Photosensitive composition, cured product, black matrix, black bank, color filter, image display device, and method for manufacturing a pattern cured film

Abstract

The present invention provides a photosensitive composition containing a light-shielding agent, a cured product of the photosensitive composition, a black matrix or black bank formed from the cured product, a color filter having the black matrix or the black bank, an image display device having the color filter, and a method for producing a patterned cured film using the photosensitive composition. The photosensitive composition can form a fine line pattern having low surface reflectivity and close adhesion to a substrate. The solution of the present invention is to use a combination of carbon black (D1) and a lactam pigment (D2) as the light-shielding agent (D) in a photosensitive composition comprising an alkali-soluble resin (A), a photopolymerizable monomer (B), a photopolymerization initiator (C), and a light-shielding agent (D), wherein the carbon black (D1) is subjected to a surface treatment selected from a coating treatment based on an organic substance and a treatment for introducing an acidic group.

Description

Technical Field

[0001] The present invention relates to a photosensitive composition, a cured product, a black matrix, a black bank, a color filter, an image display device, and a method for producing a patterned cured film. Background Art

[0002] Panels used in display devices such as liquid crystal displays (LCDs) typically include patterned light-shielding films such as black matrices and black columnar spacers. Panels used in organic EL displays also include black banks, which serve as light-shielding films for purposes such as demarcating the light-emitting layer. For such applications, various photosensitive compositions containing light-shielding black pigments and photopolymerization initiators have been proposed for forming light-shielding films.

[0003] For example, as a material for forming a black matrix, a negative photosensitive resin composition comprising a photopolymerizable compound, a photopolymerization initiator, an acrylic resin fine particle dispersion in which acrylic resin fine particles are dispersed, carbon black, and a solvent has been proposed (see Patent Document 1).

[0004] Prior art literature

[0005] Patent Literature

[0006] Patent Document 1: Japanese Patent Application Laid-Open No. 2011-170075 Summary of the Invention

[0007] Problems to be solved by the invention

[0008] Furthermore, the demand for improved image quality in panels used in image display devices is increasing. Consequently, the number of pixels is rapidly increasing as the resolution increases. Consequently, the black matrix and black banks are required to be thinner.

[0009] Furthermore, from the viewpoint of suppressing reflections of lighting devices and the like around the user of the image display device onto the image display surface, the black matrix and the black bank are required to have low reflectivity.

[0010] The present invention has been made in view of the above-mentioned problems, and its object is to provide a photosensitive composition containing a light-shielding agent, a cured product of the photosensitive composition, a black matrix or black bank formed from the cured product, a color filter including the black matrix or the black bank, an image display device including the color filter, and a method for producing a patterned cured film using the photosensitive composition, wherein the photosensitive composition can form a fine line pattern having low surface reflectivity and close adhesion to a substrate.

[0011] Means for solving problems

[0012] The inventors of the present application have repeatedly conducted in-depth research and found that by using carbon black (D1) and a lactam pigment (D2) in combination as a light-shielding agent (D) in a photosensitive composition comprising an alkali-soluble resin (A), a photopolymerizable monomer (B), a photopolymerization initiator (C) and a light-shielding agent (D), the carbon black (D1) is subjected to a surface treatment selected from a coating treatment based on an organic substance and a treatment for introducing an acidic group, thereby solving the above-mentioned problems and completing the present invention.

[0013] A first embodiment of the present invention is a photosensitive composition comprising an alkali-soluble resin (A), a photopolymerizable monomer (B), a photopolymerization initiator (C), and a light-shielding agent (D).

[0014] The sunscreen (D) contains carbon black (D1) and a lactam pigment (D2).

[0015] The carbon black (D1) is subjected to a surface treatment selected from a coating treatment with an organic substance and a treatment for introducing an acidic group.

[0016] The second aspect of the present invention is a cured product of the photosensitive composition according to the first aspect.

[0017] A third aspect of the present invention is a black matrix or a black bank formed from the cured product according to the second aspect.

[0018] A fourth aspect of the present invention is a color filter including the black matrix according to the third aspect and / or the black bank according to the third aspect.

[0019] A fifth aspect of the present invention is an image display panel including the color filter according to the fourth aspect.

[0020] A sixth aspect of the present invention is an image display device including the image display panel according to the fifth aspect.

[0021] A seventh aspect of the present invention is a method for producing a patterned cured film, comprising:

[0022] applying the photosensitive composition according to the first embodiment to form a coating film;

[0023] exposing the coating film in a site-selective manner; and

[0024] The exposed coating film is developed.

[0025] Effects of the Invention

[0026] According to the present invention, there are provided a photosensitive composition containing a light-shielding agent, a cured product of the photosensitive composition, a black matrix or black bank formed from the cured product, a color filter including the black matrix or the black bank, an image display device including the color filter, and a method for producing a patterned cured film using the photosensitive composition. The photosensitive composition can form a fine line pattern having low surface reflectivity and close adhesion to a substrate. DETAILED DESCRIPTION

[0027] Photosensitive composition

[0028] The photosensitive composition comprises an alkali-soluble resin (A), a photopolymerizable monomer (B), a photopolymerization initiator (C), and a light-shielding agent (D). The light-shielding agent (D) comprises a combination of carbon black (D1) and a lactam pigment (D2), wherein the carbon black (D1) has been subjected to a surface treatment selected from a coating treatment with an organic substance and a treatment for introducing an acidic group. The photosensitive composition may contain components such as an additive (E) and an organic solvent (S) as needed.

[0029] The thickness of the cured film formed using the photosensitive composition is not particularly limited, but is preferably 0.2 μm or more, more preferably 0.3 μm or more and 5 μm or less, further preferably 0.4 μm or more and 3 μm or less, and particularly preferably 0.5 μm or more and 2 μm or less.

[0030] Hereinafter, the essential components of the photosensitive composition, namely, the alkali-soluble resin (A), the photopolymerizable monomer (B), the photopolymerization initiator (C), and the light-shielding agent (D), as well as the optional components, and a method for producing a cured photosensitive composition will be described.

[0031] <Alkali-soluble resin (A)>

[0032] The photosensitive composition contains an alkali-soluble resin (A). The alkali-soluble resin (A) is not particularly limited and can be appropriately selected from various alkali-soluble resins conventionally blended in photosensitive resin compositions.

[0033] Here, in this specification, the alkali-soluble resin (A) refers to a resin having an alkali-soluble functional group (for example, a phenolic hydroxyl group, a carboxyl group, a sulfonic acid group, etc.) in the molecule.

[0034] Preferred examples of the alkali-soluble resin (A) include a resin (a-1) having a Cardo structure (hereinafter also referred to as "Cardo resin (a-1)").

[0035] When the resin (a-1) having a cardo structure is used as the alkali-soluble resin, a photosensitive composition with excellent resolution can be easily obtained, and a cured film that does not easily flow excessively due to heating can be easily formed using the photosensitive composition. Therefore, a cured film with a good cross-sectional shape can be easily formed.

[0036] [Resin having a Cardo structure (a-1)]

[0037] As the resin (a-1) having a cardo structure, a resin having a cardo structure and a predetermined alkali solubility can be used. The so-called cardo structure refers to a structure in which a second cyclic structure and a third cyclic structure are bonded to a single ring carbon atom constituting a first cyclic structure. It should be noted that the second cyclic structure and the third cyclic structure may be the same structure or different structures.

[0038] A representative example of the Cardo structure is a structure in which two aromatic rings (for example, benzene rings) are bonded to the carbon atom at the 9-position of a fluorene ring.

[0039] The cardo resin (a-1) is not particularly limited, and conventionally known resins can be used. Among them, the resin represented by the following formula (a-1) is preferred.

[0040] [Chemical Formula 1]

[0041]

[0042] In formula (a-1), X a represents a group represented by the following formula (a-2). t1 represents an integer of 0 or more and 20 or less.

[0043] [Chemical Formula 2]

[0044]

[0045] In the above formula (a-2), R a1 Each independently represents a hydrogen atom, a hydrocarbon group having 1 to 6 carbon atoms, or a halogen atom, and R a2 Each independently represents a hydrogen atom or a methyl group, R a3 Each independently represents a linear or branched alkylene group, t2 represents 0 or 1, W a It represents a group represented by the following formula (a-3).

[0046] [Chemical Formula 3]

[0047]

[0048] In formula (a-2), R a3, 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, most preferably ethane-1,2-diyl, propane-1,2-diyl, and propane-1,3-diyl.

[0049] Ring A in formula (a-3) represents an aliphatic ring which may be fused with an aromatic ring and may have a substituent. The aliphatic ring may be an aliphatic hydrocarbon ring or an aliphatic heterocyclic ring.

[0050] Examples of the aliphatic ring include monocycloalkanes, bicycloalkanes, tricycloalkanes, and tetracycloalkanes.

[0051] Specific examples include monocyclic alkanes such as cyclopentane, cyclohexane, cycloheptane, and cyclooctane, adamantane, norbornane, isobornane, tricyclodecane, and tetracyclododecane.

[0052] The aromatic ring that may be condensed with the aliphatic ring may be an aromatic hydrocarbon ring or an aromatic heterocyclic ring, and is preferably an aromatic hydrocarbon ring. Specifically, a benzene ring and a naphthalene ring are preferred.

[0053] Preferred examples of the divalent group represented by formula (a-3) include the following groups.

[0054] [Chemical Formula 4]

[0055]

[0056] The divalent group X in formula (a-1) a The residue Z can be provided by a The tetracarboxylic dianhydride is reacted with the diol compound represented by the following formula (a-2a) to be introduced into the Cardo resin (a-1).

[0057] [Chemical Formula 5]

[0058]

[0059] In formula (a-2a), R a1 、R a2 、R a3 , and t2 are the same as those described for formula (a-2). Ring A in formula (a-2a) is the same as that described for formula (a-3).

[0060] The diol compound represented by formula (a-2a) can be produced, for example, by the following method.

[0061] First, if necessary, the hydrogen atom in the phenolic hydroxyl group of the diol compound represented by the following formula (a-2b) is replaced with -R a3The group represented by -OH is then glycidylated using epichlorohydrin or the like to obtain an epoxy compound represented by the following formula (a-2c).

[0062] Next, the epoxy compound represented by the formula (a-2c) is reacted with acrylic acid or methacrylic acid to obtain the diol compound represented by the formula (a-2a).

[0063] In formula (a-2b) and formula (a-2c), R a1 、R a3 , and t2 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).

[0064] In addition, the production method of the diol compound represented by formula (a-2a) is not limited to the above-mentioned method.

[0065] [Chemical Formula 6]

[0066]

[0067] Preferred examples of the diol compound represented by formula (a-2b) include the following diol compounds.

[0068] [Chemical Formula 7]

[0069]

[0070] In the above formula (a-1), R a0 A hydrogen atom or -CO-Y a -COOH group. Here, Y a It 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, methylendomethylenetetrahydrophthalic anhydride, chlorendic anhydride, methyltetrahydrophthalic anhydride, and glutaric anhydride.

[0071] In the above formula (a-1), Z a Represents a residue obtained by 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 diphenyl ether tetracarboxylic dianhydride. Among them, pyromellitic dianhydride or biphenyl tetracarboxylic dianhydride is preferred. In view of the wide development process margin, pyromellitic dianhydride is preferred.

[0072] In addition, in the above formula (a-1), t1 represents an integer of 0 or more and 20 or less.

[0073] [Chemical Formula 8]

[0074]

[0075] (In formula (a-4), R a4 、R a5 , and R a6 Each independently represents one selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, and a fluorine atom, and t3 represents an integer of 0 to 12.

[0076] Can be selected as R in formula (a-4) a4 The alkyl group is an alkyl group having 1 to 10 carbon atoms. By setting the number of carbon atoms of the alkyl group to the above range, the heat resistance of the obtained carboxylic acid ester can be further improved. a4 In the case of an alkyl group, the number of carbon atoms is preferably 1 to 6, more preferably 1 to 5, further preferably 1 to 4, and particularly preferably 1 to 3, from the perspective of easily obtaining a cardo resin having excellent heat resistance.

[0077] R a4 When it is an alkyl group, the alkyl group may be linear or branched.

[0078] As R in formula (a-4) a4 , and each independently is more preferably a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, from the viewpoint of easily obtaining a Cardo resin having excellent heat resistance. a4 More preferred is a hydrogen atom, a methyl group, an ethyl group, an n-propyl group or an isopropyl group, and particularly preferred is a hydrogen atom or a methyl group.

[0079] From the perspective of easily preparing high-purity tetracarboxylic dianhydride, the plurality of R a4 The same groups are preferred.

[0080] In the formula (a-4), t3 represents an integer of 0 to 12. When the value of t3 is 12 or less, purification of tetracarboxylic dianhydride can be easily performed.

[0081] The upper limit of t3 is preferably 5, more preferably 3, from the viewpoint of facilitating purification of tetracarboxylic dianhydride.

[0082] The lower limit of t3 is preferably 1, more preferably 2, from the viewpoint of the chemical stability of tetracarboxylic dianhydride.

[0083] In the formula (a-4), t3 is particularly preferably 2 or 3.

[0084] Can be selected as R in formula (a-4) a5 and R a6 An alkyl group having 1 or more and 10 or less carbon atoms and an alkyl group which can be selected as R a4 The same applies to an alkyl group having 1 to 10 carbon atoms.

[0085] From the perspective of easy purification of tetracarboxylic dianhydride, R a5 , and R a6 Preferably, it is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and particularly preferably a hydrogen atom or a methyl group. The number of carbon atoms in the alkyl group is preferably 1 to 6, more preferably 1 to 5, further preferably 1 to 4, particularly preferably 1 to 3, and most preferably 1.

[0086] Examples of the tetracarboxylic dianhydride represented by 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'-cyclopentanone-5'-spiro-2"-norbornane-5,5",6,6"-tetracarboxylic dianhydride"). '-cyclohexanone-6'-spiro-2"-norbornane-5,5",6,6"-tetracarboxylic dianhydride"), methyl norbornane-2-spiro-α-cyclohexanone-α'-spiro-2"-(methyl norbornane)-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-cycloheptanone-α'-spiro-2"-norbornane-5,5",6,6"-tetracarboxylic dianhydride, 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-cyclododecanone-α'-spiro-2"-norbornane-5,5",6,6"-tetracarboxylic dianhydride, norbornane-2-spiro- 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.

[0087] The weight average molecular weight of the Cardo resin (a-1) is preferably from 1000 to 40000, more preferably from 1500 to 30000, and even more preferably from 2000 to 10000. Within the above range, not only good developability can be obtained, but also sufficient heat resistance and mechanical strength can be obtained in the cured film.

