TW202411327A - Photosensitive composition, method of manufacturing patterned hardened material, patterned hardened material and black matrix - Google Patents

Abstract

The subject of the present invention is to provide a photosensitive composition capable of forming a patterned cured product having excellent water resistance and excellent adhesion to a substrate, a method for manufacturing a patterned cured product using the photosensitive composition, a patterned cured product formed from the cured product of the photosensitive composition, and a black matrix formed from the cured product of the photosensitive composition. The solution is to use the following photosensitive composition: it contains alkali-soluble resin (A), photopolymerizable monomer (B), photopolymerization initiator (C), sunscreen (D) and silane coupling agent (E), the sunscreen (D) contains carbon black (D1) coated with epoxy resin, the photopolymerizable monomer (B) contains a high hydroxyl monomer (B1) with a hydroxyl value of 180 mgKOH/g or more and a low hydroxyl monomer (B2) with a hydroxyl value of less than 180 mgKOH/g, and the content of the high hydroxyl monomer (B1) is 5% by mass or more and 60% by mass or less relative to the mass of the photopolymerizable monomer (B).

Description

Photosensitive composition, method for producing patterned hardened product, patterned hardened product and black matrix

The present invention relates to a photosensitive composition, a method for manufacturing a patterned hardened product, a patterned hardened product and a black matrix.

In a panel for a display device such as a liquid crystal display device, a patterned light-shielding film such as a black matrix or a black columnar spacer is usually formed. Various photosensitive compositions containing a light-shielding black pigment and a photopolymerization initiator for forming a light-shielding film for such an application have been proposed (see Patent Document 1). [Prior Art Document] [Patent Document]

Patent document 1: Japanese Patent Application Publication No. 2012-068613

[The problem that the invention is trying to solve]

A light-shielding cured film such as a black matrix is sometimes formed on a panel that can be used in a high-humidity environment. Therefore, it is desirable to form a cured product with excellent water resistance for a photosensitive composition. In addition, it is also desirable to form a pattern (patterned cured product) with excellent adhesion to a substrate.

However, when using conventional photosensitive compositions such as the photosensitive composition described in Patent Document 1, there are problems in that the water resistance of the cured product is insufficient or the adhesion of the pattern to the substrate is poor.

The present invention is completed in view of the above-mentioned problem, and its purpose is to provide a photosensitive composition capable of forming a patterned cured product with excellent water resistance and excellent adhesion to a substrate, a method for manufacturing a patterned cured product using the photosensitive composition, a patterned cured product composed of the cured product of the above-mentioned photosensitive composition, and a black matrix composed of the cured product of the above-mentioned photosensitive composition. [Means for solving the problem]

The inventors of the present invention have found that the above-mentioned problem can be solved by using the following photosensitive composition, thereby completing the present invention, the photosensitive composition comprising: an alkali-soluble resin (A), a photopolymerizable monomer (B), a photopolymerization initiator (C), a sunscreen (D) and a silane coupling agent (E), the sunscreen (D) comprising carbon black (D1) coated with an epoxy resin, the photopolymerizable monomer (B) comprising a high hydroxyl monomer (B1) having a hydroxyl value of 180 mgKOH/g or more and a low hydroxyl monomer (B2) having a hydroxyl value of less than 180 mgKOH/g, and the content of the high hydroxyl monomer (B1) is 5 mass % or more and 60 mass % or less relative to the mass of the aforementioned photopolymerizable monomer (B). Specifically, the present invention provides the following contents.

[1] A photosensitive composition comprising an alkali-soluble resin (A), a photopolymerizable monomer (B), a photopolymerization initiator (C), a sunscreen (D) and a silane coupling agent (E), wherein the sunscreen (D) comprises carbon black (D1) coated with an epoxy resin, the photopolymerizable monomer (B) comprises a high-hydroxyl monomer (B1) having a hydroxyl value of 180 mgKOH/g or more and a low-hydroxyl monomer (B2) having a hydroxyl value of less than 180 mgKOH/g, and the content of the high-hydroxyl monomer (B1) is 5% by mass to 60% by mass relative to the mass of the photopolymerizable monomer (B).

[2] The photosensitive composition of [1] above, wherein the high hydroxyl monomer (B1) comprises a multifunctional acrylic monomer (B1-1) having two or more (meth)acryl groups.

[3] The photosensitive composition of [2] above, wherein the multifunctional acrylic monomer (B1-1) comprises at least one selected from glycerol di(meth)acrylate, trihydroxymethylpropane di(meth)acrylate, diglycerol di(meth)acrylate, diglycerol tri(meth)acrylate, pentaerythritol di(meth)acrylate and pentaerythritol tri(meth)acrylate.

[4] The photosensitive composition according to any one of [1] to [3] above, wherein the alkali-soluble resin (A) comprises at least one selected from a resin having a cardo structure (A1) and an acrylic resin (A2).

[5] The photosensitive composition as described in any one of [1] to [4] above, wherein the photopolymerization initiator (C) comprises an aminoalkylphenone-based photopolymerization initiator (C1).

[6] A method for producing a patterned cured product, comprising: a step of applying a photosensitive composition as described in any one of [1] to [5] to form a coating film; a step of selectively exposing the coating film; a step of developing the exposed coating film; and a step of heating the developed coating film.

[7] A patterned cured product, which is composed of a cured product of the photosensitive composition as described in any one of [1] to [5] above.

[8] A black matrix, which is composed of a cured product of a photosensitive composition as described in any one of [1] to [5] above. [Effect of the invention]

According to the present invention, there can be provided a photosensitive composition capable of forming a patterned cured product having excellent water resistance and excellent adhesion to a substrate, a method for producing a patterned cured product using the photosensitive composition, a patterned cured product composed of the cured product of the photosensitive composition, and a black matrix composed of the cured product of the photosensitive composition.

《Photosensitive composition (black photosensitive composition)》

The photosensitive composition comprises an alkali-soluble resin (A), a photopolymerizable monomer (B), a photopolymerization initiator (C), a sunscreen (D) and a silane coupling agent (E). The sunscreen (D) comprises carbon black (D1) coated with an epoxy resin. Furthermore, the photopolymerizable monomer (B) comprises a high-hydroxyl monomer (B1) having a hydroxyl value of 180 mgKOH/g or more and a low-hydroxyl monomer (B2) having a hydroxyl value of less than 180 mgKOH/g, and the content of the high-hydroxyl monomer (B1) is 5% by mass or more and 60% by mass or less relative to the mass of the photopolymerizable monomer (B).

Hereinafter, essential or optional components of the photosensitive composition will be described.

<Alkali-soluble resin (A)> The photosensitive composition contains an alkali-soluble resin (A) (hereinafter also referred to as component (A)). By adding the alkali-soluble resin (A) to the photosensitive composition, alkali-developability can be imparted to the photosensitive composition. Here, in this specification, the alkali-soluble resin refers to a resin having a functional group (such as a phenolic hydroxyl group, a carboxyl group, a sulfonic acid group, etc.) in the molecule that makes it alkali-soluble.

The alkali-soluble resin (A) preferably contains a resin containing a photopolymerizable group such as an ethylene unsaturated double bond in the molecule. In this case, when a cured product is formed using a photosensitive composition, crosslinking occurs between the alkali-soluble resin (A) and the photopolymerizable monomer (B). Therefore, even if the baking temperature when forming the cured product is such a low temperature as 120°C or less, further 100°C or less, or 95°C or less, it is easy to form a cured product with high solvent resistance. As typical examples of photopolymerizable groups, functional groups having unsaturated double bonds such as vinyl, allyl, and (meth)acryloyl can be listed.

The alkali-soluble resin (A) preferably contains a resin (a-1) having a cardo structure in the molecule. The cardo structure will be described in detail below. When a resin having a cardo structure in the molecule is used, a photosensitive composition having excellent resolution can be easily obtained, and a cured product having good adhesion to a substrate can be easily formed using the photosensitive composition.

[Resin having a cardo structure (a-1) (Resin having a cardo structure (A1))] As the resin having a cardo structure (a-1) (hereinafter also referred to as cardo resin (a-1)), a resin having a cardo structure in the molecule and having a predetermined alkali solubility can be used. The cardo structure refers to a skeleton in which a second ring structure and a third ring structure are bonded to one ring carbon atom constituting a first ring structure. The second ring structure and the third ring structure may be the same structure or different structures. As a representative example of the cardo structure, a skeleton in which two aromatic rings (e.g., a benzene ring) are bonded to the carbon atom at the 9th position of the fluorene ring can be cited.

There is no particular limitation on the cardo resin (a-1), and conventionally known resins can be used. Among them, a resin represented by the following formula (a-1) is preferred. The resin represented by the following formula (a-1) has a (meth)acryloyl group in the molecule as shown in the following formula (a-2). Therefore, the resin represented by the following formula (a-1) belongs to a resin containing a photopolymerizable group in the molecule.

In the formula (a-1), ^Xa represents a group represented by the following formula (a-2). m1 represents an integer of 0 or more and 20 or less.

In the above formula (a-2), ^Ra1 independently represents a hydrogen atom, a alkyl group having 1 to 6 carbon atoms, or a halogen atom, ^Ra2 independently represents a hydrogen atom or a methyl group, ^Ra3 independently represents a linear or branched alkylene group, m2 represents 0 or 1, and ^Wa represents a group represented by the following formula (a-3).

In formula (a-2), R ^a3 is preferably an alkylene group having 1 to 20 carbon atoms, more preferably an alkylene group having 1 to 10 carbon atoms, particularly preferably an alkylene group having 1 to 6 carbon atoms, and most preferably ethane-1,2-diyl, propane-1,2-diyl and propane-1,3-diyl.

Ring A in formula (a-3) represents an aliphatic ring which can be condensed with an aromatic ring and can also have a substituent. The aliphatic ring can be an aliphatic alkyl ring or an aliphatic heterocyclic ring. As the aliphatic ring, monocyclic alkanes, dicyclic alkanes, tricyclic alkanes, tetracyclic alkanes, etc. can be listed. Specifically, monocyclic alkanes such as cyclopentane, cyclohexane, cycloheptane, and cyclooctane or adamantane, norbornane, isobornane, tricyclodecane, and tetracyclododecane can be listed. The aromatic ring which can be condensed with the aliphatic ring can be an aromatic alkyl ring or an aromatic heterocyclic ring, and preferably an aromatic alkyl ring. Specifically, benzene ring and naphthyl ring are preferred.

Preferred examples of the divalent group represented by formula (a-3) include the following groups.

The divalent group ^Xa in the formula (a-1) is introduced into the carpolyresin (a-1) by reacting tetracarboxylic dianhydride which provides the residual group ^Za with a diol compound represented by the following formula (a-2a).

In formula (a-2a), ^Ra1 , ^Ra2 , ^Ra3 and m2 are the same as those described for formula (a-2). Ring A in formula (a-2a) is the same as those described for formula (a-3).

The diol compound represented by formula (a-2a) can be produced, for example, by the following method. First, the hydrogen atom in the phenolic hydroxyl group of the diol compound represented by the following formula (a-2b) is substituted with a group represented by ^-Ra3 -OH according to a conventional method as needed, and then glycerylated using epichlorohydrin or the like to obtain an epoxy compound represented by the following formula (a-2c). Next, the epoxy compound represented by formula (a-2c) is reacted with acrylic acid or methacrylic acid to obtain a diol compound represented by formula (a-2a). In formulas (a-2b) and (a-2c), ^Ra1 , ^Ra3 and m2 are the same as those described for formula (a-2). Ring A in formulas (a-2b) and (a-2c) is the same as that described for formula (a-3). In addition, the method for producing the diol compound represented by formula (a-2a) is not limited to the above method.

As preferred examples of the diol compound represented by the formula (a-2b), the following diol compounds can be cited.

In the above formula (a-1), ^Ra0 is a hydrogen atom or a group represented by -CO-Ya ^-COOH . Here, ^Ya represents a residue obtained by removing the anhydride group (-CO-O-CO-) from a dicarboxylic anhydride. Examples of dicarboxylic anhydrides include maleic anhydride, succinic anhydride, itaconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyl-methylenetetrahydrophthalic anhydride, chloro-anhydride, methyltetrahydrophthalic anhydride, glutaric anhydride, and the like.

In the above formula (a-1), ^Za represents a residue after removing two anhydride groups from tetracarboxylic dianhydride. Examples of tetracarboxylic dianhydride include tetracarboxylic dianhydride represented by the following formula (a-4), pyromellitic dianhydride, benzophenone tetracarboxylic dianhydride, biphenyl tetracarboxylic dianhydride, and biphenyl ether tetracarboxylic dianhydride. In the above formula (a-1), m1 represents an integer of 0 to 20.

(In formula (a-4), ^Ra4 , ^Ra5 and ^Ra6 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 an integer of 0 to 12).

The alkyl group that can be selected as ^Ra4 in formula (a-4) is an alkyl group having a carbon number of 1 to 10. By setting the carbon number of the alkyl group to this range, the heat resistance of the obtained carboxylic acid ester can be further improved. In the case where ^Ra4 is an alkyl group, from the viewpoint of easily obtaining a carboresin having excellent heat resistance, the carbon number is preferably 1 to 6, more preferably 1 to 5, further preferably 1 to 4, and particularly preferably 1 to 3. In the case where ^Ra4 is an alkyl group, the alkyl group may be a straight chain or a branched chain.

From the viewpoint of easily obtaining a cardo resin having excellent heat resistance, ^Ra4 in formula (a-4) is preferably independently a hydrogen atom or an alkyl group having 1 to 10 carbon atoms. ^Ra4 in formula (a-4) is further preferably a hydrogen atom, a methyl group, an ethyl group, an n-propyl group or an isopropyl group, and is particularly preferably a hydrogen atom or a methyl group. From the viewpoint of easily preparing a high-purity tetracarboxylic dianhydride, a plurality of ^Ra4 in formula (a-4) are preferably the same group.

m3 in formula (a-4) represents an integer of 0 to 12. By setting the value of m3 to 12 or less, the purification of tetracarboxylic dianhydride can be facilitated. From the viewpoint of easy purification of tetracarboxylic dianhydride, the upper limit of m3 is preferably 5, and more preferably 3. From the viewpoint of chemical stability of tetracarboxylic dianhydride, the lower limit of m3 is preferably 1, and more preferably 2. m3 in formula (a-4) is particularly preferably 2 or 3.

The alkyl group having 1 to 10 carbon atoms that can be selected as ^Ra5 and ^Ra6 in formula (a-4) is the same as the alkyl group having 1 to 10 carbon atoms that can be selected as ^Ra4 . From the viewpoint of easy purification of tetracarboxylic dianhydride, ^Ra5 and ^Ra6 are preferably hydrogen atoms or alkyl groups having 1 to 10 carbon atoms, and particularly preferably hydrogen atoms or methyl groups. The number of carbon atoms in the alkyl group is more preferably 1 to 6, further preferably 1 to 5, further preferably 1 to 4, and particularly preferably 1 to 3.

