is an integer of 0 or more and 4 or less, preferably 0 or 1, and more preferably 0.

In the above formula (C1b), X ⁰¹⁰ is an organic group. Examples of the organic group include the same groups as the organic groups described for X ⁰² and X ⁰³ . Among the organic groups, an alkyl group is preferred. The alkyl group may be linear or branched. The number of carbon atoms of the alkyl group is preferably 1 or more and 10 or less, more preferably 1 or more and 5 or less, and particularly preferably 1 or more and 3 or less. As X ⁰¹⁰ , methyl, ethyl, propyl, isopropyl, butyl, etc. are preferably exemplified, and among these, methyl is more preferred.

In the above formula (C1b), t8 is an integer of 1 to 5, preferably an integer of 1 to 3, and more preferably 1 or 2. In the above formula (C1b), t9 is 0 or more (t8+3) or less, preferably an integer of 0 or more and 3 or less, more preferably an integer of 0 or more and 2 or less, and particularly preferably 0. In the above formula (C1b), t7 is an integer of 1 or more and 8 or less, preferably an integer of 1 or more and 5 or less, more preferably an integer of 1 or more and 3 or less, and particularly preferably 1 or 2.

In formula (C1), X ⁰⁴ and X ⁰⁵ are each independently a hydrogen atom, an optionally substituted alkyl group having 1 to 11 carbon atoms, or an optionally substituted aryl group. When X ⁰⁴ and X ⁰⁵ are alkyl groups, the substituents that X ⁰⁴ and X ⁰⁵ may have are preferably exemplified by phenyl and naphthyl. When X ⁰⁴ and X ⁰⁵ are aryl groups, as substituents that X ⁰⁴ and X ⁰⁵ may have, preferred examples include alkyl groups having 1 to 5 carbon atoms, and alkoxy groups having 1 to 5 carbon atoms. Radicals, halogen atoms, etc.

In formula (C1), as X ⁰⁴ and X ⁰⁵ , hydrogen atom, methyl, ethyl, n-propyl, isopropyl, n-butyl, phenyl, benzyl, methylphenyl, naphthalene are preferably exemplified Among them, a methyl group or a phenyl group is more preferable.

As described above, X ^{01 is} preferably a group represented by formula (C1-1aa), a group represented by formula (C1-1ba), and a group represented by formula (C1-1ca). Preferred specific examples of the oxime ester compound represented by formula (C1) when X ⁰¹ is a group represented by formula (C1-1aa) include the following compounds. [化26]

[化27]

[化28]

[化29]

Preferred specific examples of the oxime ester compound represented by formula (C1) when X ⁰¹ is a group represented by formula (C1-1ba) include the following compounds. [化30]

[化31]

Preferred specific examples of the oxime ester compound represented by formula (C1) when X ⁰¹ is a group represented by formula (C1-1ca) include the following compounds. [化32]

[化33]

[化34]

[化35]

＜Photopolymerization initiator (C-II)＞ The photosensitive resin composition and the above-mentioned photopolymerization initiator (C-II) contain other photopolymerization initiators (C-II) other than the photopolymerization initiator (CI) as the photopolymerization initiator (C) . The other photopolymerization initiator (C-II) is not particularly limited as long as it is a photopolymerization initiator that is not a photopolymerization initiator (C-I).

、2-氯9-氧硫𠮿

、2-甲硫基𠮿酮、異丙基9-氧硫𠮿

、2,4-二異丙基9-氧硫𠮿

等9-氧硫𠮿

系光聚合起始劑；2,4,6-三氯-s-三𠯤、2-苯基-4,6-雙(三氯甲基)-s-三𠯤、2-(對甲氧基苯基)-4,6-雙(三氯甲基)-s-三𠯤、2-(對甲苯基)-4,6-雙(三氯甲基)-s-三𠯤、2-向日葵基-4,6-雙(三氯甲基)-s-三𠯤、2,4-雙(三氯甲基)-6-苯乙烯基-s-三𠯤、2-(萘并-1-基)-4,6-雙(三氯甲基)-s-三𠯤、2-(4-甲氧基-萘并-1-基)-4,6-雙(三氯甲基)-s-三𠯤、2,4-三氯甲基-(向日葵基)-6-三𠯤、2,4-三氯甲基-(4'-甲氧基苯乙烯基)-6-三𠯤、2-[4-(4-甲氧基苯乙烯基)苯基]-4,6-雙(三氯甲基)-1,3,5-三𠯤等三𠯤系光聚合起始劑；咔唑系光聚合起始劑；2,2'-雙(2-氯苯基)-4,4',5,5'-四(4-乙氧基羰基苯基)-1,2'-聯咪唑、2,2'-雙(2-溴苯基)-4,4',5,5'-四(4-乙氧基羰基苯基)-1,2'-聯咪唑、2,2'-雙(2-氯苯基)-4,4',5,5'-四苯基-1,2'-聯咪唑、2,2'-雙(2,4-二氯苯基)-4,4',5,5'-四苯基-1,2'-聯咪唑、2,2'-雙(2,4,6-三氯苯基)-4,4',5,5'-四苯基-1,2'-聯咪唑、2,2'-雙(2-溴苯基)-4,4,5,5'-四苯基-1,2'-聯咪唑、2,2'-雙(2,4-二溴苯基)-4,4',5,5'-四苯基-1,2'-聯咪唑、2,2'-雙(2,4,6-三溴苯基)-4,4',5,5'-四苯基-1,2'-聯咪唑等聯咪唑系光聚合起始劑；如下述式所表示之苯并咪唑啉系光聚合起始劑等。 [化36]

As a preferable example of the photopolymerization initiator (C-II), there can be exemplified: an oxime ester compound having a structure not belonging to the above formula (C1); 2-benzyl-2-dimethylamino-1-( 4-olinylphenyl)butan-1-one, 2-methyl-1-[4-(methylthio)phenyl]-2-𠰌linepropan-1one, 2-benzyl-2- Dimethylamino-1-(4-dimethylaminophenyl)butan-1-one, 2-(4-methylbenzyl)-2-diethylamino-1-(4-𠰌) (Hydroxyphenyl)butane-1one, 2-Methyl-1-phenyl-2-(hydroxypropane-1one), 2-Methyl-1-[4-(hexyl)phenyl]-2- Α-amino ketone compounds such as 𠰌line propane-1 ketone, 2-ethyl-2-dimethylamino-1-(4-𠰌line phenyl) butane-1 one; 1-phenyl- 2-Hydroxy-2-methylpropane-1one, 1-(4-isopropylphenyl)-2-hydroxy-2-methylpropane-1one, 4-(2-hydroxyethoxy)phenyl -(2-hydroxy-2-propyl)ketone, 1-hydroxycyclohexyl phenyl ketone and other α-hydroxy ketone photopolymerization initiators; benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin propyl ether, biphenyl acetone Benzoin-based photopolymerization initiators such as dimethanol; benzophenone, benzophenone benzoic acid, methyl benzophenone benzoate, 4-phenylbenzophenone, hydroxybenzophenone, propenylated benzophenone Benzophenone-based photopolymerization initiators such as ketone, 4-benzyl, 4'-methyldiphenyl sulfide, 4,4'-bisdiethylaminobenzophenone, etc.; 9-oxygen Sulfur 𠮿

, 2-Chloro 9-oxysulfur 𠮿

, 2-methylthio ketone, isopropyl 9-oxythio 𠮿

, 2,4-Diisopropyl 9-oxysulfur 𠮿

Wait 9-oxysulfur 𠮿

System photopolymerization initiator; 2,4,6-trichloro-s-tris, 2-phenyl-4,6-bis(trichloromethyl)-s-tris, 2-(p-methoxy (Phenyl)-4,6-bis(trichloromethyl)-s-tris, 2-(p-tolyl)-4,6-bis(trichloromethyl)-s-tris, 2-sunflower -4,6-bis(trichloromethyl)-s-tris, 2,4-bis(trichloromethyl)-6-styryl-s-tris, 2-(naphtho-1-yl )-4,6-bis(trichloromethyl)-s-tris, 2-(4-methoxy-naphth-1-yl)-4,6-bis(trichloromethyl)-s- Trichloromethyl, 2,4-trichloromethyl-(sunflower)-6-tris, 2,4-trichloromethyl-(4'-methoxystyryl)-6-tris, 2- [4-(4-Methoxystyryl)phenyl]-4,6-bis(trichloromethyl)-1,3,5-tris, and other three-based photopolymerization initiators; carbazole-based Photopolymerization initiator; 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetra(4-ethoxycarbonylphenyl)-1,2'-biimidazole, 2,2'-Bis(2-bromophenyl)-4,4',5,5'-tetra(4-ethoxycarbonylphenyl)-1,2'-biimidazole, 2,2'-bis (2-chlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis(2,4-dichlorophenyl)-4,4 ',5,5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis(2,4,6-trichlorophenyl)-4,4',5,5'-tetraphenyl -1,2'-biimidazole, 2,2'-bis(2-bromophenyl)-4,4,5,5'-tetraphenyl-1,2'-biimidazole, 2,2'- Bis(2,4-dibromophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis(2,4,6-tribromobenzene Group) -4,4',5,5'-tetraphenyl-1,2'-biimidazole and other biimidazole-based photopolymerization initiators; benzimidazoline-based photopolymerization initiators represented by the following formula Wait. [化36]

In terms of easily obtaining the desired effect, the photosensitive resin composition preferably contains an oxime ester compound and/or an α-amine ketone compound as the photopolymerization initiator (C-II), and more preferably The oxime ester compound and the α-amine ketone compound are included in combination.

Regarding the oxime ester compound as the photopolymerization initiator (C-II), the oxime ester compound represented by the following formula (C2) is particularly preferred. [化37]

式(C2-1)中，R^c4 為選自由一價有機基、胺基、鹵素、硝基、及氰基所組成之群中之基。A為S或O。n2為0以上4以下之整數。 式(C2-2)中，R^c5 及R^c6 分別獨立為一價有機基。 式(C2-3)中，R^c7 為氫原子、硝基或一價有機基。R^c8 及R^c9 分別為可具有取代基之鏈狀烷基、可具有取代基之環狀有機基或氫原子。R^c8 與R^c9 亦可相互鍵結而形成環。n3為0以上4以下之整數。In formula (C2), R ^c1 is a monovalent organic group. R ^c2 is a group represented by any one of the following formulas (C2-1) to (C2-3). R ^c3 is a hydrogen atom, an optionally substituted alkyl group having 1 to 11 carbon atoms, or an optionally substituted aryl group. [化38]

In the formula (C2-1), R ^c4 is a group selected from the group consisting of a monovalent organic group, an amine group, a halogen, a nitro group, and a cyano group. A is S or O. n2 is an integer of 0 or more and 4 or less. In formula (C2-2), R ^c5 and R ^c6 are each independently a monovalent organic group. In the formula (C2-3), R ^c7 is a hydrogen atom, a nitro group or a monovalent organic group. R ^c8 and R ^c9 are each a linear alkyl group which may have a substituent, a cyclic organic group which may have a substituent, or a hydrogen atom. R ^c8 and R ^c9 may be bonded to each other to form a ring. n3 is an integer of 0 or more and 4 or less.

The R ^c1 monovalent organic group in the formula (C2) is the same as the monovalent organic group described above for X ⁰² and X ⁰³ in the formula (C1). The R ^c1 monovalent organic group is preferably a group represented by the following formula (C2a) or (C2b). [化39]

In formulas (C2a) and (C2b), R ^c10 and R ^c11 are each a monovalent organic group. n4 is an integer of 0 or more and 4 or less. When R ^c10 and R ^c11 exist in adjacent positions on the benzene ring, R ^c10 and R ^c11 may also be bonded to each other to form a ring. n5 is an integer of 1 or less and 8 or less. n6 is an integer of 1 to 5. n7 is an integer of 0 or more (n6+3). R ^c12 is a monovalent organic group.

R ^c10 , R ^c11 , and n4 in formula (C2a) are the same as X ⁰⁸ , X ⁰⁹ , and t6 in formula (C1a) described in formula (C1) above, respectively. R ^c12 , n5, n6, and n7 in formula (C2b) are the same as X ⁰¹⁰ , t7, t8 and t9 in formula (C1b) described in formula (C1) above, respectively.

Hereinafter, regarding R ^c2 , the group represented by the formula (C2-1), the group represented by the formula (C2-2), and the group represented by the formula (C2-3) will be described respectively.

The group represented by the formula (C2-1) is a monovalent organic group with the following structure. [化40]

When R ^c4 in the formula (C2-1) is an organic group, it can be selected from various organic groups within a range that does not hinder the purpose of the present invention. As a preferable example when R ^c4 is an organic group in the formula (C2-1), an alkyl group having 1 to 6 carbon atoms; an alkoxy group having 1 to 6 carbon atoms; a carbon atom Saturated aliphatic acyl group with 2 to 7 and less than 7; alkoxycarbonyl group with 2 to 7 carbon atoms; saturated aliphatic acyloxy with 2 to 7 carbon atoms; phenyl group; naphthyl group; benzyl group ; Naphthyl; benzyl substituted with a group selected from the group consisting of alkyl having 1 to 6 carbon atoms, linolin-1-yl, piperid-1-yl, and phenyl ; A monoalkylamino group with an alkyl group having 1 to 6 carbon atoms; a dialkylamino group with an alkyl group having 1 to 6 carbon atoms; 𠰌line-1-yl; piper𠯤-1-yl ; Halogen; Nitro; Cyano.

In R ^c4 , preferably benzyl; naphthyl; selected from alkyl groups with 1 to 6 carbon atoms, linolin-1-yl, piper-1-yl, and phenyl group Benzyl; nitro; more preferably benzyl; naphthyl; 2-methylphenylcarbonyl; 4-(piperid-1-yl)phenylcarbonyl; 4-(phenyl)phenylcarbonyl.

Moreover, in the formula (C2-1), n2 is preferably an integer of 0 or more and 3 or less, more preferably an integer of 0 or more and 2 or less, and particularly preferably 0 or 1. In the case when n2 is 1, the position of bonding of R ^c4 is preferably bonded with respect to the R ^c4 phenyl group or a sulfur atom and an oxygen atom bonded to the bonding position for the key.

The group represented by the formula (C2-2) is a monovalent organic group with the following structure. [化41]

R ^c5 in formula (C2-2) can be selected from various organic groups within a range that does not hinder the purpose of the present invention. Preferable examples of R ^c5 include: alkyl groups with 1 to 20 carbon atoms, cycloalkyls with 3 to 10 carbon atoms, saturated aliphatic acyl groups with 2 to 20 carbon atoms, and carbon atoms Alkoxycarbonyl groups having a number of 2 or more and 20 or less, a phenyl group that may have a substituent, a benzyl group that may have a substituent, a phenoxycarbonyl group that may have a substituent, and a carbon atom number of 7 or more that may have a substituent 20 The following phenylalkyl groups, naphthyl groups that may have substituents, naphthyl groups that may have substituents, naphthyloxycarbonyl groups that may have substituents, and naphthyl groups with 11 to 20 carbon atoms that may have substituents An alkyl group, a heterocyclic group which may have a substituent, a heterocyclic carbonyl group which may have a substituent, and the like.

In R ^c5 , an alkyl group having 1 to 20 carbon atoms is preferred, an alkyl group having 1 to 6 carbon atoms is more preferred, and an ethyl group is particularly preferred.