[0088] [Novolac resin (a-2)]

[0089] From the viewpoint of suppressing excessive thermal fluidization of the cured film due to heating during post-baking, it is also preferred that the alkali-soluble resin (A) contains the Novolac resin (a-2).

[0090] As the Novolac resin (a-2), various Novolac resins conventionally incorporated into photosensitive resin compositions can be used. The Novolac resin (a-2) is preferably a resin obtained by addition condensation of an aromatic compound having a phenolic hydroxyl group (hereinafter referred to as "phenol") and an aldehyde in the presence of an acid catalyst.

[0091] (Phenols)

[0092] Examples of the phenols that can be 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, m-butylphenol, and p-butylphenol; , and tert-butylphenol; trialkylphenols such as 2,3,5-trimethylphenol and 3,4,5-trimethylphenol; polyphenols such as resorcinol, catechol, hydroquinone, hydroquinone monomethyl ether, pyrogallol, and phloroglucinol; alkyl polyphenols such as alkylresorcinol, alkylcatechol, and alkylhydroquinone (all alkyl groups have 1 to 4 carbon atoms); α-naphthol; β-naphthol; hydroxydiphenyl; and bisphenol A. These phenols may be used alone or in combination of two or more.

[0093] Among these phenols, m-cresol and p-cresol are preferred, and their combined use is more preferred. In this case, various properties such as heat resistance of the black matrix and black bank formed using the photosensitive composition can be adjusted by adjusting the mixing ratio of the two.

[0094] The mixing ratio of m-cresol and p-cresol is not particularly limited, but is preferably 3 / 7 or more and 8 / 2 or less in terms of the molar ratio of m-cresol / p-cresol. By using m-cresol and p-cresol in the above ratio, a photosensitive composition capable of forming a black matrix or black bank with excellent heat resistance can be easily obtained.

[0095] Novolac resins produced by combining m-cresol and 2,3,5-trimethylphenol are also preferred. Using such Novolac resins makes it particularly easy to obtain a photosensitive composition capable of forming a black matrix or black bank that is less likely to flow excessively due to heating during post-baking.

[0096] The mixing ratio of m-cresol and 2,3,5-trimethylphenol is not particularly limited, but is preferably 70 / 30 or more and 95 / 5 or less in terms of the molar ratio of m-cresol / 2,3,5-trimethylphenol.

[0097] (aldehydes)

[0098] Examples of aldehydes that can be used in the preparation of Novolac resin (a-2) include formaldehyde, paraformaldehyde, furfural, benzaldehyde, nitrobenzaldehyde, and acetaldehyde. These aldehydes can be used alone or in combination of two or more.

[0099] (Acid Catalyst)

[0100] Examples of acid catalysts that can be used in the production of 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, diethyl sulfate, 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.

[0101] (Molecular weight)

[0102] The weight average molecular weight (Mw; hereinafter also referred to as "weight average molecular weight") of the Novolac resin (a-2) in terms of polystyrene conversion is preferably 2000, more preferably 5000, particularly preferably 10000, further preferably 15000, and most preferably 20000, and the upper limit is preferably 50000, more preferably 45000, further preferably 40000, and most preferably 35000, from the viewpoint of the resistance of the black matrix and black bank formed using the photosensitive composition to flow caused by heating.

[0103] As the Novolac resin (a-2), at least two resins having different weight-average molecular weights in terms of polystyrene can be used in combination. By using resins having different weight-average molecular weights in combination, a good balance can be achieved between the developability of the photosensitive composition and the heat resistance of the cured film formed using the photosensitive composition.

[0104] [Modified epoxy resin (a-3)]

[0105] From the perspective of easily achieving higher fluidity resistance during baking and easily imparting high water resistance to the cured film, the alkali-soluble resin (A) may include a polybasic acid anhydride (a-3c) adduct (a-3) which is a reaction product of an epoxy compound (a-3a) and an unsaturated group-containing carboxylic acid (a-3b). This adduct is also referred to as a "modified epoxy resin (a-3)."

[0106] It should be noted that in the specification and claims of the present application, compounds that meet the above definition but do not belong to the aforementioned resin (a-1) having a Cardo structure are referred to as modified epoxy resins (a-3).

[0107] Hereinafter, the epoxy compound (a-3a), the unsaturated group-containing carboxylic acid (a-3b), and the polybasic acid anhydride (a-3c) will be described.

[0108] <Epoxy Compound (a-3a)>

[0109] The epoxy compound (a-3a) is not particularly limited as long as it is a compound having an epoxy group. It may be an aromatic epoxy compound having an aromatic group or an aliphatic epoxy compound not containing an aromatic group, but is preferably an aromatic epoxy compound having an aromatic group.

[0110] The epoxy compound (a-3a) may be a monofunctional epoxy compound or a polyfunctional epoxy compound having two or more functional groups, and is preferably a polyfunctional epoxy compound.

[0111] Specific examples of the epoxy compound (a-3a) include bifunctional epoxy resins such as bisphenol A epoxy resin, bisphenol F epoxy resin, bisphenol S epoxy resin, bisphenol AD epoxy resin, naphthalene epoxy resin, and biphenyl epoxy resin; glycidyl ester epoxy resins such as dimer acid glycidyl ester and triglycidyl ester; glycidylamine epoxy resins such as tetraglycidylaminodiphenylmethane, triglycidyl p-aminophenol, tetraglycidyl meta-xylenediamine, and tetraglycidylbisaminomethylcyclohexane; heterocyclic epoxy resins such as triglycidyl isocyanurate; phloroglucinol triglycidyl ether, trihydroxybiphenyl triglycidyl ether, trihydroxyphenyl trifunctional epoxy resins such as methylmethane triglycidyl ether, glycerol triglycidyl ether, 2-[4-(2,3-epoxypropoxy)phenyl]-2-[4-[1,1-bis[4-(2,3-epoxypropoxy)phenyl]ethyl]phenyl]propane, and 1,3-bis[4-[1-[4-(2,3-epoxypropoxy)phenyl]-1-[4-[1-[4-(2,3-epoxypropoxy)phenyl]-1-methylethyl]phenyl]ethyl]phenoxy]-2-propanol; and quadrifunctional epoxy resins such as tetrahydroxyphenylethane tetraglycidyl ether, tetraglycidyl benzophenone, bisresorcinol tetraglycidyl ether, and tetraglycidoxybiphenyl.

[0112] Moreover, as an epoxy compound (a-3a), the epoxy compound which has a biphenyl skeleton is preferable.

[0113] The epoxy compound having a biphenyl skeleton preferably has at least one biphenyl skeleton represented by the following formula (a-3a-1) in the main chain.

[0114] The epoxy compound having a biphenyl skeleton is preferably a polyfunctional epoxy compound having two or more epoxy groups.

[0115] 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 having excellent adhesion to a substrate.

[0116] [Chemical Formula 9]

[0117]

[0118] (In formula (a-3a-1), R a7 Each is independently a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, a halogen atom, or a phenyl group which may have a substituent, and j is an integer of 1 to 4.

[0119] R a7When it 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, tert-butyl, n-pentyl, isopentyl, sec-pentyl, tert-pentyl, n-hexyl, n-heptyl, n-octyl, isooctyl, sec-octyl, tert-octyl, n-nonyl, isononyl, n-decyl, isodecyl, n-undecyl, and n-dodecyl.

[0120] R a7 In the case of a halogen atom, specific examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

[0121] R a7 In the case of 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.

[0122] 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.

[0123] 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).

[0124] [Chemical Formula 10]

[0125]

[0126] (In formula (a-3a-2), R a7 and j are the same as those in formula (a-3a-1), and k is the average number of repetitions of the structural units in parentheses, which is 0 or more and 10 or less.)

[0127] Among the epoxy compounds represented by formula (a-3a-2), compounds represented by the following formula (a-3a-3) are preferred because a photosensitive composition having an excellent balance between sensitivity and developability can be easily obtained.

[0128] [Chemical Formula 11]

[0129]

[0130] (In formula (a-3a-3), k is the same as in formula (a-3a-2).

[0131] (Carboxylic acid containing an unsaturated group (a-3b))

[0132] When the modified epoxy compound (a-3) is prepared, the epoxy compound (a-3a) is reacted with the unsaturated group-containing carboxylic acid (a-3b).

[0133] The unsaturated group-containing carboxylic acid (a-3b) is preferably a monocarboxylic acid containing a reactive unsaturated double bond such as an acryl group or a methacryl group in the molecule. Examples of such unsaturated group-containing carboxylic acids include acrylic acid, methacrylic acid, β-styryl acrylic acid, β-furfuryl acrylic acid, α-cyanocinnamic acid, and cinnamic acid. The unsaturated group-containing carboxylic acid (a-3b) may be used alone or in combination of two or more.

[0134] The epoxy compound (a-3a) and the unsaturated group-containing carboxylic acid (a-3b) can be reacted by a known method. A preferred reaction method includes, for example, a method in which 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 to several dozen hours using a tertiary amine such as triethylamine or benzylethylamine, a quaternary ammonium salt such as dodecyltrimethylammonium chloride, tetramethylammonium chloride, tetraethylammonium chloride, or benzyltriethylammonium chloride, pyridine, or triphenylphosphine as a catalyst.

[0135] The ratio of the amounts 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, in terms of 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).

[0136] When the ratio of the amount of the epoxy compound (a-3a) 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, crosslinking efficiency tends to improve, which is preferred.

[0137] (Polyacid anhydride (a-3c))

[0138] The polybasic acid anhydride (a-3c) is an anhydride of a carboxylic acid having two or more carboxyl groups.

[0139] The polybasic acid 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 dianhydride, 3-methylhexahydrophthalic anhydride, 4-methylhexahydrophthalic 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 polybasic acid anhydride (a-3c) can be used alone or in combination of two or more.

[0140] [Chemical Formula 12]

[0141]

[0142] (In formula (a-3c-2), R a8 represents an alkylene group having 1 to 10 carbon atoms and optionally having a substituent.

[0143] From the perspective of easily obtaining a photosensitive composition with an excellent balance between sensitivity and developability, the polybasic acid anhydride (a-3c) is preferably a compound having two or more benzene rings. Furthermore, the polybasic acid anhydride (a-3c) more preferably comprises 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).

[0144] The method for reacting the epoxy compound (a-3a) with the unsaturated group-containing carboxylic acid (a-3b) and then reacting the polybasic acid anhydride (a-3c) can be appropriately selected from known methods.

[0145] The ratio of the used amounts is generally 1:1 to 1:0.1, preferably 1:0.8 to 1:0.2, based on the molar ratio of the OH groups in the component after the reaction of the epoxy compound (a-3a) and the unsaturated group-containing carboxylic acid (a-3b) to the equivalent ratio of the anhydride groups in the polybasic acid anhydride (a-3c). By falling within this range, a photosensitive composition with good developability can be easily obtained.

[0146] The acid value of the modified epoxy resin (a-3) is preferably 10 mgKOH / g to 150 mgKOH / g, more preferably 70 mgKOH / g to 110 mgKOH / g, based on the resin solid content. By setting the acid value of the resin to 10 mgKOH / g or higher, sufficient solubility in a developer can be achieved, while by setting the acid value to 150 mgKOH / g or lower, sufficient curability can be achieved, resulting in good surface properties.

[0147] In addition, the weight average molecular weight of the modified epoxy resin (a-3) is preferably 1000 or more and 40000 or less, more preferably 2000 or more and 30000 or less. By making the weight average molecular weight 1000 or more, it is easy to form a cured film excellent in heat resistance and strength. In addition, by making the weight average molecular weight 40000 or less, it is easy to obtain a photosensitive composition showing sufficient solubility in a developer.

[0148] [Acrylic resin (a-4)]

[0149] As a component constituting the alkali-soluble resin (A), an acrylic resin (a-4) is also preferred.

[0150] As the acrylic resin (a-4), a resin containing structural units derived from (meth)acrylic acid and / or structural units derived from other monomers such as (meth)acrylates can be used. (Meth)acrylic acid is acrylic acid or methacrylic acid. (Meth)acrylates are compounds represented by the following formula (a-4-1) and are not particularly limited as long as they do not hinder the purpose of the present invention.

[0151] [Chemical Formula 13]

[0152]

[0153] In the above formula (a-4-1), R a9 is a hydrogen atom or a methyl group, R a10 is a monovalent organic group. The organic group may contain a bond or substituent other than a hydrocarbon group such as a heteroatom. In addition, the organic group may be straight-chain, branched, or cyclic.

[0154] The organic group is preferably a group containing carbon atoms, more preferably a group containing 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. The number of carbon atoms in the group containing carbon atoms is not particularly limited, but is preferably 1 or more and 50 or less, more preferably 1 or more and 20 or less.

[0155] As R a10The substituents other than the hydrocarbon group in the organic group are 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 mercapto group, a sulfide group, a cyano group, an isocyano group, a cyanate group, an isocyanate group, a thiocyanate group, an isothiocyanate group, a silyl group, a silanol group, an alkoxy group, an alkoxycarbonyl group, a carbamoyl group, a thiocarbamoyl group, a nitro group, a nitroso group, a carboxyl group, a carboxylate group, an acyl group, an acyloxy group, a sulfinyl group, a sulfo group, a sulfonate group, a phosphino 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, and an amino group (-NH2, -NHR, -NRR': R and R' each independently represent a hydrocarbon group). The hydrogen atoms contained in the above substituents may be substituted with hydrocarbon groups. Furthermore, the hydrocarbon group contained in the above-mentioned substituent may be any of linear, branched, and cyclic.

[0156] In addition, as R a10 The organic group may have a reactive functional group such as an acryloyloxy group, a methacryloyloxy group, an epoxy group, or an oxetanyl group.

[0157] Acyl groups having an unsaturated double bond, such as an acyloxy group and a methacryloyloxy group, can be produced, for example, by reacting at least a portion of the epoxy groups in an acrylic resin (a-4) containing a structural unit having an epoxy group with an unsaturated carboxylic acid such as acrylic acid or methacrylic acid.

[0158] As R a10 , preferably an alkyl group, an aryl group, an aralkyl group, or a heterocyclic group, 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.

[0159] When the alkyl group is linear or branched, the number of carbon atoms in the alkyl group is preferably 1 to 20, more preferably 1 to 15, and particularly preferably 1 to 10. Preferred examples of the alkyl group include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, sec-pentyl, tert-pentyl, n-hexyl, n-heptyl, n-octyl, isooctyl, sec-octyl, tert-octyl, n-nonyl, isononyl, n-decyl, and isodecyl.