Examples of the tetracarboxylic dianhydride represented by the formula (a-4) include norbornane-2-spiro-α-cyclopentanone-α'-spiro-2"-norbornane-5,5",6,6"-tetracarboxylic dianhydride (also known as "norbornane-2-spiro-2'-cyclopentanone-5'-spiro-2"-norbornane-5,5",6,6"-tetracarboxylic dianhydride"), methylnorbornane-2-spiro-α-cyclopentanone-α'-spiro-2"-(methylnorbornane)-5,5",6,6"-tetracarboxylic dianhydride, norbornane-2-spiro-α-cyclohexanone-α'-spiro-2"-norbornane-5,5",6,6"-tetracarboxylic dianhydride (also known as "norbornane-2-spiro- 2'-cyclohexanone-6'-spiro-2"-norbornane-5,5",6,6"-tetracarboxylic dianhydride")), methylnorbornane-2-spiro-α-cyclohexanone-α'-spiro-2"-(methylnorbornane)-5,5",6,6"-tetracarboxylic dianhydride, norbornane-2-spiro-α-cyclopropanone-α'-spiro-2"-norbornane-5,5",6,6"-tetracarboxylic dianhydride, norbornane-2-spiro-α-cyclobutanone-α'-spiro-2"-norbornane-5,5",6,6"-tetracarboxylic dianhydride, norbornane-2-spiro-α-cycloheptanone-α'-spiro-2"-norbornane-5,5",6,6"-tetracarboxylic dianhydride, norbornane- 2-spiro-α-cyclooctanone-α'-spiro-2"-norbornane-5,5",6,6"-tetracarboxylic dianhydride, norbornane-2-spiro-α-cyclononanone-α'-spiro-2"-norbornane-5,5",6,6"-tetracarboxylic dianhydride, norbornane-2-spiro-α-cyclodecanone-α'-spiro-2"-norbornane-5,5",6,6"-tetracarboxylic dianhydride, norbornane-2-spiro-α-cycloundecanone-α'-spiro-2"-norbornane-5,5",6,6"-tetracarboxylic dianhydride, norbornane-2-spiro-α-cycloundecanone-α'-spiro-2"-norbornane-5,5",6,6"-tetracarboxylic dianhydride, norbornane-2-spiro-α-cyclododecanone-α'-spiro-2"-norbornane-5,5",6,6"-tetracarboxylic dianhydride -α-cyclotridecanone-α’-spiro-2”-norbornane-5,5”,6,6”-tetracarboxylic dianhydride, norbornane-2-spiro-α-cyclotetradecanone-α’-spiro-2”-norbornane-5,5”,6,6”-tetracarboxylic dianhydride, norbornane-2-spiro-α-cyclopentadecanone-α’-spiro-2”-norbornane-5,5”,6,6”-tetracarboxylic dianhydride, norbornane-2-spiro-α-(methylcyclopentanone)-α’-spiro-2”-norbornane-5,5”,6,6”-tetracarboxylic dianhydride, norbornane-2-spiro-α-(methylcyclohexanone)-α’-spiro-2”-norbornane-5,5”,6,6”-tetracarboxylic dianhydride, etc.

The content of the resin (a-1) having a cardo structure in the alkali-soluble resin (A) is not particularly limited, but is preferably 50 mass % or more, more preferably 70 mass % or more, and further preferably 90 mass % or more.

The mass average molecular weight of the carboresin (a-1) is preferably 1000 to 40000, more preferably 1500 to 30000, and further preferably 2000 to 10000. By setting the above range, good developability can be obtained, and sufficient heat resistance and mechanical strength for the cured film can be obtained. In this specification, the mass average molecular weight Mw is a measured value obtained by gel permeation chromatography (GPC) in terms of polystyrene.

[Novolac resin (a-2)] From the viewpoint of imparting high heat resistance to the cured film that makes it difficult to flow or deform due to heat, the alkali-soluble resin (A) preferably includes a novolac resin (a-2). As the novolac resin (a-2), various novolac resins that have been mixed with photosensitive compositions in the past can be used. As the novolac resin (a-2), a resin obtained by addition condensation of an aromatic compound having a phenolic hydroxyl group (hereinafter referred to as "phenols") and an aldehyde under an acid catalyst is preferred.

(Phenols) Examples of phenols used in the preparation of the novolac resin (a-2) include: phenol; cresols such as o-cresol, m-cresol, and p-cresol; xylenols such as 2,3-xylenol, 2,4-xylenol, 2,5-xylenol, 2,6-xylenol, 3,4-xylenol, and 3,5-xylenol; ethylphenols such as o-ethylphenol, m-ethylphenol, and p-ethylphenol; 2-isopropylphenol, 3-isopropylphenol, 4-isopropylphenol, o-butylphenol, Alkylphenols such as m-butylphenol, p-butylphenol and p-tert-butylphenol; trialkylphenols such as 2,3,5-trimethylphenol and 3,4,5-trimethylphenol; polyphenols such as resorcinol, catechol, hydroquinone, hydroquinone monomethyl ether, o-pyrogallol and pyrogallol; alkyl polyphenols such as alkylresorcinol, alkylcatechol and alkylhydroquinone (any alkyl group has 1 to 4 carbon atoms); α-naphthol; β-naphthol; hydroxybiphenyl; and bisphenol A. These phenols can be used alone or in combination of two or more.

Among these phenols, m-cresol and p-cresol are particularly preferred, and it is more preferred to use m-cresol and p-cresol together. In this case, by adjusting the mixing ratio of the two, the heat resistance and other properties of the cured film formed using the photosensitive composition can be adjusted. The mixing ratio of m-cresol and p-cresol is not particularly limited, and the molar ratio of m-cresol/p-cresol is preferably 3/7 or more and 8/2 or less. By using m-cresol and p-cresol at a ratio within this range, it is easy to obtain a photosensitive composition that can form a cured film with excellent heat resistance.

In addition, a novolac resin produced by combining meta-cresol and 2,3,5-trimethylphenol is also preferred. When such a novolac resin is used, it is particularly easy to obtain a photosensitive composition that can form a highly heat-resistant cured film that is difficult to flow or deform due to heat. The mixing ratio of meta-cresol and 2,3,5-trimethylphenol is not particularly limited, and the molar ratio of meta-cresol/2,3,5-trimethylphenol is preferably 70/30 or more and 95/5 or less.

(Aldehydes) Examples of aldehydes used in the preparation of novolac resin (a-2) include formaldehyde, paraformaldehyde, furfural, benzaldehyde, nitrobenzaldehyde, and acetaldehyde. These aldehydes may be used alone or in combination of two or more.

(Acid catalyst) Examples of the acid catalyst used in the preparation of the novolac resin (a-2) include inorganic acids such as hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, and phosphorous acid; organic acids such as formic acid, oxalic acid, acetic acid, diethylsulfuric acid, and p-toluenesulfonic acid; and metal salts such as zinc acetate. These acid catalysts may be used alone or in combination of two or more.

(Molecular weight) From the viewpoint of heat resistance of a cured film formed using a photosensitive composition, the polystyrene-equivalent mass average molecular weight (Mw) of the novolac resin (a-2) is preferably 2,000 as the lower limit, more preferably 5,000, particularly preferably 10,000, further preferably 15,000, and optimally 20,000, and is preferably 50,000 as the upper limit, more preferably 45,000, further preferably 40,000, and optimally 35,000.

As the novolac resin (a-2), at least two novolac resins having different mass average molecular weights in terms of polystyrene can be used in combination. By using novolac resins having different mass average molecular weights in large and small combinations, a balance can be achieved between the developability of the photosensitive composition and the heat resistance of a cured film formed using the photosensitive composition.

[Modified epoxy resin (a-3)] From the viewpoint of easily imparting high water resistance to the cured film, the alkali-soluble resin (A) may also include a polybasic acid anhydride (a-3c) adduct (a-3) of the reaction product of an epoxy compound (a-3a) and an unsaturated group-containing carboxylic acid (a-3b). Such an adduct is also referred to as "modified epoxy resin (a-3)". In addition, in the specification and patent scope of this application, a compound that meets the above definition and does not belong to the above-mentioned resin (a-1) having a cardo structure is referred to as a 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 may be an aromatic epoxy compound having an aromatic group or an aliphatic epoxy compound not containing 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 polyfunctional epoxy compound having two or more functional groups, preferably a polyfunctional epoxy compound.

Specific examples of the epoxy compound (a-3a) include bifunctional epoxy resins such as bisphenol A type epoxy resins, bisphenol F type epoxy resins, bisphenol S type epoxy resins, bisphenol AD type epoxy resins, naphthalene type epoxy resins, and biphenyl type epoxy resins; glycidyl ester type epoxy resins such as dimer acid glycidyl ester and triglycidyl ester; tetrakis Glycerylamine epoxy resins such as glycidylaminodiphenylmethane, triglycidylparaaminophenol, tetraglycidylm-xylenediamine and tetraglycidylbisaminomethylcyclohexane; miscellaneous epoxy resins such as triglycidylisocyanurate; phloroglucinol triglycidyl ether, trihydroxybiphenyl triglycidyl ether, trihydroxybenzene trifunctional epoxy resins such as methane triglycidyl ether, glycerol triglycidyl ether, 2-[4-(2,3-glycidyloxy)phenyl]-2-[4-[1,1-bis[4-(2,3-glycidyloxy)phenyl]ethyl]phenyl]propane and 1,3-bis[4-[1-[4-(2,3-glycidyloxy)phenyl]-1-[4-[1-[4-(2,3-glycidyloxy)phenyl]-1-methylethyl]phenyl]ethyl]phenoxy]-2-propanol; and quadrifunctional epoxy resins such as tetrahydroxyphenylethane tetraglycidyl ether, tetraglycidyl benzophenone, bisresorcinol tetraglycidyl ether and tetraglycidyl biphenyl.

In addition, as the epoxy compound (a-3a), an epoxy compound having a biphenyl skeleton is preferred. The epoxy compound having a biphenyl skeleton preferably has at least one biphenyl skeleton represented by the following formula (a-3a-1) on 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 composition that has an excellent balance between sensitivity and developability and can form a cured film with excellent adhesion to the substrate.

(In formula (a-3a-1), ^Ra7 independently represents a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, a halogen atom or a phenyl group which may have a substituent, and j represents 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, sec-butyl, t-butyl, n-pentyl, iso-pentyl, sec-pentyl, t-pentyl, n-hexyl, n-heptyl, n-octyl, iso-octyl, sec-octyl, t-octyl, n-nonyl, iso-nonyl, n-decyl, iso-decyl, 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 to 5, preferably 0 or 1. Examples of the substituent include an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, an aliphatic acyl group having 2 to 4 carbon atoms, a halogen atom, a cyano group, and a nitro group.

The epoxy compound (a-3a) having a biphenyl skeleton represented by the above formula (a-3a-1) is not particularly limited, and examples thereof include epoxy compounds represented by the following formula (a-3a-2). (In formula (a-3a-2), ^Ra7 and j are the same as those in formula (a-3a-1), and k is the average repetition number of the structural unit in parentheses, which is greater than or equal to 0 and less than or equal to 10).

Among the epoxy compounds represented by the formula (a-3a-2), the compounds represented by the following formula (a-3a-3) are preferred because they can easily provide a photosensitive composition having an excellent balance between sensitivity and developability. (In formula (a-3a-3), k is the same as in formula (a-3a-2)).

(Unsaturated group-containing carboxylic acid (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). As the unsaturated group-containing carboxylic acid (a-3b), it is preferred to use a monocarboxylic acid containing a reactive unsaturated double bond such as an acrylic group or a methacrylic group in the molecule. As such an unsaturated group-containing carboxylic acid, for example, acrylic acid, methacrylic acid, β-styryl acrylic acid, β-furfuryl acrylic acid, α-cyanocinnamic acid, cinnamic acid, etc. can be listed. In addition, the unsaturated group-containing carboxylic acid (a-3b) can be used alone or in combination of two or more.

The epoxy compound (a-3a) and the unsaturated group-containing carboxylic acid (a-3b) can be reacted by a known method. As a preferred reaction method, for example, the following method can be cited: using a tertiary amine such as triethylamine and benzylethylamine; a quaternary ammonium salt such as dodecyltrimethylammonium chloride, tetramethylammonium chloride, tetraethylammonium chloride, benzyltriethylammonium chloride; pyridine or triphenylphosphine as a catalyst, the epoxy compound (a-3a) and the unsaturated group-containing carboxylic acid (a-3b) are reacted in an organic solvent at a reaction temperature of 50°C to 150°C for several hours to several tens of hours.

The ratio of the amount of the epoxy compound (a-3a) and the unsaturated group-containing carboxylic acid (a-3b) used in the reaction is preferably 1:0.5 to 1:2, more preferably 1:0.8 to 1:1.25, and particularly preferably 1:0.9 to 1:1.1, as the ratio of the epoxy equivalent of the epoxy compound (a-3a) to the carboxylic acid equivalent of the unsaturated group-containing carboxylic acid (a-3b). If the ratio of the amount of the epoxy compound (a-3a) used to the amount of the unsaturated group-containing carboxylic acid (a-3b) used is 1:0.5 to 1:2 in terms of the equivalent ratio, it is preferred because the crosslinking efficiency tends to be improved.

(Polyacid anhydride (a-3c)) Polyacid anhydride (a-3c) is a carboxylic anhydride having two or more carboxyl groups. Polyacid anhydride (a-3c) is not particularly limited, and examples thereof include maleic anhydride, succinic anhydride, itaconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, trimellitic anhydride, pyromellitic anhydride, benzophenonetetracarboxylic anhydride, 3-methylhexahydrophthalic anhydride, 4-methylhexahydrophthalic anhydride, and the like. Phthalic anhydride, 3-ethylhexahydrophthalic anhydride, 4-ethylhexahydrophthalic anhydride, tetrahydrophthalic anhydride, 3-methyltetrahydrophthalic anhydride, 4-methyltetrahydrophthalic anhydride, 3-ethyltetrahydrophthalic anhydride, 4-ethyltetrahydrophthalic anhydride, a compound represented by the following formula (a-3c-1), and a compound represented by the following formula (a-3c-2). In addition, the polyacid anhydride (a-3c) can be used alone or in combination of two or more.

(In the formula (a-3c-2), ^Ra8 represents an alkylene group having 1 to 10 carbon atoms and optionally having a substituent).

As the polyacid anhydride (a-3c), a compound having two or more benzene rings is preferred because it is easy to obtain a photosensitive composition with an excellent balance between sensitivity and developability. In addition, the polyacid anhydride (a-3c) 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 polyacid anhydride (a-3c) can be appropriately selected from known methods. In addition, as the usage ratio, the molar number of OH groups in the component after the epoxy compound (a-3a) and the unsaturated group-containing carboxylic acid (a-3b) react and the equivalent ratio of the anhydride group of the polyacid anhydride (a-3c) are usually 1:1 to 1:0.1, preferably 1:0.8 to 1:0.2. By setting it within the above range, a photosensitive composition with good developability can be easily obtained.

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, based on the resin solid content. By making the acid value of the resin 10 mgKOH/g or more, sufficient solubility in the developer can be obtained, and by making the acid value 150 mgKOH/g or less, sufficient curability can be obtained, and the surface properties can be made good.

The mass average molecular weight of the modified epoxy resin (a-3) is preferably 1000 to 40000, more preferably 2000 to 30000. When the mass average molecular weight is 1000 or more, a cured film having excellent heat resistance and strength can be easily formed. When the mass average molecular weight is 40000 or less, a photosensitive composition having sufficient solubility in a developer can be easily obtained.

[Acrylic resin (a-4)] As the alkali-soluble resin (A), an acrylic resin (A2) (acrylic resin (a-4)) is also preferred. As the acrylic resin (A2) (acrylic resin (a-4)), an acrylic resin containing a structural unit derived from (meth)acrylic acid and/or a structural unit derived from other monomers such as (meth)acrylic acid ester can be used. (Meth)acrylic acid is acrylic acid or methacrylic acid. (Meth)acrylic acid ester is represented by the following formula (a-4-1), and is not particularly limited as long as it does not hinder the purpose of the present invention.

In the above formula (a-4-1), ^Ra9 is a hydrogen atom or a methyl group, and ^Ra10 is a monovalent organic group. The organic group may contain a bond or a substituent other than a carbon group such as a heteroatom in the organic group. In addition, the organic group may be any of a linear chain, a branched chain, and a ring.

The substituent other than the alkyl group in the organic group of R ^a10 is not particularly limited as long as the effects of the present invention are not impaired, and examples thereof include a halogen atom, a hydroxyl group, a hydroxyl group, a thioether group, a cyano group, an isocyano group, a cyanoxy group, an isocyanate group, a thiocyanate group, an isothiocyanate group, a silyl group, a silanol group, an alkoxy group, an alkoxycarbonyl group, a carbamyl group, a thiocarbamyl group, a nitro group, a nitroso group, a carboxyl group, a carboxylate group, an acyl group, an acyloxy group, a sulfino group, a sulfo group, a sulfonate group, a phosphine group, a phosphinyl group, a phosphono group, a phosphonato group, a hydroxyimino group, an alkyl ether group, an alkyl thioether group, an aryl ether group, an aryl thioether group, an amino group (—NH ₂ , -NHR, -NRR': R and R' independently represent a alkyl group) etc. The hydrogen atom contained in the above substituents may also be substituted by a alkyl group. In addition, the alkyl group contained in the above substituents may be any of a linear chain, a branched chain and a ring.