R ^c6 in the formula (C2-2) is not particularly limited within a range that does not interfere with the purpose of the present invention, and can be selected from various organic groups. Specific examples of groups suitable as R ^c6 include: alkyl groups having 1 to 20 carbon atoms, phenyl groups which may have substituents, naphthyl groups which may have substituents, and heterocyclic groups which may have substituents . As R ^c6 , among these groups, a phenyl group which may have a substituent is more preferable, and a 2-methylphenyl group is particularly preferable.

Examples of the substituent when the phenyl, naphthyl, and heterocyclic group contained in R ^c5 or R ^c6 further have a substituent include: an alkyl group having 1 to 6 carbon atoms and 1 or more carbon atoms Alkoxy groups with 6 or less, saturated aliphatic acyl groups with 2 to 7 carbon atoms, alkoxycarbonyl groups with 2 to 7 carbon atoms, saturated aliphatic acyloxy groups with 2 to 7 carbon atoms, Monoalkylamino groups of alkyl groups with 1 to 6 carbon atoms, dialkylamino groups with alkyl groups with 1 to 6 carbon atoms, linolin-1-yl, piperidine-1-yl, halogen , Nitro, and cyano, etc. When the phenyl, naphthyl, and heterocyclic groups contained in R ^c5 or R ^c6 further have substituents, the number of substituents is not limited within a range that does not hinder the purpose of the present invention, but it is preferred It is 1 or more and 4 or less. When the phenyl group, naphthyl group, and heterocyclic group contained in R ^c5 or R ^c6 have a plurality of substituents, the plurality of substituents may be the same or different.

The group represented by the formula (C2-3) is a monovalent organic group with the following structure. [化42]

In the formula (C2-3), R ^c7 is a hydrogen atom, a nitro group or a monovalent organic group. R ^c8 and R ^c9 are each a linear alkyl group which may have a substituent, a cyclic organic group which may have a substituent, or a hydrogen atom. R ^c8 and R ^c9 may be bonded to each other to form a ring. n3 is an integer of 0 or more and 4 or less.

In the formula (C2-3), R ^c7 is a hydrogen atom, a nitro group or a monovalent organic group. R ^c7 is bonded to the six-membered aromatic ring different from the six-membered aromatic ring bonded to the group represented by -(CO) _n1 -on the sulphur ring in the formula (C2-3). In the formula (C2-3), R ^c7 has no particular limitation on the bonding position of the chrysanthemum ring. When the compound represented by formula (C2-3) has one or more R ^c7 , in terms of easy synthesis of the compound represented by formula (C2-3), etc., preferably one or more R ^c7 One of the bonds is in the second position of the tea ring. When R ^c7 is plural, the plural R ^c7 may be the same or different.

When R ^c7 is an organic group, R ^c7 is not particularly limited within a range that does not hinder the purpose of the present invention, and is appropriately selected from various organic groups. Preferable examples when R ^c7 is an organic group include: alkyl, alkoxy, cycloalkyl, cycloalkoxy, saturated aliphatic acyl group, saturated aliphatic acyloxy group, and alkoxycarbonyl group. , Phenyl which may have substituents, phenoxy which may have substituents, benzyloxy which may have substituents, phenoxycarbonyl which may have substituents, benzyloxy which may have substituents, A substituted phenylalkyl group, a substituted naphthyl group, a substituted naphthyloxy group, a substituted naphthyloxy group, a substituted naphthoxycarbonyl group, a substituted naphthyl group The naphthyloxy group, the naphthyl alkyl group that may have substituents, the heterocyclic group that may have substituents, the heterocyclic carbonyl group that may have substituents, the amino group substituted by 1 or 2 organic groups, 𠰌 Lin-1-yl, piper-1-yl, etc.

When R ^c7 is an alkyl group, the number of carbon atoms of the alkyl group is preferably 1 or more and 20 or less, more preferably 1 or more and 6 or less. In addition, when R ^c7 is an alkyl group, it may be a straight chain or a branched chain. Specific examples when R ^c7 is an alkyl group include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, second butyl, tertiary butyl, n-pentyl Base, isopentyl, second pentyl, third pentyl, n-hexyl, n-heptyl, n-octyl, isooctyl, second octyl, third octyl, n-nonyl, isononyl, n Decyl, and isodecyl, etc. In addition, when R ^c7 is an alkyl group, the alkyl group may include an ether bond (-O-) in the carbon chain. Examples of alkyl groups having ether bonds in the carbon chain include: methoxyethyl, ethoxyethyl, methoxyethoxyethyl, ethoxyethoxyethyl, and propoxy Ethoxyethyl, and methoxypropyl, etc.

When R ^c7 is an alkoxy group, the number of carbon atoms of the alkoxy group is preferably 1 or more and 20 or less, and more preferably 1 or more and 6 or less. In addition, when R ^c7 is an alkoxy group, it may be linear or branched. Specific examples when R ^c7 is an alkoxy group include: methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, and second butoxy , Tertiary butoxy, n-pentyloxy, isopentyloxy, second pentyloxy, third pentyloxy, n-hexyloxy, n-heptyloxy, n-octyloxy, isooctyloxy, second Octyloxy, tertiary octyloxy, n-nonyloxy, isononyloxy, n-decyloxy, and isodecyloxy, etc. In addition, when R ^c7 is an alkoxy group, the alkoxy group may include an ether bond (-O-) in the carbon chain. Examples of alkoxy groups having ether bonds in the carbon chain include: methoxyethoxy, ethoxyethoxy, methoxyethoxyethoxy, and ethoxyethoxyethoxy Group, propoxyethoxyethoxy, and methoxypropoxy, etc.

When R ^c7 is a cycloalkyl group or a cycloalkoxy group, the number of carbon atoms of the cycloalkyl group or a cycloalkoxy group is preferably 3 or more and 10 or less, more preferably 3 or more and 6 or less. Specific examples when R ^c7 is a cycloalkyl group include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, and cyclooctyl. Specific examples when R ^c7 is a cycloalkoxy group include cyclopropoxy, cyclobutoxy, cyclopentyloxy, cyclohexyloxy, cycloheptyloxy, and cyclooctyloxy.

When R ^c7 is a saturated aliphatic acyl group or a saturated aliphatic acyloxy group, the number of carbon atoms of the saturated aliphatic acyl group or saturated aliphatic acyloxy group is preferably from 2 to 21, more preferably from 2 to 7 the following. Specific examples when R ^c7 is a saturated aliphatic aliphatic group include: acetyl group, propionyl group, n-butyryl group, 2-methylpropionyl group, n-pentanyl group, 2,2-dimethyl Propyl, n-hexyl, n-heptanyl, n-octyl, n-nonanyloxy, n-decanoyl, n-undecanoyl, n-dodecanoyl, n-tridecanoyl, n-decyl Four-carbon acyl group, pentadecyl acyl group, and hexadecyl acyl group, etc. Specific examples of the case where R ^c7 is a saturated aliphatic oxy group include: acetoxy group, acetoxy group, n-butoxy group, 2-methyl acetoxy group, n-pentoxy group , 2,2-Dimethylacetoxy, n-hexyloxy, n-heptyloxy, n-octyloxy, n-nonyloxy, n-decanoyloxy, n-undecanoyloxy, N-dodecanoyloxy, n-tridecanoyloxy, n-tetradecanoyloxy, n-pentadecanoyloxy, and n-hexadecanoyloxy.

When R ^c7 is an alkoxycarbonyl group, the number of carbon atoms of the alkoxycarbonyl group is preferably 2 or more and 20 or less, more preferably 2 or more and 7 or less. Specific examples when R ^c7 is an alkoxycarbonyl group include: methoxycarbonyl, ethoxycarbonyl, n-propoxycarbonyl, isopropoxycarbonyl, n-butoxycarbonyl, and isobutoxy Carbonyl, second butoxycarbonyl, third butoxycarbonyl, n-pentoxycarbonyl, isopentoxycarbonyl, second pentoxycarbonyl, third pentoxycarbonyl, n-hexoxycarbonyl, n-heptoxy Carbonyl, n-octyloxycarbonyl, isooctyloxycarbonyl, second octyloxycarbonyl, third octyloxycarbonyl, n-nonyloxycarbonyl, isononyloxycarbonyl, n-decyloxycarbonyl, and isodecyl Oxycarbonyl and so on.

When R ^c7 is a phenylalkyl group, the number of carbon atoms of the phenylalkyl group is preferably 7 or more and 20 or less, more preferably 7 or more and 10 or less. ^Furthermore , when R ^c7 is a naphthylalkyl group, the number of carbon atoms of the naphthylalkyl group is preferably 11 or more and 20 or less, more preferably 11 or more and 14 or less. Specific examples when R ^c7 is a phenylalkyl group include benzyl, 2-phenylethyl, 3-phenylpropyl, and 4-phenylbutyl. Specific examples when R ^c7 is naphthylalkyl include α-naphthylmethyl, β-naphthylmethyl, 2-(α-naphthyl)ethyl, and 2-(β-naphthalene基)ethyl. When R ^c7 is phenylalkyl or naphthylalkyl, R ^c7 may further have a substituent on the phenyl or naphthyl group.

When R ^c7 is a heterocyclic group, the heterocyclic group is a five-membered or six-membered monocyclic ring containing more than one N, S, O, or a condensation of the monocyclic rings or the monocyclic ring with a benzene ring Heterocyclic group. When the heterocyclic group is a condensed ring, the number of rings is 3 at most. The heterocyclic group may be an aromatic group (heteroaryl group) or a non-aromatic group. Examples of the heterocyclic ring constituting the heterocyclic group include furan, thiophene, pyrrole, oxazole, isooxazole, thiazole, thiadiazole, isothiazole, imidazole, pyrazole, triazole, pyridine, pyridine, pyrimidine, Da, benzofuran, benzothiophene, indole, isoindole, indole, benzimidazole, benzotriazole, benzoxazole, benzothiazole, carbazole, purine, quinoline, isoquine Phytoline, quinazoline, phthaloline, quinazoline, quinoline, piperidine, piperidine, quinoline, piperidine, tetrahydropyran, and tetrahydrofuran, etc. When R ^c7 is a heterocyclic group, the heterocyclic group may further have a substituent.

When R ^c7 is a heterocyclic carbonyl group, the heterocyclic group contained in the heterocyclic carbonyl group is the same as the case where R ^c7 is a heterocyclic group.

When R ^c7 is an amine group substituted with one or two organic groups, preferable examples of the organic group include: alkyl groups with 1 to 20 carbon atoms, and cycloalkanes with 3 to 10 carbon atoms. Groups, saturated aliphatic acyl groups with 2 to 21 carbon atoms, phenyl groups that may have substituents, benzoyl groups that may have substituents, phenylalkanes with 7 to 20 carbon atoms that may have substituents Group, optionally substituted naphthyl group, optionally substituted naphthylmethyl group, optionally substituted naphthylalkyl group having 11 to 20 carbon atoms, heterocyclic group, etc. The specific examples of these preferable organic groups are the same as R ^c7 . Specific examples of the amino group substituted with one or two organic groups include: methylamino, ethylamino, diethylamino, n-propylamino, di-n-propylamino, Isopropylamino, n-butylamino, di-n-butylamino, n-pentylamino, n-hexylamino, n-heptylamino, n-octylamino, n-nonylamino, n- Decylamino, phenylamino, naphthylamino, acetylamino, propionylamino, n-butyrylamino, n-pentylamino, n-hexylamino, n-heptanylamine Group, n-octylamino group, n-decanoylamino group, benzylamino group, α-naphthoylamino group, β-naphthoylamino group, etc.

Examples of the substituent when the phenyl, naphthyl, and heterocyclic group contained in R ^c7 further have a substituent include: an alkyl group having 1 to 6 carbon atoms, and an alkyl group having 1 to 6 carbon atoms Alkoxy groups, saturated aliphatic acyl groups with 2 to 7 carbon atoms, alkoxycarbonyl groups with 2 to 7 carbon atoms, saturated aliphatic oxy groups with 2 to 7 carbon atoms, and carbon atoms A monoalkylamino group of an alkyl group of 1 to 6 or less, a dialkylamino group of an alkyl group of 1 to 6 carbon atoms, linolin-1-yl, piperidine-1-yl, halogen, nitro , And cyano etc. When the phenyl, naphthyl, and heterocyclic groups contained in R ^c7 further have substituents, the number of substituents is not limited within a range that does not interfere with the purpose of the present invention, but it is preferably 1 or more 4 or less. When the phenyl group, the naphthyl group, and the heterocyclic group contained in R ^c7 have a plurality of substituents, the plurality of substituents may be the same or different.

Among the groups described above, if R ^{c7 is a} group represented by a nitro group or R ^c12 -CO-, the sensitivity tends to increase. R ^c12 is not particularly limited within a range that does not interfere with the purpose of the present invention, and it can be selected from various organic groups. Examples of groups suitable as R ^c12 include alkyl groups having 1 to 20 carbon atoms, phenyl groups which may have substituents, naphthyl groups which may have substituents, and heterocyclic groups which may have substituents. As R ^c12 , among these groups, 2-methylphenyl, thiophen-2-yl, and α-naphthyl are particularly preferred.

In the formula (C2-3), R ^c8 and R ^c9 are each a linear alkyl group which may have a substituent, a cyclic organic group which may have a substituent, or a hydrogen atom. R ^c8 and R ^c9 may be bonded to each other to form a ring. Among these groups, R ^c8 and R ^{c9 are} preferably a chain alkyl group which may have a substituent. When R ^c8 and R ^c9 are a chain alkyl group which may have a substituent, the chain alkyl group may be a straight chain alkyl group or a branched chain alkyl group.

When R ^c8 and R ^c9 are chain alkyl groups without substituents, the number of carbon atoms of the chain alkyl group is preferably 1 or more and 20 or less, more preferably 1 or more and 10 or less, and particularly preferably 1 or more and 6 the following. Specific examples when R ^c8 and R ^c9 are chain alkyl groups include: methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, second butyl, and third Butyl, n-pentyl, isopentyl, second pentyl, third pentyl, n-hexyl, n-heptyl, n-octyl, isooctyl, second octyl, third octyl, n-nonyl, Isononyl, n-decyl, and isodecyl, etc. In addition, when R ^c8 and R ^c9 are an alkyl group, the alkyl group may include an ether bond (-O-) in the carbon chain. Examples of alkyl groups having ether bonds in the carbon chain include: methoxyethyl, ethoxyethyl, methoxyethoxyethyl, ethoxyethoxyethyl, and propoxy Ethoxyethyl, and methoxypropyl, etc.

When R ^c8 and R ^c9 are chain alkyl groups with substituents, the number of carbon atoms of the chain alkyl group is preferably from 1 to 20, more preferably from 1 to 10, and particularly preferably from 1 to 6 . In this case, the number of carbon atoms of the substituent is not included in the number of carbon atoms of the chain alkyl group. The chain alkyl group having a substituent is preferably linear. The substitution that the alkyl group may have is not particularly limited as long as it does not interfere with the purpose of the present invention. Preferred examples of the substituent include a cyano group, a halogen atom, a cyclic organic group, and an alkoxycarbonyl group. Examples of halogen atoms include fluorine atoms, chlorine atoms, bromine atoms, and iodine atoms. Among these, a fluorine atom, a chlorine atom, and a bromine atom are preferable. Examples of the cyclic organic group include cycloalkyl groups, aromatic hydrocarbon groups, and heterocyclic groups. The specific examples of the cycloalkyl group are the same as the preferred examples when R ^c7 is a cycloalkyl group. Specific examples of aromatic hydrocarbon groups include phenyl, naphthyl, biphenyl, anthracenyl, and phenanthryl. The specific examples of the heterocyclic group are the same as the preferable examples when R ^c7 is a heterocyclic group. When the substituent is an alkoxycarbonyl group, the alkoxy group contained in the alkoxycarbonyl group may be linear or branched, and is preferably linear. The number of carbon atoms of the alkoxy group contained in the alkoxycarbonyl group is preferably 1 or more and 10 or less, more preferably 1 or more and 6 or less.