[0160] 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, tricyclononyl, tricyclodecanyl, and tetracyclododecyl.

[0161] 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.

[0162] In addition, the compound represented by formula (a-4-1) can be a (meth)acrylate containing an alicyclic epoxy group. The alicyclic group constituting the alicyclic epoxy group can be a monocyclic ring or a polycyclic ring. Examples of monocyclic alicyclic groups include cyclopentyl and cyclohexyl. In addition, examples of polycyclic alicyclic groups include norbornyl, isobornyl, tricyclononyl, tricyclodecyl, and tetracyclododecyl.

[0163] Specific examples of the compound represented by formula (a-4-1) when it is an alicyclic epoxy group-containing (meth)acrylate include compounds represented by the following formulas (a-4-1a) to (a-4-1o). Among these, in order to achieve an appropriate developability range, 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.

[0164] [Chemical Formula 14]

[0165]

[0166] [Chemical Formula 15]

[0167]

[0168] [Chemical Formula 16]

[0169]

[0170] In the above formula, R a20 represents a hydrogen atom or a methyl group, R a21 represents a divalent aliphatic saturated hydrocarbon group having 1 to 6 carbon atoms, R a22 represents a divalent hydrocarbon group having 1 to 10 carbon atoms, and t represents an integer of 0 to 10. a21, is a linear or branched alkylene group, and preferably, for example, methylene, ethylene, propylene, 1,4-butylene, ethylethylene, 1,5-pentylene, or 1,6-hexylene. a22 , for example, methylene, ethylene, propylene, 1,4-butylene, ethylethylene, 1,5-pentylene, 1,6-hexylene, phenylene, cyclohexylene, -CH2-Ph-CH2- (Ph represents phenylene) are preferred.

[0171] Alternatively, the acrylic resin (a-4) may be a copolymer obtained by further polymerizing monomers other than (meth)acrylates. Examples of monomers other than (meth)acrylates include (meth)acrylamides, unsaturated carboxylic acids, allyl compounds, vinyl ethers, vinyl esters, and styrenes. These monomers may be used alone or in combination of two or more.

[0172] Examples of the (meth)acrylamides 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.

[0173] Examples of the unsaturated carboxylic acids include monocarboxylic acids such as crotonic acid; dicarboxylic acids such as maleic acid, fumaric acid, citraconic acid, mesaconic acid, and itaconic acid; and anhydrides of these dicarboxylic acids.

[0174] Examples of the allyl compound include allyl acetate, allyl hexanoate, allyl octanoate, allyl laurate, allyl palmitate, allyl stearate, allyl benzoate, allyl acetoacetate, and allyl lactate; allyloxyethanol; and the like.

[0175] 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.

[0176] 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 phenylacetate, vinyl acetoacetate, vinyl lactate, vinyl β-phenylbutyrate, vinyl benzoate, vinyl salicylate, vinyl chlorobenzoate, vinyl tetrachlorobenzoate, and vinyl naphthoate.

[0177] Examples of the styrenes include styrene; alkyl styrenes such as methylstyrene, dimethylstyrene, trimethylstyrene, ethylstyrene, diethylstyrene, isopropylstyrene, butylstyrene, hexylstyrene, cyclohexylstyrene, decylstyrene, benzylstyrene, chloromethylstyrene, trifluoromethylstyrene, ethoxymethylstyrene, and acetoxymethylstyrene; alkoxystyrenes such as methoxystyrene, 4-methoxy-3-methylstyrene, and dimethoxystyrene; 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.

[0178] The amount of the structural units derived from (meth)acrylic acid in the acrylic resin (a-4) and the amount of the structural units derived from other monomers are not particularly limited within the range not hindering the purpose of the present invention. The amount of the structural units derived from (meth)acrylic acid in the acrylic resin (a-4) is preferably 5% by mass or more and 50% by mass or less, and more preferably 10% by mass or more and 30% by mass or less, relative to the mass of the acrylic resin (a-4).

[0179] When the acrylic resin (a-4) contains a structural unit having an unsaturated double bond, the amount of the structural unit having an unsaturated double bond in the acrylic resin (a-4) is preferably from 1% by mass to 50% by mass, more preferably from 1% by mass to 30% by mass, and particularly preferably from 1% by mass to 20% by mass.

[0180] When the acrylic resin (a-4) contains the structural unit having an unsaturated double bond in an amount within the above range, the acrylic resin can be introduced into the crosslinking reaction in the resist film and made uniform, thereby effectively improving the heat resistance and mechanical properties of the cured film.

[0181] The weight average molecular weight of the acrylic resin (a-4) is preferably 2000 to 50000, more preferably 3000 to 30000. Within the above range, a good balance between the film-forming ability of the photosensitive composition and the developability after exposure tends to be easily achieved.

[0182] The content of the alkali-soluble resin (A) is preferably 10% by mass or more and 65% by mass or less, and more preferably 15% by mass or more and 50% by mass or less, relative to the total mass of the solid content of the photosensitive composition. By falling within the above range, a photosensitive composition having excellent developability can be easily obtained.

[0183] <Photopolymerizable Monomer (B)>

[0184] As the photopolymerizable monomer (B), a compound having an ethylenically unsaturated double bond can be preferably used. Preferred examples of the compound having an ethylenically unsaturated double bond include monofunctional monomers and polyfunctional monomers.

[0185] Examples of the monofunctional monomer include (meth)acrylamide, hydroxymethyl (meth)acrylamide, methoxymethyl (meth)acrylamide, ethoxymethyl (meth)acrylamide, propoxymethyl (meth)acrylamide, butoxymethoxymethyl (meth)acrylamide, N-hydroxymethyl (meth)acrylamide, N-hydroxymethyl (meth)acrylamide, (meth)acrylic acid, fumaric acid, maleic acid, maleic anhydride, itaconic acid, itaconic anhydride, citraconic acid, citraconic anhydride, crotonic acid, 2-acrylamido-2-methylpropanesulfonic acid, tert-butylacrylamidesulfonic acid, methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, and (meth)acrylic acid. 2-Ethylhexyl acrylate, cyclohexyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 2-phenoxy-2-hydroxypropyl (meth)acrylate, 2-(meth)acryloyloxy-2-hydroxypropyl phthalate, glycerol mono(meth)acrylate, tetrahydrofurfuryl (meth)acrylate, N,N-dimethylaminoethyl (meth)acrylate, glycidyl (meth)acrylate, 2,2,2-trifluoroethyl (meth)acrylate, 2,2,3,3-tetrafluoropropyl (meth)acrylate, (meth)acrylic acid half esters of phthalic acid derivatives, etc. These monofunctional monomers can be used alone or in combination of two or more.

[0186] On the other hand, examples of the multifunctional monomer include 1,3-butanediol di(meth)acrylate, 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, 1,10-decanediol di(meth)acrylate, 1,12-dodecanediol di(meth)acrylate, ethoxylated hexanediol di(meth)acrylate, tricyclodecane dimethanol di(meth)acrylate, 2-hydroxy-3-(meth)acryloyloxypropyl (meth)acrylate, dipentaerythritol di(meth)acrylate, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, dipropylene glycol di(meth)acrylate, and tripropylene glycol di(meth)acrylate. ) acrylate, ethoxylated neopentyl glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, poly(ethylene glycol-propylene glycol) di(meth)acrylate, polytetramethylene glycol di(meth)acrylate, ethoxylated bisphenol A di(meth)acrylate, propoxylated bisphenol A di(meth)acrylate, propoxylated ethoxylated bisphenol A di(meth)acrylate, ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, butanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, trimethylolpropane alkyl tri(meth)acrylate, glycerol di(meth)acrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, pentaerythritol di(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, 2,2-bis(4-(meth)acryloyloxydiethoxyphenyl)propane, 2,2-bis(4-(meth)acryloyloxypolyethoxyphenyl)propane, 2-hydroxy-3-(meth)acryloyloxypropyl(meth)acrylate, ethylene glycol diglycidyl ether di(methacrylate), diethylene glycol diglycidyl ether Oleyl ether di(meth)acrylate, diglycidyl phthalate di(meth)acrylate, glycerol triacrylate, glycerol polyglycidyl ether poly(meth)acrylate, urethane (meth)acrylate (i.e., a reaction product of toluene diisocyanate, trimethyl-1,6-hexane diisocyanate, or 1,6-hexane diisocyanate and 2-hydroxyethyl (meth)acrylate), methylenebis(meth)acrylamide, (meth)acrylamide methylene ether, a condensation product of a polyol and N-methylol (meth)acrylamide, 1,3,5-triacryloylhexahydro-1,3,5-triazine (triacrylformal), 2,4,6-trioxohexahydro-1,3,5-triazine-1,3,5-triethanol triacrylate, and 2,4,6-trioxohexahydro-1,3,5-triazine-1,3,5-triethanol diacrylate, etc. These multifunctional monomers can be used alone or in combination of two or more.

[0187] Among these compounds with ethylenically unsaturated double bonds, from the perspective of obtaining a photosensitive composition that provides a cured product having excellent strength and adhesion to the substrate, polyfunctional monomers having more than two functions are preferred. Among these, polyfunctional monomers having more than three functions are particularly preferred. For example, pentaerythritol tetra(meth)acrylate (a tetrafunctional monomer), dipentaerythritol penta(meth)acrylate (a pentafunctional monomer), and dipentaerythritol hexa(meth)acrylate (a hexafunctional monomer) can be preferably used.

[0188] From the viewpoint of controlling the glass transition temperature (Tg), a monofunctional monomer or a bifunctional monomer may be used in combination with a trifunctional or higher polyfunctional monomer. Among these, 1,6-hexanediol di(meth)acrylate is preferred.

[0189] The content of the photopolymerizable monomer (B) in the photosensitive composition is preferably from 1% by mass to 50% by mass, more preferably from 5% by mass to 40% by mass, relative to the total mass of the solid components of the photosensitive composition. By falling within the above range, a well-balanced sensitivity, developability, and resolution tends to be easily achieved.

[0190] <Photopolymerization Initiator (C)>

[0191] The photopolymerization initiator (C) is not particularly limited, and a conventionally known photopolymerization initiator can be used.

[0192] Specific examples of the photopolymerization initiator (C) include 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenylpropane-1-one, 1-[4-(2-hydroxyethoxy)phenyl]-2-hydroxy-2-methyl-1-propane-1-one, 1-(4-isopropylphenyl)-2-hydroxy-2-methylpropane-1-one, 1-(4-dodecylphenyl)-2-hydroxy-2-methylpropane-1-one, 2,2-dimethoxy-1,2-diphenylethane-1-one, bis(4-dimethylamino)-1-one, and the like. phenyl) ketone, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butan-1-one, O-acetyl-1-[6-(2-methylbenzoyl)-9-ethyl-9H-carbazol-3-yl]ethanone oxime, (9-ethyl-6-nitro-9H-carbazol-3-yl)[4-(2-methoxy-1-methylethoxy)-2-methylphenyl]methanone O-acetyl oxime , 2-(Benzoyloxyimino)-1-[4-(phenylthio)phenyl]-1-octanone, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 4-benzoyl-4'-methyldimethyl sulfide, 4-dimethylaminobenzoic acid, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, butyl 4-dimethylaminobenzoate, 4-dimethylamino-2-ethylhexylbenzoic acid, 4-dimethylamino-2-isoamylbenzoic acid, benzyl-β-methoxyethyl acetal, benzyldimethyl ketal, 1-phenyl-1,2-propanedione-2-(O-ethoxycarbonyl)oxime, methyl o-benzoylbenzoate, 2,4-diethylthioxanthone, 2-chlorothioxanthone, 2,4-dimethylthioxanthone, 1-chloro-4-propoxythioxanthone, thioxanthene, 2-chlorothioxanthene, 2,4-diethylthioxanthene, 2-methylthioxanthene, 2-isopropylthioxanthene, 2-ethylanthraquinone, octamethylanthraquinone, 1,2-benzanthraquinone, 2,3-diphenylanthraquinone, azobisisobutyronitrile, benzoyl peroxide, cumene hydroperoxide (cumene hydroperoxide), 2-mercaptobenzimidazole, 2-mercaptobenzoxazole, 2-mercaptobenzothiazole, 2-(o-chlorophenyl)-4,5-bis(m-methoxyphenyl)-imidazolyl dimer, benzophenone, 2-chlorobenzophenone, 4,4'-bisdimethylaminobenzophenone, 4,4'-bisdiethylaminobenzophenone, 4,4'-dichlorobenzophenone, 3,3-dimethyl-4-methoxybenzophenone Benzophenone, benzil, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin n-butyl ether, benzoin isobutyl ether, benzoin butyl ether, acetophenone, 2,2-diethoxyacetophenone, p-dimethylacetophenone, p-dimethylaminoacetophenone, dichloroacetophenone, trichloroacetophenone, p-tert-butylacetophenone, p-dimethylaminoacetophenone, p-tert-butyltrichloroacetophenone, p-tert-butyldichloroacetophenone, α,α-Dichloro-4-phenoxyacetophenone, thioxanthone, 2-methylthioxanthone, 2-isopropylthioxanthone, dibenzosuberone, 4-dimethylaminobenzoic acid pentyl ester, 9-phenylacridine, 1,7-bis-(9-acridinyl)heptane, 1,5-bis-(9-acridinyl)pentane, 1,3-bis-(9-acridinyl)propane, p-methoxytriazine, 2,4,6-tris(trichloromethyl)-s-triazine, 2-methyl-4,6-bis(trichloromethyl)-s-triazine, 2-[2-(5-methylfuran-2-yl)vinyl]-4,6-bis(trichloromethyl)-s-triazine, 2-[2-(furan-2-yl)vinyl]-4,6-bis(trichloromethyl)-s-triazine, 2-[2-(4-diethylamino-2-methylphenyl)vinyl] phenyl]-4,6-bis(trichloromethyl)-s-triazine, 2-[2-(3,4-dimethoxyphenyl)vinyl]-4,6-bis(trichloromethyl)-s-triazine, 2-(4-methoxyphenyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(4-ethoxyphenyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(4-n-butoxyphenyl)-4,6-bis(trichloromethyl)-s-triazine, 2,4-bistrichloromethyl-6-(3-bromo-4-methoxy)phenyl-s-triazine, 2,4-bistrichloromethyl-6-(2-bromo-4-methoxy)phenyl-s-triazine, 2,4-bistrichloromethyl-6-(3-bromo-4-methoxy)phenylphenyl-s-triazine, 2,4-bistrichloromethyl-6-(2-bromo-4-methoxy)phenylphenyl-s-triazine, etc. These photopolymerization initiators can be used alone or in combination of two or more.