In addition, the organic group as R ^a10 may have a reactive functional group such as an acryloxy group, a methacryloxy group, an epoxy group, or an oxacyclobutyl group. Acyl groups having an unsaturated double bond such as an acryloxy group or a methacryloxy group can be produced by reacting an unsaturated carboxylic acid such as acrylic acid or methacrylic acid with at least a portion of the epoxy groups in an acrylic resin (a-4) containing a structural unit having an epoxy group.

As R ^a10 , an alkyl group, an aryl group, an aralkyl group or a heterocyclic group is preferred, and these groups may be substituted by a halogen atom, a hydroxyl group, an alkyl group or a heterocyclic group. In addition, when these groups contain an alkylene moiety, the alkylene moiety may be interrupted by an ether bond, a thioether bond or an ester bond.

When the alkyl group is a linear or branched alkyl group, the number of carbon atoms is preferably 1 to 20, more preferably 1 to 15, and particularly preferably 1 to 10. Examples of preferred alkyl groups include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, t-butyl, n-pentyl, isopentyl, sec-pentyl, t-pentyl, n-hexyl, n-heptyl, n-octyl, isooctyl, sec-octyl, t-octyl, n-nonyl, isononyl, n-decyl, isodecyl, and the like.

When the alkyl group is an alicyclic group or a group containing an alicyclic group, preferred alicyclic groups contained in the alkyl group include monocyclic alicyclic groups such as cyclopentyl and cyclohexyl, and polycyclic alicyclic groups such as adamantyl, norbornyl, isobornyl, tricyclic nonyl, tricyclic decanyl and tetracyclic dodecyl.

When the compound represented by formula (a-4-1) contains a chain group having an epoxy group as R ^a10 , specific examples of the compound represented by formula (a-4-1) include epoxyalkyl (meth)acrylates such as glycidyl (meth)acrylate, 2-methylglycidyl (meth)acrylate, 3,4-epoxybutyl (meth)acrylate, and 6,7-epoxyheptyl (meth)acrylate.

In addition, the compound represented by formula (a-4-1) may also be a (meth)acrylate containing an alicyclic cyclooxy group. The alicyclic group constituting the alicyclic cyclooxy group may be monocyclic or polycyclic. Examples of monocyclic alicyclic groups include cyclopentyl and cyclohexyl. In addition, examples of polycyclic alicyclic groups include norbornyl, isobornyl, tricyclic nonyl, tricyclic decyl, and tetracyclic dodecyl.

As specific examples of the case where the compound represented by formula (a-4-1) is a (meth)acrylate containing an alicyclic epoxy group, for example, compounds represented by the following formulas (a-4-1a) to (a-4-1o) can be cited. Among these, in order to make the developing property appropriate, compounds represented by the following formulas (a-4-1a) to (a-4-1e) are preferred, and compounds represented by the following formulas (a-4-1a) to (a-4-1c) are more preferred.

In the above formula, ^Ra20 represents a hydrogen atom or a methyl group, ^Ra21 represents a divalent aliphatic saturated alkyl group having 1 to 6 carbon atoms, ^Ra22 represents a divalent alkyl group having 1 to 10 carbon atoms, and t represents an integer of 0 to 10. ^Ra21 is preferably a linear or branched alkylene group, for example, a methylene group, an ethylene group, a propylene group, a tetramethylene group, an ethylethylene group, a pentamethylene group, and a hexamethylene group. ^Ra22 is preferably a methylene group, an ethylene group, a propylene group, a tetramethylene group, an ethylethylene group, a pentamethylene group, a hexamethylene group, a phenylene group, a cyclohexylene group, and _-CH2 -Ph- _CH2- (Ph represents a phenylene group).

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

Examples of the (meth)acrylamide include (meth)acrylamide, N-alkyl(meth)acrylamide, N-aryl(meth)acrylamide, N,N-dialkyl(meth)acrylamide, N,N-aryl(meth)acrylamide, N-methyl-N-phenyl(meth)acrylamide, and N-hydroxyethyl-N-methyl(meth)acrylamide.

Examples of the unsaturated carboxylic acids include monocarboxylic acids such as crotonic acid; dicarboxylic acids such as maleic acid, fumaric acid, liraconic acid, mesaconic acid, and itaconic acid; and anhydrides of these dicarboxylic acids.

As the allyl compound, there can be mentioned allyl esters such as allyl acetate, allyl caproate, allyl octanoate, allyl laurate, allyl palmitate, allyl stearate, allyl benzoate, allyl acetoacetate, allyl lactate, etc.; allyloxyethanol, etc.

Examples of the vinyl ethers include alkyl vinyl ethers such as 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-dimethylpropyl vinyl ether, 2-ethylbutyl vinyl ether, hydroxyethyl vinyl ether, diethylene glycol vinyl ether, dimethylaminoethyl vinyl ether, diethylaminoethyl vinyl ether, butylaminoethyl vinyl ether, benzyl vinyl ether, and tetrahydrofurfuryl vinyl ether; and vinyl aryl ethers such as vinyl phenyl ether, vinyl tolyl ether, vinyl chlorophenyl ether, vinyl-2,4-dichlorophenyl ether, vinyl naphthyl ether, and vinyl anthracenyl ether.

Examples of the vinyl esters include vinyl butyrate, vinyl isobutyrate, vinyl pivalate, vinyl diethyl acetate, vinyl valerate, vinyl hexanoate, vinyl chloroacetate, vinyl dichloroacetate, vinyl methoxyacetate, vinyl butoxyacetate, vinyl phenyl acetate, vinyl acetylacetate, vinyl lactate, vinyl-β-phenylbutyrate, vinyl benzoate, vinyl salicylate, vinyl chlorobenzoate, vinyl tetrachlorobenzoate, and vinyl naphthoate.

Examples of the styrenes include styrene; alkyl styrenes such as methyl styrene, dimethyl styrene, trimethyl styrene, ethyl styrene, diethyl styrene, isopropyl styrene, butyl styrene, hexyl styrene, cyclohexyl styrene, decyl styrene, benzyl styrene, chloromethyl styrene, trifluoromethyl styrene, ethoxymethyl styrene, and acetyloxymethyl styrene; alkoxy styrenes such as methoxy styrene, 4-methoxy-3-methyl styrene, and dimethoxy styrene; halogenated styrenes such as chlorostyrene, dichlorostyrene, trichlorostyrene, tetrachlorostyrene, pentachlorostyrene, bromostyrene, dibromostyrene, iodostyrene, fluorostyrene, trifluorostyrene, 2-bromo-4-trifluoromethylstyrene, and 4-fluoro-3-trifluoromethylstyrene; and the like.

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

When the acrylic resin (a-4) contains structural units having unsaturated double bonds, the amount of structural units having unsaturated double bonds in the acrylic resin (a-4) is preferably 1% by mass to 50% by mass, more preferably 1% by mass to 30% by mass, and particularly preferably 1% by mass to 20% by mass. The acrylic resin (a-4) contains structural units having unsaturated double bonds in an amount within the above range, which can make the crosslinking reaction of the acrylic resin into the resist film uniform, and is therefore effective in improving the heat resistance and mechanical properties of the cured film.

The mass average molecular weight of the acrylic resin (a-4) is preferably 2000 to 50000, more preferably 3000 to 30000. By setting the molecular weight within the above range, it tends to be easy to strike a balance between the film-forming ability of the photosensitive composition and the developing property after exposure.

The content of the alkali-soluble resin (A) in the total solid content of the photosensitive composition is preferably 10 mass % to 75 mass %, more preferably 15 mass % to 65 mass %, and further preferably 20 mass % to 50 mass %. If the content of the alkali-soluble resin (A) in the total solid content of the photosensitive composition is within the above range, the solid components of the photosensitive composition in the unexposed part are well dissolved in the developer, while the solid components of the photosensitive composition cured in the exposed part are difficult to dissolve in the developer, and it is easy to obtain a photosensitive composition with excellent developability and resolution. In addition, in this specification, the solid components refer to the components other than the organic solvent.

<Photopolymerizable monomer (B)> The photosensitive composition contains a photopolymerizable monomer (B). The photopolymerizable monomer (B) contains a high hydroxyl monomer (B1) having a hydroxyl value of 180 mgKOH/g or more and a low hydroxyl monomer (B2) having a hydroxyl value of less than 180 mgKOH/g. In addition, the content of the high hydroxyl monomer (B1) is 5% by mass or more and 60% by mass or less relative to the mass of the photopolymerizable monomer (B).

As the photopolymerizable monomer (B), i.e., the high hydroxyl monomer (B1) having a hydroxyl value of 180 mgKOH/g or more and the low hydroxyl monomer (B2) having a hydroxyl value of less than 180 mgKOH/g, a compound having an ethylenically unsaturated group is preferred, and a compound having a (meth)acryloyl group is preferred. The compound having an ethylenically unsaturated group includes a monofunctional compound and a polyfunctional compound, and a polyfunctional compound is preferred.

In addition, in this specification, "(meth)acrylate" refers to both "acrylate" and "methacrylate", "(meth)acrylic acid" refers to both "acrylic acid" and "methacrylic acid", "(meth)acryl" refers to both "acryl" and "methacryl", and "(meth)acryloxy" refers to both "acryloxy" and "methacryloxy".

The high hydroxyl monomer (B1) is a photopolymerizable monomer having one or more hydroxyl groups and a hydroxyl value of 180 mgKOH/g or more. The high hydroxyl monomer (B1) preferably includes a multifunctional acrylic monomer (B1-1) having two or more (meth)acryloyl groups. As the multifunctional acrylic monomer (B1-1), glycerol di(meth)acrylate, trihydroxymethylpropane di(meth)acrylate, diglycerol di(meth)acrylate, diglycerol tri(meth)acrylate, pentaerythritol di(meth)acrylate and pentaerythritol tri(meth)acrylate can be listed. These can be used alone or in combination of two or more.

The low hydroxyl monomer (B2) having a hydroxyl value of less than 180 mgKOH/g is a photopolymerizable monomer having no hydroxyl group or having a hydroxyl group but having a low hydroxyl value of less than 180 mgKOH/g. The low hydroxyl monomer (B2) preferably includes a multifunctional acrylic monomer having no hydroxyl group and having a (meth)acryl group, or a multifunctional acrylic monomer having one hydroxyl group and having 5 or more (meth)acryl groups. As the low hydroxyl monomer (B2), dipentaerythritol hexa(meth)acrylate and dipentaerythritol penta(meth)acrylate can be listed. These can be used alone or in combination.

Here, the hydroxyl value refers to the number of mg of potassium hydroxide required to neutralize acetic acid produced as a byproduct when the hydroxyl groups contained in 1 g of a sample are acetylated by acetic anhydride. For example, when 1 mol of a compound A (molecular weight M) having N hydroxyl groups in one molecule is completely acetylated by an excess amount of acetic anhydride, N mol of acetic acid is produced. The amount of KOH (molecular weight: 56.1056) required to neutralize N mol of acetic acid is N×56.1056 g (1 mol). Here, N is an integer. Therefore, the hydroxyl value (mgKOH/g) of a compound A having N hydroxyl groups in one molecule and a molecular weight of M can be calculated by the following formula (1). In this specification, the hydroxyl value is defined as the value calculated by the following formula (1). Hydroxyl value (mgKOH/g) = (N×56.1056/M)×1000･･･(1)

The hydroxyl value of the high hydroxyl monomer (B1) is preferably 185 mgKOH/g or more. The upper limit of the hydroxyl value of the high hydroxyl monomer (B1) is not particularly limited, but the hydroxyl value of the high hydroxyl monomer (B1) is preferably 500 mgKOH/g or less, and more preferably 460 mgKOH/g or less.

The hydroxyl value of the low hydroxyl monomer (B2) is preferably 140 mgKOH/g or less, more preferably 120 mgKOH/g or less.

The content of the high hydroxyl monomer (B1) is 5 mass % or more and 60 mass % or less relative to the mass of the photopolymerizable monomer (B). In a photosensitive composition comprising an alkali-soluble resin (A), a photopolymerizable monomer (B), a photopolymerization initiator (C), carbon black (D1) coated with an epoxy resin as a light-shielding agent (D), and a silane coupling agent (E), by making the photopolymerizable monomer (B) contain a high hydroxyl monomer (B1) and a low hydroxyl monomer (B2) having a hydroxyl value within a specific range in a specific ratio, a patterned cured product having excellent water resistance and excellent adhesion to a substrate can be formed.

On the other hand, when the photopolymerizable monomer (B) contains a low-hydroxy monomer (B2) but does not contain a high-hydroxy monomer (B1), or when the photopolymerizable monomer (B) contains a high-hydroxy monomer (B1) and a low-hydroxy monomer (B2) but the content of the high-hydroxy monomer (B1) is less than 5% by mass relative to the mass of the photopolymerizable monomer (B), the water resistance of the resulting cured product is poor. In addition, when the photosensitive composition does not contain carbon black (D1) coated with an epoxy resin, the water resistance of the resulting cured product is poor. When the photopolymerizable monomer (B) does not contain the low-hydroxy monomer (B2), or when the photopolymerizable monomer (B) contains the high-hydroxy monomer (B1) and the low-hydroxy monomer (B2) but the content of the high-hydroxy monomer (B1) exceeds 60% by mass relative to the mass of the photopolymerizable monomer (B), the formed patterned cured product has poor adhesion to the substrate.

The content of the high hydroxyl monomer (B1) is preferably 7 mass % to 55 mass %, more preferably 10 mass % to 50 mass %, based on the mass of the photopolymerizable monomer (B).

By using the above-mentioned photosensitive composition, a cured product with a high volume resistance value, for example, a cured product with a volume resistance value of 1.0×10 ¹⁵ Ω･cm or more can be formed. In addition, by using the above-mentioned photosensitive composition, a patterned cured product with excellent straightness can be formed. In addition, by using the above-mentioned photosensitive composition, a patterned cured product with a cross section having a tapered shape with an appropriate tapered angle in which heat flow is suppressed can be formed. Therefore, the photosensitive composition can be preferably used for the purpose of forming a tapered cured product with an appropriate tapered angle, such as a black matrix.

The content of the photopolymerizable monomer (B) in the total solid content of the photosensitive composition is preferably 1 mass % to 30 mass %, more preferably 5 mass % to 20 mass %.

<Photopolymerization initiator (C)> The photopolymerization initiator (C) is not particularly limited, and any conventionally known photopolymerization initiator can be used. The photopolymerization initiator (C) preferably includes an aminoalkylphenone-based photopolymerization initiator (C1). As a preferred example of the aminoalkylphenone-based photopolymerization initiator (C1), a compound represented by the following formula (C-I) can be cited.

In formula (CI), R ^c01 is a linear, branched or cyclic alkyl group having 1 to 12 carbon atoms. R ^c02 and R ^c03 are independently a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms or a benzyl group. The alkyl group as R ^c02 or R ^c03 may be a linear or branched chain. R ^c04 , R ^c05 , R ^c07 and R ^c08 are independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms or an alkoxy group having 1 to 4 carbon atoms. The alkyl group and alkoxy group as R ^c04 , R ^c05 , R ^c07 and R ^c08 may be a linear or branched chain. R ^c06 is a hydrogen atom, a halogen atom, an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms, or an alkoxy group having 1 to 4 carbon atoms. The alkyl group and the alkoxy group as R ^c06 may be linear or branched. In addition, the alkyl group, cycloalkyl group and alkoxy group as R ^c06 may be substituted by one or more substituents. The substituent is one or more selected from the group consisting of a hydroxyl group and an alkoxy group having 1 to 4 carbon atoms. The alkoxy group as a substituent in R ^c06 may be linear or branched.