When the chain alkyl group has a substituent, the number of substituents is not particularly limited. The number of preferred substituents varies according to the number of carbon atoms of the chain alkyl group. The number of substituents is typically 1 or more and 20 or less, preferably 1 or more and 10 or less, more preferably 1 or more and 6 or less.

When R ^c8 and R ^c9 are cyclic organic groups, the cyclic organic group may be an alicyclic group or an aromatic group. Examples of the cyclic organic group include an aliphatic cyclic hydrocarbon group, an aromatic hydrocarbon group, and a heterocyclic group. When R ^c8 and R ^c9 are cyclic organic groups, the substituents that the cyclic organic group may have are the same as when R ^c8 and R ^c9 are chain alkyl groups.

When R ^c8 and R ^c9 are aromatic hydrocarbon groups, the aromatic hydrocarbon group is preferably a phenyl group, or a group formed by bonding multiple benzene rings via carbon-carbon bonds, or a group formed by condensation of multiple benzene rings . When the aromatic hydrocarbon group is a phenyl group or a group formed by bonding or condensation of a plurality of benzene rings, the number of benzene rings contained in the aromatic hydrocarbon group is not particularly limited, and it is preferably 3 or less, more preferably It is 2 or less, particularly preferably 1. Preferable specific examples of the aromatic hydrocarbon group include phenyl, naphthyl, biphenyl, anthracenyl, and phenanthryl.

When R ^c8 and R ^c9 are an aliphatic cyclic hydrocarbon group, the aliphatic cyclic hydrocarbon group may be monocyclic or polycyclic. The number of carbon atoms of the aliphatic cyclic hydrocarbon group is not particularly limited, but it is preferably 3 or more and 20 or less, and more preferably 3 or more and 10 or less. Examples of monocyclic cyclic hydrocarbon groups include: cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, nordoxyl, isooxyl, tricyclononyl, Tricyclodecyl, tetracyclododecyl, adamantyl, etc.

When R ^c8 and R ^c9 are heterocyclic groups, the heterocyclic group is a five-membered or six-membered monocyclic ring containing more than one N, S, O, or the monocyclic rings are condensed with each other or the monocyclic ring and benzene ring From the heterocyclic group. When the heterocyclic group is a condensed ring, the number of rings is 3 at most. The heterocyclic group may be an aromatic group (heteroaryl group) or a non-aromatic group. Examples of the heterocyclic ring constituting the heterocyclic group include furan, thiophene, pyrrole, oxazole, isooxazole, thiazole, thiadiazole, isothiazole, imidazole, pyrazole, triazole, pyridine, pyridine, pyrimidine, Da, benzofuran, benzothiophene, indole, isoindole, indole, benzimidazole, benzotriazole, benzoxazole, benzothiazole, carbazole, purine, quinoline, isoquine Phytoline, quinazoline, phthaloline, quinazoline, quinoline, piperidine, piperidine, quinoline, piperidine, tetrahydropyran, and tetrahydrofuran, etc.

R ^c8 and R ^c9 may be bonded to each other to form a ring. The group including the ring formed by R ^c8 and R ^c9 is preferably a cycloalkylene group. When R ^c8 and R ^{c9 are} bonded to form a cycloalkylene group, the ring constituting the cycloalkylene group is preferably a five-membered ring to a six-membered ring, and more preferably a five-membered ring.

When the group formed by the bonding of R ^c8 and R ^c9 is a cycloalkylene group, the cycloalkylene group may be condensed with one or more other rings. Examples of the ring that can be condensed with the cycloalkylene ring include benzene ring, naphthalene ring, cyclobutane ring, cyclopentane ring, cyclohexane ring, cycloheptane ring, cyclooctane ring, furan ring, Thiophene ring, pyrrole ring, pyridine ring, pyridine ring, and pyrimidine ring, etc.

Among R ^c8 and R ^c9 described above, examples of preferable groups include groups represented by the formula -A ⁰¹ -A ⁰² . In the formula, A ⁰¹ is a linear alkylene group, and A ^{02 can} be exemplified by an alkoxy group, a cyano group, a halogen atom, a halogenated alkyl group, a cyclic organic group, or an alkoxycarbonyl group.

The number of carbon atoms of the linear alkylene group of A ⁰¹ is preferably 1 or more and 10 or less, more preferably 1 or more and 6 or less. When A ⁰² is an alkoxy group, the alkoxy group may be linear or branched, preferably linear. The number of carbon atoms of the alkoxy group is preferably 1 or more and 10 or less, more preferably 1 or more and 6 or less. When A ⁰² is a halogen atom, it is preferably a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom, and more preferably a fluorine atom, a chlorine atom, or a bromine atom. When A ⁰² is a halogenated alkyl group, the halogen atom contained in the halogenated alkyl group is preferably a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom, and more preferably a fluorine atom, a chlorine atom, or a bromine atom. The halogenated alkyl group may be linear or branched, and is preferably linear. When A ⁰² is a cyclic organic group, examples of the cyclic organic group are the same as the cyclic organic groups that R ^c8 and R ^{c9 have} as substituents. When A ⁰² is an alkoxycarbonyl group, examples of the alkoxycarbonyl group are the same as the alkoxycarbonyl group that R ^c8 and R ^{c9 have} as substituents.

Preferred specific examples of R ^c8 and R ^c9 include alkyl groups such as ethyl, n-propyl, n-butyl, n-hexyl, n-heptyl, and n-octyl; 2-methoxyethyl, 3 -Methoxy-n-propyl, 4-methoxy-n-butyl, 5-methoxy-n-pentyl, 6-methoxy-n-hexyl, 7-methoxy-n-heptyl, 8- Methoxy-n-octyl, 2-ethoxyethyl, 3-ethoxy-n-propyl, 4-ethoxy-n-butyl, 5-ethoxy-n-pentyl, 6-ethoxy Alkyl-n-hexyl, 7-ethoxy-n-heptyl, and 8-ethoxy-n-octyl and other alkoxyalkyl groups; 2-cyanoethyl, 3-cyano-n-propyl, 4- Cyanoalkyl groups such as cyano-n-butyl, 5-cyano-n-pentyl, 6-cyano-n-hexyl, 7-cyano-n-heptyl, and 8-cyano-n-octyl; 2- Phenylethyl, 3-phenyl-n-propyl, 4-phenyl-n-butyl, 5-phenyl-n-pentyl, 6-phenyl-n-hexyl, 7-phenyl-n-heptyl, and Phenylalkyl such as 8-phenyl-n-octyl; 2-cyclohexylethyl, 3-cyclohexyl-n-propyl, 4-cyclohexyl-n-butyl, 5-cyclohexyl-n-pentyl, 6- Cyclohexyl-n-hexyl, 7-cyclohexyl-n-heptyl, 8-cyclohexyl-n-octyl, 2-cyclopentylethyl, 3-cyclopentyl-n-propyl, 4-cyclopentyl-n-butyl Cycloalkylalkyl groups such as 5-cyclopentyl-n-pentyl, 6-cyclopentyl-n-hexyl, 7-cyclopentyl-n-heptyl, and 8-cyclopentyl-n-octyl; 2- Methoxycarbonylethyl, 3-methoxycarbonyl-n-propyl, 4-methoxycarbonyl-n-butyl, 5-methoxycarbonyl-n-pentyl, 6-methoxycarbonyl-n-hexyl, 7-Methoxycarbonyl-n-heptyl, 8-methoxycarbonyl-n-octyl, 2-ethoxycarbonylethyl, 3-ethoxycarbonyl-n-propyl, 4-ethoxycarbonyl-n Alkoxy groups such as butyl, 5-ethoxycarbonyl-n-pentyl, 6-ethoxycarbonyl-n-hexyl, 7-ethoxycarbonyl-n-heptyl, and 8-ethoxycarbonyl-n-octyl Carbonyl alkyl; 2-chloroethyl, 3-chloro-n-propyl, 4-chloro-n-butyl, 5-chloro-n-pentyl, 6-chloro-n-hexyl, 7-chloro-n-heptyl, 8 -Chloro-n-octyl, 2-bromoethyl, 3-bromo-n-propyl, 4-bromo-n-butyl, 5-bromo-n-pentyl, 6-bromo-n-hexyl, 7-bromo-n-heptyl Alkyl, 8-bromo-n-octyl, 3,3,3-trifluoropropyl, and 3,3,4,4,5,5,5-heptafluoro-n-pentyl and other halogenated alkyl groups.

As R ^c8 and R ^c9 , among the above, preferred groups are ethyl, n-propyl, n-butyl, n-pentyl, 2-methoxyethyl, 2-cyanoethyl, 2-phenylethyl Group, 2-cyclohexylethyl, 2-methoxycarbonylethyl, 2-chloroethyl, 2-bromoethyl, 3,3,3-trifluoropropyl, and 3,3,4,4, 5,5,5-Heptafluoro-n-pentyl.

Among the oxime ester compounds represented by the formula (C2), R ^c1 is preferably a compound represented by the formula (C2a), R ^c10 is a methyl group, and R ^c2 is a compound represented by the formula (C2-1). The oxime ester compound is specifically a compound represented by the following formula (C2-I). [化43]

In the formula (C2-I), R ^c3 and the same as the formula (C2) R ^c3. In the formula ^{(C2-II), R c4} , in the A, and n2 in the formula (C2-1) R ^c4, the same as A, and n2. In the formula (C2-I), the same as R ^c11 and R ^c11 n4 and n4 in the formula (C2a).

Moreover, among the oxime ester compounds represented by formula (C2), it is preferable that R ^c3 is also a compound represented by formula (C2-3). The oxime ester compound is specifically a compound represented by the following formula (C2-II). [化44]

Of formula (C2-II), the same as R ^c1 and R ^c3 of the formula (C2) R ^c1 and R ^c3. In formula (C2-II), R ^c7 and R ^c are the same as R ^c1 and R ^c3 in formula (C2).

Preferred specific examples of the oxime ester compound represented by the formula (C2-I) include the following compounds.

[化45]

[化46]

[化47]

[化48]

[化49]

[化50]

Preferred specific examples of the oxime ester compound represented by formula (C2-II) include the following compounds.

[化51]

[化52]

The content of the photopolymerization initiator (C) is preferably 0.1% by mass or more and 30% by mass or less, and more preferably 0.5% by mass or more and 20% by mass or less with respect to the total mass of the solid components of the photosensitive resin composition. By setting the content of the photopolymerization initiator (C) in the above range, it is possible to obtain a photosensitive resin composition having good curability and less likely to cause defects in the pattern shape.

As described above, the photosensitive resin composition contains the photopolymerization initiator (CI) represented by the following formula (C1) and the photopolymerization initiator (C-II) other than the photopolymerization initiator (CI) As a photopolymerization initiator (C). The mass ratio of the photopolymerization initiator (CI) in the mass of the photopolymerization initiator (C) is 20% by mass to 95% by mass, more preferably 25% by mass to 90% by mass, and more preferably 30 The mass% is above 85% by mass.

When the photopolymerization initiator (C-II) contains an α-aminoketone compound, the mass ratio of the α-aminoketone compound in the mass of the photopolymerization initiator (C-II) is not particularly limited. When the photopolymerization initiator (C-II) contains an α-aminoketone compound, the mass ratio of the α-aminoketone compound in the mass of the photopolymerization initiator (C-II) is preferably 5 mass % Or more and 100 mass% or less, more preferably 10 mass% or more and 50 mass% or less, and still more preferably 20 mass% or more and 40 mass% or less.

When the photopolymerization initiator (C-II) is a combination of an oxime ester compound other than the photopolymerization initiator (CI) and an α-amine ketone compound, the photopolymerization initiator (C-II) The ratio of the total mass of the oxime ester compound to the mass of the α-amine ketone compound in the mass is not particularly limited. The total ratio of the mass of the oxime ester compound to the mass of the α-aminoketone compound in the mass of the photopolymerization initiator (C-II) is preferably 50% by mass or more, more preferably 70% by mass or more, and more It is preferably 80% by mass or more, more preferably 90% by mass or more, and particularly preferably 100% by mass.

When the photopolymerization initiator (C-II) combines an oxime ester compound other than the photopolymerization initiator (CI) and an α-aminoketone-based compound to include, the mass of the α-aminoketone-based compound is relative to the oxime The ratio of the total mass of the ester compound to the mass of the α-amine ketone compound is preferably 5% by mass to 50% by mass, more preferably 10% by mass to 45% by mass, and particularly preferably 20% by mass to 40% by mass %the following.

＜Colorant (D)＞ The photosensitive resin composition may further contain a coloring agent (D). By containing the colorant (D), the photosensitive resin composition is preferably used for forming a color filter of a liquid crystal display, for example. In addition, the photosensitive resin composition contains a light-shielding agent (D1) as a coloring agent (D), for example, it is preferably used for the purpose of forming a black matrix in a color filter of a display device.

The coloring agent (D) contained in the photosensitive resin composition is not particularly limited. For example, it is preferably used in the dye index (CI; issued by The Society of Dyers and Colourists) and is classified as a pigment (Pigment) Compounds are specifically those marked with the following dye index (CI) numbers.

Examples of yellow pigments that can be used appropriately include: CI Pigment Yellow 1 (hereinafter, "CI Pigment Yellow" is the same, and only the numbers are described), 3, 11, 12, 13, 14, 15, 16, 17, 20, 24, 31, 53, 55, 60, 61, 65, 71, 73, 74, 81, 83, 86, 93, 95, 97, 98, 99, 100, 101, 104, 106, 108, 109, 110, 113, 114, 116, 117, 119, 120, 125, 126, 127, 128, 129, 137, 138, 139, 147, 148, 150, 151, 152, 153, 154, 155, 156, 166, 167, 168, 175, 180, and 185.

Examples of orange pigments that can be suitably used include: CI Pigment Orange 1 (hereinafter, "CI Pigment Orange" is the same, and only the numbers are described), 5, 13, 14, 16, 17, 24, 34, 36, 38, 40, 43, 46, 49, 51, 55, 59, 61, 63, 64, 71, and 73.

Examples of purple pigments that can be suitably used include: CI Pigment Violet 1 (hereinafter, "CI Pigment Violet" is the same, and only the numbers are described), 19, 23, 29, 30, 32, 36, 37, 38, 39, 40, and 50.

Examples of red pigments that can be used appropriately include: CI Pigment Red 1 (hereinafter, "CI Pigment Red" is the same, only the numbers are described) 2, 3, 4, 5, 6, 7, 8, 9, 10, 11 , 12, 14, 15, 16, 17, 18, 19, 21, 22, 23, 30, 31, 32, 37, 38, 40, 41, 42, 48: 1, 48: 2, 48: 3, 48 : 4, 49:1, 49:2, 50:1, 52:1, 53:1, 57, 57:1, 57:2, 58:2, 58:4, 60:1, 63:1, 63 : 2, 64:1, 81:1, 83, 88, 90:1, 97, 101, 102, 104, 105, 106, 108, 112, 113, 114, 122, 123, 144, 146, 149, 150 , 151, 155, 166, 168, 170, 171, 172, 174, 175, 176, 177, 178, 179, 180, 185, 187, 188, 190, 192, 193, 194, 202, 206, 207, 208 , 209, 215, 216, 217, 220, 223, 224, 226, 227, 228, 240, 242, 243, 245, 254, 255, 264, and 265.