[0193] Among these, the use of oxime-based photopolymerization initiators is particularly preferred in terms of sensitivity. Among oxime-based photopolymerization initiators, particularly preferred examples include O-acetyl-1-[6-(2-methylbenzoyl)-9-ethyl-9H-carbazol-3-yl]ethanone oxime, 1-[9-ethyl-6-(pyrrol-2-ylcarbonyl)-9H-carbazol-3-yl]ethanone-1-(O-acetoxime), and 2-(benzoyloxyimino)-1-[4-(phenylthio)phenyl]-1-octanone.

[0194] As the photopolymerization initiator, an oxime compound represented by the following formula (c1) is also preferably used.

[0195] The compound is represented by the following formula (c1) and satisfies at least one of the following conditions (1) to (3).

[0196] [Chemical Formula 17]

[0197]

[0198] (In formula (c1), R 1 is a monovalent organic group, R2 is a hydrocarbon group which may have a substituent, or a heterocyclic group which may have a substituent, R 3 is a monovalent organic group, R 4 is a monovalent organic group, R 5 , and R 6 Each is independently a benzene ring which may have a substituent, or a naphthalene ring which may have a substituent, and m1, m2, and m3 are each 0 or 1.)

[0199] (1)R 1 Contains-OR 7 The group represented by R 7 It is a halogenated alkyl group.

[0200] (2) m2 is 1, R 4 Contains-OR 7 The group represented by R 7 It is a halogenated alkyl group.

[0201] (3)R 3 It is a branched alkyl group which may have a substituent.

[0202] The organic group possessed by the oxime compound represented by formula (c1) is preferably a group containing carbon atoms, more preferably a group containing 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. The number of carbon atoms in the carbon-containing group is not particularly limited, but is preferably 1 or more and 50 or less, more preferably 1 or more and 20 or less.

[0203] In formula (c1), R 5 and R 6 It is a benzene ring which may have a substituent, or a naphthalene ring which may have a substituent.

[0204] The compound shown in formula (c1) includes 3 The ring to which the nitrogen atom is bonded is fused with the benzene ring or the naphthalene ring by sharing any carbon-carbon bond in the benzene ring or the naphthalene ring.

[0205] Therefore, in formula (c1), including R 3 The ring of the nitrogen atom is composed of nitrogen atom, R 5 The two carbon atoms and the 6 The two carbon atoms in the ring serve as ring-constituting atoms to form a 5-membered ring.

[0206] That is, the compound represented by formula (c1) has a 3- to 5-ring fused ring as a central skeleton, wherein the fused ring is composed of R 5 and R 6 , and the above-mentioned 5-membered ring.

[0207] R 5 and / or R6 When it is a naphthalene ring, it contains 3 The condensation form of the above-mentioned 5-membered ring to which the nitrogen atom is bonded and the naphthalene ring is not particularly limited.

[0208] R 5 and R 6 When at least one of the rings is a naphthalene ring, R 5 and R 6 , and contains R 3 The condensed ring consisting of the above-mentioned 5-membered ring bonded to the nitrogen atom may be any of the following.

[0209] [Chemical Formula 18]

[0210]

[0211] As R 5 and R 6 When the benzene ring or naphthalene ring has a substituent, the type and number of the substituent are not particularly limited within the range not hindering the purpose of the present invention.

[0212] Preferred examples of the substituent include 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 acyloxy 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 halogen atom, and a cyano group.

[0213] As R 5 and R 6 When the benzene ring or naphthalene ring has a substituent, the number of the substituent is not limited within the range not hindering the purpose of the present invention, but is preferably 1 to 4. When there are multiple substituents, the multiple substituents may be the same or different.

[0214] R 5 When there is a substituent, R 5 The substituents may be 1 or R 3 bonded to form a ring.

[0215] In addition, R 6 When there is a substituent, R 6 The substituents may be 3 bonded to form a ring.

[0216] R 5 The substituents possessed are similar to R 1The ring formed by the bonding may be a hydrocarbon ring or a heterocyclic ring. The heteroatoms contained in the heterocyclic ring are not particularly limited. Preferred heteroatoms include N, O, and S.

[0217] R 5 and / or R 6 The substituents possessed are similar to R 3 The ring formed by bonding includes R 3 In addition to the bonded nitrogen atom, other heteroatoms may be included. The heteroatoms included in the heterocycle are not particularly limited. Preferred heteroatoms include N, O, and S.

[0218] R 5 The substituents or R 6 The substituents possessed by R 3 When the compounds are bonded to form a ring, the compounds represented by the formula (c1) are preferably compounds represented by the following formulas (c1-1-a) to (c1-1-h):

[0219] [Chemical Formula 19]

[0220]

[0221] (In formula (c1-1-a) ~ (c1-1-h), R 1 、R 2 、R 4 , m1, m2, and m3 are the same as those in formula (c1), R 8 is an alkyl group. ).

[0222] As R 8 The alkyl group of R may be linear or branched. 7 The number of carbon atoms in the alkyl group is not particularly limited, but is preferably 1 or more and 20 or less, more preferably 1 or more and 10 or less.

[0223] R 5 The substituents possessed are similar to R 1 When they are bonded to form a ring, in formula (c1), m1 is preferably 0. In this case, the compound represented by formula (c1) is preferably a compound represented by the following formulas (c1-1-i) to (c1-1-1):

[0224] [Chemical Formula 20]

[0225]

[0226] (In formula (c1-1-i) ~ (c1-1-l), R 2 、R 3 、R 4 , m2, and m3 are the same as those in formula (c1), R 8is an alkyl group having 1 to 20 carbon atoms. ).

[0227] As R 8 The alkyl group may be linear or branched.

[0228] Considering the R 5 and R 6 Based on the preferred combination of the above, the compound represented by formula (c1) is preferably a compound represented by the following formulas (c1-I) to (c1-IV):

[0229] [Chemical Formula 21]

[0230]

[0231] (In formulas (c1-I) to (c1-IV), R 1 、R 2 、R 3 、R 4 , m1, m2, and m3 are the same as those in formula (c1).

[0232] The compound represented by formula (c1-II) or formula (c1-III) is more preferred, and the compound represented by formula (c1-III) is particularly preferred.

[0233] As the compounds represented by the above-mentioned formulas (c1-I) to (c1-IV), preferred are compounds represented by the following formulas (c1-Ia) to (c1-IV-a), more preferred are compounds represented by formula (c1-II-a) or formula (c1-III-a), and particularly preferred are compounds represented by formula (c1-III-a).

[0234] [Chemical Formula 22]

[0235]

[0236] As the compounds represented by the above-mentioned formulas (c1-Ia) to (c1-IV-a), preferred are compounds represented by the following formulas (c1-Ib) to (c1-IV-b), more preferred are compounds represented by formula (c1-II-b) or formula (c1-III-b), and particularly preferred are compounds represented by formula (c1-III-b).

[0237] [Chemical Formula 23]

[0238]

[0239] About R 1Preferred examples of the monovalent organic group include an alkyl group, an alkoxy group, a cycloalkyl group, a cycloalkoxy group, a saturated aliphatic acyl group, an alkoxycarbonyl group, a saturated aliphatic acyloxy group, a phenyl group which may have a substituent, a phenoxy group which may have a substituent, a benzoyl group which may have a substituent, a phenoxycarbonyl group which may have a substituent, a benzoyloxy group which may have a substituent, a phenylalkyl group which may have a substituent, a naphthyloxy group which may have a substituent, a naphthyloxy group which may have a substituent, a naphthyloxycarbonyl group which may have a substituent, a naphthyloxyoxy group which may have a substituent, a naphthylalkyl group which may have a substituent, a heterocyclic group which may have a substituent, a heterocyclic carbonyl group which may have a substituent, an amino group substituted with one or two organic groups, a morpholin-1-yl group, and a piperazin-1-yl group.

[0240] R 1 When it is an alkyl group, the number of carbon atoms of the alkyl group is preferably 1 or more and 20 or less, more preferably 1 or more and 6 or less. 1 When it is an alkyl group, it may be a straight chain or a branched chain. 1 Specific examples of alkyl groups include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, sec-pentyl, tert-pentyl, n-hexyl, n-heptyl, n-octyl, isooctyl, sec-octyl, tert-octyl, n-nonyl, isononyl, n-decyl, and isodecyl. 1 In the case of an alkyl group, the alkyl group may contain an ether bond (-O-) in the carbon chain. Examples of alkyl groups having an ether bond in the carbon chain include methoxyethyl, ethoxyethyl, methoxyethoxyethyl, ethoxyethoxyethyl, propoxyethoxyethyl, and methoxypropyl.

[0241] R 1 When it is an alkoxy group, the number of carbon atoms of the alkoxy group is preferably 1 or more and 20 or less, more preferably 1 or more and 6 or less. 1 When it is an alkoxy group, it may be a straight chain or a branched chain. 1 Specific examples of alkoxy groups include methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy, tert-butoxy, n-pentoxy, isopentoxy, sec-pentoxy, tert-pentoxy, n-hexyloxy, n-heptyloxy, n-octyloxy, isooctyloxy, sec-octyloxy, tert-octyloxy, n-nonyloxy, isononyloxy, n-decyloxy, and isodecyloxy. 1 In the case of an alkoxy group, the alkoxy group may contain an ether bond (-O-) in the carbon chain. Examples of alkoxy groups having an ether bond in the carbon chain include methoxyethoxy, ethoxyethoxy, methoxyethoxyethoxy, ethoxyethoxyethoxy, propoxyethoxyethoxy, and methoxypropoxy.

[0242] R 1When it 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, more preferably 3 or more and 6 or less. 1 Specific examples of cycloalkyl include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, and cyclooctyl. 1 Specific examples of the cycloalkoxy group include cyclopropyloxy, cyclobutyloxy, cyclopentyloxy, cyclohexyloxy, cycloheptyloxy, and cyclooctyloxy.

[0243] R 1 When it is a saturated aliphatic acyl group or a saturated aliphatic acyloxy group, the number of carbon atoms in the saturated aliphatic acyl group or the saturated aliphatic acyloxy group is preferably 2 or more and 21 or less, more preferably 2 or more and 7 or less. 1 Specific examples of saturated aliphatic acyl groups include acetyl, propionyl, n-butyryl, 2-methylpropionyl, n-pentanoyl, 2,2-dimethylpropionyl, n-hexanoyl, n-heptanoyl, n-octanoyl, n-nonanoyl, n-decanoyl, n-undecanoyl, n-dodecanoyl, n-tridecanoyl, n-tetradecanoyl, n-pentadecanoyl, and n-hexadecanoyl. 1 Specific examples of the saturated aliphatic acyloxy group include an acetyloxy group, a propionyloxy group, an n-butyryloxy group, a 2-methylpropionyloxy group, an n-pentanoyloxy group, a 2,2-dimethylpropionyloxy group, an n-hexanoyloxy group, an n-heptanoyloxy group, an n-octanoyloxy group, an n-nonanoyloxy group, an n-decanoyloxy group, an n-undecanoyloxy group, an n-dodecanoyloxy group, an n-tridecanoyloxy group, an n-tetradecanoyloxy group, an n-pentadecanoyloxy group, and an n-hexadecanoyloxy group.

[0244] R 1 In the case of an alkoxycarbonyl group, the number of carbon atoms in the alkoxycarbonyl group is preferably 2 or more and 20 or less, more preferably 2 or more and 7 or less. 1 Specific examples of the alkoxycarbonyl group include methoxycarbonyl, ethoxycarbonyl, n-propyloxycarbonyl, isopropyloxycarbonyl, n-butyloxycarbonyl, isobutyloxycarbonyl, sec-butyloxycarbonyl, tert-butyloxycarbonyl, n-pentyloxycarbonyl, isopentyloxycarbonyl, sec-pentyloxycarbonyl, tert-pentyloxycarbonyl, n-hexyloxycarbonyl, n-heptyloxycarbonyl, n-octyloxycarbonyl, isooctyloxycarbonyl, sec-octyloxycarbonyl, tert-octyloxycarbonyl, n-nonyloxycarbonyl, isononyloxycarbonyl, n-decyloxycarbonyl, and isodecyloxycarbonyl.

[0245] R 1 When it is a phenylalkyl group, the number of carbon atoms of the phenylalkyl group is preferably 7 or more and 20 or less, more preferably 7 or more and 10 or less. 1In the case of a naphthylalkyl group, the number of carbon atoms of the naphthylalkyl group is preferably 11 or more and 20 or less, more preferably 11 or more and 14 or less. 1 Specific examples of phenylalkyl include benzyl, 2-phenylethyl, 3-phenylpropyl, and 4-phenylbutyl. 1 Specific examples of naphthylalkyl include α-naphthylmethyl, β-naphthylmethyl, 2-(α-naphthyl)ethyl, and 2-(β-naphthyl)ethyl. 1 When R is phenylalkyl or naphthylalkyl, 1 The phenyl group or the naphthyl group may further have a substituent.

[0246] R 1 When it is a heterocyclic group, the heterocyclic group is a 5-membered or 6-membered monocyclic ring containing one or more N, S, or O, or a heterocyclic group formed by condensing the monocyclic rings with each other or condensing the monocyclic ring with a benzene ring. When the heterocyclic group is a condensed ring, the number of rings is 3 or less. The heterocyclic group can be an aromatic group (heteroaryl) or a non-aromatic group. As the heterocyclic ring constituting the heterocyclic group, furan, thiophene, pyrrole, oxazole, isoxazole, thiazole, thiadiazole, isothiazole, imidazole, pyrazole, triazole, pyridine, pyrazine, pyrimidine, pyridazine, benzofuran, benzothiophene, indole, isoindole, indoleazine, benzimidazole, benzotriazole, benzoxazole, benzothiazole, carbazole, purine, quinoline, isoquinoline, quinazoline, phthalazine, cinnoline, and quinoxaline etc. can be mentioned. R 1 In the case of a heterocyclic group, the heterocyclic group may further have a substituent.

[0247] R 1 When it is a heterocyclic carbonyl group, the heterocyclic group contained in the heterocyclic carbonyl group and R 1 The same applies to the case of a heterocyclic group.