When ^Rc01 is an alkyl group, preferred specific examples include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, t-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, n-undecyl and n-dodecyl. Among them, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, t-butyl, n-pentyl and n-hexyl are preferred, and ethyl is more preferred.

Specific examples of the case where R ^c01 is a cycloalkyl group include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl, cycloundecyl and cyclododecyl.

When ^Rc02 and ^Rc03 are alkyl or cycloalkyl, preferred specific examples are the same as the preferred specific examples when ^Rc01 is alkyl or cycloalkyl. ^Rc02 and ^Rc03 are preferably methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, n-hexyl, n-heptyl and n-octyl, and more preferably methyl.

Specific examples of the case where ^Rc04 , ^Rc05 , ^Rc07 and ^Rc08 are halogen atoms include chlorine atoms, iodine atoms, bromine atoms and fluorine atoms. Preferred specific examples of the case where ^Rc04 , ^Rc05 , ^Rc07 and ^Rc08 are alkyl groups or cycloalkyl groups are the same as the preferred specific examples of the case where ^Rc01 is an alkyl group or a cycloalkyl group. Specific examples of the case where ^Rc04 , ^Rc05 , ^Rc07 and ^Rc08 are alkoxy groups include methoxy groups, ethoxy groups, n-propoxy groups, isopropoxy groups, n-butoxy groups, isobutoxy groups, sec-butoxy groups and tert-butoxy groups. As R ^c04 , R ^c05 , R ^c07 and R ^c08 , from the viewpoint of good sensitivity and depth of focus of the photosensitive composition and easy formation of a cured film having good adhesion to the substrate, preferably a hydrogen atom, a methyl group and an ethyl group, and more preferably a hydrogen atom.

Specific examples when ^Rc06 is a halogen atom, an alkyl group, a cycloalkyl group or an alkoxy group are the same as the specific examples when ^Rc04 , ^Rc05 , ^Rc07 and ^Rc08 are a halogen atom, an alkyl group, a cycloalkyl group or an alkoxy group. When the alkyl group, cycloalkyl group and alkoxy group as ^Rc06 are substituted with one or more substituents, the substituents are preferably hydroxyl group and methoxy group.

Preferred specific examples of R ^c06 include a hydrogen atom, a methyl group, an ethyl group, a n-propyl group, an isopropyl group, a n-butyl group, an isobutyl group, a sec-butyl group, a t-butyl group, a n-pentyl group, a n-hexyl group, a n-heptyl group, a n-octyl group, a n-decyl group, a n-dodecyl group, a hydroxymethyl group, a 2-hydroxyethyl group, a methoxymethyl group, a 2-methoxyethyl group, a methoxy group, an ethoxy group, a n-propoxy group, an isopropoxy group, a n-butoxy group, a hydroxymethoxy group, a 2-hydroxyethoxy group, a methoxymethoxy group, and a 2-methoxyethoxy group, and more preferably a hydrogen atom, a methyl group, and an ethyl group.

Preferably, R ^c01 is methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, t-butyl, n-pentyl or n-hexyl, R ^c02 is methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, t-butyl, n-pentyl, n-hexyl, n-heptyl or n-octyl, R ^c03 is methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, t-butyl, n-pentyl, n-hexyl, n-heptyl or n-octyl, R ^c04 is a hydrogen atom, methyl or ethyl, R ^c05 is a hydrogen atom, methyl or ethyl, R ^c07 is a hydrogen atom, methyl or ethyl, R ^c08 is a hydrogen atom, methyl or ethyl, and R ^c06 is a methyl or a hydrogen atom.

Examples of aminoalkylphenone compounds represented by formula (C-I) include 2-benzyl-2-(dimethylamino)-1-(4-morpholinophenyl)butan-1-one (e.g., Omnirad 369, manufactured by IGM Resins B.V.), 2-(4-methylbenzyl)-2-(dimethylamino)-1-(4-morpholinophenyl)butan-1-one (e.g., Omnirad 379, manufactured by IGM Resins B.V.), and 2-(4-methylbenzyl)-2-(dimethylamino)-1-(4-morpholinophenyl)butan-1-one. B.V.), 2-(4-ethylbenzyl)-2-(dimethylamino)-1-(4-morpholinophenyl)butan-1-one, 2-(4-isopropylbenzyl)-2-(dimethylamino)-1-(4-morpholinophenyl)butan-1-one, 2-(4-n-butylbenzyl)-2-(dimethylamino)-1-(4-morpholinophenyl)butan-1-one, 2-(4-isobutylbenzyl)-2-(dimethylamino)-1-(4-morpholinophenyl)butan-1-one, 2-(4-n-dodecylbenzyl)-2-(dimethylamino)-1 -(4-Fluorophenyl)butan-1-one, 2-(3,4-dimethylbenzyl)-2-(dimethylamino)-1-(4-Fluorophenyl)butan-1-one, 2-(4-methoxybenzyl)-2-(dimethylamino)-1-(4-Fluorophenyl)butan-1-one, 2-(4-ethoxybenzyl)-2-(dimethylamino)-1-(4-Fluorophenyl)butan-1-one, 2-(4-hydroxymethylbenzyl)-2-(dimethylamino)-1-(4-Fluorophenyl)butan-1-one, 2-[4-(2-hydroxyethoxy)benzyl ]-2-(dimethylamino)-1-(4-morpholinophenyl)butan-1-one, 2-[4-(2-methoxyethoxy)benzyl]-2-(dimethylamino)-1-(4-morpholinophenyl)butan-1-one, 2-(4-isopropylbenzyl)-2-[(n-butyl)(methyl)amino]-1-(4-morpholinophenyl)butan-1-one, 2-(4-n-butylbenzyl)-2-[(n-butyl)(methyl)amino]-1-(4-morpholinophenyl)butan-1-one, 2-(4-isopropylbenzyl)-2-(dimethylamino)-1-(4-morpholinophenyl)butan-1-one (4-Fluorophenyl)pentane-1-one, 2-(4-isobutylbenzyl)-2-[(n-butyl)(methyl)amino]-1-(4-Fluorophenyl)pentane-1-one, 2-(4-n-butoxybenzyl)-2-[(n-butyl)(methyl)amino]-1-(4-Fluorophenyl)pentane-1-one, 2-(4-methylbenzyl)-2-[di(n-octyl)amino]-1-(4-Fluorophenyl)hexane-1-one and 2-(4-n-dodecylbenzyl)-2-(dimethylamino)-1-(4-Fluorophenyl)octane-1-one, etc. Among them, 2-(4-methylbenzyl)-2-(dimethylamino)-1-(4-Fluorophenyl)butane-1-one is particularly preferred.

When an aminoalkylphenone-based polymerization initiator (C1) is used as a photopolymerization initiator (C), especially when the aminoalkylphenone-based polymerization initiator (C1) is combined with an oxime ester compound (C2), it is easy to control the cross-sectional shape of a cured film formed using a photosensitive composition. This is considered to be due to the following reasons. The aminoalkylphenone-based photopolymerization initiator (C1) has a tendency to generate photopolymerization radicals for the surface portion of the photosensitive composition (the surface facing the exposure light and its vicinity). On the other hand, the oxime ester compound (C2) has a tendency to generate photopolymerization radicals for the deep layer portion of the photosensitive composition. The thicker the film thickness of the coating composed of the photosensitive composition, the more prominently this tendency is manifested. This tendency can also be confirmed when the coating film is thin, such as when the film pressure is 1 μm or less. In addition, as a secondary effect of using the aminoalkylphenone polymerization initiator (C1) and the oxime ester compound (C2) in combination, the sensitivity can be comprehensively improved, and a cured product of the photosensitive composition can be obtained with a smaller exposure amount. Furthermore, when the aminoalkylphenone polymerization initiator (C1) and the oxime ester compound (C2) are used in combination, the straightness of the line edge of the cured film and the adhesion of the cured film to the substrate are good, and it is easy to form a black matrix with fewer pattern defects.

As the oxime ester compound (C2), oxime ester compounds that have been mixed in various photosensitive compositions in the past can be used without particular limitation. As the oxime ester compound (C2), a compound having a partial structure represented by the following formula (c1) is preferred.

(In formula (c1), n1 is 0 or 1, R ^c2 is a monovalent organic group, R ^c3 is a hydrogen atom, an aliphatic hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, or an aryl group which may have a substituent, and * is a bonding site).

The compound having a partial structure represented by formula (c1) preferably has a carbazole skeleton, a fluorene skeleton, a diphenyl ether skeleton, or a phenylene sulfide skeleton. The compound having a partial structure represented by formula (c1) preferably has one or two partial structures represented by formula (c1).

Examples of the compound having the partial structure represented by the formula (c1) include compounds represented by the following formula (c2).

(In formula (c2), R ^c1 is a group represented by the following formula (c3), (c4) or (c5), n1 is 0 or 1, R ^c2 is a monovalent organic group, and R ^c3 is a hydrogen atom, an aliphatic hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, or an aryl group which may have a substituent).

(In formula (c3), R ^c4 and R ^c5 are each independently a monovalent organic group, n2 is an integer from 0 to 3, and when n2 is 2 or 3, a plurality of R ^c5 may be the same or different, and a plurality of R ^c5 may be bonded to each other to form a ring. * is a bonding site).

(In formula (c4), ^Rc6 and ^Rc7 are independently a chain alkyl group which may have a substituent, a chain alkoxy group which may have a substituent, a cyclic organic group which may have a substituent, or a hydrogen atom, ^Rc6 and ^Rc7 may bond to each other to form a ring, ^Rc7 and the benzene ring in the fluorene skeleton may bond to each other to form a ring, ^Rc8 is a nitro group or a monovalent organic group, n3 is an integer from 0 to 4, and * is a bonding site).

(In formula (c5), R ^c9 is a monovalent organic group, a halogen atom, a nitro group or a cyano group, A is S or O, n4 is an integer from 0 to 4, and * is a bonding site).

In formula (c3), R ^c4 is a monovalent organic group. R ^c4 can be selected from various organic groups within the scope that does not hinder the purpose of the present invention. As an organic group, a carbon atom-containing group is preferred, and a group consisting of one or more carbon atoms and one or more atoms selected from the group consisting of H, O, S, Se, N, B, P, Si and halogen atoms is more preferred. The number of carbon atoms in the carbon atom-containing group is not particularly limited, and is preferably 1 to 50, and more preferably 1 to 20. Preferred examples of R ^c4 include an alkyl group having 1 to 20 carbon atoms which may have a substituent, a cycloalkyl group having 3 to 20 carbon atoms which may have a substituent, a saturated aliphatic acyl group having 2 to 20 carbon atoms which may have a substituent, an alkoxycarbonyl group having 2 to 20 carbon atoms which may have a substituent, a phenyl group which may have a substituent, a benzyl group which may have a substituent, a phenoxycarbonyl group which may have a substituent, a phenylalkyl group having 7 to 20 carbon atoms which may have a substituent, a naphthyl group which may have a substituent, a naphthylcarbonyl group which may have a substituent, a naphthylalkyl group having 11 to 20 carbon atoms which may have a substituent, a heterocyclic group which may have a substituent, and a heterocycliccarbonyl group which may have a substituent.

Among R ^c4 , an alkyl group having 1 to 20 carbon atoms is preferred. The alkyl group may be linear or branched. From the viewpoint of good solubility of the compound represented by formula (c3) in the photosensitive composition, the carbon number of the alkyl group as R ^c4 is preferably 2 or more, more preferably 5 or more, and particularly preferably 7 or more. Furthermore, from the viewpoint of good compatibility of the compound represented by formula (c3) with other components in the photosensitive composition, the carbon number of the alkyl group as R ^c4 is preferably 15 or less, more preferably 10 or less.

When R ^c4 has a substituent, preferred examples of the substituent include a hydroxyl group, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an aliphatic acyl group having 2 to 20 carbon atoms, an aliphatic acyloxy group having 2 to 20 carbon atoms, a phenoxy group, a benzyl group, a benzyloxy group, a group represented by -PO(OR) ₂ (R is an alkyl group having 1 to 6 carbon atoms), a halogen atom, a cyano group, a heterocyclic group, and the like.

When R ^c4 is a heterocyclic group, the heterocyclic group may be an aliphatic heterocyclic group or an aromatic heterocyclic group. When R ^c4 is a heterocyclic group, the heterocyclic group is a five-membered or six-membered monocyclic ring containing one or more N, S, and O, or a heterocyclic group formed by condensing the monocyclic rings with each other, or a heterocyclic group formed by condensing the monocyclic ring with a benzene ring. When the heterocyclic group is a condensed ring, the number of monocyclic rings constituting the condensed ring is 3 or less. Examples of the heterocyclic ring constituting the heterocyclic group include furan, thiophene, pyrrole, oxazole, isoxazole, thiazole, thiadiazole, isothiazole, imidazole, pyrazole, triazole, pyridine, pyrazine, pyrimidine, pyridazine, benzofuran, benzothiophene, indole, isoindole, indolizine, benzimidazole, benzotriazole, benzoxazole, benzothiazole, carbazole, purine, quinoline, isoquinoline, quinazoline, pyrazine, cinnoline, quinoxaline, piperidine, piperazine, morpholine, piperidine, tetrahydropyran, and tetrahydrofuran. When R ^c4 is a heterocyclic group, examples of the substituent that the heterocyclic group may have include a hydroxyl group, an alkoxy group having 1 to 6 carbon atoms, a halogen atom, a cyano group, and a nitro group.

As preferred specific examples of R ^c4 described above, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, t-butyl, n-pentyl, isopentyl, neopentyl, pentane-3-yl, sec-pentyl, t-pentyl, n-hexyl, n-heptyl, n-octyl and 2-ethylhexyl can be listed. In addition, from the viewpoint of good solubility of the compound represented by formula (c3) in the photosensitive composition, n-octyl and 2-ethylhexyl are preferred, and 2-ethylhexyl is more preferred.

In formula (c3), R ^c5 is a monovalent organic group, a halogen atom or a nitro group. R ^c5 can be selected from various organic groups within the scope that does not hinder the purpose of the present invention. As an organic group, a carbon atom-containing group is preferred, and a group consisting of one or more carbon atoms and one or more atoms selected from the group consisting of H, O, S, Se, N, B, P, Si and halogen atoms is more preferred. The number of carbon atoms in the carbon atom-containing group is not particularly limited, and is preferably 1 to 50, and more preferably 1 to 20. As R Examples of preferred monovalent organic groups for ^C5 include alkyl, alkoxy, cycloalkyl, cycloalkoxy, saturated aliphatic acyl, alkoxycarbonyl, saturated aliphatic acyloxy, phenyl which may have a substituent, phenoxy which may have a substituent, benzyl which may have a substituent, phenoxycarbonyl which may have a substituent, benzyloxy which may have a substituent, phenylalkyl which may have a substituent, a substituted naphthyl group, a substituted naphthyloxy group, a substituted naphthylcarbonyl group, a substituted naphthyloxy group, a substituted naphthylalkyl group, a substituted heterocyclic group, a substituted heterocyclic carbonyl group, an amino group substituted with one or two organic groups, a morpholin-1-yl group, a piperazin-1-yl group, a halogen group, a nitro group, a cyano group, and a substituent group containing a group represented by _HX2C- or _H2XC- (provided that X is independently a halogen atom).

When R ^c5 is an alkyl group, the number of carbon atoms of the alkyl group is preferably 1 to 20, and more preferably 1 to 6. In addition, when R ^c5 is an alkyl group, it may be a straight chain or a branched chain. Specific examples of when R ^c5 is an alkyl group include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, t-butyl, n-pentyl, iso-pentyl, sec-pentyl, t-pentyl, n-hexyl, n-heptyl, n-octyl, iso-octyl, sec-octyl, t-octyl, n-nonyl, iso-nonyl, n-decyl, and iso-decyl. In addition, when R ^c5 is an alkyl group, the alkyl group may contain an ether bond (-O-) in the carbon chain. Examples of the alkyl group having an ether bond in the carbon chain include methoxyethyl, ethoxyethyl, methoxyethoxyethyl, ethoxyethoxyethyl, propyloxyethoxyethyl, and methoxypropyl.