Examples of blue pigments that can be suitably used include: CI Pigment Blue 1 (hereinafter, "CI Pigment Blue" is the same, and only the numbers are described), 2, 15, 15: 3, 15: 4, 15: 6, 16 , 22, 60, 64, and 66.

Examples of pigments of other hue than the above that can be suitably used include: CI Pigment Green 7, CI Pigment Green 36, CI Pigment Green 37 and other green pigments, CI Pigment Brown 23, CI Pigment Brown 25, CI Pigment Brown 26 , CI Pigment Brown 28 and other brown pigments, CI Pigment Black 1, CI Pigment Black 7 and other black pigments.

Moreover, when providing light-shielding property to a photosensitive resin composition, it is preferable that the photosensitive resin composition contains a black pigment as a light-shielding agent (D1). The photosensitive resin composition containing black pigment is suitable for the formation of black matrix or black columnar spacers in liquid crystal displays, or the formation of contact rows for dividing the light-emitting layer in organic EL (Electroluminescence) devices .

Examples of black pigments include carbon black, perylene pigments, internal amine pigments, titanium black, copper, iron, manganese, cobalt, chromium, nickel, zinc, calcium, silver and other metal oxides, composite oxides Pigments that are not related to organic or inorganic substances, such as metal sulfides, metal sulfates, or metal carbonates. Among these black pigments, carbon black is preferable in terms of easy availability or easy formation of a cured film having excellent light-shielding properties and high electrical resistance. Furthermore, the hue of the black pigment is not limited to achromatic achromatic color in the color theory, that is, black. It can also be a purplish black, a bluish black, or a reddish black.

As the carbon black, well-known carbon blacks such as chimney black, furnace black, thermal black, and lamp black can be used, but chimney black having excellent light-shielding properties is preferred. In addition, resin-coated carbon black can also be used.

Resin-coated carbon black has lower conductivity than carbon black without resin coating. Therefore, when used as the black matrix of liquid crystal display elements such as liquid crystal displays, it can produce less current leakage and higher reliability. The low power consumption display.

As carbon black, it is also preferable to carry out the treatment of introducing acidic groups. The acidic group introduced into the carbon black means an acidic functional group according to Brunst's definition. As a specific example of an acidic group, a carboxyl group, a sulfonic acid group, a phosphoric acid group, etc. are mentioned. The acidic groups introduced into carbon black can also form salts. The cation forming a salt with an acidic group is not particularly limited within a range that does not interfere with the purpose of the present invention. Examples of cations include various metal ions, cations of nitrogen-containing compounds, ammonium ions, etc., and alkali metal ions such as sodium ions, potassium ions, and lithium ions, or ammonium ions are preferred.

In the carbon black after the treatment of introducing the acidic group described above, it is preferable to have a high resistance selected from the group consisting of carboxylic acid group and carboxylic acid group from the viewpoint of achieving high resistance of a light-shielding cured film formed using a photosensitive resin composition. Carbon black with one or more functional groups in the group consisting of acid salt groups, sulfonic acid groups, and sulfonate groups.

The method of introducing acidic groups into carbon black is not particularly limited. As a method of introducing an acidic group, for example, the following methods can be cited. Method 1) The sulfonic acid group is introduced into the carbon black by a direct substitution method using concentrated sulfuric acid, oleum, chlorosulfonic acid, etc., or an indirect substitution method using sulfite, bisulfite, etc. Method 2) Diazo coupling of an organic compound with an amine group and an acid group and carbon black. Method 3) The organic compound with halogen atom and acidic group is reacted with carbon black with hydroxyl group by Williamson's etherification method. Method 4) Reacting an organic compound having a halogenated carbonyl group and an acidic group protected by a protecting group with a carbon black having a hydroxyl group. Method 5) Use an organic compound with a halogenated carbonyl group and an acidic group protected by a protecting group to perform the Friedel-Crafts reaction on carbon black, and then deprotect it.

Among these methods, in terms of easy and safe introduction of acidic groups, method 2) is preferred. The organic compound having an amine group and an acidic group used in the method 2) is preferably a compound having an amine group and an acidic group bonded to an aromatic group. Examples of such compounds include aminobenzenesulfonic acid such as sulfanilic acid, or aminobenzoic acid such as 4-aminobenzoic acid.

The number of moles of acidic groups introduced into carbon black is not particularly limited within a range that does not hinder the purpose of the present invention. The number of moles of acidic groups introduced into the carbon black is preferably 1 mmol or more and 200 mmol or less, and more preferably 5 mmol or more and 100 mmol or less relative to 100 g of carbon black.

Carbon black with acidic groups can also be coated with resin. When a photosensitive resin composition containing carbon black coated with a resin is used, it is easy to form a light-shielding cured film with excellent light-shielding and insulating properties and low surface reflectance. Furthermore, the coating process of the resin does not have an adverse effect on the dielectric constant of the light-shielding cured film formed using the photosensitive resin composition. Examples of resins that can be used for the coating of carbon black include: phenol resins, melamine resins, xylene resins, diallyl phthalate resins, glycolphthalein resins, epoxy resins, alkylbenzene resins and other thermal resins. Curable resin, or polystyrene, polycarbonate, polyethylene terephthalate, polybutylene terephthalate, modified polyphenylene ether, polysulfide, poly(terephthalamide), and poly(p-phenylene diamine) , Polyamide imide, polyimide, polyamino bismaleimide, polyether sulfopolyphenylene oxide, polyarylate, polyether ether ketone and other thermoplastic resins. The amount of resin coating carbon black relative to the total of the mass of carbon black and the mass of the resin is preferably 1% by mass to 30% by mass.

Moreover, as a black pigment, a perylene-based pigment can also be preferably used. Specific examples of perylene pigments include: a perylene pigment represented by the following formula (d-1), a perylene pigment represented by the following formula (d-2), and the following formula (d-3) The indicated perylene pigments. Among the commercially available products, the product names K0084 and K0086 manufactured by BASF Corporation, or pigment black 21, 30, 31, 32, 33, and 34, etc. can be preferably used as perylene pigments.

式(d-1)中，R^d1 及R^d2 分別獨立表示碳原子數1以上3以下之伸烷基，R^d3 及R^d4 分別獨立表示氫原子、羥基、甲氧基、或乙醯基。[化53]

In the formula ^(d1), R d1 and R ^d2 each independently represent or more carbon atoms, alkylene of 1 to 3, R ^d3 and R ^d4 each independently represent a hydrogen atom, a hydroxyl group, a methoxy group, or acetyl group.

式(d-2)中，R^d5 及R^d6 分別獨立表示碳原子數1以上7以下之伸烷基。[化54]

In the formula (d-2), R ^d5 and R ^d6 each independently represent an alkylene group having 1 to 7 carbon atoms.

式(d-3)中，R^d7 及R^d8 分別獨立為氫原子、碳原子數1以上22以下之烷基，亦可包含N、O、S、或P之雜原子。於R^d7 及R^d8 為烷基之情形時，該烷基可為直鏈狀，亦可為支鏈狀。[化55]

In formula (d-3), ^Rd7 and ^Rd8 are each independently a hydrogen atom, an alkyl group having 1 to 22 carbon atoms, and may include N, O, S, or P heteroatoms. When R ^d7 and R ^d8 are alkyl groups, the alkyl group may be linear or branched.

The compound represented by the above formula (d-1), the compound represented by the formula (d-2), and the compound represented by the formula (d-3) can be used, for example, Japanese Patent Laid-Open No. 62-1753 and Japanese Patent It was synthesized by the method described in JP 63-26784. That is, using perylene-3,5,9,10-tetracarboxylic acid or its dianhydride and amines as raw materials, the heating reaction is carried out in water or an organic solvent. Then, the obtained crude product is reprecipitated in sulfuric acid, or recrystallized in water, an organic solvent, or a mixed solvent of these, thereby obtaining the target product.

In order to disperse the perylene-based pigment well in the photosensitive resin composition, the average particle diameter of the perylene-based pigment is preferably 10 nm or more and 1000 nm or less.

In addition, as a light-shielding agent, internal amide-based pigments may also be included. As an internal amine type pigment, the compound represented by following formula (d-4) is mentioned, for example.

[化56]

In the formula (d-4), X ^d represents a double bond, and as geometric isomers, each independently represents an E form or a Z form, and R ^d9 independently represents a hydrogen atom, a methyl group, a nitro group, a methoxy group, a bromine atom, A chlorine atom, a fluorine atom, a carboxyl group, or a sulfo group, R ^d10 each independently represents a hydrogen atom, a methyl group, or a phenyl group, and R ^d11 each independently represents a hydrogen atom, a methyl group, or a chlorine atom. The compound represented by formula (d-4) can be used alone or in combination of two or more kinds. In terms of easy production of the compound represented by formula (d-4), R ^{d9 is} preferably bonded to the 6-position of the indoline ring, and R ^{d11 is} preferably bonded to the 4 of the indoline ring. Bit. From the same viewpoint, R ^d9 , R ^d10 and R ^{d11 are} preferably hydrogen atoms. The compound represented by formula (d-4) has EE form, ZZ form, and EZ form as geometric isomers, and may be any single compound of these, or a mixture of these geometric isomers. The compound represented by formula (d-4) can be produced, for example, by the method described in International Publication No. 2000/24736 and International Publication No. 2010/081624.

In order to disperse the internal amine-based pigment well in the photosensitive resin composition, the average particle diameter of the internal amine-based pigment is preferably 10 nm or more and 1000 nm or less.

Furthermore, fine particles mainly composed of silver tin (AgSn) alloy (hereinafter referred to as "AgSn alloy fine particles") are also preferably used as black pigments. The AgSn alloy fine particles may have an AgSn alloy as a main component, and other metal components may include, for example, Ni, Pd, Au, and the like. The average particle size of the AgSn alloy particles is preferably 1 nm or more and 300 nm or less.

When the AgSn alloy is represented by the chemical formula AgxSn, the range of x for obtaining a chemically stable AgSn alloy is 1≦x≦10, and the range of x for obtaining chemical stability and blackness is 3≦x≦4. Here, if the mass ratio of Ag in the AgSn alloy is obtained within the range of x, then When x = 1, Ag/AgSn = 0.4762; In the case of x=3, 3·Ag/Ag3Sn=0.7317; In the case of x=4, 4·Ag/Ag4Sn=0.7843; In the case of x = 10, 10·Ag/Ag10Sn = 0.9008. Therefore, the AgSn alloy becomes chemically stable when it contains Ag of 47.6 mass% to 90 mass%, and when it contains Ag of 73.17 mass% to 78.43 mass%, it can effectively obtain a chemical effect relative to the amount of Ag. Stability and blackness.

The AgSn alloy fine particles can be produced using a normal fine particle synthesis method. The fine particle synthesis method includes a gas phase reaction method, a spray thermal decomposition method, an atomization method, a liquid phase reaction method, a freeze drying method, a hydrothermal synthesis method, and the like.

The AgSn alloy fine particles have high insulating properties, but depending on the application of the photosensitive resin composition, in order to further improve the insulating properties, the surface may be covered with an insulating film. As the material of such an insulating film, a metal oxide or an organic polymer compound is suitable. As the metal oxide, metal oxides with insulating properties are suitably used, such as silica (silica), alumina (alumina), zirconia (zircon), yttria (yttrium), and titanium oxide (titanium oxide) Wait. In addition, as the organic polymer compound, resins having insulating properties, such as polyimide, polyether, polyacrylate, and polyamine compounds, are suitably used.

In order to sufficiently improve the insulation of the surface of the AgSn alloy particles, the thickness of the insulating film is preferably 1 nm or more and 100 nm or less, and more preferably 5 nm or more and 50 nm or less. The insulating film can be easily formed by surface modification technology or surface coating technology. In particular, if an alkoxide such as tetraethoxysilane or aluminum triethoxide is used, it is possible to form an insulating film with a uniform film thickness at a relatively low temperature, which is preferable.

As the black pigment, the above-mentioned perylene-based pigments, internal amine-based pigments, and AgSn alloy fine particles may be used alone or in combination. In addition, the black pigment may also include pigments of red, blue, green, and yellow hue according to the purpose of adjusting the color tone. Pigments of other hues other than black pigments can be appropriately selected from known pigments. For example, as pigments of other hue than black pigments, the above-mentioned various pigments can be used. The usage amount of pigments of other hues other than the black pigment is preferably 15% by mass or less, and more preferably 10% by mass or less relative to the total mass of the black pigment.

A black composition containing two or more black or colored pigments and/or dyes can be used together with the black pigment described above, or the black composition can be used instead of the black pigment. The content of carbon black in the black composition is preferably 3% by mass or less. By using a black composition with a carbon black content of 3% by mass or less, it is easy to suppress the generation of suspended solids or development residues after development. The content of carbon black in the black composition is more preferably 2% by mass or less, still more preferably 1% by mass or less, and particularly preferably 0% by mass.

The hue of the pigment and dye contained in the black composition is not particularly limited. The black composition may also include black pigments and/or dyes. The black composition can also be a combination of a plurality of black coloring agents. In this case, as a black coloring agent, for example, perylene black, aniline black, and black azo compounds can be used. In the black composition, two or more kinds of pigments and/or dyes of hues other than black can also be combined to make the composition appear black.

In terms of being able to subtly adjust the hue of black, or easily suppressing the generation of suspended solids or development residues after development, the black composition is better than a coloring agent composed of a single type of coloring agent A combination of multiple color colorants.

The black composition is preferably, for example, a combination of two or more organic pigments selected from organic pigments of five colors of blue, purple, yellow, red, and orange. By combining two or more organic pigments from the above five organic pigments, it is possible to display a pseudo-black hue. Here, "pseudo-black" is black in ideal chromatology, but it only needs to be a hue that is allowed in the use of a black film formed using a black composition.

The ratio (mass ratio) of the organic pigments of each hue in the pseudo-black black composition is preferably (blue organic pigment)/(yellow organic pigment + orange organic pigment)/(red organic pigment + purple organic pigment) = (30 mass% to 60 mass%)/(0 mass% to 50 mass%)/(5 mass% to 70 mass%).

As the organic pigments of the above five colors, known ones used in the past can be used. Examples of blue organic pigments include C.I. Pigment Blue 15:3, C.I. Pigment Blue 15:4, C.I. Pigment Blue 15:6, and C.I. Pigment Blue 60. Examples of the purple organic pigments include C.I. Pigment Violet 19 and C.I. Pigment Violet 23. Examples of yellow organic pigments include CI Pigment Yellow 83, CI Pigment Yellow 110, CI Pigment Yellow 128, CI Pigment Yellow 138, CI Pigment Yellow 139, CI Pigment Yellow 150, CI Pigment Yellow 151, CI Pigment Yellow 154, CI Pigment Yellow 155, CI Pigment Yellow 180, and CI Pigment Yellow 181. As orange organic pigments, C.I. Pigment Orange 38, C.I. Pigment Orange 43, C.I. Pigment Orange 64, C.I. Pigment Orange 69, C.I. Pigment Orange 71, and C.I. Pigment Orange 73 can be mentioned. Examples of red organic pigments include CI Pigment Red 122, CI Pigment Red 166, CI Pigment Red 177, CI Pigment Red 179, CI Pigment Red 242, CI Pigment Red 224, CI Pigment Red 254, CI Pigment Red 256, CI Pigment Red 264, and CI Pigment Red 272.