[0248] R 1 When it 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 naphthoyl group which may have a substituent, a naphthylalkyl group which may have 11 to 20 carbon atoms, and a heterocyclic group. Specific examples of these preferred organic groups are the same as those in R 1Specific examples of the amino group substituted with one or two organic groups include methylamino, ethylamino, diethylamino, n-propylamino, di-n-propylamino, isopropylamino, n-butylamino, di-n-butylamino, n-pentylamino, n-hexylamino, n-heptylamino, n-octylamino, n-nonylamino, n-decylamino, phenylamino, naphthylamino, acetylamino, propionylamino, n-butyrylamino, n-pentanoylamino, n-hexanoylamino, n-heptanoylamino, n-octanoylamino, n-decanoylamino, benzoylamino, α-naphthoylamino, and β-naphthoylamino.

[0249] As R 1 When the phenyl, naphthyl, and heterocyclic group contained in further has a substituent, the substituent includes 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 acyloxy 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 halogen group, a nitro group, and a cyano group. R 1 When the phenyl group, naphthyl group, and heterocyclic group contained in further have a substituent, the number of the substituent is not limited within the range not hindering the purpose of the present invention, but is preferably 1 or more and 4 or less. 1 When the phenyl group, naphthyl group, and heterocyclic group included in have a plurality of substituents, the plurality of substituents may be the same or different.

[0250] As R 1 Also preferred are cycloalkylalkyl, phenoxyalkyl which may have a substituent on the aromatic ring, and phenylthioalkyl which may have a substituent on the aromatic ring. The substituents that phenoxyalkyl and phenylthioalkyl may have are the same as those in R 1 The substituents that the phenyl group contained in may have are similar.

[0251] In a monovalent organic group, as R 1, preferably an alkyl group, a cycloalkyl group, a phenyl group which may have a substituent, a cycloalkylalkyl group, and a phenylthioalkyl group which may have a substituent on the aromatic ring. As the alkyl group, an alkyl group having 1 or more and 20 or less carbon atoms is preferred, an alkyl group having 1 or more and 8 or less carbon atoms is more preferred, an alkyl group having 1 or more and 4 or less 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 or more and 10 or less, more preferably 5 or more and 8 or less, and particularly preferably 5 or 6. The number of carbon atoms of the alkylene group contained in the cycloalkylalkyl group is preferably 1 or more and 8 or less, more preferably 1 or more and 4 or less, and particularly preferably 2. Among the cycloalkylalkyl groups, cyclopentylethyl is preferred. The number of carbon atoms of the alkylene group contained in the phenylthioalkyl group which may have a substituent on the aromatic ring is preferably 1 or more and 8 or less, more preferably 1 or more and 4 or less, and particularly preferably 2. Among the phenylthioalkyl groups which may have a substituent on the aromatic ring, 2-(4-chlorophenylthio)ethyl is preferred.

[0252] As described above, the compound represented by the formula (c1) needs to satisfy at least one of the following conditions (1) to (3):

[0253] (1) R 1 contains a group represented by -OR 7 and R 7 is a haloalkyl group.

[0254] (2) m2 is 1, R 4 contains a group represented by -OR 7 and R 7 is a haloalkyl group.

[0255] (3) R 3 is a branched alkyl group which may have a substituent.

[0256] Therefore, R 1 is preferably substituted by a substituent represented by -OR 7 . R 7 is a haloalkyl group. When R 1 is substituted by a group represented by -OR 7 , the number of groups represented by -OR 1 contained in R 7 is not particularly limited. When R 1 is substituted by a group represented by -OR 7 , the number of groups represented by -OR 1 contained in R 7 is preferably 1 or 2, and more preferably 1.

[0257] In addition, the -OR 7The number of groups represented is also preferably 1 or 2, more preferably 1.

[0258] Examples of the halogen atom contained in the haloalkyl group include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. The haloalkyl group may contain one type of halogen atom or a combination of two or more types of halogen atoms.

[0259] The number of halogen atoms in the haloalkyl group is not particularly limited within the range not hindering the purpose of the present invention. The number of halogen atoms in the haloalkyl group is preferably 1 or more, more preferably 2 or more, and particularly preferably 3 or more. From the perspective of good compatibility of the compound represented by formula (c1) with other components in the photosensitive composition, the upper limit of the number of halogen atoms in the haloalkyl group is preferably 7 or less, more preferably 6 or less, and particularly preferably 5 or less.

[0260] The number of halogen atoms contained in the compound represented by formula (c1) is also preferably 1 or more, more preferably 2 or more, particularly preferably 3 or more, and preferably 7 or less, more preferably 6 or less, particularly preferably 5 or less.

[0261] The number of carbon atoms in the haloalkyl group is not particularly limited within the range not hindering the purpose of the present invention. The number of carbon atoms in the haloalkyl group is preferably 1 or more, more preferably 2 or more, and particularly preferably 3 or more. The upper limit of the number of carbon atoms in the haloalkyl group is preferably 10 or less, more preferably 7 or less, and particularly preferably 5 or less.

[0262] As haloalkyl, fluoroalkyl is particularly preferred. As preferred specific examples of haloalkyl, 2,2,3,3-tetrafluoropropyl, 2,2,2-trifluoroethyl, 3,3,3-trifluoropropyl, 2,2,3,3,3-pentafluoropropyl, and 2,2,3,3,4,4,5,5-octafluoropentyl etc. can be mentioned. Among these, from the aspect of easily manufacturing the compound represented by formula (c1), 2,2,3,3-tetrafluoropropyl is preferred.

[0263] About R 1 The group substituted by a haloalkyl group is preferably a phenyl group substituted by 1 or 2 haloalkyl groups. 1 The group substituted by a haloalkyl group is preferably a group represented by the following formula (c1-01):

[0264] [Chemical Formula 24]

[0265]

[0266] (In formula (c1-01), R 7 As mentioned above, R 9 For R 1The phenyl group may have a substituent, m4 is 1 or 2, and m4+m5 is an integer of 1 to 5. ).

[0267] As R 9 , preferably an alkyl group having 1 to 6 carbon atoms, and an alkoxy group having 1 to 6 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms, further preferably a methyl group and an ethyl group, and particularly preferably a methyl group.

[0268] m5 is preferably 1.

[0269] In addition, R 1 It may also be a group represented by the following formula (c1-02):

[0270] [Chemical Formula 25]

[0271]

[0272] (In formula (c1-02), R 1 、R 2 、R 3 、R 4 、R 5 、R 6 , m1, m2, and m3 are the same as those in formula (c1), R 10 is a divalent organic group. ).

[0273] As R 10 The divalent organic group as R is not particularly limited within the scope not hindering the purpose of the present invention. 10 Preferred examples of the divalent organic group include alkane diyl groups having 1 to 10 carbon atoms (for example, methylene, ethane-1,2-diyl, propane-1,3-diyl, butane-1,4-diyl, etc.), and arylene groups (p-phenylene, m-phenylene, o-phenylene, 1,1'-biphenyl-4,4'-diyl, etc.).

[0274] As R 1 In the case of a group represented by the above formula (c1-02), specific examples of the compound represented by formula (c1) include compounds of the following formulas.

[0275] [Chemical Formula 26]

[0276]

[0277] R described above 1 Among them, groups represented by the following formula are preferred.

[0278] [Chemical Formula 27]

[0279]

[0280] In formula (c1), R 2 is a hydrocarbon group which may have a substituent, or a heterocyclic group which may have a substituent. As the hydrocarbon group which may have a substituent, an alkyl group having 1 or more and 11 or less carbon atoms which may have a substituent, or an aryl group which may have a substituent, is preferred. As the aryl group, phenyl and naphthyl are preferred, and phenyl is preferred. 2 When it is an alkyl group, the substituent group that can be possessed is preferably phenyl, naphthyl, etc. 2 Preferred examples of the substituent that the aryl group may have include an alkyl group having 1 to 5 carbon atoms, an alkoxy group, and a halogen atom.

[0281] R 2 When it is a heterocyclic group, the heterocyclic group may be an aliphatic heterocyclic group or an aromatic heterocyclic group. 2 When it is a heterocyclic group, the heterocyclic group is a 5-membered or 6-membered monocyclic ring containing one or more N, S, or O, or a heterocyclic group formed by condensing the monocyclic rings with each other or condensing the monocyclic ring with a benzene ring. When the heterocyclic group is a condensed ring, the number of rings is 3 or less. As the heterocyclic ring constituting the heterocyclic group, 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, phthalazine, cinnoline, quinoxaline, piperidine, piperazine, morpholine, piperidine, tetrahydropyran, and tetrahydrofuran can be mentioned.

[0282] R 2 In the case of 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.

[0283] As R 2 , preferably methyl, phenyl, and thienyl, more preferably methyl.

[0284] In formula (c1), R 3 Is a monovalent organic group. 3 It can be selected from various organic groups within the range that does not hinder the purpose of the present invention. 3Preferred examples 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 benzoyl 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 naphthyloxycarbonyl 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.

[0285] R 3 Among them, an alkyl group having 1 or more and 20 or less carbon atoms is preferred. The alkyl group may be linear or branched. From the perspective of good solubility of the compound represented by formula (c1) in the photosensitive composition, R 3 The number of carbon atoms of the alkyl group is preferably 2 or more, more preferably 5 or more, and particularly preferably 7 or more. In addition, from the perspective of good compatibility between the compound represented by formula (c1) and other components in the photosensitive composition, R 3 The number of carbon atoms in the alkyl group is preferably 15 or less, more preferably 10 or less.

[0286] R 3 When the group 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 benzoyl group, a benzoyloxy 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. Preferred examples of the heterocyclic group as a substituent are the same as those as R. 2 The same applies to preferred examples of the heterocyclic group.

[0287] As mentioned above, the compound represented by formula (c1) needs to satisfy at least one of the following conditions (1) to (3):

[0288] (1)R 1 Contains-OR 7 The group represented by R 7 It is a halogenated alkyl group.

[0289] (2) m2 is 1, R 4 Contains-OR 7 The group represented by R 7 It is a halogenated alkyl group.

[0290] (3)R 3 It is a branched alkyl group which may have a substituent.

[0291] Therefore, R 3 A branched alkyl group which may have a substituent is preferred.

[0292] In addition, as R 3 , which may be a group represented by the following formula (c1-03):

[0293] [Chemical Formula 28]

[0294]

[0295] (In formula (c1-03), R 1 、R 2 、R 4 、R 5 、R 6 , m1, m2, and m3 are the same as those in formula (c1), R 11 is a divalent organic group.)

[0296] As R 11 The divalent organic group as R is not particularly limited within the scope not hindering the purpose of the present invention. 11 Preferred examples of the divalent organic group include alkane diyl groups having 1 to 10 carbon atoms (for example, methylene, ethane-1,2-diyl, propane-1,3-diyl, butane-1,4-diyl, pentane-1,5-diyl, hexane-1,6-diyl, heptane-1,7-diyl, octane-1,8-diyl, etc.), and arylene groups (p-phenylene, m-phenylene, o-phenylene, 1,1'-biphenyl-4,4'-diyl, etc.).

[0297] In addition, regarding the 11 The following divalent organic groups are also preferred. 12 It is an alkylene group having 1 to 20 carbon atoms. 12 The alkylene group is preferably a methylene group, an ethane-1,2-diyl group, a propane-1,3-diyl group, a butane-1,4-diyl group, a pentane-1,5-diyl group, a hexane-1,6-diyl group, a heptane-1,7-diyl group, or an octane-1,8-diyl group.

[0298] [Chemical Formula 29]

[0299]

[0300] As R 3 In the case of a group represented by the above formula (c1-03), specific examples of the compound represented by formula (c1) include compounds of the following formulas.

[0301] [Chemical formula 30]

[0302]

[0303] As described above, R 3 Preferred specific examples include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, neopentyl, pentane-3-yl, sec-pentyl, tert-pentyl, n-hexyl, n-heptyl, n-octyl, and 2-ethylhexyl.

[0304] As mentioned above, as R 3 , preferably a branched alkyl group, and therefore among the above-mentioned alkyl groups, preferably isopropyl, isobutyl, sec-butyl, tert-butyl, isopentyl, neopentyl, pentane-3-yl, sec-pentyl, tert-pentyl, and 2-ethylhexyl.

[0305] In addition, from the viewpoint of good solubility of the compound represented by formula (c1) in the photosensitive composition, n-octyl group and 2-ethylhexyl group are preferred, and 2-ethylhexyl group is more preferred.

[0306] R in formula (c1) 4 Is a monovalent organic group. 4 The monovalent organic group of R 1 The same group as the monovalent organic group.

[0307] R 4 R 4 -(CO) m3 - is bonded to the main skeleton of the compound represented by formula (c1). 4 -(CO) m3 Preferred specific examples of the group represented by - include groups represented by the following formula: In the following formula, m3 is the same as in formula (c1) and is 1 or 0.

[0308] [Chemical Formula 31]

[0309]

[0310] [Chemical Formula 32]

[0311]

[0312] [Chemical Formula 33]

[0313]

[0314] The above R 4 -(CO) m3 Among the preferred examples of the group represented by -, 1,3,5-trimethylbenzoyl is particularly preferred.

[0315] As mentioned above, the compound represented by formula (c1) needs to satisfy at least one of the following conditions (1) to (3):

[0316] (1)R 1 Contains-OR 7 The group represented by R 7 It is a halogenated alkyl group.

[0317] (2) m2 is 1, R 4 Contains-OR 7 The group represented by R 7 It is a halogenated alkyl group.

[0318] (3)R 3 It is a branched alkyl group which may have a substituent.

[0319] Therefore, R 4 Preferred by -OR 7 The substituent represented by R 7 is a halogenated alkyl group. 7 , as mentioned above.

[0320] About R 4 The group substituted by a haloalkyl group is preferably a phenyl group substituted by 1 or 2 haloalkyl groups. 1 Similarly, the group substituted with a haloalkyl group is preferably a group represented by the aforementioned formula (c1-01).

[0321] In addition, as R 4 , is also preferably a group represented by the following formula (c1-04):

[0322] [Chemical Formula 34]

[0323]

[0324] (In formula (c1-04), R 1 、R 3 、R 5 、R 6 , m1, m2, and m3 are the same as those in formula (c1), R 13 is a divalent organic group. ).

[0325] As R 13 The divalent organic group as R is not particularly limited within the scope not hindering the purpose of the present invention. 13Preferred examples of the divalent organic group include alkane diyl groups having 1 to 10 carbon atoms (for example, methylene, ethane-1,2-diyl, propane-1,3-diyl, butane-1,4-diyl, pentane-1,5-diyl, hexane-1,6-diyl, heptane-1,7-diyl, octane-1,8-diyl, etc.), and arylene groups (p-phenylene, m-phenylene, o-phenylene, 1,1'-biphenyl-4,4'-diyl, etc.).