When R ^c5 is an alkoxy group, the number of carbon atoms of the alkoxy group is preferably 1 to 20, and more preferably 1 to 6. In addition, when R ^c5 is an alkoxy group, it may be a straight chain or a branched chain. As specific examples of when R ^c5 is an alkoxy group, there can be listed a methoxy group, an ethoxy group, a n-propoxy group, an isopropoxy group, a n-butoxy group, an isobutoxy group, a 2-butoxy group, a 3-butoxy group, a n-pentoxy group, an isopentoxy group, a 2-pentoxy group, a 3-pentoxy group, a n-hexoxy group, a n-heptyl group, a n-octyl group, an isooctyl group, a 2-octyl group, a 3-octyl group, a n-nonyl group, an isononyl group, a n-decyl group, and an isodecyl group. In addition, when R ^c5 is an alkoxy group, the alkoxy group may contain an ether bond (-O-) in the carbon chain. Examples of the alkoxy group having an ether bond in the carbon chain include a methoxyethoxy group, an ethoxyethoxy group, a methoxyethoxyethoxy group, an ethoxyethoxyethoxy group, a propoxyethoxyethoxy group, and a methoxypropoxy group.

When R ^c5 is a cycloalkyl group or a cycloalkoxy group, the number of carbon atoms of the cycloalkyl group or the cycloalkoxy group is preferably 3 or more and 10 or less, and more preferably 3 or more and 6 or less. Specific examples of the case where R ^c5 is a cycloalkyl group include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, and cyclooctyl. Specific examples of the case where R ^c5 is a cycloalkoxy group include cyclopropyloxy, cyclobutoxy, cyclopentyloxy, cyclohexyloxy, cycloheptyloxy, and cyclooctyloxy.

When R ^c5 is a saturated aliphatic acyl group or a saturated aliphatic acyloxy group, the number of carbon atoms of the saturated aliphatic acyl group or the saturated aliphatic acyloxy group is preferably 2 to 21, and more preferably 2 to 7. Specific examples of the case where R ^c5 is a saturated aliphatic acyl group include acetyl, propionyl, n-butyryl, 2-methylpropionyl, n-pentyl, 2,2-dimethylpropionyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl, n-tridecyl, n-tetradecyl, n-pentadecanyl and n-hexadecyl. Specific examples of the case where R ^c5 is a saturated aliphatic acyloxy group include an acetyloxy group, a propionyloxy group, an n-butyryloxy group, a 2-methylpropionyloxy group, an n-pentyloxy group, a 2,2-dimethylpropionyloxy group, an n-hexyloxy group, an n-heptyloxy group, an n-octyloxy group, an n-nonyloxy group, an n-decyloxy group, an n-undecyloxy group, an n-dodecyloxy group, an n-tridecyloxy group, an n-tetradecyloxy group, an n-pentadecanyloxy group, and an n-hexadecyloxy group.

When R ^c5 is an alkoxycarbonyl group, the number of carbon atoms of the alkoxycarbonyl group is preferably 2 to 20, and more preferably 2 to 7. Specific examples of the ^{alkoxycarbonyl} group include methoxycarbonyl, ethoxycarbonyl, n-propyloxycarbonyl, isopropyloxycarbonyl, n-butyloxycarbonyl, isobutyloxycarbonyl, sec-butyloxycarbonyl, t-butyloxycarbonyl, n-pentyloxycarbonyl, isopentyloxycarbonyl, sec-pentyloxycarbonyl, t-pentyloxycarbonyl, n-hexyloxycarbonyl, n-heptyloxycarbonyl, n-octyloxycarbonyl, isooctyloxycarbonyl, sec-octyloxycarbonyl, t-octyloxycarbonyl, n-nonyloxycarbonyl, isononyloxycarbonyl, n-decyloxycarbonyl, and isodecyloxycarbonyl.

When R ^c5 is a phenylalkyl group, the number of carbon atoms of the phenylalkyl group is preferably 7 or more and 20 or less, and more preferably 7 or more and 10 or less. In addition, when R ^c5 is a naphthylalkyl group, the number of carbon atoms of the naphthylalkyl group is preferably 11 or more and 20 or less, and more preferably 11 or more and 14 or less. Specific examples of the case where R ^c5 is a phenylalkyl group include benzyl, 2-phenylethyl, 3-phenylpropyl, and 4-phenylbutyl. Specific examples of the case where R ^c5 is a naphthylalkyl group include α-naphthylmethyl, β-naphthylmethyl, 2-(α-naphthyl)ethyl, and 2-(β-naphthyl)ethyl. When R ^c5 is a phenylalkyl group or a naphthylalkyl group, R ^c5 may further have a substituent on the phenyl group or the naphthyl group.

When R ^c5 is a heterocyclic group, the heterocyclic group is the same as when R ^c4 in formula (c3) is a heterocyclic group, and the heterocyclic group may further have a substituent. When R ^c5 is a heterocyclic carbonyl group, the heterocyclic group contained in the heterocyclic carbonyl group is the same as when R ^c5 is a heterocyclic group.

When R ^c5 is an amino group substituted with one or two organic groups, preferred examples of the organic group include an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, a saturated aliphatic acyl group having 2 to 21 carbon atoms, a phenyl group which may have a substituent, a benzoyl group which may have a substituent, a phenylalkyl group which may have a substituent and has 7 to 20 carbon atoms, a naphthyl group which may have a substituent, a naphthylcarbonyl group which may have a substituent, a naphthylalkyl group which may have 11 to 20 carbon atoms, and a heterocyclic group. Specific examples of such preferred organic groups are the same as those for R ^c5 . 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-butylamino, n-pentylamino, n-hexylamino, n-heptylamino, n-octylamino, n-decylamino, benzylamino, α-naphthylamino, and β-naphthylamino.

When the phenyl group, naphthyl group and heterocyclic group included in R ^c5 further have a substituent, examples of the substituent include a substituent including a group represented by HX ₂ C- or H ₂ XC- (e.g., a halogenated alkoxy group including a group represented by HX ₂ C- or H ₂ XC-, a halogenated alkoxy group including a group represented by HX ₂ C- or H ₂ The invention also includes a halogenated alkyl group represented by XC-), an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a saturated aliphatic acyl group having 2 to 7 carbon atoms, an alkoxycarbonyl group having 2 to 7 carbon atoms, a saturated aliphatic acyl group having 2 to 7 carbon atoms, a monoalkylamino group having an alkyl group having 1 to 6 carbon atoms, a dialkylamino group having an alkyl group having 1 to 6 carbon atoms, a morpholin-1-yl group, a piperazin-1-yl group, a benzoyl group, a halogen group, a nitro group, and a cyano group. When the phenyl group, the naphthyl group, and the heterocyclic group included in R ^c5 further have a substituent, the number of the substituent is not limited within the range not hindering the purpose of the present invention, and is preferably 1 to 4. When the phenyl group, naphthyl group and heterocyclic group included in R ^c5 have a plurality of substituents, the plurality of substituents may be the same or different.

When the benzoyl group included in ^Rc5 further has a substituent, examples of the substituent include an alkyl group having 1 to 6 carbon atoms, a morpholin-1-yl group, a piperazin-1-yl group, a 2-thienylcarbonyl group (thiophen-2-ylcarbonyl group), a furan-3-ylcarbonyl group, and a phenyl group.

Examples of the halogen atom represented by X include a fluorine atom, a chlorine atom, a bromine atom and the like, and a fluorine atom is preferred.

Examples of the substituent containing a group represented by _HX2C- or _H2XC- include a halogenated alkoxy group containing a group represented by _HX2C- or _H2XC- , a group having a halogenated alkoxy group containing a group represented by _HX2C- or _H2XC- , a halogenated alkyl group containing a group represented by _HX2C- or _H2XC- , a group having a halogenated alkyl group containing a group represented by _HX2C- or _H2XC- , and the like. More preferred is a halogenated alkoxy group containing a group represented by _HX2C- or _H2XC- , or a group having a halogenated alkoxy group containing a group represented by _HX2C- or _H2XC- .

Examples of the group having a halogenated alkyl group containing a group represented by _HX2C- or _H2XC- include an aromatic group substituted with a halogenated alkyl group containing a group represented by _HX2C- or _H2XC- (e.g., phenyl, naphthyl, etc.), and a cycloalkyl group substituted with a halogenated alkyl group containing a group represented by _HX2C- or _H2XC- (e.g., cyclopentyl, cyclohexyl, etc.). Preferred are aromatic groups substituted with a halogenated alkyl group containing a group represented by _HX2C- or _H2XC- .

Examples of the group having a halogenated alkoxy group containing a group represented by _HX2C- or _H2XC- include an aromatic group substituted with a halogenated alkoxy group containing a group represented by _HX2C- or _H2XC- (e.g., phenyl, naphthyl, etc.), an alkyl group substituted with a halogenated alkoxy group containing a group represented by _HX2C- or _H2XC- (e.g., methyl, ethyl, n-propyl, isopropyl, etc.), and a cycloalkyl group substituted with a halogenated alkoxy group containing a group represented by _HX2C- or _H2XC- (e.g., cyclopentyl, cyclohexyl, etc.). Preferred are aromatic groups substituted with a halogenated alkoxy group containing a group represented by _HX2C- or _H2XC- .

R ^c5 is also preferably a cycloalkylalkyl group, a phenoxyalkyl group which may have a substituent on the aromatic ring, or a phenylthioalkyl group which may have a substituent on the aromatic ring. The substituents which may be possessed by the phenoxyalkyl group and the phenylthioalkyl group are the same as the substituents which may be possessed by the phenyl group included in R ^c5 .

In the monovalent organic group, R ^c5 is preferably an alkyl group, a cycloalkyl group, a phenyl group which may have a substituent, or a cycloalkylalkyl group, or a phenylthioalkyl group which may have a substituent on the aromatic ring. As the alkyl group, an alkyl group having 1 to 20 carbon atoms is preferred, an alkyl group having 1 to 8 carbon atoms is more preferred, an alkyl group having 1 to 4 carbon atoms is particularly preferred, and a methyl group is most preferred. Among the phenyl groups which may have a substituent, a methylphenyl group is preferred, and a 2-methylphenyl group is more preferred. The number of carbon atoms of the cycloalkyl group contained in the cycloalkylalkyl group is preferably 5 to 10, more preferably 5 to 8, and particularly preferably 5 or 6. The number of carbon atoms of the alkylene group contained in the cycloalkylalkyl group is preferably 1 to 8, more preferably 1 to 4, and particularly preferably 2. Among the cycloalkylalkyl groups, a cyclopentylethyl group is preferred. The number of carbon atoms in the alkylene group contained in the phenylthioalkyl group which may have a substituent on the aromatic ring is preferably 1 to 8, more preferably 1 to 4, and particularly preferably 2. Among the phenylthioalkyl groups which may have a substituent on the aromatic ring, 2-(4-chlorophenylthio)ethyl is preferred.

In the group represented by formula (c3), when there are multiple R ^c5 , and multiple R ^c5 are bonded to each other to form a ring, examples of the formed ring include alkyl rings, heterocyclic rings, etc. Examples of heteroatoms contained in the heterocyclic ring include N, O, and S. As the ring formed by multiple R ^{c5 s} bonded to each other, an aromatic ring is particularly preferred. The aromatic ring may be an aromatic alkyl ring or an aromatic heterocyclic ring. As the aromatic ring, an aromatic alkyl ring is preferred. In formula (c3), a specific example of the case where multiple R ^{c5 s} bonded to each other to form a benzene ring is shown below.

In the group represented by formula (c4), R ^c8 is a nitro group or a monovalent organic group. R ^c8 is bonded to a six-membered aromatic ring different from the aromatic ring to which the group represented by -(CO) _n1 - is bonded on the condensed ring in formula (c4). In formula (c4), the bonding position of R ^c8 is not particularly limited. When the group represented by formula (c4) has one or more R ^c8 , it is preferred that one of the one or more R ^c8 is bonded to the 7-position of the fluorene skeleton from the viewpoint of easier synthesis of the compound represented by formula (c4). That is, when the group represented by formula (c4) has one or more R ^c8 , the group represented by formula (c4) is preferably represented by the following formula (c6). When there are plural R ^c8s , the plural R ^c8s may be the same or different.

(In formula (c6), R ^c6 , R ^c7 , R ^c8 , and n3 are the same as R ^c6 , R ^c7 , R ^c8 , and n3 in formula (c4), respectively).

When R ^c8 is a monovalent organic group, R ^c8 is not particularly limited within the scope that does not hinder the purpose of the present invention. As an organic group, a carbon atom-containing group is preferred, and a group consisting of one or more carbon atoms and one or more atoms selected from the group consisting of H, O, S, Se, N, B, P, Si and halogen atoms is more preferred. The number of carbon atoms in the carbon atom-containing group is not particularly limited, but is preferably 1 to 50, and more preferably 1 to 20. As preferred examples of the case where R ^c8 is a monovalent organic group, the same groups as preferred examples of the monovalent organic group of R ^c5 in formula (c3) can be cited.

In formula (c4), ^Rc6 and ^Rc7 are respectively a chain alkyl group which may have a substituent, a chain alkoxy group which may have a substituent, a cyclic organic group which may have a substituent, or a hydrogen atom. ^Rc6 and ^Rc7 may be bonded to each other to form a ring. Among these groups, ^Rc6 and ^Rc7 are preferably a chain alkyl group which may have a substituent. When ^Rc6 and ^Rc7 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 ^Rc6 and ^Rc7 are unsubstituted chain alkyl groups, the number of carbon atoms of the chain alkyl group is preferably 1 to 20, more preferably 1 to 10, and particularly preferably 1 to 6. Specific examples of the chain ^alkyl group include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, t-butyl, n- ^pentyl , iso-pentyl, sec-pentyl, t-pentyl, n-hexyl, n-heptyl, n-octyl, iso-octyl, sec-octyl, t-octyl, n-nonyl, iso-nonyl, n-decyl, and iso-decyl. In addition, when ^Rc6 and ^Rc7 are alkyl groups, the alkyl group may contain an ether bond (—O—) in the carbon chain. Examples of the alkyl group having an ether bond in the carbon chain include methoxyethyl, ethoxyethyl, methoxyethoxyethyl, ethoxyethoxyethyl, propyloxyethoxyethyl, and methoxypropyl.

When ^Rc6 and ^Rc7 are chain alkyl groups having a substituent, the number of carbon atoms in the chain alkyl group is preferably 1 to 20, more preferably 1 to 10, and particularly preferably 1 to 6. In this case, the number of carbon atoms in the substituent is not included in the number of carbon atoms in the chain alkyl group. The chain alkyl group having a substituent is preferably a linear chain.

As long as the purpose of the present invention is not impeded, the substituents that the alkyl group may have are not particularly limited. As preferred examples of substituents, alkoxy groups, cyano groups, halogen atoms, halogenated alkyl groups, cyclic organic groups, and alkoxycarbonyl groups can be listed. As halogen atoms, fluorine atoms, chlorine atoms, bromine atoms, and iodine atoms can be listed. Among these atoms, fluorine atoms, chlorine atoms, and bromine atoms are preferred. As cyclic organic groups, cycloalkyl groups, aromatic alkyl groups, and heterocyclic groups can be listed. As specific examples of cycloalkyl groups, they are the same as the preferred examples in the case where R ^c8 is a cycloalkyl group. As specific examples of aromatic alkyl groups, phenyl groups, naphthyl groups, biphenyl groups, anthracenyl groups, and phenanthrenyl groups can be listed. Specific examples of heterocyclic groups are the same as the preferred examples when R ^c8 is a heterocyclic group. When R ^c8 is an alkoxycarbonyl group, the alkoxy group contained in the alkoxycarbonyl group may be linear or branched, preferably linear. The number of carbon atoms in the alkoxy group contained in the alkoxycarbonyl group is preferably 1 to 10, more preferably 1 to 6.