Among them, preferably, the blue organic pigment is at least one selected from the group consisting of CI Pigment Blue 15:3, CI Pigment Blue 15:4, and CI Pigment Blue 15:6, and the purple organic pigment is CI pigment Violet 23, the yellow organic pigment is CI Pigment Yellow 83 and/or CI Pigment Yellow 139, the orange organic pigment is CI Pigment Orange 43 and/or CI Pigment Orange 64, the red organic pigment is CI Pigment Red 254 and/or CI Pigment Red 256 . By using these organic pigments in combination, it is easy to form a black cured film with good black hue and excellent optical density (OD value).

In order to obtain a pseudo-black black composition, it is preferable to combine at least one selected from blue organic pigments, yellow organic pigments, and orange organic pigments, and it is more preferable to further combine these organic pigments with those selected from A combination of at least one organic pigment among red organic pigments and purple organic pigments. As specific combinations of pigments belonging to organic pigments of each color, for example, the following combinations are preferred, ・The combination of C.I. Pigment Blue 15:4, C.I. Pigment Yellow 139 and C.I. Pigment Red 254, ・Combination of C.I. Pigment Blue 15: 6, C.I. Pigment Orange 64 and C.I. Pigment Violet 23, ・The combination of C.I. Pigment Blue 15:4 or 15:3, C.I. Pigment Yellow 83, C.I. Pigment Violet 23 and C.I. Pigment Red 254, and ・The combination of C.I. Pigment Blue 15: 6, C.I. Pigment Violet 23 and C.I. Pigment Red 256.

In order to uniformly disperse the said coloring agent (D) in the photosensitive resin composition, you may use further a dispersing agent. As such a dispersant, it is preferable to use a polyethyleneimine-based, polyurethane resin-based, or acrylic resin-based polymer dispersant. Especially in the case of using carbon black as the colorant (D), it is preferable to use an acrylic resin-based dispersant as the dispersant. Furthermore, there are cases where corrosive gas generated by the dispersant is generated from the cured film. Therefore, it is also an example of a preferable aspect that the pigment does not use a dispersant but performs a dispersion treatment.

染料、花青染料、萘醌染料、醌亞胺染料、次甲基染料、酞菁染料等。 又，關於該等染料，藉由進行色澱化(成鹽化)能夠使其分散於有機溶劑等，從而將其用作著色劑(D)。 該等染料以外，例如亦可較佳地使用日本專利特開2013-225132號公報、日本專利特開2014-178477號公報、日本專利特開2013-137543號公報、日本專利特開2011-38085號公報、日本專利特開2014-197206號公報等中記載之染料等。Furthermore, in the photosensitive resin composition, a pigment and a dye may be used in combination. The dye may be appropriately selected from known materials. Examples of dyes that can be applied to the photosensitive resin composition include azo dyes, metal complex salt azo dyes, anthraquinone dyes, triphenylmethane dyes, 𠮿

Dyes, cyanine dyes, naphthoquinone dyes, quinoneimine dyes, methine dyes, phthalocyanine dyes, etc. In addition, these dyes can be dispersed in an organic solvent or the like by being laked (salted), and can be used as a colorant (D). In addition to these dyes, for example, Japanese Patent Application Publication No. 2013-225132, Japanese Patent Application Publication No. 2014-178477, Japanese Patent Application Publication No. 2013-137543, Japanese Patent Application Publication No. 2011-38085 may also be preferably used. Dyes and the like described in gazettes, Japanese Patent Laid-Open No. 2014-197206 etc.

The amount of the coloring agent (D) used in the photosensitive resin composition can be appropriately selected within a range that hinders the purpose of the present invention. Typically, the amount of the colorant (D) used is preferably 2% by mass or more and 75% by mass or less, more preferably 3% by mass or more and 70% by mass relative to the total mass of the solid components of the photosensitive resin composition .

In particular, when a photosensitive resin composition is used to form a black matrix, it is preferable to adjust the amount of the light-shielding agent in the photosensitive resin composition so that the OD value of the film per 1 μm of the black matrix becomes 4 or more. If the OD value of the film per 1 μm in the black matrix is 4 or more, when used in the case of the black matrix of a liquid crystal display, sufficient display contrast can be obtained.

When a pigment is used as the colorant (D), it is preferable that the pigment be added to the photosensitive resin composition after making it into a dispersion liquid dispersed at an appropriate concentration in the presence or absence of a dispersant. Furthermore, in this specification, the use amount of the above-mentioned pigment can be defined as a value that includes the dispersant present.

＜Sensitizer (E)＞ The photosensitive resin composition may contain a sensitizer (E) together with the above-mentioned photopolymerization initiator. Since the photosensitive resin composition contains the sensitizer (E), even if it is exposed to a light source with low irradiating energy such as LED (Light Emitting Diode), it is cured well.

As the sensitizer (E), a compound conventionally used for the purpose of sensitization of a photopolymerization initiator in a photosensitive resin composition can be used without particular limitation.

The sensitizer (E) is preferably a compound having one or more substituents selected from the group consisting of an alkoxy group, a substituted carbonyloxy group, and a pendant oxy group (=O). The compound having the substituent is preferably a condensed polycyclic aromatic hydrocarbon compound or a condensed polycyclic aromatic heterocyclic compound. The condensed polycyclic aromatic hydrocarbon compound or the condensed polycyclic aromatic heterocyclic compound may have a substituent other than an alkoxy group, a substituted carbonyloxy group, and a pendant oxy group (=O). Examples of the substituent include: alkyl groups with 1 to 20 carbon atoms, halogenated alkyl groups with 1 to 20 carbon atoms, alkoxyalkyl groups with 2 to 20 carbon atoms, and carbon atoms. 2 aliphatic acyl groups of more than 20 and less than 20, aromatic acyl groups (aryl groups) of 7 to 11 carbon atoms, cyano groups, nitro groups, nitroso groups, halogen atoms, hydroxyl groups, and mercapto groups, etc.

The alkoxy group may be linear or branched. The number of carbon atoms of the alkoxy group is not particularly limited, but is preferably 1 or more and 20 or less, more preferably 1 or more and 12 or less, and particularly preferably 1 or more and 6 or less. Preferred examples of alkoxy groups include: methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, tert-butoxy, n-pentoxy , N-hexyloxy, n-heptyloxy, n-octyloxy, 2-ethylhexyl, n-nonyloxy, and n-decyloxy, etc.

The substituted carbonyloxy group is a group represented by -O-CO-A ^e . A ^e is not particularly limited as long as it has the sensitizing effect required by the sensitizer (E), and it may be various organic groups. A is preferably an alkyl group with 1 to 20 carbon atoms, an aryl group with 6 to 10 carbon atoms, an alkoxy group with 1 to 20 carbon atoms, and an aryloxy group with 6 to 10 carbon atoms. base.

The aryl group or aryloxy group may have one or more substituents. The type of substituent is not particularly limited as long as it does not interfere with the purpose of the present invention. When the aryl group or the aryloxy group has a plurality of substituents, the plurality of substituents may be the same or different. Preferable examples of substituents include: alkoxy groups having 1 to 6 carbon atoms, aryloxy groups having 6 to 10 carbon atoms, aliphatic acyl groups having 2 to 7 carbon atoms, and carbon atoms Aromatic acyl groups (aryl acyl groups), cyano groups, nitro groups, nitroso groups, halogen atoms, hydroxyl groups, and mercapto groups having the number 7 to 11.

When A ^e is an alkyl group or an alkoxy group, these groups may be linear or branched. Preferable examples of alkyl groups include: methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tertiary butyl, n-pentyl, n-hexyl, n-heptyl, n- Octyl, and 2-ethylhexyl, etc. Preferable examples of aryl groups include phenyl, o-tolyl, m-tolyl, p-tolyl, α-naphthyl, β-naphthyl, and the like. Preferred examples of alkoxy groups include: methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, tert-butoxy, n-pentoxy , N-hexyloxy, n-heptyloxy, n-octyloxy, and 2-ethylhexyloxy, etc.

Condensed polycyclic aromatic hydrocarbon compound, or condensed polycyclic aromatic heterocyclic ring substituted by one or more selected from the group consisting of alkoxy, substituted carbonyloxy, and pendant oxy (=O) In the compound, the number of rings constituting the condensed ring is not particularly limited as long as the desired sensitization effect is obtained. The number of rings is preferably 2 or more, more preferably 3 or more, particularly preferably 3 or more and 6 or less, and most preferably 3 or 4. Furthermore, as long as the condensed polycyclic aromatic hydrocarbon compound or the condensed polycyclic aromatic heterocyclic compound has aromaticity, the monocyclic ring forming the condensed polycyclic ring may not necessarily be an aromatic ring.

環、及硫𠮿

環。該等環中，較佳為蒽環、稠四苯環、及硫𠮿

環。Preferable examples of the condensed polycyclic ring contained in the condensed polycyclic aromatic hydrocarbon compound or the condensed polycyclic aromatic heterocyclic compound include: acenaphthene ring, phenanthrene ring, anthracene ring, fused tetraphenyl ring, 𠮿

Ring, and sulfur 𠮿

ring. Among these rings, anthracene ring, fused tetraphenyl ring, and sulfur are preferred.

ring.

Specific examples of compounds containing anthracene rings and suitable as sensitizers (E) include 9,10-bis(acetoxy)anthracene, 9,10-bis(propionoxy)anthracene, 9 ,10-bis(n-propylcarbonyloxy)anthracene, 9,10-bis(isopropylcarbonyloxy)anthracene, 9,10-bis(n-butylcarbonyloxy)anthracene, 9,10-bis( Isobutylcarbonyloxy)anthracene, 9,10-bis(n-pentylcarbonyloxy)anthracene, 9,10-bis(n-hexylcarbonyloxy)anthracene, 9,10-bis(n-heptylcarbonyloxy) )Anthracene, 9,10-bis(2-ethylhexyloxy)anthracene, 9,10-bis(n-octylcarbonyloxy)anthracene, 9,10-bis(n-nonylcarbonyloxy)anthracene, 9,10-bis(n-decylcarbonyloxy)anthracene, 9,10-bis(benzyloxy)anthracene, 9,10-bis(4-methylbenzyloxy)anthracene, 9,10 -Bis(2-naphthyloxy)anthracene, 2-methyl-9,10-bis(acetoxy)anthracene, 2-methyl-9,10-bis(propionyloxy)anthracene, 2 -Methyl-9,10-bis(n-propylcarbonyloxy)anthracene, 2-methyl-9,10-bis(isopropylcarbonyloxy)anthracene, 2-methyl-9,10-bis( N-butylcarbonyloxy)anthracene, 2-methyl-9,10-bis(isobutylcarbonyloxy)anthracene, 2-methyl-9,10-bis(n-pentylcarbonyloxy)anthracene, 2 -Methyl-9,10-bis(n-hexylcarbonyloxy)anthracene, 2-methyl-9,10-bis(benzyloxy)anthracene, 2-methyl-9,10-bis(4- Methylbenzyloxy)anthracene, 2-methyl-9,10-bis(2-naphthyloxy)anthracene, 1-methyl-9,10-bis(acetoxy)anthracene, 1 -Methyl-9,10-bis(propionyloxy)anthracene, 1-methyl-9,10-bis(n-propylcarbonyloxy)anthracene, 1-methyl-9,10-bis(isopropyl) Carbonyloxy)anthracene, 1-methyl-9,10-bis(n-butylcarbonyloxy)anthracene, 1-methyl-9,10-bis(isobutylcarbonyloxy)anthracene, 1-methyl -9,10-bis(n-pentylcarbonyloxy)anthracene, 1-methyl-9,10-bis(n-hexylcarbonyloxy)anthracene, 1-methyl-9,10-bis(benzyl Oxy)anthracene, 1-methyl-9,10-bis(4-methylbenzyloxy)anthracene, 1-methyl-9,10-bis(2-naphthyloxy)anthracene, 2 -Ethyl-9,10-bis(acetoxy)anthracene, 2-ethyl-9,10-bis(propionoxy)anthracene, 2-ethyl-9,10-bis(n-propylcarbonyl) Oxy)anthracene, 2-ethyl-9,10-bis(isobutylcarbonyloxy)anthracene, 2-ethyl-9,10-bis(n-butylcarbonyloxy)anthracene, 2-ethyl- 9,10-bis(isobutylcarbonyloxy)anthracene, 2-ethyl-9,10-bis(n-pentylcarbonyloxy)anthracene, 2-ethyl-9,10-bis(n-hexylcarbonyloxy) Yl)anthracene, 2-ethyl-9,10-bis(benzyloxy)anthracene, 2-ethyl-9,10-bis(4-ethyl-benzyloxy)anthracene, 2-ethyl Base-9,10-bis(2-naphthyloxy)anthracene, 1-ethyl-9,10-bis(acetoxy)anthracene, 1-ethyl -9,10-bis(propionyloxy)anthracene, 1-ethyl-9,10-bis(n-propylcarbonyloxy)anthracene, 1-ethyl-9,10-bis(isopropylcarbonyl) Oxy)anthracene, 1-ethyl-9,10-bis(n-butylcarbonyloxy)anthracene, 1-ethyl-9,10-bis(isobutylcarbonyloxy)anthracene, 1-ethyl- 9,10-bis(n-pentylcarbonyloxy)anthracene, 1-ethyl-9,10-bis(n-hexylcarbonyloxy)anthracene, 1-ethyl-9,10-bis(benzyloxy) )Anthracene, 1-ethyl-9,10-bis(4-ethyl-benzyloxy)anthracene, 1-ethyl-9,10-bis(2-naphthyloxy)anthracene, 1- (Tertiary butyl)-9,10-bis(n-propylcarbonyloxy)anthracene, 1-(tertiary butyl)-9,10-bis(isopropylcarbonyloxy)anthracene, 1-(th Tributyl)-9,10-bis(n-butylcarbonyloxy)anthracene, 1-(tert-butyl)-9,10-bis(isobutylcarbonyloxy)anthracene, 1-(tert-butyl) Base)-9,10-bis(n-pentylcarbonyloxy)anthracene, 1-(tertiary butyl)-9,10-bis(n-hexylcarbonyloxy)anthracene, 1-(tertiarybutyl)- 9,10-bis(benzyloxy)anthracene, 1-(tert-butyl)-9,10-bis(4-(tert-butyl)-benzyloxy)anthracene, 1-(th Tributyl)-9,10-bis(2-naphthoxy)anthracene, 2-(tertiary butyl)-9,10-bis(n-propylcarbonyloxy)anthracene, 2-(third Butyl)-9,10-bis(isopropylcarbonyloxy)anthracene, 2-(tert-butyl)-9,10-bis(n-butylcarbonyloxy)anthracene, 2-(tert-butyl) )-9,10-bis(isobutylcarbonyloxy)anthracene, 2-(tert-butyl)-9,10-bis(n-pentylcarbonyloxy)anthracene, 2-(tert-butyl)- 9,10-bis(n-hexylcarbonyloxy)anthracene, 2-(tertiary butyl)-9,10-bis(benzyloxy)anthracene, 2-(tertiary butyl)-9,10- Bis(4-(tert-butyl)-benzyloxy)anthracene, 2-(tert-butyl)-9,10-bis(2-naphthyloxy)anthracene, 2-pentyl-9 ,10-bis(n-propylcarbonyloxy)anthracene, 2-pentyl-9,10-bis(isopropylcarbonyloxy)anthracene, 2-pentyl-9,10-bis(n-butylcarbonyloxy) Yl)anthracene, 2-pentyl-9,10-bis(isobutylcarbonyloxy)anthracene, 2-pentyl-9,10-bis(n-pentylcarbonyloxy)anthracene, 2-pentyl-9 , 10-bis(n-hexylcarbonyloxy)anthracene, 2-pentyl-9,10-bis(benzyloxy)anthracene, 2-pentyl-9,10-bis(4-(tertiary butyl) )-Benzyloxy)anthracene, and 2-pentyl-9,10-bis(2-naphthyloxy)anthracene.