[0326] In addition, regarding the 13 The following divalent organic groups are also preferred. 13 is an alkylene group having 1 to 20 carbon atoms which may be substituted with a halogen atom. 14 The alkylene group is preferably a methylene group, an ethane-1,2-diyl group, a propane-1,3-diyl group, a butane-1,4-diyl group, a pentane-1,5-diyl group, a hexane-1,6-diyl group, a heptane-1,7-diyl group, or an octane-1,8-diyl group.

[0327] In addition, groups in which all hydrogen atoms in these alkylene groups are replaced by halogen atoms, especially fluorine atoms, are also preferred as R. 14 .

[0328] [Chemical Formula 35]

[0329]

[0330] In formula (c1), m1, m2, and m3 are all 0 or 1. m1 is preferably 0. m2 is preferably 1, and m3 is preferably 1.

[0331] Preferred specific examples of the compound represented by the formula (c1) described above include the following compounds.

[0332] [Chemical Formula 36]

[0333]

[0334] [Chemical Formula 37]

[0335]

[0336] [Chemical Formula 38]

[0337]

[0338] [Chemical Formula 39]

[0339]

[0340] [Chemical Formula 40]

[0341]

[0342] [Chemical Formula 41]

[0343]

[0344] [Chemical Formula 42]

[0345]

[0346] As mentioned above, the compound represented by formula (c1) needs to satisfy at least one of the following conditions (1) to (3):

[0347] (1)R 1 Contains-OR 7 The group represented by R 7 It is a halogenated alkyl group.

[0348] (2) m2 is 1, R 4 Contains-OR 7 The group represented by R 7 It is a halogenated alkyl group.

[0349] (3)R 3 It is a branched alkyl group which may have a substituent.

[0350] If this condition is satisfied, two or more different compounds may be mixed and used as the photopolymerization initiator (C).

[0351] As the oxime ester compound, a compound represented by the following formula (c2) is also preferred.

[0352] [Chemical Formula 43]

[0353]

[0354] (In formula (c2), CR is a group represented by the following formula (c2a) or the following formula (c2b):

[0355] [Chemical Formula 44]

[0356]

[0357] R c1 is a hydrogen atom, a nitro group or a monovalent organic group, R c2 and R c3 Each of them is 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, and R c2 With R c3 Can bond with each other to form a ring, R c4 is a monovalent organic group, R c5is 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, n1 is an integer of 0 to 4, and n2 is 0 or 1.).

[0358] The organic group in the oxime ester compound represented by formula (c2) is preferably a group containing carbon atoms, more preferably a group containing 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. The number of carbon atoms in the carbon-containing group is not particularly limited, but is preferably 1 or more and 50 or less, more preferably 1 or more and 20 or less.

[0359] From the synthesis and availability of the oxime ester compound represented by formula (c2), it is easy to c2 and R c3 In view of adjusting the properties of the oxime ester compound by selecting , CR in formula (c2) is preferably a group represented by formula (c2a).

[0360] In the group represented by formula (c2a) or formula (c2b) as CR in formula (c2), R c1 is a hydrogen atom, a nitro group or a monovalent organic group. c1 The fused ring in formula (c2a) or formula (c2b) is bonded to the following 6-membered aromatic ring, which is different from -(CO) n2 - is an aromatic ring bonded to a group represented by c1 The compound represented by formula (c2) has one or more R c1 In the case of the compound represented by formula (c2), it is preferred that one or more R c1 One of them is bonded to the position indicated by * in the structures represented by the following formula (c2a-1) and formula (c2b-1):

[0361] [Chemical Formula 45]

[0362]

[0363] R c1 In the case of multiple R c1 Can be the same or different.

[0364] R c1 When it is an organic group, R c1 There are no particular restrictions within the scope of not hindering the purpose of the present invention, and it can be appropriately selected from various organic groups. c1Preferred examples of the organic group include an alkyl group, an alkoxy group, a cycloalkyl group, a cycloalkoxy group, a saturated aliphatic acyl group, a saturated aliphatic acyloxy group, an alkoxycarbonyl group, a phenyl group which may have a substituent, a phenoxy group which may have a substituent, a benzoyl group which may have a substituent, a phenoxycarbonyl group which may have a substituent, a benzoyloxy group which may have a substituent, a phenylalkyl group which may have a substituent, a naphthyloxy group which may have a substituent, a naphthyloxy group which may have a substituent, a naphthyloxycarbonyl group which may have a substituent, a naphthyloxyoxy group which may have a substituent, a naphthylalkyl group which may have a substituent, a heterocyclic group which may have a substituent, a heterocyclic carbonyl group which may have a substituent, an amino group substituted with one or two organic groups, a morpholin-1-yl group, and a piperazin-1-yl group.

[0365] R c1 When it is an alkyl group, the number of carbon atoms of the alkyl group is preferably 1 or more and 20 or less, more preferably 1 or more and 6 or less. c1 When it is an alkyl group, it may be a straight chain or a branched chain. c1 Specific examples of alkyl groups include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, sec-pentyl, tert-pentyl, n-hexyl, n-heptyl, n-octyl, isooctyl, sec-octyl, tert-octyl, n-nonyl, isononyl, n-decyl, and isodecyl. c1 In the case of an alkyl group, the alkyl group may contain an ether bond (-O-) in the carbon chain. Examples of alkyl groups having an ether bond in the carbon chain include methoxyethyl, ethoxyethyl, methoxyethoxyethyl, ethoxyethoxyethyl, propoxyethoxyethyl, and methoxypropyl.

[0366] R c1 When it is an alkoxy group, the number of carbon atoms of the alkoxy group is preferably 1 or more and 20 or less, more preferably 1 or more and 6 or less. c1 When it is an alkoxy group, it may be a straight chain or a branched chain. c1 Specific examples of alkoxy groups include methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy, tert-butoxy, n-pentoxy, isopentoxy, sec-pentoxy, tert-pentoxy, n-hexyloxy, n-heptyloxy, n-octyloxy, isooctyloxy, sec-octyloxy, tert-octyloxy, n-nonyloxy, isononyloxy, n-decyloxy, and isodecyloxy. c1 In the case of an alkoxy group, the alkoxy group may contain an ether bond (-O-) in the carbon chain. Examples of alkoxy groups having an ether bond in the carbon chain include methoxyethoxy, ethoxyethoxy, methoxyethoxyethoxy, ethoxyethoxyethoxy, propoxyethoxyethoxy, and methoxypropoxy.

[0367] R c1When it 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, more preferably 3 or more and 6 or less. c1 Specific examples of cycloalkyl include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, and cyclooctyl. c1 Specific examples of the cycloalkoxy group include cyclopropyloxy, cyclobutyloxy, cyclopentyloxy, cyclohexyloxy, cycloheptyloxy, and cyclooctyloxy.

[0368] R c1 When it is a saturated aliphatic acyl group or a saturated aliphatic acyloxy group, the number of carbon atoms in the saturated aliphatic acyl group or the saturated aliphatic acyloxy group is preferably 2 or more and 21 or less, more preferably 2 or more and 7 or less. c1 Specific examples of saturated aliphatic acyl groups include acetyl, propionyl, n-butyryl, 2-methylpropionyl, n-pentanoyl, 2,2-dimethylpropionyl, n-hexanoyl, n-heptanoyl, n-octanoyl, n-nonanoyl, n-decanoyl, n-undecanoyl, n-dodecanoyl, n-tridecanoyl, n-tetradecanoyl, n-pentadecanoyl, and n-hexadecanoyl. c1 Specific examples of the saturated aliphatic acyloxy group include an acetyloxy group, a propionyloxy group, an n-butyryloxy group, a 2-methylpropionyloxy group, an n-pentanoyloxy group, a 2,2-dimethylpropionyloxy group, an n-hexanoyloxy group, an n-heptanoyloxy group, an n-octanoyloxy group, an n-nonanoyloxy group, an n-decanoyloxy group, an n-undecanoyloxy group, an n-dodecanoyloxy group, an n-tridecanoyloxy group, an n-tetradecanoyloxy group, an n-pentadecanoyloxy group, and an n-hexadecanoyloxy group.

[0369] R c1 In the case of an alkoxycarbonyl group, the number of carbon atoms in the alkoxycarbonyl group is preferably 2 or more and 20 or less, more preferably 2 or more and 7 or less. c1 Specific examples of the alkoxycarbonyl group include methoxycarbonyl, ethoxycarbonyl, n-propyloxycarbonyl, isopropyloxycarbonyl, n-butyloxycarbonyl, isobutyloxycarbonyl, sec-butyloxycarbonyl, tert-butyloxycarbonyl, n-pentyloxycarbonyl, isopentyloxycarbonyl, sec-pentyloxycarbonyl, tert-pentyloxycarbonyl, n-hexyloxycarbonyl, n-heptyloxycarbonyl, n-octyloxycarbonyl, isooctyloxycarbonyl, sec-octyloxycarbonyl, tert-octyloxycarbonyl, n-nonyloxycarbonyl, isononyloxycarbonyl, n-decyloxycarbonyl, and isodecyloxycarbonyl.

[0370] R c1 When it is a phenylalkyl group, the number of carbon atoms of the phenylalkyl group is preferably 7 or more and 20 or less, more preferably 7 or more and 10 or less. c1In the case of a naphthylalkyl group, the number of carbon atoms of the naphthylalkyl group is preferably 11 or more and 20 or less, more preferably 11 or more and 14 or less. c1 Specific examples of phenylalkyl include benzyl, 2-phenylethyl, 3-phenylpropyl, and 4-phenylbutyl. c1 Specific examples of naphthylalkyl include α-naphthylmethyl, β-naphthylmethyl, 2-(α-naphthyl)ethyl, and 2-(β-naphthyl)ethyl. c1 When it is phenylalkyl or naphthylalkyl, R c1 The phenyl group or the naphthyl group may further have a substituent.

[0371] R c1 When the heterocyclic group is a 5- or 6-membered monocyclic ring containing one or more N, S, or O atoms, or a fused monocyclic ring or a fused monocyclic ring with a benzene ring. When the heterocyclic group is a fused ring, the number of monocyclic rings constituting the fused ring is 3 or less. The heterocyclic group may be an aromatic group (heteroaryl) or a non-aromatic group. 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, phthalazine, cinnoline, quinoxaline, piperidine, piperazine, morpholine, piperidine, tetrahydropyran, and tetrahydrofuran. c1 In the case of a heterocyclic group, the heterocyclic group may further have a substituent.

[0372] R c1 When it is a heterocyclic carbonyl group, the heterocyclic group contained in the heterocyclic carbonyl group and R c1 The same applies to the case of a heterocyclic group.

[0373] R c1 In the case of 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 naphthoyl group which may have a substituent, a naphthylalkyl group which may have 11 to 20 carbon atoms, and a heterocyclic group. Specific examples of these preferred organic groups are the same as those in R c1Specific examples of the amino group substituted with one or two organic groups include methylamino, ethylamino, diethylamino, n-propylamino, di-n-propylamino, isopropylamino, n-butylamino, di-n-butylamino, n-pentylamino, n-hexylamino, n-heptylamino, n-octylamino, n-nonylamino, n-decylamino, phenylamino, naphthylamino, acetylamino, propionylamino, n-butyrylamino, n-pentanoylamino, n-hexanoylamino, n-heptanoylamino, n-octanoylamino, n-decanoylamino, benzoylamino, α-naphthoylamino, and β-naphthoylamino.

[0374] As R c1 When the phenyl, naphthyl, and heterocyclic group contained in further has a substituent, the substituent includes 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 acyloxy 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 halogen group, a nitro group, and a cyano group. R c1 When the phenyl group, naphthyl group, and heterocyclic group contained in further have a substituent, the number of the substituent is not limited within the range not hindering the purpose of the present invention, but is preferably 1 or more and 4 or less. c1 When the phenyl group, naphthyl group, and heterocyclic group included in have a plurality of substituents, the plurality of substituents may be the same or different.

[0375] In the groups described above, R c1 , is nitro, or R c6 When the group is represented by -CO-, the sensitivity tends to be improved, which is preferred. c6 There are no particular restrictions within the scope of not hindering the purpose of the present invention, and the organic group can be selected from various organic groups. c6 Examples of the group include an alkyl group having 1 to 20 carbon atoms, a phenyl group which may have a substituent, a naphthyl group which may have a substituent, and a heterocyclic group which may have a substituent. c6 , particularly preferably 2-methylphenyl, thiophen-2-yl, and α-naphthyl.

[0376] In formula (c2a), R c2 and R c3 Each is 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. c2 With R c3 Can be bonded to each other to form a ring.c2 and R c3 , preferably a chain alkyl group which may have a substituent. c2 and R c3 In the case of a chain alkyl group which may have a substituent, the chain alkyl group may be a linear alkyl group or a branched alkyl group.

[0377] R c2 and R c3 In the case of an unsubstituted chain alkyl group, the number of carbon atoms in the chain alkyl group is preferably 1 or more and 20 or less, more preferably 1 or more and 10 or less, and particularly preferably 1 or more and 6 or less. c2 and R c3 Specific examples of chain alkyl groups include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, sec-pentyl, tert-pentyl, n-hexyl, n-heptyl, n-octyl, isooctyl, sec-octyl, tert-octyl, n-nonyl, isononyl, n-decyl, and isodecyl. c2 and R c3 In the case of an alkyl group, the alkyl group may contain an ether bond (-O-) in the carbon chain. Examples of alkyl groups having an ether bond in the carbon chain include methoxyethyl, ethoxyethyl, methoxyethoxyethyl, ethoxyethoxyethyl, propoxyethoxyethyl, and methoxypropyl.

[0378] R c2 and R c3 In the case of a chain alkyl group 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 of 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 straight-chain.

[0379] The substituents that the alkyl group may have are not particularly limited within the scope that does not hinder the purpose of the present invention. Preferred examples of substituents include cyano groups, halogen atoms, cyclic organic groups, and alkoxycarbonyl groups. Examples of halogen atoms include fluorine atoms, chlorine atoms, bromine atoms, and iodine atoms. Among these, fluorine atoms, chlorine atoms, and bromine atoms are preferred. Examples of cyclic organic groups include cycloalkyl groups, aromatic hydrocarbon groups, and heterocyclic groups. Specific examples of cycloalkyl groups include R c1 The preferred examples of the case of cycloalkyl are the same. Specific examples of aromatic hydrocarbon groups include phenyl, naphthyl, biphenyl, anthracenyl, and phenanthrenyl. Specific examples of heterocyclic groups include R c1 The same is true for the case of a heterocyclic group. c1In the case of 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.