When the chain alkyl group has a substituent, the number of the substituent is not particularly limited. The preferred number of substituents varies depending on the number of carbon atoms in the chain alkyl group. The typical number of substituents is 1 to 20, preferably 1 to 10, and more preferably 1 to 6.

When ^Rc6 and ^Rc7 are chain alkoxy groups having no substituent, the number of carbon atoms in the chain alkoxy group is preferably 1 to 20, more preferably 1 to 10, and particularly preferably 1 to 6. Specific examples of the chain alkoxy group include ^methoxy , ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, 2- ^butoxy , 3-butoxy, n-pentoxy, isopentoxy, 2-pentoxy, 3-pentoxy, n-hexoxy, n-heptyloxy, n-octyloxy, isooctyloxy, 2-octyloxy, 3-octyloxy, n-nonyloxy, isononyloxy, n-decyloxy, and isodecyloxy. In addition, when ^Rc6 and ^Rc7 are alkoxy groups, the alkoxy group may contain an ether bond (—O—) in the carbon chain. Examples of the alkoxy group having an ether bond in the carbon chain include a methoxyethoxy group, an ethoxyethoxy group, a methoxyethoxyethoxy group, an ethoxyethoxyethoxy group, a propoxyethoxyethoxy group, and a methoxypropoxy group.

When R ^c6 and R ^c7 are a chain alkoxy group having a substituent, the substituent that the alkoxy group may have is the same as the case where R ^c6 and R ^c7 are a chain alkyl group.

When ^Rc6 and ^Rc7 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 alkyl group, an aromatic alkyl group, and a heterocyclic group. When ^Rc6 and ^Rc7 are cyclic organic groups, the substituents that the cyclic organic group may have are the same as those when ^Rc6 and ^Rc7 are chain alkyl groups.

When ^Rc6 and ^Rc7 are aromatic alkyl groups, the aromatic alkyl group is preferably a phenyl group, or a group formed by a plurality of benzene rings bonded via carbon-carbon bonds, or a group formed by condensation of a plurality of benzene rings. When the aromatic alkyl group is a phenyl group or a group formed by a plurality of benzene rings bonded or condensed, the number of benzene rings contained in the aromatic alkyl group is not particularly limited, but is preferably 3 or less, more preferably 2 or less, and particularly preferably 1. Preferred specific examples of the aromatic alkyl group include phenyl, naphthyl, biphenyl, anthracenyl, and phenanthryl.

When ^Rc6 and ^Rc7 are aliphatic cyclic hydrocarbon groups, the aliphatic cyclic hydrocarbon group may be monocyclic or polycyclic. The number of carbon atoms in the aliphatic cyclic hydrocarbon group is not particularly limited, but 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, norbornyl, isobornyl, tricyclononyl, tricyclodecyl, tetracyclododecyl, and adamantyl.

When R ^c6 and R ^c7 are heterocyclic groups, the same groups as those exemplified as the heterocyclic group for R ^c5 in formula (c3) can be cited.

R ^c6 and R ^c7 may bond to each other to form a ring. The group consisting of the ring formed by R ^c6 and R ^c7 is preferably a cycloalkylene group. When R ^c6 and R ^c7 bond to form a cycloalkylene group, the ring constituting the cycloalkylene group is preferably a 5- to 6-membered ring, more preferably a 5-membered ring.

When R ^c7 forms a ring with the benzene ring of the fluorene skeleton, the ring may be an aromatic ring or an aliphatic ring.

When the group formed by the bonding of ^Rc6 and ^Rc7 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 group include a benzene ring, a naphthalene ring, a cyclobutane ring, a cyclopentane ring, a cyclohexane ring, a cycloheptane ring, a cyclooctane ring, a furan ring, a thiophene ring, a pyrrole ring, a pyridine ring, a pyrazine ring, and a pyrimidine ring.

As examples of particularly preferred groups among R ^c6 and R ^c7 described above, groups represented by the formula -A1-A2 can be cited: wherein A1 is a linear alkyl group, and A2 can be alkoxy, cyano, halogen atom, halogenated alkyl, cyclic organic group or alkoxycarbonyl.

The number of carbon atoms of the linear alkyl group of A1 is preferably 1 to 10, more preferably 1 to 6. When A2 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 to 10, more preferably 1 to 6. When A2 is a halogen atom, it is preferably a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom, more preferably a fluorine atom, a chlorine atom, or a bromine atom. When A2 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, more preferably a fluorine atom, a chlorine atom, or a bromine atom. The halogenated alkyl group may be linear or branched, preferably linear. When A2 is a cyclic organic group, examples of the cyclic organic group are the same as the cyclic organic group that ^Rc6 and ^Rc7 have as a substituent. When A2 is an alkoxycarbonyl group, examples of the alkoxycarbonyl group are the same as the alkoxycarbonyl group that ^Rc6 and ^Rc7 have as a substituent.

Preferred specific examples of ^Rc6 and ^Rc7 include alkyl groups such as ethyl, n-propyl, n-butyl, n-hexyl, n-heptyl and n-octyl; alkoxyalkyl groups such as 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-n-hexyl, 7-ethoxy-n-heptyl and 8-ethoxy-n-octyl; 2-cyanoethyl, 3- Cyanoalkyl such as cyano-n-propyl, 4-cyano-n-butyl, 5-cyano-n-pentyl, 6-cyano-n-hexyl, 7-cyano-n-heptyl and 8-cyano-n-octyl; phenylalkyl such as 2-phenylethyl, 3-phenyl-n-propyl, 4-phenyl-n-butyl, 5-phenyl-n-pentyl, 6-phenyl-n-hexyl, 7-phenyl-n-heptyl and 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-cyclopentyl cycloalkylalkyl such as ethyl, 3-cyclopentyl-n-propyl, 4-cyclopentyl-n-butyl, 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-butyl, 5-ethoxycarbonyl-n-pentyl, 6-methoxycarbonyl-n-hexyl, 7-methoxycarbonyl-n-heptyl, 8-methoxycarbonyl-n-octyl alkyl, such as 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, 8-bromo-n-octyl, 3,3,3-trifluoropropyl and 3,3,4,4,5,5,5-heptafluoro-n-pentyl.

Among the above, preferred R ^c6 and R ^c7 are ethyl, n-propyl, n-butyl, n-pentyl, 2-methoxyethyl, 2-cyanoethyl, 2-phenylethyl, 2-cyclohexylethyl, 2-methoxycarbonylethyl, 2-chloroethyl, 2-bromoethyl, 3,3,3-trifluoropropyl and 3,3,4,4,5,5,5-heptafluoro-n-pentyl.

In view of the high sensitivity of the oxime ester compound, in the formula (c5), A is particularly preferably S.

In formula (c5), R ^c9 is a monovalent organic group, a halogen atom, a nitro group or a cyano group. When R ^c9 in formula (c5) is a monovalent organic group, it can be selected from various organic groups within the scope that does not hinder the purpose of the present invention. As an organic group, a carbon atom-containing group is preferred, and a group consisting of one or more carbon atoms and one or more atoms selected from the group consisting of H, O, S, Se, N, B, P, Si and a halogen atom is more preferred. The number of carbon atoms in the carbon atom-containing group is not particularly limited, and is preferably 1 to 50, and more preferably 1 to 20. As a preferred example of the case where R ^c9 in formula (c5) is an organic group, the same groups as the monovalent organic group as R ^c5 in formula (c3) can be listed.

Among R ^c9 , preferred are: benzoyl; naphthyl; benzoyl substituted by a group selected from the group consisting of alkyl having 1 to 6 carbon atoms, morpholin-1-yl, piperazin-1-yl and phenyl; nitro; benzofuranylcarbonyl which may have a substituent, and more preferred are: benzoyl; naphthyl; 2-methylphenylcarbonyl; 4-(piperazin-1-yl)phenylcarbonyl; and 4-(phenyl)phenylcarbonyl.

In formula (c5), n4 is preferably an integer of 0 to 3, more preferably an integer of 0 to 2, and particularly preferably 0 or 1. When n4 is 1, the bonding position of R ^c9 is preferably the para position relative to the bonding site of the phenyl group to which R ^c9 is bonded and the oxygen atom or sulfur atom.

In formulas (c1) and (c2), the monovalent organic group as R ^c2 is not particularly limited within the scope that does not hinder the purpose of the present invention. As the organic group, a carbon atom-containing group is preferred, and a group consisting of one or more carbon atoms and one or more atoms selected from the group consisting of H, O, S, Se, N, B, P, Si and halogen atoms is more preferred. The number of carbon atoms in the carbon atom-containing group is not particularly limited, but is preferably 1 to 50, and more preferably 1 to 20. Preferred examples of the monovalent organic group as R ^c2 include the same groups as the monovalent organic group as R ^c5 in formula (c3). Specific examples of these groups are the same as the groups described for R ^c5 in formula (c3). In addition, R ^c2 is also preferably a cycloalkylalkyl group, a phenoxyalkyl group which may have a substituent on the aromatic ring, or a phenylthioalkyl group which may have a substituent on the aromatic ring. The substituents which may be possessed by the phenoxyalkyl group and the phenylthioalkyl group are the same as those in the case where the phenyl group, the naphthyl group and the heterocyclic group included in R ^c5 in the formula (c3) further have a substituent.

Among the organic groups, R ^c2 is preferably a substituent containing a group represented by HX ₂ C- or H ₂ XC-, an alkyl group, a cycloalkyl group, a phenyl group which may have a substituent, or a cycloalkylalkyl group, or a phenylthioalkyl group which may have a substituent on the aromatic ring. The number of carbon atoms in the alkyl group, the phenyl group which may have a substituent, the cycloalkyl group contained in the cycloalkylalkyl group, the number of carbon atoms in the alkylene group contained in the cycloalkylalkyl group, the number of carbon atoms in the alkylene group contained in the cycloalkylalkyl group, the number of carbon atoms in the alkylene group contained in the phenylthioalkyl group which may have a substituent on the aromatic ring, or the phenylthioalkyl group which may have a substituent on the aromatic ring is the same as R ^c5 in formula (c3).

Furthermore, R ^c2 is also preferably a group represented by -A3-CO-O-A4. A3 is a divalent organic group, preferably a divalent alkyl group, and preferably an alkylene group. A4 is a monovalent organic group, preferably a monovalent alkyl group.

When A3 is an alkylene group, the alkylene group may be linear or branched, preferably linear. When A3 is an alkylene group, the number of carbon atoms in the alkylene group is preferably 1 to 10, more preferably 1 to 6, and particularly preferably 1 to 4.

Preferred examples of A4 include alkyl groups having 1 to 10 carbon atoms, aralkyl groups having 7 to 20 carbon atoms, and aromatic alkyl groups having 6 to 20 carbon atoms. Preferred specific examples of A4 include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, t-butyl, n-pentyl, n-hexyl, phenyl, naphthyl, benzyl, phenethyl, α-naphthylmethyl, and β-naphthylmethyl.

Preferred specific examples of the group represented by -A3-CO-O-A4 include 2-methoxycarbonylethyl, 2-ethoxycarbonylethyl, 2-n-propyloxycarbonylethyl, 2-n-butyloxycarbonylethyl, 2-n-pentyloxycarbonylethyl, 2-n-hexyloxycarbonylethyl, 2-benzyloxycarbonylethyl, 2-phenoxycarbonylethyl, 3-methoxycarbonyl-n-propyl, 3-ethoxycarbonyl-n-propyl, 3-n-propyloxycarbonyl-n-propyl, 3-n-butyloxycarbonyl-n-propyl, 3-n-pentyloxycarbonyl-n-propyl, 3-n-hexyloxycarbonyl-n-propyl, 3-benzyloxycarbonyl-n-propyl and 3-phenoxycarbonyl-n-propyl.

Furthermore, R ^c2 is also preferably a group represented by the following formula (c7) or (c8). (In formulas (c7) and (c8), R ^c10 and R ^c11 are each independently a monovalent organic group, n5 is an integer from 0 to 4, when R ^c10 and R ^c11 are present at adjacent positions on the benzene ring, R ^c10 and R ^c11 can bond to each other to form a ring, R ^c12 is a monovalent organic group, n6 is an integer from 1 to 8, n7 is an integer from 1 to 5, and n8 is an integer from 0 to (n7+3)).

The organic groups for R ^c10 and R ^c11 in formula (c7) are the same as R ^c8 in formula (c4). R ^c10 is preferably a halogenated alkoxy group containing a group represented by HX ₂ C- or H ₂ XC-, a halogenated alkyl group containing a group represented by HX ₂ C- or H ₂ XC-, an alkyl group, or a phenyl group. When R ^c10 and R ^c11 are bonded to form a ring, the ring may be an aromatic ring or an aliphatic ring. Preferred examples of the group represented by formula (c7) in which R ^c10 and R ^c11 form a ring include naphthalene-1-yl, 1,2,3,4-tetrahydronaphthalene-5-yl, and the like. In the above formula (c7), n7 is an integer of 0 to 4, preferably 0 or 1, and more preferably 0.

In the above formula (c8), R ^c12 is an organic group. As the organic group, the same groups as those described for R ^c8 in formula (c4) can be cited. Among the organic groups, an alkyl group is preferred. The alkyl group may be linear or branched. The number of carbon atoms in the alkyl group is preferably 1 to 10, more preferably 1 to 5, and particularly preferably 1 to 3. As R ^c12 , methyl, ethyl, propyl, isopropyl, butyl, etc. can be preferably exemplified, and among them, methyl is particularly preferred.

In the above formula (c8), n7 is an integer of 1 to 5, preferably an integer of 1 to 3, more preferably 1 or 2. In the above formula (c8), n8 is 0 to (n7+3), preferably an integer of 0 to 3, more preferably an integer of 0 to 2, and particularly preferably 0. In the above formula (c8), n8 is an integer of 1 to 8, preferably an integer of 1 to 5, more preferably an integer of 1 to 3, and particularly preferably 1 or 2.

In formula (c2), R ^c3 is a hydrogen atom, an aliphatic alkyl group having 1 to 20 carbon atoms which may have a substituent, or an aryl group which may have a substituent. When R ^c3 is an aliphatic alkyl group, the substituent which may have a substituent is preferably a phenyl group, a naphthyl group, or the like.

In formula (c1) and formula (c2), R ^c3 is preferably exemplified by a hydrogen atom, methyl, ethyl, n-propyl, isopropyl, n-butyl, 2-cyclopentylethyl, 2-cyclobutylethyl, cyclohexylmethyl, phenyl, benzyl, methylphenyl, naphthyl and the like, and among these, a methyl group or a phenyl group is more preferred.

Preferred specific examples of the compound represented by formula (c2) and having a group represented by formula (c3) as R ^c1 include the following compounds.

Preferred specific examples of the compound represented by formula (c2) and having a group represented by formula (c4) as R ^c1 include the following compounds.

Preferred specific examples of the compound represented by formula (c2) and having a group represented by formula (c5) as R ^c1 include the following compounds.

The oxime ester compound (C2) is also preferably the following oxime ester compounds.