Anthracene compounds substituted with halogen atoms are also preferred as sensitizers (E). Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom.

Specific examples of anthracene compounds substituted by halogen atoms and preferably used as sensitizers (E) include: 2-chloro-9,10-bis(acetoxy)anthracene, 2-chloro-9 , 10-bis(propionyloxy)anthracene, 2-chloro-9,10-bis(n-propylcarbonyloxy)anthracene, 2-chloro-9,10-bis(isopropylcarbonyloxy)anthracene, 2-chloro-9,10-bis(n-butylcarbonyloxy)anthracene, 2-chloro-9,10-bis(isobutylcarbonyloxy)anthracene, 2-chloro-9,10-bis(n-pentyl Carbonyloxy)anthracene, 2-chloro-9,10-bis(n-hexylcarbonyloxy)anthracene, 2-chloro-9,10-bis(benzyloxy)anthracene, 2-chloro-9,10 -Bis(4-methylbenzyloxy)anthracene, 2-chloro-9,10-bis(2-naphthyloxy)anthracene, 1-chloro-9,10-bis(acetoxy) Anthracene, 1-chloro-9,10-bis(propionyloxy)anthracene, 1-chloro-9,10-bis(n-propylcarbonyloxy)anthracene, 1-chloro-9,10-bis(isopropyl) Carbonyloxy)anthracene, 1-chloro-9,10-bis(n-butylcarbonyloxy)anthracene, 1-chloro-9,10-bis(isobutylcarbonyloxy)anthracene, 1-chloro-9 , 10-bis(n-pentylcarbonyloxy)anthracene, 1-chloro-9,10-bis(n-hexylcarbonyloxy)anthracene, 1-chloro-9,10-bis(benzyloxy)anthracene, 1-chloro-9,10-bis(4-methylbenzyloxy)anthracene, 1-chloro-9,10-bis(2-naphthyloxy)anthracene, 2-fluoro-9,10- Bis(acetoxy)anthracene, 2-fluoro-9,10-bis(propionoxy)anthracene, 2-fluoro-9,10-bis(n-propylcarbonyloxy)anthracene, 2-fluoro-9 , 10-bis(isopropylcarbonyloxy)anthracene, 2-fluoro-9,10-bis(n-butylcarbonyloxy)anthracene, 2-fluoro-9,10-bis(isobutylcarbonyloxy) Anthracene, 2-fluoro-9,10-bis(n-pentylcarbonyloxy)anthracene, 2-fluoro-9,10-bis(n-hexylcarbonyloxy)anthracene, 2-fluoro-9,10-bis(benzene Formyloxy)anthracene, 2-fluoro-9,10-bis(4-methylbenzyloxy)anthracene, 2-fluoro-9,10-bis(2-naphthyloxy)anthracene, 1 -Fluoro-9,10-bis(acetoxy)anthracene, 1-fluoro-9,10-bis(propionyloxy)anthracene, 1-fluoro-9,10-bis(n-propylcarbonyloxy) Anthracene, 1-fluoro-9,10-bis(isopropylcarbonyloxy)anthracene, 1-fluoro-9,10-bis(n-butylcarbonyloxy)anthracene, 1-fluoro-9,10-bis( Isobutylcarbonyloxy)anthracene, 1-fluoro-9,10-bis(n-pentylcarbonyloxy)anthracene, 1-fluoro-9,10-bis(n-hexylcarbonyloxy)anthracene, 1-fluoro- 9,10-bis(benzyloxy)anthracene, 1-fluoro-9,10-bis(4-methylbenzyloxy)anthracene, 1-fluoro-9,10-bis(2-naphthylmethyl) Acetyloxy)anthracene, 2-bromo-9,10-bis(acetoxy)anthracene, 2-bromo-9,10-bis(propionyloxy)anthracene, 2-bromo-9,10-bis( N-Propylcarbonyloxy)anthracene, 2-bromo-9,10-bis(isopropylcarbonyloxy)anthracene, 2-bromo-9,10- Bis(n-butylcarbonyloxy)anthracene, 2-bromo-9,10-bis(isobutylcarbonyloxy)anthracene, 2-bromo-9,10-bis(n-pentylcarbonyloxy)anthracene, 2 -Bromo-9,10-bis(n-hexylcarbonyloxy)anthracene, 2-bromo-9,10-bis(benzyloxy)anthracene, 2-bromo-9,10-bis(4-methylbenzene) Formyloxy)anthracene, 2-bromo-9,10-bis(2-naphthyloxy)anthracene, 1-bromo-9,10-bis(acetoxy)anthracene, 1-bromo-9, 10-bis(propionyloxy)anthracene, 1-bromo-9,10-bis(n-propylcarbonyloxy)anthracene, 1-bromo-9,10-bis(isopropylcarbonyloxy)anthracene, 1 -Bromo-9,10-bis(n-butylcarbonyloxy)anthracene, 1-bromo-9,10-bis(isobutylcarbonyloxy)anthracene, 1-bromo-9,10-bis(n-pentyl) Carbonyloxy)anthracene, 1-bromo-9,10-bis(n-hexylcarbonyloxy)anthracene, 1-bromo-9,10-bis(benzyloxy)anthracene, 1-bromo-9,10- Bis(4-methylbenzyloxy)anthracene, 1-bromo-9,10-bis(2-naphthyloxy)anthracene, etc.

Anthracene compounds substituted with alkoxy groups are also preferred as sensitizers (E). Specific examples of anthracene compounds substituted with alkoxy groups and preferably as sensitizer (E) include: 9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, 9 ,10-bis(n-propoxy)anthracene, 9,10-bis(n-butoxy)anthracene, 9,10-bis(n-pentoxy)anthracene, 9,10-bis(isopentoxy)anthracene , 9,10-bis(n-hexyloxy)anthracene, 9,10-bis(n-heptyloxy)anthracene, 9,10-bis(n-octyloxy)anthracene, 9,10-bis(2-ethylhexyl) Oxy)anthracene, 9-methoxyanthracene, 9-ethoxyanthracene, 9-(n-propoxy)anthracene, 9-(n-butoxy)anthracene, 9-(n-pentoxy)anthracene, 9 -(Isopentyloxy)anthracene, 9-(n-hexyloxy)anthracene, 9-(n-heptyloxy)anthracene, 9-(n-octyloxy)anthracene, 9-(2-ethylhexyloxy)anthracene , 2-methyl-9,10-dimethoxyanthracene, 2-methyl-9,10-diethoxyanthracene, 2-methyl-9,10-bis(n-propoxy)anthracene, 2 -Methyl-9,10-bis(n-butoxy)anthracene, 2-methyl-9,10-bis(n-pentoxy)anthracene, 2-methyl-9,10-bis(isopentoxy) )Anthracene, 2-methyl-9,10-bis(n-hexyloxy)anthracene, 2-methyl-9,10-bis(n-heptyloxy)anthracene, 2-methyl-9,10-bis(n Octyloxy)anthracene, 2-methyl-9,10-bis(2-ethylhexyloxy)anthracene, 2-ethyl-9,10-dimethoxyanthracene, 2-ethyl-9,10 -Diethoxyanthracene, 2-ethyl-9,10-bis(n-propoxy)anthracene, 2-ethyl-9,10-bis(n-butoxy)anthracene, 2-ethyl-9, 10-bis(n-pentyloxy)anthracene, 2-ethyl-9,10-bis(isopentyloxy)anthracene, 2-ethyl-9,10-bis(n-hexyloxy)anthracene, 2-ethyl -9,10-bis(n-heptyloxy)anthracene, 2-ethyl-9,10-bis(n-octyloxy)anthracene, 2-ethyl-9,10-bis(2-ethylhexyloxy) )Anthracene, 2-methyl-9-methoxyanthracene, 2-methyl-9-ethoxyanthracene, 2-methyl-9-(n-propoxy)anthracene, 2-methyl-9-( N-Butoxy)anthracene, 2-methyl-9-(n-pentyloxy)anthracene, 2-methyl-9-(isopentyloxy)anthracene, 2-methyl-9-(n-hexyloxy)anthracene , 2-methyl-9-(n-heptyloxy)anthracene, 2-methyl-9-(n-octyloxy)anthracene, 2-methyl-9-(2-ethylhexyloxy)anthracene, 2 -Ethyl-9-methoxyanthracene, 2-ethyl-9-ethoxyanthracene, 2-ethyl-9-(n-propoxy)anthracene, 2-ethyl-9-(n-butoxy) )Anthracene, 2-ethyl-9-(n-pentyloxy)anthracene, 2-ethyl-9-(isopentyloxy)anthracene, 2-ethyl-9-(n-hexyloxy)anthracene, 2-ethyl Base-9-(n-heptyloxy)anthracene, 2-ethyl-9-(n-octyloxy)anthracene, 2-ethyl-9-(2-ethylhexyloxy)anthracene, 2-chloro-9 ,10-Dimethoxyanthracene, 2-chloro-9,10-diethoxyanthracene, 2-chloro-9,10-bis(n-propoxy)anthracene, 2-chloro-9,10-bis( positive Butoxy)anthracene, 2-chloro-9,10-bis(n-pentyloxy)anthracene, 2-chloro-9,10-bis(isopentyloxy)anthracene, 2-chloro-9,10-bis( N-hexyloxy)anthracene, 2-chloro-9,10-bis(n-heptyloxy)anthracene, 2-chloro-9,10-bis(n-octyloxy)anthracene, 2-chloro-9,10-bis( 2-ethylhexyloxy)anthracene, 2-bromo-9,10-dimethoxyanthracene, 2-bromo-9,10-diethoxyanthracene, 2-bromo-9,10-bis(n-propyl Oxy)anthracene, 2-bromo-9,10-bis(n-butoxy)anthracene, 2-bromo-9,10-bis(n-pentoxy)anthracene, 2-bromo-9,10-bis(iso Pentyloxy)anthracene, 2-bromo-9,10-bis(n-hexyloxy)anthracene, 2-bromo-9,10-bis(n-heptyloxy)anthracene, 2-bromo-9,10-bis(n Octyloxy)anthracene, 2-bromo-9,10-bis(2-ethylhexyloxy)anthracene, 2-chloro-9-methoxyanthracene, 2-chloro-9-ethoxyanthracene, 2- Chloro-9-(n-propoxy)anthracene, 2-chloro-9-(n-butoxy)anthracene, 2-chloro-9-(n-pentoxy)anthracene, 2-chloro-9-(isopentoxy) Yl)anthracene, 2-chloro-9-(n-hexyloxy)anthracene, 2-chloro-9-(n-heptyloxy)anthracene, 2-chloro-9-(n-octyloxy)anthracene, 2-chloro-9 -(2-Ethylhexyloxy)anthracene, 2-bromo-9-methoxyanthracene, 2-bromo-9-ethoxyanthracene, 2-bromo-9-(n-propoxy)anthracene, 2- Bromo-9-(n-butoxy)anthracene, 2-bromo-9-(n-pentyloxy)anthracene, 2-ethyl-9-(isopentyloxy)anthracene, 2-bromo-9-(n-hexyloxy) Yl)anthracene, 2-bromo-9-(n-heptyloxy)anthracene, 2-bromo-9-(n-octyloxy)anthracene, and 2-bromo-9-(2-ethylhexyloxy)anthracene, etc. .

Among the anthracene compounds described above, in terms of ease of production and performance as a sensitizer (E), 9,10-bis(acetoxy)anthracene, 9,10-bis( Propyloxy)anthracene, 9,10-bis(n-propylcarbonyloxy)anthracene, 9,10-bis(isopropylcarbonyloxy)anthracene, 9,10-bis(n-butylcarbonyloxy) Anthracene, 9,10-bis(isobutylcarbonyloxy)anthracene, 9,10-bis(n-hexyloxy)anthracene, 9,10-bis(n-heptanyloxy)anthracene, 9,10-bis( N-octyloxy)anthracene, 9,10-bis(2-ethylhexyloxy)anthracene, 9,10-bis(n-nonanoyloxy)anthracene, 9,10-diethoxyanthracene, 9,10 10-dipropoxyanthracene, and 9,10-dibutoxyanthracene.