[0380] When the chain alkyl group has a substituent, the number of the substituents is not particularly limited. The preferred number of substituents varies depending on the number of carbon atoms in the chain alkyl group. The number of substituents is typically 1 or more and 20 or less, preferably 1 or more and 10 or less, and more preferably 1 or more and 6 or less.

[0381] R c2 and R c3 In the case of an unsubstituted chain alkoxy group, the number of carbon atoms in the chain alkoxy group is preferably 1 or more and 20 or less, more preferably 1 or more and 10 or less, and particularly preferably 1 or more and 6 or less. c2 and R c3 Specific examples of chain alkoxy groups include methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy, tert-butoxy, n-pentoxy, isopentoxy, sec-pentoxy, tert-pentoxy, n-hexyloxy, n-heptyloxy, n-octyloxy, isooctyloxy, sec-octyloxy, tert-octyloxy, n-nonyloxy, isononyloxy, n-decyloxy, and isodecyloxy. c2 and R c3 In the case of an alkoxy group, the alkoxy group may contain an ether bond (-O-) in the carbon chain. Examples of alkoxy groups having an ether bond in the carbon chain include methoxyethoxy, ethoxyethoxy, methoxyethoxyethoxy, ethoxyethoxyethoxy, propoxyethoxyethoxy, and methoxypropoxy.

[0382] R c2 and R c3 When it is a chain alkoxy group having a substituent, the substituent that the alkoxy group may have is the same as R c2 and R c3 The same applies to the case of a chain alkyl group.

[0383] R c2 and R c3 When it is a cyclic organic group, the cyclic organic group may be an alicyclic group or an aromatic group. Examples of the cyclic organic group include aliphatic cyclic hydrocarbon groups, aromatic hydrocarbon groups, and heterocyclic groups. c2 and R c3 When it is a cyclic organic group, the substituents that the cyclic organic group may have are the same as R c2 and R c3 The same applies to the case of a chain alkyl group.

[0384] R c2 and R c3When it is an aromatic hydrocarbon group, the aromatic hydrocarbon group is preferably a phenyl group, a group formed by bonding multiple benzene rings via a carbon-carbon bond, or a group formed by condensing multiple benzene rings. When the aromatic hydrocarbon group is a phenyl group, or a group formed by bonding or condensing multiple benzene rings, the number of benzene rings contained in the aromatic hydrocarbon group is not particularly limited, but is preferably 3 or less, more preferably 2 or less, and particularly preferably 1. Specific examples of preferred aromatic hydrocarbon groups include phenyl, naphthyl, biphenyl, anthracenyl, and phenanthrenyl.

[0385] R c2 and R c3 In the case of an aliphatic cyclic hydrocarbon group, 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, 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.

[0386] R c2 and R c3 When the heterocyclic group is a 5- or 6-membered monocyclic ring containing one or more N, S, or O atoms, or a fused monocyclic ring or a fused monocyclic ring with a benzene ring. When the heterocyclic group is a fused ring, the number of monocyclic rings constituting the fused ring is 3 or less. The heterocyclic group may be an aromatic group (heteroaryl) or a non-aromatic group. 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, phthalazine, cinnoline, quinoxaline, piperidine, piperazine, morpholine, piperidine, tetrahydropyran, and tetrahydrofuran.

[0387] R c2 and R c3 Can be bonded to each other to form a ring. c2 With R c3 The group forming the ring is preferably a cycloalkylidene group. c2 With R c3 When the cycloalkylidene groups are bonded to form a cycloalkylidene group, the ring constituting the cycloalkylidene group is preferably a 5- to 6-membered ring, more preferably a 5-membered ring.

[0388] R c2 With R c3When the group formed by the bond is a cycloalkylidene group, the cycloalkylidene group may be fused with one or more other rings. Examples of rings that may be fused with the cycloalkylidene 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.

[0389] R described above c2 and R c3 As an example of a preferred group, there can be mentioned the formula -A 1 -A 2 In the formula, A 1 is a straight chain alkylene group, A 2 Examples thereof include an alkoxy group, a cyano group, a halogen atom, a haloalkyl group, a cyclic organic group, and an alkoxycarbonyl group.

[0390] A 1 The number of carbon atoms of the linear alkylene group is preferably 1 or more and 10 or less, more preferably 1 or more and 6 or less. 2 When it is an alkoxy group, the alkoxy group may be linear or branched, preferably linear. The number of carbon atoms in the alkoxy group is preferably 1 or more and 10 or less, more preferably 1 or more and 6 or less. 2 When it is a halogen atom, it is preferably a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom, and more preferably a fluorine atom, a chlorine atom, or a bromine atom. 2 When it is a haloalkyl group, the halogen atom contained in the haloalkyl group is preferably a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom, and more preferably a fluorine atom, a chlorine atom, or a bromine atom. The haloalkyl group may be linear or branched, but is preferably linear. 2 When it is a cyclic organic group, examples of cyclic organic groups are the same as R c2 and R c3 The same applies to the cyclic organic group possessed as a substituent. 2 When it is an alkoxycarbonyl group, examples of the alkoxycarbonyl group are the same as R c2 and R c3 The same applies to the alkoxycarbonyl group which may be a substituent.

[0391] As R c2 and R c3Preferred specific examples 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-cyanoethyl, cyanoalkyl groups 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 groups 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, cycloalkylalkyl groups 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-propyl, Alkoxycarbonylalkyl groups such as n-pentyl, 6-ethoxycarbonyl-n-hexyl, 7-ethoxycarbonyl-n-heptyl, and 8-ethoxycarbonyl-n-octyl; and haloalkyl groups 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.

[0392] As R c2 and R c3 Among the above, preferred groups 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.

[0393] As R c4 Examples of preferred organic groups, with R c1Similarly, alkyl, alkoxy, cycloalkyl, cycloalkyloxy, saturated aliphatic acyl, alkoxycarbonyl, saturated aliphatic acyloxy, phenyl which may have a substituent, phenoxy which may have a substituent, benzoyl which may have a substituent, phenoxycarbonyl which may have a substituent, benzoyloxy which may have a substituent, phenylalkyl which may have a substituent, naphthyloxy which may have a substituent, naphthyloxy which may have a substituent, naphthyloxycarbonyl which may have a substituent, naphthyloxy which may have a substituent, naphthylalkyl which may have a substituent, heterocyclic group which may have a substituent, heterocyclic carbonyl which may have a substituent, amino group substituted with one or two organic groups, morpholin-1-yl, and piperazin-1-yl, etc. Specific examples of these groups are the same as those for R c1 The same applies to the groups described above. c4 , cycloalkylalkyl, phenoxyalkyl which may have a substituent on the aromatic ring, and phenylthioalkyl which may have a substituent on the aromatic ring are also preferred. c1 The substituents that the phenyl group contained in may have are similar.

[0394] In organic groups, as R c4 , preferably an alkyl group, a cycloalkyl group, a phenyl group or cycloalkylalkyl group which may have a substituent, 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 cycloalkyl group contained in the cycloalkylalkyl group preferably has 5 to 10 carbon atoms, more preferably 5 to 8 carbon atoms, and particularly preferably 5 or 6 carbon atoms. The alkylene group contained in the cycloalkylalkyl group preferably has 1 to 8 carbon atoms, more preferably 1 to 4 carbon atoms, and particularly preferably 2 carbon atoms. Among the cycloalkylalkyl groups, a cyclopentylethyl group is preferred. The alkylene group contained in the phenylthioalkyl group which may have a substituent on the aromatic ring preferably has 1 to 8 carbon atoms, more preferably 1 to 4 carbon atoms, and particularly preferably 2 carbon atoms. Among the phenylthioalkyl groups which may have a substituent on the aromatic ring, a 2-(4-chlorophenylthio)ethyl group is preferred.

[0395] In addition, as R c4 , also preferably -A 3 -CO-OA 4 A 3 A is a divalent organic group, preferably a divalent hydrocarbon group, preferably an alkylene group. 4 It is a monovalent organic group, preferably a monovalent hydrocarbon group.

[0396] A 3When it is an alkylene group, the alkylene group may be linear or branched, but is preferably linear. 3 In the case of an alkylene group, the number of carbon atoms of the alkylene group is preferably 1 or more and 10 or less, more preferably 1 or more and 6 or less, particularly preferably 1 or more and 4 or less.

[0397] As A 4 Preferred examples of include alkyl groups having 1 to 10 carbon atoms, cycloalkyl groups having 3 to 10 carbon atoms, cycloalkylalkyl groups having 4 to 10 carbon atoms, aralkyl groups having 7 to 20 carbon atoms, and aromatic hydrocarbon groups having 6 to 20 carbon atoms. 4 Preferred specific examples include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, n-hexyl, phenyl, naphthyl, benzyl, phenethyl, α-naphthylmethyl, and β-naphthylmethyl.

[0398] AS-A 3 -CO-OA 4 Preferred specific examples of the group represented include 2-methoxycarbonylethyl, 2-ethoxycarbonylethyl, 2-n-propoxycarbonylethyl, 2-n-butoxycarbonylethyl, 2-n-pentoxycarbonylethyl, 2-n-hexyloxycarbonylethyl, 2-benzyloxycarbonylethyl, 2-phenoxycarbonylethyl, 3-methoxycarbonyl-n-propyl, 3-ethoxycarbonyl-n-propyl, 3-n-propoxycarbonyl-n-propyl, 3-n-butoxycarbonyl-n-propyl, 3-n-pentoxycarbonyl-n-propyl, 3-n-hexyloxycarbonyl-n-propyl, 3-benzyloxycarbonyl-n-propyl, and 3-phenoxycarbonyl-n-propyl.

[0399] The above R c4 Explained, but as R c4 , preferably a group represented by the following formula (c2-a) or (c2-b).

[0400] [Chemical Formula 46]

[0401]

[0402] (In formula (c2-a) and (c2-b), R c7 and R c8 Each is an organic group, n3 is an integer of 0 to 4, R c7 and R c8 When present in adjacent positions on the benzene ring, R c7 With R c8 may be bonded to each other to form a ring, n4 is an integer of 1 to 8, n5 is an integer of 1 to 5, n6 is an integer of 0 to (n5+3), R c9 is an organic group.)

[0403] R in formula (c2-a) c7 and R c8 Examples of organic groups involved are related to R c1 Same as R c7 , preferably alkyl or phenyl. c7 When it is an alkyl group, the number of carbon atoms is preferably 1 or more and 10 or less, more preferably 1 or more and 5 or less, particularly preferably 1 or more and 3 or less, and most preferably 1. c7 Most preferably, it is methyl. c7 With R c8 When the ring is formed by bonding, the ring may be an aromatic ring or an aliphatic ring. c7 With R c8 Preferred examples of the ring-forming group represented by formula (c2-a) include naphthalene-1-yl, 1,2,3,4-tetrahydronaphthalene-5-yl, etc. In the above formula (c2-a), n3 is an integer of 0 or more and 4 or less, preferably 0 or 1, more preferably 0.

[0404] In the above formula (c2-b), R c9 As an organic group, there can be mentioned the organic group c1 The same organic groups as described above are also included. Among the organic groups, alkyl groups are preferred. Alkyl groups may be linear or branched. The number of carbon atoms in the alkyl group is preferably 1 or more and 10 or less, more preferably 1 or more and 5 or less, and particularly preferably 1 or more and 3 or less. c9 Preferred examples include methyl, ethyl, propyl, isopropyl, and butyl. Among these, methyl is more preferred.

[0405] In the above formula (c2-b), n5 is an integer of 1 to 5, preferably an integer of 1 to 3, more preferably 1 or 2. In the above formula (c2-b), n6 is 0 to (n5+3), preferably an integer of 0 to 3, more preferably an integer of 0 to 2, and particularly preferably 0. In the above formula (c2-b), n4 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.

[0406] In formula (c2), R c5 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. c5 When it is an aliphatic hydrocarbon group, the substituent group that can be possessed is preferably phenyl, naphthyl, etc. c1 Preferred examples of the substituent that the aryl group may have include an alkyl group having 1 to 5 carbon atoms, an alkoxy group, and a halogen atom.

[0407] In formula (c2), R c5 Preferred examples include a hydrogen atom, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a 2-cyclopentylethyl group, a 2-cyclobutylethyl group, a cyclohexylmethyl group, a phenyl group, a benzyl group, a methylphenyl group, and a naphthyl group. Among these, a methyl group or a phenyl group is more preferred.

[0408] Preferred specific examples of the compound represented by formula (c2) include the following compounds.

[0409] [Chemical Formula 47]

[0410]

[0411] [Chemical Formula 48]

[0412]

[0413] [Chemical Formula 49]

[0414]

[0415] [Chemical Formula 50]

[0416]

[0417] [Chemical Formula 51]

[0418]

[0419] As mentioned above, the photosensitive composition preferably includes an oxime ester compound as a photopolymerization initiator (C). Oxime ester compounds have an excellent ability to absorb ultraviolet rays and generate free radicals. Therefore, oxime ester compounds are highly sensitive and can easily fully cure the photosensitive composition with a small exposure amount even when a high concentration of sunscreen (D) is included. In the case of a photosensitive composition containing a large amount of sunscreen (D), when the optical density of the film formed by the photosensitive composition is 3, the ultraviolet exposure amount of the deep layer is quite less than the ultraviolet exposure amount of the surface layer (outermost surface), but the oxime ester compound generates free radicals even under such a relatively small ultraviolet exposure amount, which can well cure the photosensitive composition.

[0420] Furthermore, when a light-shielding agent (D), described later, is incorporated into a photosensitive composition at a high concentration, primary aggregates (aggregates) of the light-shielding agent (D) inevitably form in a coating film formed from the photosensitive composition. However, when a photosensitive composition containing an oxime ester compound as the photopolymerization initiator (C) is used, the photopolymerization initiator (C) generates free radicals even in minute gaps where aggregates are intricately stacked upon exposure to ultraviolet light.

[0421] As a result, the cured product of the photosensitive composition not only exhibits excellent adhesion to the substrate and resistivity (insulation properties) under normal temperature, humidity, and atmospheric pressure, but also exhibits little degradation in adhesion to the substrate and resistivity (insulation properties) even when the cured product is exposed to high temperature, high humidity, and high pressure environments. Durability in high temperature, high humidity, and high pressure environments can be confirmed using the so-called PCT test (pressure cook test).

[0422] Therefore, image display panels using a black matrix or black bank formed from a cured product of a photosensitive composition containing an oxime ester compound (especially an oxime ester compound represented by formula (c1)) are less likely to experience performance degradation even when used in a high-temperature, high-humidity environment.