The photopolymerization initiator (C) may include other photopolymerization initiators (C3) other than the aminoalkylphenone-based photopolymerization initiator (C1) and the oxime ester compound (C2). Examples of other photopolymerization initiators (C3) include α-hydroxy ketone-based photopolymerization initiators such as 1-phenyl-2-hydroxy-2-methylpropane-1-one, 1-(4-isopropylphenyl)-2-hydroxy-2-methylpropane-1-one, 4-(2-hydroxyethoxy)phenyl-(2-hydroxy-2-propyl)ketone, and 1-hydroxycyclohexylphenylketone; Benzoin-based photopolymerization initiators such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin propyl ether, and benzyl methyl ketal; benzophenone, benzoylbenzoic acid, benzoylbenzoic acid methyl ester, 4-phenylbenzophenone, hydroxybenzophenone, acrylated benzophenone, 4-benzoyl, 4'-methyldiphenyl sulfide, 4,4'-bis(diethylamino)benzophenone, Benzophenone-based photopolymerization initiators such as benzophenone; thiothione, 2-chlorothiothione, 2-methylthiothione, isopropylthiothione, 2,4-diisopropylthiothione, etc. thiothione-based photopolymerization initiators; 2,4,6-trichloro-s-triazine, 2-phenyl-4,6-bis(trichloromethyl)-s-triazine, 2-(p-methoxyphenyl)-4,6-bis(trichloromethyl) -s-triazine, 2-(p-tolyl)-4,6-bis(trichloromethyl)-s-triazine, 2-piperonyl-4.6-bis(trichloromethyl)-s-triazine, 2,4-bis(trichloromethyl)-6-phenylvinyl-s-triazine, 2-(naphthalen-1-yl)-4,6-bis(trichloromethyl)-s-triazine, 2-(4-methoxy-naphthalen-1-yl)- 4,6-bis(trichloromethyl)-s-triazine, 2,4-trichloromethyl-(piperonyl)-6-triazine, 2,4-trichloromethyl-(4'-methoxyphenylvinyl)-6-triazine, 2-[4-(4-methoxyphenylvinyl)phenyl]-4,6-bis(trichloromethyl)-1,3,5-triazine and other triazine photopolymerization initiators; carbazole photopolymerization initiators; 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetrakis(4-ethoxycarbonylphenyl)-1,2'-biimidazole, 2,2'-bis(2-bromophenyl)-4,4',5,5'-tetrakis(4-ethoxycarbonylphenyl)-1,2'-biimidazole, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetrakis(4-ethoxycarbonylphenyl)-1,2'-biimidazole, Biimidazole type photopolymerization initiators such as 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, and 2,2'-bis(2,4,6-tribromophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole; and benzimidazolinyl type photopolymerization initiators represented by the following formula.

As described above, the photopolymerization initiator (C) can be used alone or in combination of two or more. By using two or more in combination, it is easy to effectively utilize the wide range of wavelengths contained in the exposure light, and it is easy to adjust the sensitivity of the photosensitive composition to an appropriate range.

The content of the photopolymerization initiator (C) in the total solid content of the photosensitive composition is preferably from 0.5 mass % to 15 mass %, more preferably from 1 mass % to 10 mass %.

The mass ratio of the aminoalkylphenone-based photopolymerization initiator (C1) to the mass ratio of the photopolymerization initiator (C) is preferably 10 mass% to 50 mass%, more preferably 20 mass% to 40 mass%. The total mass ratio of the aminoalkylphenone-based photopolymerization initiator (C1) and the oxime ester compound (C2) to the mass ratio of the photopolymerization initiator (C) is preferably 50 mass% to 100 mass%, more preferably 70 mass% to 100 mass%, further preferably 80 mass% to 100 mass%, particularly preferably 90 mass% to 100 mass%, and most preferably 100 mass%.

<Light-shielding agent (D)> The photosensitive composition contains a light-shielding agent (D). The light-shielding agent (D) contains carbon black (D1) coated with an epoxy resin. The coating amount of the epoxy resin relative to the carbon black is preferably 1 mass % or more and 30 mass % or less relative to the total amount of the carbon black and the epoxy resin. By setting it to above the lower limit, dispersibility, dispersion stability, and insulation properties that are higher than those of untreated carbon black can be obtained. In addition, by setting it to below the upper limit, the dispersibility can be made good.

Furthermore, when carbon black (D1) coated with epoxy resin is used as the light shielding agent (D), the OD (Optical Density) value of the formed film per 1 μm film thickness is preferably adjusted to 2.0 or more, more preferably 2.5 or more, and further preferably 3.0 or more. If the OD value per 1 μm film thickness is 2.0 or more, when used as a black matrix of a color filter, sufficient display contrast can be obtained, and the necessary performance can be obtained.

When a cured product formed using a photosensitive composition is used as a black matrix, the optical density (OD value) of the black matrix increases if the content of carbon black is increased. On the other hand, increasing the content of conductive carbon black causes a decrease in the intrinsic volume resistance of the black matrix. It is estimated that by using carbon black (D1) coated with epoxy resin in the light shielding agent (black coloring agent) added to the photosensitive composition, the OD value of the cured product or black matrix can be increased, and the intrinsic volume resistance can also be increased.

The sunscreen (D) may contain sunscreens other than the epoxy-coated carbon black (D1). Examples of sunscreens other than the epoxy-coated carbon black include inorganic black pigments such as carbon black not epoxy-coated, and organic black pigments such as lactam-based pigments and perylene-based pigments.

The ratio of the carbon black (D1) coated with epoxy resin to the light shielding agent (D) is preferably 80% by mass or more, more preferably 90% by mass or more, and further preferably 95 to 100% by mass.

The form of the sunscreen (D) used in the preparation of the photosensitive composition is not particularly limited. The sunscreen (D) can be used as a powder or as a dispersion. The sunscreen (D) is preferably used as a dispersion for the preparation of the photosensitive composition. As the dispersion, a dispersion containing two or more sunscreens (D) can be used. In addition, two or more dispersions each containing different types of sunscreens can also be used.

As the dispersion medium, for example, an organic solvent such as propylene glycol monomethyl ether acetate, acetic acid solvent, 3-methoxybutyl acetate, methoxypropyl acetate, 2-methoxyethyl acetate, 3-ethoxyethyl propionate, and propylene glycol monomethyl ether propionate can be used.

In order to stabilize the dispersion of the light-shielding agent (D) in the dispersion liquid or to improve the dispersibility of the light-shielding agent (D) in the photosensitive composition, a dispersant may be used. As the dispersant, a high molecular weight dispersant such as a polyethyleneimine-based, polyurethane resin-based, or acrylic resin-based one is preferably used. Among these, a polyurethane resin-based dispersant is preferred from the viewpoint of good solubility in the developer and less likely to produce residues attached to the substrate, developing equipment, pipes, etc. after development. When a dispersant is used, the content of the dispersant in the photosensitive composition is, for example, 5% by mass to 50% by mass, preferably 10% by mass to 40% by mass, relative to the content of the light-shielding agent (D). In addition, there are cases where corrosive gases are generated from the cured product due to the dispersant. Therefore, it is also an example of a better aspect to disperse the light shielding agent (D) without using a dispersant.

The viscosity of the dispersion of the sunscreen (D) is not particularly limited. The viscosity of the dispersion is preferably 3 mPa·s or more and 200 mPa·s or less, as measured by an E-type viscometer at 25°C.

The particle size of the sunscreen (D) in the dispersion is preferably 80 nm or more and 300 nm or less, calculated as a dispersed average particle size. The dispersed average particle size can be measured using a laser diffraction particle size distribution analyzer.

The content of the sunscreen (D) in the total solid content of the photosensitive composition is preferably 30 mass % to 80 mass %, more preferably 40 mass % to 70 mass %, further preferably 50 mass % to 60 mass %.

<Silane coupling agent (E)> The photosensitive composition contains a silane coupling agent (E). By making the photosensitive composition contain a silane coupling agent (E), a cured product having good adhesion to the substrate can be formed.

Preferred examples of the silane coupling agent (E) include: monoalkyltrialkoxysilanes such as methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, n-propyltrimethoxysilane, n-propyltriethoxysilane, n-butyltrimethoxysilane, n-butyltriethoxysilane; dialkyldialkoxysilanes such as dimethyldimethoxysilane and dimethyldiethoxysilane; monophenyltrialkoxysilanes such as phenyltrimethoxysilane and phenyltriethoxysilane; diphenyldialkoxysilanes such as diphenyldimethoxysilane and diphenyldiethoxysilane; monovinyltrialkoxysilanes such as vinyltrimethoxysilane and vinyltriethoxysilane; alkane; (meth)acryloxyalkyl monoalkyldialkoxysilanes such as 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane; (meth)acryloxyalkyltrialkoxysilanes such as 3-acryloxypropyltrimethoxysilane; amine-containing trialkoxysilanes such as 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N-(1,3-dimethyl-butylene)propylamine, and N-phenyl-3-aminopropyltrimethoxysilane; 3-epoxypropyl alkyltrialkoxysilanes containing non-aliphatic cyclic epoxy groups such as oxypropyltrimethoxysilane and 3-glycidoxypropyltriethoxysilane; alkylmonoalkyldialkoxysilanes containing non-aliphatic cyclic epoxy groups such as 3-glycidoxypropylmethyldiethoxysilane; alkyltrialkoxysilanes containing aliphatic cyclic epoxy groups such as 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane and 2-(3,4-epoxycyclohexyl)ethyltriethoxysilane; alkylmonoalkyldialkoxysilanes containing aliphatic cyclic epoxy groups such as 2-(3,4-epoxycyclohexyl)ethylmethyldiethoxysilane; [(3-ethyl-3-oxacyclobutane)methoxy]propyltrimethoxysilane, [(3- Alkyltrialkoxysilanes containing an oxygen heterocyclobutane group such as ethyl-3-oxocyclobutane)methoxy]propyltriethoxysilane; alkyltrialkoxysilanes containing an oxygen heterocyclobutane group such as 3-butylpropyltrimethoxysilane; alkylmonoalkyldialkoxysilanes such as 3-butylpropylmethyldimethoxysilane; ureatrialkoxysilanes such as 3-ureapropyltriethoxysilane; isocyanatealkyltrialkoxysilanes such as 3-isocyanatepropyltriethoxysilane; alkyltrialkoxysilanes containing anhydride groups such as 3-trimethoxysilylpropylsuccinic anhydride; alkyltrialkoxysilanes containing imide groups such as N-tert-butyl-3-(3-trimethoxysilylpropyl)succinimide; etc. These silane coupling agents may be used alone or in combination of two or more.

The content of the silane coupling agent (E) in the photosensitive composition is not particularly limited. The content of the silane coupling agent (E) is preferably 0.1% by mass to 10% by mass, more preferably 0.1% by mass to 5% by mass, and particularly preferably 0.1% by mass to 1% by mass, relative to the mass of the solid content of the photosensitive composition.

<Organic solvent (S)> The photosensitive composition preferably contains an organic solvent (S) for the purpose of adjusting coating properties. Examples of the organic solvent (S) include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol n-propyl ether, ethylene glycol mono-n-butyl ether, diethylene glycol monomethyl ether, diethylene 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, (Poly) alkylene glycol monoalkyl ethers such as dipropylene glycol mono-n-butyl ether, tripropylene glycol monomethyl ether, tripropylene glycol monoethyl ether; (Poly) alkylene glycol monoalkyl ether acetates such as 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; other ethers such as diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol diethyl ether, tetrahydrofuran; methyl ethyl ketone, cyclohexane ketones such as 2-heptanone, 2-heptanone, 3-heptanone; alkyl lactates such as methyl 2-hydroxypropionate and ethyl 2-hydroxypropionate; ethyl 2-hydroxy-2-methylpropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl ethoxyacetate, ethyl hydroxyacetate, methyl 2-hydroxy-3-methylbutanoate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, 3-methyl-3-methoxybutyl propionate, Ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, n-amyl formate, isoamyl acetate, n-butyl propionate, ethyl butyrate, n-propyl butyrate, isopropyl butyrate, n-butyl butyrate, methyl pyruvate, ethyl pyruvate, n-propyl pyruvate, methyl acetylacetate, ethyl acetylacetate, ethyl 2-hydroxybutyrate and other esters; aromatic hydrocarbons such as toluene and xylene; amides such as N-methylpyrrolidone, N,N-dimethylformamide, N,N-dimethylacetamide, etc.

Among them, preferred are alkanediol monoalkyl ethers, alkanediol monoalkyl ether acetates, the above-mentioned other ethers, ketones, and the above-mentioned other esters, and more preferred are alkanediol monoalkyl ether acetates, the above-mentioned other ethers, and the above-mentioned other esters. These solvents can be used alone or in combination of two or more.

The content of the organic solvent (S) is preferably an amount that makes the solid content concentration of the photosensitive composition 10 mass % or more, more preferably an amount that makes the solid content concentration of the photosensitive composition 15 mass % or more. The upper limit of the solid content concentration of the photosensitive composition is preferably 40 mass % or less, more preferably 30 mass % or less.

<Other ingredients> The photosensitive composition may also contain various additives other than those mentioned above as needed. Specifically, examples include sensitizers, curing accelerators, photocrosslinkers, photosensitizers, dispersing aids, fillers, antioxidants, ultraviolet absorbers, anti-aggregants, thermal polymerization inhibitors, defoamers, surfactants, chain transfer agents, photoinitiator aids, solvents, etc. Any additive can be a conventionally known additive.

Examples of surfactants include anionic compounds, cationic compounds, and nonionic compounds. Examples of thermal polymerization inhibitors include hydroquinone and hydroquinone monoethyl ether. Examples of defoamers include polysilicone compounds and fluorine compounds. Examples of chain transfer agents include thiol compounds, halogen compounds, quinone compounds, and α-methylstyrene dimer. By including a chain transfer agent, the shape of the pattern can be well controlled. Among them, 2,4-diphenyl-4-methyl-1-pentene (α-methylstyrene dimer) is particularly preferred from the viewpoint of reducing sublimation products, coloring, and odor in addition to the above effects. Examples of photoinitiator aids include triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, 2-ethylhexyl 4-dimethylaminobenzoate, 2-dimethylaminoethyl benzoate, N,N-dimethyl-p-toluidine, 4,4'-bis(dimethylamino)benzophenone (commonly known as Michler's ketone), 4,4'-bis(diethylamino)benzophenone, 9,10-dimethoxyanthracene, 2-ethyl-9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, and 2-ethyl-9,10-diethoxyanthracene. These photoinitiator aids may be used alone or in combination of two or more.

<Preparation method of photosensitive composition> The photosensitive composition is prepared by mixing the above-mentioned components with a stirrer. In addition, in order to make the prepared photosensitive composition more uniform, it can also be filtered using a membrane filter that allows components such as a sunscreen (D) to pass through.

《Method for producing a patterned cured product and a cured product》 By curing the photosensitive composition described above by exposure, a light-shielding film as a cured product can be obtained. The patterned cured product produced using the above-mentioned photosensitive composition has excellent water resistance and excellent adhesion to the substrate. Therefore, the photosensitive composition can be preferably used for forming a black matrix in a panel that can be used in a high-humidity environment, etc. In this way, the above-mentioned photosensitive composition can be preferably used to form a patterned cured product.

As a preferred method for manufacturing a patterned hardened product, a method including the following steps can be cited: A step of applying the aforementioned photosensitive composition to form a coating film; A step of selectively exposing the coating film; A step of developing the exposed coating film; A step of heating the developed coating film.

Each step is described below. Applying a photosensitive composition to form a coating film is referred to as a "coating film forming step". Selectively exposing the coating film position is referred to as an "exposure step". Developing the exposed coating film is referred to as a "development step". Heating the developed coating film is referred to as a "heating step".

<Coating film forming step> In the coating film forming step, a photosensitive composition is applied on a substrate to form a coating film. The type of substrate is not particularly limited, and various substrates used in optical devices such as liquid crystal display devices, organic EL display devices, and organic TFT arrays can be appropriately used. Examples of the substrate include quartz, glass, optical films, ceramic materials, evaporated films, magnetic films, reflective films, metal substrates such as Ni, Cu, Cr, and Fe, polymer substrates such as SOG (Spin On Glass), polyester films, polycarbonate films, and polyimide films, TFT array substrates, PDP electrode plates, glass or transparent plastic substrates, conductive substrates such as ITO or metal, insulating substrates, semiconductor substrates such as silicon, silicon nitride, polycrystalline silicon, silicon oxide, and amorphous silicon, etc. Furthermore, when a laminate structure is formed on a substrate, for example, some layers formed on the substrate as the lower structure are also included in the concept of the substrate to which the photosensitive composition is applied. In addition, the shape of the substrate is not particularly limited, and it may be a plate or a roll. The substrate may have a concave-convex surface by various patterns, for example. In addition, as the above-mentioned substrate, a light-transmitting or non-light-transmitting substrate can be selected.

In the coating film forming step, a photosensitive composition is applied on the substrate using a contact transfer coating device such as a roll coater, a reverse coater, or a rod coater, or a non-contact coating device such as a spin coater (rotary coater) or a curtain coater, and the solvent is removed by drying (pre-baking) as needed to form a coating film.