Specific examples of compounds containing fused tetraphenyl ring and suitable for use as sensitizer (E) include: 2-methyl-5,11-di-side oxy-6,12-bis(acetoxy) fused tetrabenzene, 2-methyl-5,11-di-side oxy-6,12-bis(propyl (Oxy) fused tetrabenzene, 2-methyl-5,11-dilateral oxy-6,12-bis(n-propylcarbonyloxy) fused tetrabenzene, 2-methyl-5,11-dilateral Oxy-6,12-bis(isopropylcarbonyloxy) fused tetrabenzene, 2-methyl-5,11-di-side oxy-6,12-bis(n-butylcarbonyloxy) fused tetrabenzene , 2-methyl-5,11-di-side oxy-6,12-bis(isobutylcarbonyloxy) fused tetrabenzene, 2-methyl-5,11-di-side oxy-6,12- Bis(n-pentylcarbonyloxy) fused tetrabenzene, 2-methyl-5,11-di-side oxy-6,12-bis(n-hexylcarbonyloxy) fused tetrabenzene, 2-methyl-5, 11-dilateral oxy-6,12-bis(n-heptylcarbonyloxy) fused tetrabenzene, 2-ethyl-5,11-dilateral oxy-6,12-bis(acetoxy) fused Tetrabenzene, 2-Ethyl-5,11-di-side oxy-6,12-bis(propionyloxy) fused tetraphenyl, 2-ethyl-5,11-di-side oxy-6,12- Bis(n-propylcarbonyloxy) fused tetrabenzene, 2-ethyl-5,11-di-side oxy-6,12-bis(isopropylcarbonyloxy) fused tetrabenzene, 2-ethyl-5 ,11-Di-side oxy-6,12-bis(n-butylcarbonyloxy) fused tetrabenzene, 2-methyl-5,11-di-side oxy-6,12-bis(isobutylcarbonyloxy) Group) fused tetrabenzene, 2-ethyl-5,11-dilateral oxy-6,12-bis(n-pentylcarbonyloxy) fused tetrabenzene, 2-ethyl-5,11-dilateral oxy -6,12-bis(n-hexylcarbonyloxy) fused tetrabenzene, and 2-ethyl-5,11-di-side oxy-6,12-bis(n-heptylcarbonyloxy) fused tetrabenzene and other alkanes Carbonyloxy substituted fused tetraphenyl compound; 2-methyl-5,11-dilateral oxy-6,12-bis(benzyloxy) fused tetrabenzene, 2-methyl-5,11-dilateral oxy-6,12-bis( O-toluene oxy) fused tetrabenzene, 2-methyl-5,11-di-side oxy-6,12-bis (m-toluene oxy) fused tetrabenzene, 2-methyl-5,11-bis Pendant oxy-6,12-bis(p-tolueneoxy) fused tetrabenzene, 2-methyl-5,11-diside oxy-6,12-bis(α-naphthoxy) fused tetrabenzene Benzene, 2-methyl-5,11-di-oxy-6,12-bis(β-naphthoxy) fused tetrabenzene, 2-ethyl-5,11-di-oxy-6, 12-bis(benzyloxy) fused tetrabenzene, 2-ethyl-5,11-di-side oxy-6,12-bis(o-tolueneoxy) fused tetrabenzene, 2-ethyl-5 ,11-Di-side oxy-6,12-bis(m-tolyloxy) fused tetrabenzene, 2-ethyl-5,11-di-side oxy-6,12-bis(p-tolueneoxy) Condensed tetrabenzene, 2-ethyl-5,11-di-side oxy-6,12-bis(α-naphthyloxy) fused tetrabenzene, and 2-ethyl-5,11-di-side oxy -6,12-bis(β-naphthoxy) fused tetrabenzene and other aryloxy substituted fused tetrabenzene compounds; 2-methyl-5,11-di-side oxy-6,12-bis(methoxycarbonyloxy) fused tetrabenzene, 2-methyl-5,11-di-side oxy-6,12-bis (Ethoxycarbonyloxy) fused tetrabenzene, 2-methyl-5,11-di-side oxy-6,12-bis(n-propoxycarbonyloxy) fused tetrabenzene, 2-methyl-5 ,11-Di-side oxy-6,12-bis(isopropoxycarbonyloxy) fused tetrabenzene, 2-methyl-5,11-di-side oxy-6,12-bis(n-butoxy) Carbonyloxy) fused tetrabenzene, 2-methyl-5,11-di-side oxy-6,12-bis(isobutoxycarbonyloxy) fused tetrabenzene, 2-methyl-5,11-di Pendant oxy-6,12-bis(n-pentyloxycarbonyloxy) condensed tetrabenzene, 2-methyl-5,11-dilateral oxy-6,12-bis(n-hexyloxycarbonyloxy) condensed Tetrabenzene, 2-methyl-5,11-di-side oxy-6,12-bis(n-heptyloxycarbonyloxy) fused tetraphenyl, 2-methyl-5,11-di-side oxy-6 ,12-bis(n-octyloxycarbonyloxy) fused tetrabenzene, 2-ethyl-5,11-di-side oxy-6,12-bis(methoxycarbonyloxy) fused tetrabenzene, 2- Ethyl-5,11-di-side oxy-6,12-bis(ethoxycarbonyloxy) fused tetrabenzene, 2-ethyl-5,11-di-side oxy-6,12-bis(normal Propoxycarbonyloxy) fused tetrabenzene, 2-ethyl-5,11-di-side oxy-6,12-bis(isopropoxycarbonyloxy) fused tetrabenzene, 2-ethyl-5, 11-dilateral oxy-6,12-bis(n-butoxycarbonyloxy) fused tetrabenzene, 2-ethyl-5,11-dilateral oxy-6,12-bis(isobutoxycarbonyl) Oxy) fused tetrabenzene, 2-ethyl-5,11-dilateral oxy-6,12-bis(n-pentyloxycarbonyloxy) fused tetrabenzene, 2-ethyl-5,11-dilateral Oxy-6,12-bis(n-hexyloxycarbonyloxy) fused tetrabenzene, 2-ethyl-5,11-di-side oxy-6,12-bis(n-heptyloxycarbonyloxy) fused tetrabenzene Benzene, and 2-ethyl-5,11-di-side oxy-6,12-bis(n-octyloxycarbonyloxy) fused tetrabenzene and other alkoxycarbonyloxy substituted fused tetrabenzene compounds; and 2-methyl-5,11-di-side oxy-6,12-bis(phenoxycarbonyloxy) fused tetrabenzene, 2-methyl-5,11-di-side oxy-6,12-bis (O-tolyloxycarbonyloxy) fused tetrabenzene, 2-methyl-5,11-di-side oxy-6,12-bis(m-tolyloxycarbonyloxy) fused tetrabenzene, 2-methyl- 5,11-Di-side oxy-6,12-bis(p-tolyloxycarbonyloxy) fused tetrabenzene, 2-methyl-5,11-di-side oxy-6,12-bis(α-naphthalene Oxycarbonyloxy) fused tetrabenzene, 2-methyl-5,11-di-side oxy-6,12-bis(β-naphthyloxycarbonyloxy) fused tetrabenzene, 2-ethyl-5, 11-dilateral oxy-6,12-bis(phenoxycarbonyloxy) fused tetrabenzene, 2-ethyl-5,11-dilateral oxy-6,12-bis(o-tolyloxycarbonyloxy) Group) fused tetrabenzene, 2-ethyl-5,11-dioxo-6,12-bis(m-tolyloxycarbonyloxy) fused tetrabenzene, 2-ethyl-5,11-dioxo Group-6,12-bis(p-tolyloxycarbonyloxy) fused tetrabenzene, 2-ethyl-5,11-di-side oxy-6,12-bis(α-naphthyloxycarbonyloxy) fused Tetrabenzene, and 2-ethyl-5,11-di-side oxy-6,12-bis(β-naphthyloxycarbonyloxy) fused tetrabenzene and other aryloxycarbonyloxy substituted fused tetrabenzene compounds .

Among the above-mentioned compounds containing fused tetraphenyl ring, 5,11-dilateral oxy-6,12-bis(methoxycarbonyloxy) fused tetrabenzene, 5,11-dilateral oxy-6, 12-bis(ethoxycarbonyloxy) fused tetrabenzene, 5,11-di-side oxy-6,12-bis(isopropoxycarbonyloxy) fused tetrabenzene, 5,11-di-side oxy -6,12-bis(isobutoxycarbonyloxy) fused tetrabenzene, 5,11-di-side oxy-6,12-bis(n-butylcarbonyloxy) fused tetrabenzene, 5,11-di Pendant oxy-6,12-bis(n-pentylcarbonyloxy) fused tetrabenzene, 5,11-dipened oxy-6,12-bis(n-heptanoyloxy) fused tetrabenzene.

環之化合物之具體例，可列舉：硫𠮿

-9酮、2-甲基-9H-硫𠮿

-9酮、2-異丙基-9H-硫𠮿

-9酮、1,4-二甲硫基𠮿

-9酮、及3-甲基-9-側氧基-9H-硫𠮿

-2-基乙酸酯。Containing sulfur as suitable as a sensitizer (E)

Specific examples of ring compounds include: sulfur 𠮿

-9 ketone, 2-methyl-9H-sulfur 𠮿

-9 Ketone, 2-isopropyl-9H-sulfur𠮿

-9 Ketone, 1,4-Dimethylthio 𠮿

-9 ketone, and 3-methyl-9-side oxy-9H-sulfur 𠮿

-2-yl acetate.

The content of the sensitizer (E) relative to 100 parts by mass of the photopolymerization initiator (C) in the photosensitive resin composition is preferably from 5 parts by mass to 60 parts by mass, more preferably from 15 parts by mass to 50 parts by mass the following. If the photosensitive resin composition contains a sensitizer within the above-mentioned range, the curing reaction by exposure proceeds uniformly, and it is easy to form a patterned cured film with a particularly good edge angle.

＜Organic solvent (S)＞ The photosensitive resin composition may typically contain an organic solvent (S) according to the purpose of adjusting coatability. As the organic solvent (S), for example, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol-n-propyl ether, ethylene glycol mono-n-butyl ether, diethylene glycol monomethyl ether, two Ethylene glycol monoethyl ether, diethylene glycol mono-n-propyl ether, diethylene glycol mono-n-butyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, Propylene glycol mono-n-propyl ether, propylene glycol mono-n-butyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol mono-n-propyl ether, dipropylene glycol mono-n-butyl ether, tripropylene glycol monomethyl ether, tripropylene glycol mono (Poly) alkylene glycol monoalkyl ethers such as ether; ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol Monoethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate and other (poly)alkylene glycol monoalkyl ether acetates; diethylene glycol dimethyl ether, diethylene glycol methyl Methyl ethyl ether, diethylene glycol diethyl ether, tetrahydrofuran and other ethers; methyl ethyl ketone, cyclohexanone, 2-heptanone, 3-heptanone and other ketones; 2-hydroxypropionic acid methyl ester, 2-hydroxyl Alkyl lactate such as ethyl propionate; ethyl 2-hydroxy-2-methylpropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, 3-ethoxypropionate Methyl ester, ethyl 3-ethoxypropionate, ethyl ethoxy acetate, ethyl hydroxyacetate, methyl 2-hydroxy-3-methylbutanoate, 3-methoxybutyl acetate, 3 -Methyl-acetate 3-methoxybutyl ester, 3-methyl-3-methoxybutyl propionate, ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, isoacetate Butyl ester, n-pentyl formate, isoamyl acetate, n-butyl propionate, ethyl butyrate, n-propyl butyrate, isopropyl butyrate, n-butyl butyrate, methyl pyruvate, ethyl pyruvate Ester, n-propyl pyruvate, methyl acetylacetate, ethyl acetacetate, ethyl 2-oxobutanoate and other esters; aromatic hydrocarbons such as toluene and xylene; N-methylpyrrole Amines such as pyridone, N,N-dimethylformamide, and N,N-dimethylacetamide. These solvents may be used alone or in combination of two or more kinds.

The use amount of the organic solvent (S) can be appropriately determined according to the use of the photosensitive resin composition. As an example of the usage amount of the organic solvent (S), the solid content concentration of the photosensitive resin composition is in the range of 1% by mass to 50% by mass.

＜Other ingredients＞ The photosensitive resin composition may also contain various other additives as needed. Specifically, examples thereof include dispersion aids, fillers, fillers, adhesion promoters, antioxidants, ultraviolet absorbers, anti-agglomeration agents, thermal polymerization inhibitors, defoamers, surfactants, and the like.

As a thermal polymerization inhibitor used for a photosensitive resin composition, hydroquinone, hydroquinone monoethyl ether, etc. are mentioned, for example. In addition, examples of the defoaming agent include compounds such as silicone-based and fluorine-based compounds, and examples of surfactants include compounds such as anionic, cationic, and nonionic compounds.

<Method for preparing photosensitive resin composition> The photosensitive resin composition is prepared by uniformly mixing the above-mentioned components in respective required amounts. Furthermore, when the prepared photosensitive resin composition does not contain insoluble components such as pigments, it is also possible to perform filtration with a filter to make the photosensitive resin composition uniform.

≪Method of manufacturing patterned cured film≫ By using the photosensitive resin composition described above, it is possible to form a patterned cured film having excellent linearity and adhesion to a substrate, and having a good cross-sectional shape. Specifically, a patterned hardened film is manufactured by a method including the following steps: Coating the above-mentioned photosensitive resin composition on a substrate to form a coating film; Area selective exposure of the coated film; and The above-mentioned coating film after exposure is developed.

The method of applying the photosensitive resin composition on the substrate is not particularly limited. Typically, roller coaters, reverse coaters, bar coaters and other contact transfer coating devices or spinners (rotary coating devices), curtain-type flat coating machines, etc. are used. The contact type coating device coats the photosensitive resin composition on the substrate.

Then, the coating film is dried if necessary. The drying method is not particularly limited. Examples of the drying method include the following methods: (1) Using a hot plate to dry at a temperature of 80°C or more and 120°C or less, preferably 90°C or more and 100°C or less, for a time of 60 seconds or more and 120 seconds or less; 2) Place it at room temperature for several hours to several days; (3) Put it into a hot air heater or an infrared heater for tens of minutes to several hours to remove the solvent.

Then, with respect to the coated film, area selective exposure is performed according to the pattern shape of the cured film. Typically, the coating film is partially exposed by irradiating active energy rays such as ultraviolet rays and excimer laser light through a negative mask. The amount of energy rays to be irradiated also depends on the composition of the photosensitive resin composition, but for example, it is preferably 10 mJ/cm ² or more and 2000 mJ/cm ² or less.

Then, the exposed coating film is developed with a developer to form a patterned cured film. The development method is not particularly limited, and for example, a dipping method, a spray method, etc. can be used. Examples of the developing solution include organic developing solutions such as monoethanolamine, diethanolamine, and triethanolamine, or aqueous solutions of sodium hydroxide, potassium hydroxide, sodium carbonate, ammonia, and quaternary ammonium salts.

After development, the patterned cured film can be post-baked at a temperature above 200°C and below 250°C as needed. [Example]

Hereinafter, the present invention will be described in more detail through examples, but the present invention is not limited to these examples.

[Examples 1-28, and Comparative Examples 1-13] In the Examples and Comparative Examples, as the alkali-soluble resin (A) ((A) component), the Cardo resin synthesized by the following method was used. First, a 500 mL four-necked flask was charged with 235 g of bisphenol phenol epoxy resin (epoxy equivalent 235), 110 mg of tetramethylammonium chloride, and 100 mg of 2,6-di-tert-butyl 4-methylphenol and 72.0 g of acrylic acid were heated and dissolved at 90-100°C while blowing air at a rate of 25 mL/min. Then, maintain the white turbid state of the solution and gradually increase the temperature, and heat to 120°C to completely dissolve it. At this time, the solution gradually became transparent and viscous, but continued to stir in this state. In the meantime, the acid value was measured, and heating and stirring were continued until it did not reach 1.0 mgKOH/g. It takes 12 hours until the acid value reaches the target value. Then, it was cooled to room temperature, and a colorless, transparent, and solid bisphenol-type epoxy acrylate represented by the following formula was obtained.

[化57]

Then, 600 g of 3-methoxybutyl acetate was added to 307.0 g of the above-mentioned bisphenol phenol epoxy acrylate obtained in the above manner to dissolve, and then 80.5 g of biphenyltetracarboxylic dianhydride and 1 g Mix the tetraethylammonium bromide and gradually increase the temperature, and react at 110-115°C for 4 hours. After confirming the disappearance of the acid anhydride group, 38.0 g of 1,2,3,6-tetrahydrophthalic anhydride was mixed and reacted at 90°C for 6 hours to obtain a Cardo resin. The disappearance of the acid anhydride group was confirmed by IR spectroscopy.

In the Examples and Comparative Examples, dipentaerythritol hexaacrylate was used as the photopolymerizable monomer (B) ((B) component).

In the Examples and Comparative Examples, the compounds described below are used as the photopolymerization initiator (C) ((C) component). In the Examples and Comparative Examples, the following CI1 and CI2 were used as the photopolymerization initiator (CI) of the oxime ester compound represented by the above formula (C1). [化58]

In the Examples and Comparative Examples, the following CII1 to CII5 were used as oxime ester compounds as photopolymerization initiators (C-II) other than the photopolymerization initiator (CI). [化59]

In the Examples and Comparative Examples, the following CII6 was used as the amine ketone compound as the photopolymerization initiator (C-II). CII6: 2-benzyl-2-dimethylamino-1-(4-𠰌olinylphenyl)butan-1-one

In the Examples and Comparative Examples, the following D1 and D2 were used as the colorant (D) ((D) component). In addition, the amount of the coloring agent (D) described in the following Table 1 refers to the amount of solid content (amount of pigment and dispersant) in the dispersion, not the amount of the dispersion. D1: Carbon black dispersion (carbon black content 20% by mass, dispersant content 5% by mass) D2: Organic pigment mixed dispersion (C.I. Pigment Blue 15: 6/C.I. Pigment Violet 23/C.I. Pigment Red 256=40% by mass/20% by mass/40% by mass, solid content concentration 15% by mass)

The alkali-soluble resin (A), the photopolymerizable monomer (B), the photopolymerization initiator (C) of the type described in Table 1 and the type of the type described in Table 1 are respectively colored Agent (D), 0.2 parts by mass of silane coupling agent ((3-phenylaminopropyl)trimethoxysilane), and 0.5 parts by mass of surfactant are uniformly distributed so that the solid content concentration becomes 15% by mass It was dissolved and dispersed in the organic solvent (S) to obtain the photosensitive resin composition of each Example and Comparative Example. As the organic solvent (S), a mixed solvent containing 15% by mass of 3-methoxybutyl acetate and 85% by mass of propylene glycol monomethyl ether acetate was used.

The photosensitive resin composition of each Example and Comparative Example was coated on a glass substrate (100 mm×100 mm) using a spin coater, and prebaked at 90°C for 120 seconds to form a coating with a thickness of 1.0 μm. membrane. Then, using a proximity exposure device (product name: TME-150RTO, manufactured by TOPCON Co., Ltd.), the exposure pitch was set to 50 μm, and the coating film was irradiated with ultraviolet rays through a negative mask formed with a line pattern with a width of 6 μm. The exposure level is set to 3 stages of 20, 40, and 60 mJ/cm ² . After the exposed coating film was developed in a 0.04% by mass KOH aqueous solution at 26°C for 40 seconds, post-baking was performed at 230°C for 30 minutes, thereby forming a line pattern.

＜Straightforward evaluation＞ The tooth gap at the edge of the formed line pattern was observed with an optical microscope to evaluate the straightness of the pattern. The case where there is no backlash is set to "○", and the case where there is backlash is set to "bad" for evaluation.

＜Adhesion evaluation＞ The presence or absence of peeling of the formed line pattern was observed with an optical microscope, and the pattern adhesion was evaluated. The case where peeling was not observed was set to "○", and the case where peeling was observed was set to "×" for evaluation.

<Taper angle> In the cross section in the width direction of the line portion 10 in the line pattern formed by exposure of 40 mJ/cm ² , the angle θ formed by the substrate 90a and the side surface of the line portion 10 as shown in FIG. 1 is measured, The cone angle is evaluated. Furthermore, in the case of the trapezoidal shape as shown in FIG. 1, θ exceeds 0 degrees and does not reach 90 degrees, which is a forward cone shape. Moreover, in the case of the inverted trapezoid shape as shown in FIG. 2, θ exceeds 90 degrees and does not reach 180 degrees, which is an inverted cone shape. In FIGS. 1 and 2, the surface of the substrate 90a and the line portion 10 of the cured photosensitive resin composition pattern is taken as the reference plane, and the angle between the parallel line of the reference plane and the side surface of the line is represented by θ , But it is the same as the above θ. The taper angle (the cross-sectional shape of the pattern) was evaluated based on the following criteria. ◎: The measurement angle θ is 70 degrees or more and 85 degrees or less ○: The measurement angle θ is 86 degrees or more and 90 degrees or less △: The measurement angle θ is 91 degrees or more and 100 degrees or less ×: The measurement angle θ is 101 degrees or more × ×: The measurement angle θ is 69 degrees or less

In the following, the technical significance of the taper angle θ will be supplemented. The cone angle θ is the meaning of ensuring the fidelity to the mask pattern, and the ideal is 90 degrees. When assembling a black matrix formed using a photosensitive resin composition in an image display panel, there is a case where liquid crystal is arranged in contact with the black matrix. The molecular alignment of the liquid crystal is controlled by voltage. With the control of the molecular alignment, the light transmittance changes rapidly in the optical system including the polarizer. As a result, characters, images, etc. are displayed on the image display panel. When the liquid crystal is arranged in contact with the black matrix, the pattern boundary of the black matrix is affected by the boundary step, and the alignment behavior of the liquid crystal is different from that of the flat portion of the pattern (equivalent to the above-mentioned line or space) . As an optical phenomenon, even if the light transmittance in the flat part of the pattern is 0%, the light will pass through the border of the pattern. It is observed in the form of light leakage or light leakage at the border of the pattern. It is not suitable for image display panels. And image display device. This bleed phenomenon is more obvious when the taper angle θ of the black matrix pattern exceeds 90 degrees, and is reduced by making the line taper angle θ less than 90 degrees. If a drive test is performed as an image display panel and an image display device, it is particularly suitable as the taper angle θ of 85 degrees or less. Furthermore, if it is less than 70 degrees, the light transmission area becomes narrower (in FIG. 1, the space outside the line 10 becomes narrower) and the amount of light decreases. Therefore, it is not suitable for image display panels and image display devices. . Therefore, as a liquid crystal display panel and a liquid crystal display device, the line taper angle θ is desirably 90 degrees or less, and most desirably 70 degrees or more and 85 degrees or less.

[Table 1] (A) Ingredients (B) Ingredients (C) Ingredients (D) Ingredients Straightforwardness Adhesion Cone angle (CI) (C-II) Exposure (mJ/cm ² ) Exposure (mJ/cm ² ) Mass parts Mass parts species Mass parts species Mass parts species Mass parts 20 40 60 20 40 60 Evaluation degree Example 1 28 17 CI1 4 CII5 1 D1 50 ○ ○ ○ ○ ○ ○ ○ 89 Example 2 28 17 CI2 4 CII5 1 D1 50 ○ ○ ○ ○ ○ ○ ○ 88 Example 3 28 17 CI1 3 CII1 2 D1 50 ○ ○ ○ ○ ○ ○ ○ 85 Example 4 28 17 CI1 3 CII2 2 D1 50 ○ ○ ○ ○ ○ ○ ○ 86 Example 5 28 17 CI1 3 CII3 2 D1 50 ○ ○ ○ ○ ○ ○ ○ 87 Example 6 28 17 CI1 3 CII4 2 D1 50 ○ ○ ○ ○ ○ ○ ○ 89 Example 7 28 17 CI1 3 CII5 2 D1 50 ○ ○ ○ ○ ○ ○ ○ 87 Example 8 28 17 CI2 3 CII1 2 D1 50 ○ ○ ○ ○ ○ ○ ○ 87 Example 9 28 17 CI2 3 CII2 2 D1 50 ○ ○ ○ ○ ○ ○ ○ 87 Example 10 28 17 CI2 3 CII3 2 D1 50 ○ ○ ○ ○ ○ ○ ○ 88 Example 11 28 17 CI2 3 CII4 2 D1 50 ○ ○ ○ ○ ○ ○ ○ 89 Example 12 28 17 CI2 3 CII5 2 D1 50 ○ ○ ○ ○ ○ ○ ○ 88 Example 13 28 17 CI1 2 CII1/CII6 2/1 D1 50 ○ ○ ○ ○ ○ ○ ◎ 75 Example 14 28 17 CI1 2 CII2/CII6 2/1 D1 50 ○ ○ ○ ○ ○ ○ ◎ 77 Example 15 28 17 CI1 2 CII3/CII6 2/1 D1 50 ○ ○ ○ ○ ○ ○ ◎ 79 Example 16 28 17 CI1 2 CII4/CII6 2/1 D1 50 ○ ○ ○ ○ ○ ○ ◎ 76 Example 17 28 17 CI1 2 CII5/CII6 2/1 D1 50 ○ ○ ○ ○ ○ ○ ◎ 77 Example 18 28 17 CI2 2 CII1/CII6 2/1 D1 50 ○ ○ ○ ○ ○ ○ ◎ 82 Example 19 28 17 CI2 2 CII2/CII6 2/1 D1 50 ○ ○ ○ ○ ○ ○ ◎ 81 Example 20 28 17 CI2 2 CII3/CII6 2/1 D1 50 ○ ○ ○ ○ ○ ○ ◎ 83 Example 21 28 17 CI2 2 CII4/CII6 2/1 D1 50 ○ ○ ○ ○ ○ ○ ◎ 84 Example 22 28 17 CI2 2 CII4/CII6 2/1 D1 50 ○ ○ ○ ○ ○ ○ ◎ 83 Example 23 20.8 9.2 CI1 2 CII1/CII6 2/1 D2 65 ○ ○ ○ ○ ○ ○ ◎ 80 Example 24 20.8 9.2 CI2 2 CII1/CII6 2/1 D2 65 ○ ○ ○ ○ ○ ○ ◎ 81 Example 25 61.5 33.5 CI1 2 CII1/CII6 2/1 - - ○ ○ ○ ○ ○ ○ ◎ 77 Example 26 61.5 33.5 CI2 2 CII1/CII6 2/1 - - ○ ○ ○ ○ ○ ○ ◎ 79 Example 27 28 17 CI1 1 CII1/CI/6 3/1 D1 50 ○ ○ ○ ○ ○ ○ ○ 87 Example 28 28 17 CI2 1 CII1/CI/6 3/1 D1 50 ○ ○ ○ ○ ○ ○ ○ 86 Example 29 28 17 CI1 4.75 CII6 0.25 D1 50 ○ ○ ○ ○ ○ ○ ○ 89 Example 30 28 17 CI2 4.75 CII6 0.25 D1 50 ○ ○ ○ ○ ○ ○ ○ 89 Comparative example 1 28 17 CI1 5 - - D1 50 × × × ○ ○ ○ × ＞100 Comparative example 2 28 17 CI2 5 - - D1 50 × × × ○ ○ ○ × ＞100 Comparative example 3 28 17 - - CII1 5 D1 50 × ○ ○ × ○ ○ △ 92 Comparative example 4 28 17 - - CII2 5 D1 50 × ○ ○ × ○ ○ △ 95 Comparative example 5 28 17 - - CII3 5 D1 50 × × ○ × × ○ × ＞100 Comparative example 6 28 17 - - CII4 5 D1 50 × × × × × × × ＞100 Comparative example 7 28 17 - - CII5 5 D1 50 × ○ ○ × ○ ○ △ 91 Comparative example 8 20.8 9.2 CI1 5 - - D2 65 × × × ○ ○ ○ ×× ＜60 Comparative example 9 20.8 9.2 CI2 5 - - D2 65 × × × ○ ○ ○ ×× ＜60 Comparative example 10 61.5 33.5 CI1 5 - - - - × × × ○ ○ ○ ×× ＜60 Comparative example 11 61.5 33.5 CI2 5 - - - - × × × ○ ○ ○ ×× ＜60 Comparative example 12 28 17 CI1 0.5 CII1 4.5 D1 50 × ○ ○ ○ ○ ○ △ 91 Comparative example 13 28 17 CI2 0.5 CII1 4.5 D1 50 × ○ ○ ○ ○ ○ △ 92

According to Table 1, it can be seen that the patterned cured film formed using the photosensitive resin composition of the example has excellent straightness and adhesion to the substrate, and the cross-sectional shape is also good. The photosensitive resin composition of the example is The specific ratio includes the alkali-soluble resin (A), the photopolymerizable monomer (B), the oxime ester compound represented by the above formula (C1), that is, the photopolymerization initiator (CI), and the photopolymerization initiator ( Other photopolymerization initiators (C-II) other than CI). On the other hand, the patterned cured film formed using the photosensitive resin composition of the comparative example cannot have both good straightness and good adhesion to the substrate, and the cross-sectional shape is also poor. The photosensitive resin of the comparative example The composition contains only any one of the photopolymerization initiator (CI) and the photopolymerization initiator (C-II), or does not contain the photopolymerization initiator (CI) and the photopolymerization initiator ( C-II).

10: Line 90a: substrate

1 is a diagram schematically showing the cross-sectional shape in the pattern width direction of a cured film formed using a photosensitive resin composition having a cross-sectional shape of a positive cone. 2 is a diagram schematically showing the cross-sectional shape in the pattern width direction of a cured film formed using a photosensitive resin composition having an inverted cone cross-sectional shape.

Claims (9)

A photosensitive resin composition containing an alkali-soluble resin (A), a photopolymerizable monomer (B), and a photopolymerization initiator (C), and the photopolymerization initiator (C) includes the following The photopolymerization initiator (CI) represented by the formula (C1), and other photopolymerization initiators (C-II) other than the above-mentioned photopolymerization initiator (CI), [化1]

(In formula (C1), X ⁰¹ is in the structure represented by the following formula (C1-1), the group obtained by removing t2+t3 hydrogen atoms from the hydrogen atoms bonded to the aromatic ring, X ⁰² and X ^{03 is} each independently a monovalent organic group, X ⁰⁴ and X ⁰⁵ are each independently a hydrogen atom, an optionally substituted alkyl group having 1 to 11 carbon atoms, or an optionally substituted aryl group, t0 to t3, respectively Independent is 0 or 1, at least one of t2 and t3 is 1, [化2]

In the formula (C1-1), X ⁰⁶ is a monovalent organic group bonded to the nitrogen atom in the carbazole ring by a CN bond, t4 and t5 are independently 0 or 1, and at least one of t4 and t5 is 1) The mass ratio of the photopolymerization initiator (CI) in the mass of the photopolymerization initiator (C) is 20% by mass or more and 95% by mass or less. The photosensitive resin composition according to claim 1, wherein the photopolymerization initiator (C-II) is an oxime ester compound and/or an amine ketone compound. The photosensitive resin composition according to claim 2, wherein the photopolymerization initiator (C) contains the oxime ester compound and the amine ketone compound as the photopolymerization initiator (C-II). The photosensitive resin composition of claim 2 or 3, wherein the oxime ester compound as the photopolymerization initiator (C-II) is a compound represented by the following formula (C2), [化3]

(In formula (C2), R ^c1 is a monovalent organic group, R ^c2 is a group represented by any of the following formulas (C2-1) to (C2-3), R ^c3 is a hydrogen atom, which may be substituted An alkyl group having 1 to 11 carbon atoms or an aryl group that may have a substituent, [formation 4]

In formula (C2-1), R ^c4 is a group selected from the group consisting of monovalent organic groups, amine groups, halogens, nitro groups, and cyano groups, A is S or O, and n2 is 0 or more and 4 or less Integer, in formula (C2-2), R ^c5 and R ^c6 are each independently a monovalent organic group, in formula (C2-3), R ^c7 is a hydrogen atom, a nitro group or a monovalent organic group, R ^c8 and R ^c9 Each is a chain alkyl group which may have a substituent, a cyclic organic group which may have a substituent, or a hydrogen atom. R ^c8 and R ^c9 may be bonded to each other to form a ring, and n3 is an integer of 0 to 4). The photosensitive resin composition according to claim 4, wherein said R ^c1 is a group represented by the following formula (C2a) or (C2b), [化5]

(In formulas (C2a) and (C2b), R ^c10 and R ^c11 are respectively a monovalent organic group, n4 is an integer from 0 to 4, when R ^c10 and R ^c11 exist at adjacent positions on the benzene ring When R ^c10 and R ^c11 can also be bonded to each other to form a ring, n5 is an integer of 1 and less than 8; n6 is an integer of 1 to 5; n7 is an integer of 0 or more (n6+3); R ^c12 is a monovalent Organic base). The photosensitive resin composition according to any one of claims 1 to 3, which further contains a colorant (D). The photosensitive resin composition according to claim 6, wherein the colorant (D) is a sunscreen (D1). A method for manufacturing a patterned hardened film, which includes the following steps: Coating the photosensitive resin composition according to any one of claims 1 to 7 on a substrate to form a coating film; Regioselective exposure of the above-mentioned coated film; and The above-mentioned coating film after exposure is developed. A patterned cured film comprising the cured product of the photosensitive resin composition according to any one of claims 1 to 7.

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