The thickness of the coating film is not particularly limited. As the thickness of the coating film, it is preferably 0.05 μm or more, and more preferably 1 μm or more. The thickness of the coating film can be, for example, 7 μm or more, or 10 μm or more. The upper limit of the thickness of the coating film is not particularly limited, and for example, it can be 50 μm or less, or 20 μm or less. As the thickness of the coating film, it is preferably 10 μm or less, and more preferably 5 μm or less.

The drying method is not particularly limited, and examples thereof include: (1) a method of drying at a temperature of 80°C to 120°C, preferably 90°C to 100°C, for 60 seconds to 180 seconds using a hot plate; (2) a method of leaving the sample at room temperature for several hours to several days; (3) a method of placing the sample in a warm air heater or an infrared heater for several tens of minutes to several hours to remove the solvent, etc.

<Exposure step> In the exposure step, the coating film formed in the coating film forming step is selectively exposed. By selectively exposing and developing according to the desired pattern shape position, a patterned cured film can be obtained.

In the exposure step, active energy rays such as ultraviolet rays and excimer lasers are irradiated for exposure. When a patterned cured film is formed, for example, the coating film is selectively exposed through a negative mask. The exposure amount also varies depending on the composition of the photosensitive composition, and is preferably 10 mJ/ ^cm2 or more and 600 mJ/ ^cm2 or less, for example.

<Developing step> In the developing step, the coating film exposed in the exposure step is developed by a developer such as an alkaline developer. In the developing step, the exposed coating film is developed by a developer, thereby forming a hardened material patterned into a desired shape. The developing method is not particularly limited, and for example, an immersion method, a spray method, etc. can be used. The developer can be appropriately selected according to the composition of the photosensitive composition. As the developer, an organic developer such as monoethanolamine, diethanolamine, triethanolamine, or an aqueous solution of sodium hydroxide, potassium hydroxide, sodium carbonate, ammonia, quaternary ammonium salt, etc. can be used.

Post-baking can be performed as needed after development. The post-baking temperature after development is preferably 80°C to 250°C, and more preferably 100°C to 230°C. The post-baking time after development is preferably 1 minute to 240 minutes, and more preferably 5 minutes to 60 minutes. [Example]

Hereinafter, the present invention will be described in more detail with reference to embodiments, but the scope of the present invention is not limited to these embodiments.

In the Examples and Comparative Examples, as the alkali-soluble resin (A), the resin A-1 obtained in the following Preparation Example 1 of the alkali-soluble cardo resin and the following resin A-2 as the alkali-soluble acrylic resin were used. In the resin A-2, the symbols k, l, m, and n at the lower right of the parentheses in each structural unit in the following structural formula represent the content (mass %) of the structural unit in the resin, k+l=15, m=30, and n=55. The mass average molecular weight Mw of the resin A-2 measured by gel permeation chromatography in terms of polystyrene was 6000.

(Preparation Example 1) First, in a 500 ml four-necked flask, add 235 g of bisphenol fluorene type epoxy resin (epoxy equivalent 235), 110 mg of tetramethylammonium chloride, 100 mg of 2,6-di-tert-butyl-4-methylphenol and 72.0 g of acrylic acid, and heat and dissolve at 90-100°C while passing air at a rate of 25 ml/min. Then, the solution is slowly heated in a milky state and heated to 120°C to completely dissolve it. At this time, the solution gradually becomes transparent and viscous, and stirring is continued in this state. During this period, the acid value is measured, and heating and stirring are continued until it is less than 1.0 mgKOH/g. It took 12 hours for the acid value to reach the target value. Then, the mixture was cooled to room temperature to obtain a colorless transparent solid bisphenol fluorene type epoxy acrylate represented by the following formula.

Next, 600 g of 3-methoxybutyl acetate was added to 307.0 g of the above-mentioned bisphenol fluorene type epoxy acrylate obtained in this way and dissolved, and then 80.5 g of 3,3',4,4'-biphenyltetracarboxylic dianhydride and 1 g of tetraethylammonium bromide were mixed, and the temperature was slowly raised and allowed to react at 110-115°C for 4 hours. After confirming that the anhydride group disappeared, 38.0 g of 1,2,3,6-tetrahydrophthalic anhydride was mixed and allowed to react at 90°C for 6 hours to obtain Resin A-1. The disappearance of the anhydride group was confirmed by IR spectroscopy. The mass average molecular weight of Resin A-1 measured by gel permeation chromatography in terms of polystyrene was 3100.

In the examples and comparative examples, the following B-1 to B-8 were used as photopolymerizable monomers (B). For B-1 to B-8, the hydroxyl values calculated by the above formula (1) are described below. B-4 to B-7 are high hydroxyl monomers (B1), and B-1 to B-3 and B-8 are low hydroxyl monomers (B2). B-1: 107 mgKOH/g B-2: 0 mgKOH/g B-3: 0 mgKOH/g B-4: 281 mgKOH/g B-5: 281 mgKOH/g B-6: 460 mgKOH/g B-7: 188 mgKOH/g B-8: 0 mgKOH/g

In the Examples and Comparative Examples, the following C-1 to C-3 were used as photopolymerization initiators (C).

In the examples and comparative examples, the following D-1 and D-2 were used as the sunscreen (D). D-1 and D-2 were used as carbon black dispersions. The method for preparing the carbon black dispersion is described below as Preparation Example 2. D-1: Carbon black coated with epoxy resin D-2: Regal 250R, manufactured by Cabot Corporation (carbon black not subjected to coating treatment)

(Preparation Example 2: Preparation of Carbon Black Dispersion) Using D-1 and D-2 as carbon black, a carbon black dispersion was prepared according to the following formula. 15 g of carbon black, 4.5 g of dispersant (BYK-167, manufactured by Beck Chemical Japan Co., Ltd.) and 50 g of propylene glycol monomethyl ether acetate (PM) were mixed and stirred using a bead mill to disperse the carbon black in the propylene glycol monomethyl ether acetate. Then, the mixture was diluted with propylene glycol monomethyl ether acetate to a solid content concentration of 30% by mass to obtain a carbon black dispersion.

In Examples and Comparative Examples, the following E-1 was used as the silane coupling agent (E).

In the Examples and Comparative Examples, a surfactant (BYK310, manufactured by Beck Chemical Co., Ltd.) was used.

[Examples 1 to 10 and Comparative Examples 1 to 6] The types and weight proportions of alkali-soluble resin (A), photopolymerizable monomer (B), photopolymerization initiator (C), sunscreen (D), silane coupling agent (E) and surfactant listed in Table 1 were uniformly dissolved and dispersed so that the mass ratio of the solvent (organic solvent (S)) in the obtained photosensitive composition was 50 weight % 3-methoxybutyl acetate (MA), 20 weight % propylene glycol monomethyl ether acetate (PM), 30 weight % cyclohexanone (AN), and the solid content concentration including the polyurethane resin dispersant of the carbon black dispersion was 20 weight %, thereby preparing the photosensitive compositions of Examples 1 to 10 and Comparative Examples 1 to 6. The content of the high hydroxyl monomer (B1) relative to the mass of the photopolymerizable monomer (B) ((total mass of the high hydroxyl monomer (B1))/(total mass of the photopolymerizable monomer (B))) is shown in the "High hydroxyl monomer (B1) content (mass %)" column of Table 1.

The photosensitive compositions of the Examples and Comparative Examples were used to evaluate OD value, water resistance, volume resistivity, pattern straightness, pattern adhesion, taper shape, and taper angle according to the following methods. The results are shown in Table 2.

[Evaluation of OD value] After applying the photosensitive composition on a 100mm×100mm×0.7mm glass substrate (EAGLE XG manufactured by Corning), heat (dry) at 80°C for 120 seconds to form a coating film. Next, use a proximity exposure device (product name: TME-150RTO, manufactured by TOPCON Co., Ltd.) to irradiate the coating film with broadband light including i-line (365nm). The exposure amount is set to 100mJ/ ^cm2 . Then, heat (bake) is performed at 90°C on a heating plate for 30 minutes. The film thickness of the formed film (cured product) is 1.0μm. For the film (cured product), the OD value is measured using D200-II (manufactured by Macbeth).

[Evaluation of water resistance (water-resistant adhesion)] The photosensitive composition of the embodiment and the comparative example was applied on a glass substrate of 100 mm × 100 mm × 0.7 mm (EAGLE XG, manufactured by Corning) using a spin coater, and pre-baked at 100°C for 120 seconds to form a coating film. Then, a proximity exposure device (product name: TME-150RTO, manufactured by TOPCON Co., Ltd.) was used to irradiate the entire surface of the coating film with broadband light including i-line (365 nm). The exposure amount was set to 100 mJ/cm ^2. The exposed coating film was spray developed with a 0.04 mass % KOH aqueous solution at 25°C for 90 seconds, and then heated (baked) at 150°C for 30+180 minutes (a total of 210 minutes). The film thickness of the formed film (cured product) was 2.0 μm. A cross cut (a grid-like cut with a width of 1 mm) was applied to the surface of the formed cured product, and the product was immersed in pure water at 120°C and 2 atmospheres for 36 hours. The cured product after immersion was subjected to the tape test specified in ASTM D3359-09e2 to confirm the peeling of the cured product from the substrate. The case where there is no peeling at all is set to 5B, the case where the peeling area is less than 5% is set to 4B, the case where the peeling area is between 5% and 15% is set to 3B, the case where the peeling area is more than 15% and less than 35% is set to 2B, the case where the peeling area is more than 35% and less than 65% is set to 1B, and the case where the peeling area is more than 65% is set to 0B.

[Measurement of volume resistance] The photosensitive composition of the embodiment and the comparative example was applied onto a 5-inch low-resistance silicon wafer (surface resistance: 0.01-0.03Ω) using a spin coater, and pre-baked at 100°C for 120 seconds to form a coating film. Next, a proximity exposure device (product name: TME-150RTO, manufactured by TOPCON Co., Ltd.) was used to irradiate the entire surface of the coating film with broadband light including i-line (365nm). The exposure amount was set to 100mJ/ ^cm2 . The exposed coating film was spray developed with a 0.04 mass% KOH aqueous solution at 25°C for 90 seconds, and then heated (baked) at 230°C for 30+180 minutes (a total of 210 minutes). The film thickness of the formed film (cured product) was 1.2 μm. The formed cured product was placed in an environment of 120°C, 100% humidity, and 2 atmospheres for 1 hour. Then, the volume resistance of the cured product was calculated using a resistivity meter Hiresta MCP HT-450 (manufactured by Mitsubishi Chemical) according to the method of JIS-K6911 (measurement conditions: voltage 10 V, 60 seconds).

[Evaluation of Pattern Straightness] The photosensitive compositions of Examples and Comparative Examples were coated on a 100 mm × 100 mm × 0.7 mm glass substrate (Corning, EAGLE XG) using a spin coater and pre-baked at 100°C for 120 seconds to form a coating film. Next, the coating film was exposed through a mask having a line and space pattern of 6.5 μm in line width and 6.5 μm in spacing using a mirror projection exposure machine (MPA-600FA, Canon Inc., 365 mW, NA=0.10, 100 mJ/cm ² ). The exposure amount was set to 100 mJ/cm ² . The exposed coating film was spray developed with a 0.04 mass% KOH aqueous solution at 25°C for 90 seconds, and then heated (baked) at 150°C for 30 minutes to form a wiring pitch pattern (patterned cured product) with a film thickness of 2.0μm. The patterned cured product was observed under a 50x optical microscope, and the condition with no wobbling of the line edge was evaluated as good, and the condition with wobbling of the line edge was evaluated as poor.

[Pattern peeling (adhesion) evaluation] The patterned hardened material formed in the same manner as in [Pattern straightness evaluation] was observed under a 50x optical microscope. The case where there was no pattern peeling was evaluated as ○, the case where there was peeling at the 1/10 to 2/10 line was evaluated as △, and the case where there was peeling at the 3/10 to 10/10 line was evaluated as ×.

[Taper angle] In the cross section of the patterned hardened product formed in the same manner as in [Evaluation of pattern straightness], the angle θ (taper angle) formed between the surface of the substrate 1 and the side wall of the patterned hardened product 2 as shown in FIG. 1 was determined, and the tapered shape was evaluated by the taper angle according to the following criteria. θ is shown in the "Taper angle (°)" column of Table 2. ◎: θ is 70° to 90°. ○: θ is 50° to 69°. △: θ is 30° to 49°. ×: θ is less than 30°.

According to Examples 1 to 10, it can be seen that by using a photosensitive composition comprising an alkali-soluble resin (A), a photopolymerizable monomer (B), a photopolymerization initiator (C), carbon black (D1) coated with an epoxy resin as a light-shielding agent (D), and a silane coupling agent (E), the photopolymerizable monomer (B) comprising a high-hydroxyl monomer (B1) having a hydroxyl value of 180 mgKOH/g or more and a low-hydroxyl monomer (B2) having a hydroxyl value of less than 180 mgKOH/g, and the content of the high-hydroxyl monomer (B1) being 5 mass % or more and 60 mass % or less relative to the mass of the photopolymerizable monomer (B), a patterned cured product having excellent water resistance and excellent adhesion to a substrate can be formed. Furthermore, as can be seen from the above table, by using the photosensitive compositions of Examples 1 to 10, it is possible to form a patterned cured product having a high volume resistance value, a tapered cross section with an appropriate tapered angle, and excellent straightness.

On the other hand, according to Comparative Examples 1 to 6, when the photopolymerizable monomer (B) contains the low-hydroxy monomer (B2) but does not contain the high-hydroxy monomer (B1), or when the photopolymerizable monomer (B) contains the high-hydroxy monomer (B1) and the low-hydroxy monomer (B2) but the content of the high-hydroxy monomer (B1) is outside the range of 5 mass % to 60 mass % relative to the mass of the photopolymerizable monomer (B), or when the photosensitive composition does not contain the carbon black (D1) coated with an epoxy resin, the water resistance of the formed cured product is poor, or the adhesion of the formed patterned cured product to the substrate is poor.

1: Substrate 2: Patterned hardened material

[Figure 1] is a cross-sectional view illustrating a method for evaluating a taper.

Claims (8)

A photosensitive composition comprising an alkali-soluble resin (A), a photopolymerizable monomer (B), a photopolymerization initiator (C), a sunscreen (D) and a silane coupling agent (E), wherein the sunscreen (D) comprises carbon black (D1) coated with an epoxy resin, the photopolymerizable monomer (B) comprises a high-hydroxyl monomer (B1) having a hydroxyl value of 180 mgKOH/g or more and a low-hydroxyl monomer (B2) having a hydroxyl value of less than 180 mgKOH/g, and the content of the high-hydroxyl monomer (B1) is 5% by mass or more and 60% by mass or less relative to the mass of the photopolymerizable monomer (B). The photosensitive composition of claim 1, wherein the high hydroxyl monomer (B1) comprises a multifunctional acrylic monomer (B1-1) having two or more (meth)acryl groups. A photosensitive composition as claimed in claim 2, wherein the multifunctional acrylic monomer (B1-1) comprises at least one selected from glycerol di(meth)acrylate, trihydroxymethylpropane di(meth)acrylate, diglycerol di(meth)acrylate, diglycerol tri(meth)acrylate, pentaerythritol di(meth)acrylate and pentaerythritol tri(meth)acrylate. The photosensitive composition of claim 1, wherein the alkali-soluble resin (A) comprises at least one selected from a resin (A1) having a cardo structure and an acrylic resin (A2). The photosensitive composition of claim 1, wherein the photopolymerization initiator (C) comprises an aminoalkylphenone-based photopolymerization initiator (C1). A method for manufacturing a patterned hardened material, comprising: a step of coating a photosensitive composition as described in any one of claims 1 to 5 to form a coating film; a step of selectively exposing the coating film; a step of developing the exposed coating film; and a step of heating the developed coating film. A patterned cured product is composed of a cured product of the photosensitive composition of any one of claims 1 to 5. A black matrix is formed by a cured product of the photosensitive composition of any one of claims 1 to 5.

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