[0423] As the photopolymerization initiator (C), an oxime ester compound may be used in combination with a photopolymerization initiator other than the oxime ester compound. In this case, the ratio of the mass of the oxime ester compound to the total mass of the photopolymerization initiator (C) is preferably 20% by mass or more, more preferably 30% by mass or more, even more preferably 35% by mass or more, and particularly preferably 40% by mass or more.

[0424] As a photopolymerization initiator other than the oxime ester compound, for example, an aminoalkylphenone-based photopolymerization initiator can be preferably used.

[0425] Preferred examples of the aminoalkylphenone-based photopolymerization initiator include compounds represented by the following formula (c3-1).

[0426] [Chemical Formula 52]

[0427]

[0428] In formula (c3-1), R c01 It is a linear, branched or cyclic alkyl group having 1 to 12 carbon atoms.

[0429] R c02 and R c03 Each independently represents 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. c02 or R c03 The alkyl group may be linear or branched.

[0430] R c04 、R c05 、R c07 , and R c08 Each independently represents 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. c04、R c05 、R c07 , and R c08 The alkyl group and the alkoxy group may be linear or branched.

[0431] 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. c06 The alkyl group and alkoxy group of R may be straight chain or branched chain. c06 The alkyl, cycloalkyl, and alkoxy groups may be substituted with one or more substituents. The substituents are one or more selected from the group consisting of hydroxyl groups and alkoxy groups having 1 or more and 4 or less carbon atoms. c06 The alkoxy group as a substituent in may be linear or branched.

[0432] As R c01 Preferred specific examples of the alkyl group include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, n-undecyl, and n-dodecyl. Among these, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, and n-hexyl are preferred, and ethyl is more preferred.

[0433] As R c01 Preferred specific examples of the cycloalkyl group include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl, cycloundecyl, and cyclododecyl.

[0434] R c02 and R c03 When it is an alkyl group or a cycloalkyl group, the preferred specific examples are the same as R c01 The preferred specific examples when it is an alkyl group or a cycloalkyl group are the same. c02 and R c03 , preferably methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, n-hexyl, n-heptyl, and n-octyl, more preferably methyl.

[0435] As R c04 、R c05 、R c07 , and R c08 Specific examples of the halogen atom include a chlorine atom, an iodine atom, a bromine atom, and a fluorine atom.

[0436] R c04 、R c05 、R c07 , and R c08When it is an alkyl group or a cycloalkyl group, the preferred specific examples are the same as R c01 Preferred specific examples in the case of an alkyl group or a cycloalkyl group are the same.

[0437] As R c04 、R c05 、R c07 , and R c08 Specific examples of the alkoxy group include a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, an n-butoxy group, an isobutoxy group, a sec-butoxy group, and a tert-butoxy group.

[0438] As R c04 、R c05 、R c07 , and R c08 From the perspective of good sensitivity and depth of focus of the photosensitive composition and easy formation of a cured film with good adhesion to the substrate, a hydrogen atom, a methyl group, and an ethyl group are preferred, and a hydrogen atom is more preferred.

[0439] R c06 Specific examples of when R is a halogen atom, an alkyl group, a cycloalkyl group, or an alkoxy group are the same as c04 、R c05 、R c07 , and R c08 The specific examples in the case of a halogen atom, an alkyl group, a cycloalkyl group, or an alkoxy group are the same.

[0440] As R c06 When the alkyl group, cycloalkyl group, and alkoxy group are substituted with one or more substituents, the substituents are preferably hydroxyl group and methoxy group.

[0441] As R c06 Preferred specific examples include a hydrogen atom, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, an n-pentyl group, an n-hexyl group, an n-heptyl group, an n-octyl group, an n-decyl group, an n-dodecyl group, a hydroxymethyl group, a 2-hydroxyethyl group, a methoxymethyl group, a 2-methoxyethyl group, a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, an 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.

[0442] Preferably, R c01 is methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, or n-hexyl, R c02 is methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, n-hexyl, n-heptyl, or n-octyl, R c03 is methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, n-hexyl, n-heptyl, and n-octyl, etc., R c04is a hydrogen atom, a methyl group, or an ethyl group, R c05 is a hydrogen atom, a methyl group, or an ethyl group, R c07 is a hydrogen atom, a methyl group, or an ethyl group, R c08 is a hydrogen atom, a methyl group, or an ethyl group, R c06 is a methyl group or a hydrogen atom.

[0443] Examples of aminoalkylphenone compounds represented by formula (c3-1) include 2-benzyl-2-(dimethylamino)-1-(4-morpholinophenyl)butan-1-one (e.g., IRGACURE369 manufactured by Ciba Specialty Chemicals), 2-(4-methylbenzyl)-2-(dimethylamino)-1-(4-morpholinophenyl)butan-1-one (e.g., Ciba Specialty Chemicals Chemicals IRGACURE379), 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-morpholinophenyl)butan-1-one, 2-(3,4-dimethylbenzyl)-2-(dimethylamino)-1-(4-morpholinophenyl)butan-1-one, 2-(4-methoxybenzyl)-2-(dimethylamino)-1-(4-morpholinophenyl)butan-1-one, 2-(4-ethoxybenzyl)-2-(dimethylamino)-1-(4-morpholinophenyl)butan-1-one, 2-(4-hydroxymethylbenzyl)-2-(dimethylamino)-1-(4-morpholinophenyl)butan-1-one, 2-[4-(2- 1-(4-morpholinophenyl)butan-1-one, 2-[(4-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)pentan-1-one, 2-(4-isobutylbenzyl)-2-[(n-butyl)(methyl)amino]]-1-(4-morpholinophenyl)pentan-1-one, 2-(4-n-butyloxybenzyl)-2-[(n-butyl)(methyl)amino]-1-(4-morpholinophenyl)pentan-1-one, 2-(4-methylbenzyl)-2-[di(n-octyl)amino]-1-(4-morpholinophenyl)hexane-1-one, and 2-(4-n-dodecylbenzyl)-2-(dimethylamino)-1-(4-morpholinophenyl)octan-1-one.

[0444] Among them, 2-(4-methylbenzyl)-2-(dimethylamino)-1-(4-morpholinophenyl)butan-1-one is preferred.

[0445] When an aminoalkylphenone-based photopolymerization initiator is used in combination with an oxime ester compound, it becomes easy to control the cross-sectional shape of a black matrix formed using the photosensitive composition.

[0446] This is believed to be because aminoalkylphenone-based photopolymerization initiators tend to generate photopolymerization radicals relatively in the surface layer of the photosensitive composition (the surface facing the exposed light and its vicinity), while oxime ester compounds tend to generate photopolymerization radicals relatively deep in the photosensitive composition. This tendency becomes more pronounced as the thickness of the photosensitive composition increases, but it is observed even in thin films of 1 μm or less.

[0447] As a secondary effect of using an aminoalkylphenone-based photopolymerization initiator with an oxime ester compound, sensitivity is comprehensively improved, enabling the production of a cured photosensitive composition with a reduced exposure dose. Furthermore, using an aminoalkylphenone-based photopolymerization initiator with an oxime ester compound improves line edge straightness and adhesion to the substrate, making it easier to form black matrices and black banks with fewer pattern defects.

[0448] In the photosensitive composition, when the photopolymerization initiator (C) comprises an oxime ester compound and an aminoalkylphenone-based photopolymerization initiator, the ratio of the mass of the aminoalkylphenone-based photopolymerization initiator to the total mass of the oxime ester compound and the mass of the aminoalkylphenone-based photopolymerization initiator is preferably 20% by mass or more and 75% by mass or less, more preferably 25% by mass or more and 70% by mass or less, and particularly preferably 30% by mass or more and 60% by mass or less. It should be noted that the oxime ester compound is preferably blended into the photosensitive composition so that the mixing ratio of the oxime ester compound when forming a thick cured film is higher than the mixing ratio of the oxime ester compound when forming a thin cured film.

[0449] The content of the photopolymerization initiator (C) in the photosensitive composition is not particularly limited within a range that does not hinder the purpose of the present invention. The content of the photopolymerization initiator (C) is preferably from 0.1% to 50% by mass, more preferably from 0.3% to 30% by mass, and particularly preferably from 0.5% to 20% by mass, relative to the mass of the solids content of the photosensitive composition. Using an amount of the photopolymerization initiator (C) within this range makes it easier to achieve the desired effects of using the photopolymerization initiator (C) without compromising the mechanical properties, solvent resistance, chemical resistance, etc. of the cured product.

[0450] <Sunscreen (D)>

[0451] The photosensitive composition contains a light-shielding agent (D). The light-shielding agent (D) must contain carbon black (D1) and a lactam pigment (D2). The carbon black (D1) is subjected to a surface treatment selected from a coating treatment with an organic substance and a treatment for introducing an acidic group.

[0452] By using the surface-treated carbon black (D1) and the lactam pigment in combination, a fine line pattern having low reflectivity from the substrate side and close adhesion to the substrate can be formed using the photosensitive composition.

[0453] [Carbon black (D1)]

[0454] As described above, carbon black (D1) has been subjected to a surface treatment selected from a coating treatment with an organic substance and a treatment for introducing an acidic group. The untreated carbon black to be used as the surface treatment target is not particularly limited, and various carbon blacks conventionally used as light-shielding agents can be used. Specifically, known carbon blacks such as channel black, furnace black, thermal black, and lamp black can be used as the untreated carbon black.

[0455] In the surface treatment, untreated carbon black may be used alone or in combination of two or more.

[0456] The average primary particle size of untreated carbon black is preferably 5 nm or more and 60 nm or less, more preferably 10 nm or more and 50 nm or less, and particularly preferably 20 nm or more and 45 nm or less. Here, the average primary particle size refers to the arithmetic mean of the primary particle sizes obtained by observing 1500 carbon black primary particles with an electron microscope. If the average primary particle size of the raw carbon black is too small, agglomeration is likely to occur, the stability of the mill base deteriorates, and it is difficult to achieve dispersion at high concentrations. On the other hand, if the average primary particle size of the raw carbon black is too large, it is easy to produce poor shape in the cured film formed using the photosensitive composition, and it is easy to form a cured film with a rough surface.

[0457] The DBP oil absorption of untreated carbon black is preferably 100 ml / 100 g or less. Here, DBP oil absorption refers to the volume of dibutyl phthalate (DBP) absorbed by 100 g of carbon black (JIS 6217). Excessively high DBP oil absorption of untreated carbon black can easily lead to increased viscosity of the photosensitive composition, which can worsen coating properties and reduce the OD and / or electrical resistance of the cured film.

[0458] The pH of untreated carbon black is preferably 2 or higher and 10 or lower, more preferably 5 or higher and 9 or lower, and particularly preferably 4 or higher and 8 or lower. Here, the pH value refers to the value obtained by measuring a mixture of carbon black and distilled water using a glass electrode pH meter (JIS 6221). If the pH of the untreated carbon black is too low, the stability of the surface-treated carbon black is likely to deteriorate, while if the pH is too high, film peeling is likely to occur.

[0459] The ash content of the raw carbon black is preferably 1.0% or less. In addition, the specific surface area of the raw carbon black is preferably 20 m 2 / g and above and 300m 2 / g or less.

[0460] If the ash content is too high, the resistance of the cured film tends to decrease. If the specific surface area is too small, the cured film tends to have poor shape. If it is too large, a large amount of dispersant, resin, dye, etc. is required, which is disadvantageous in terms of the production cost of the surface-treated carbon black.

[0461] The coating treatment with an organic substance may be any treatment that covers at least a portion of the surface of the untreated carbon black with an organic substance. As long as the desired effect can be obtained, the entire surface of the carbon black may not be coated with the organic substance.

[0462] The organic substance is not particularly limited as long as it can be physically or chemically bonded to the surface of carbon black. Preferred examples of the organic substance include resins, waxes, oils, long-chain fatty acids, dyes, and coupling agents such as silane coupling agents.

[0463] Among the above-mentioned organic substances, resins and dyes are preferred in view of their easy availability and ease of coating treatment.

[0464] The method of coating the untreated carbon black with the resin is not particularly limited.

[0465] Examples of the coating method include a method in which carbon black particles are coated with a resin solution, a dispersion containing resin fine particles, or an emulsion, and then the solvent is removed from the coating layer.

[0466] Furthermore, when coating with a curable resin, the monomer or uncured resin precursor may be attached to the surface of the carbon black particles, and then the monomer may be polymerized or the uncured resin precursor may be cured. In this case, the carbon black particles are preferably coated with a solution of the monomer or uncured resin precursor, thereby attaching the monomer or uncured resin precursor to the surface of the carbon black particles. Furthermore, a polymerization initiator or curing agent may be used together with the monomer or uncured resin precursor as needed.

[0467] The resin-coated carbon black (D1) can also be produced by dispersing carbon black particles in a matrix composed of a resin and then finely pulverizing the resin containing the carbon black particles.

[0468] The thickness of the resin coating layer in the resin-coated carbon black (D1) is preferably 0.5 nm or more and 50 nm or less.

[0469] The resistivity of the dry powder of the resin-coated carbon black (D1), that is, the so-called powder resistance, is preferably 0.5 Ω·cm or more and 50 Ω·cm or less.

[0470] When a photosensitive composition containing such a resin-coated carbon black (D1) is used, a cured film having high volume resistivity and excellent adhesion to a substrate and light-shielding properties can be easily formed.

[0471] Examples of resins that can be used to coat untreated carbon black include thermosetting resins such as phenolic resins, melamine resins, xylene resins, diallyl phthalate resins, glyphthalate resins, epoxy resins, and alkylbenzene resins; and thermoplastic resins such as polystyrene, polycarbonate, polyethylene terephthalate, polybutylene terephthalate, modified polyphenylene ether, polysulfone, poly(p-phenylene terephthalamide), polyamide-imide, polyimide, polyaminobismaleimide, polyethersulfone, polyphenylsulfone, polyarylate, and polyetheretherketone. Among these, epoxy resins are particularly preferred.

[0472] In addition, the carbon black (D1) subjected to the treatment for introducing an acidic group described later may also be subjected to a coating treatment with an organic substance.

[0473] For untreated carbon black, it is preferred to perform an oxidation treatment before coating with a dye so that at least one functional group generated by the oxidation treatment is present on its surface, and it is more preferred to perform multiple oxidation treatments so that two or more functional groups generated by the oxidation treatment are present on its surface.

[0474] For untreated carbon black that has not undergone oxidation treatment, there are no functional groups generated by oxidation treatment on the surface or the number of such functional groups is insufficient. Therefore, the dispersibility of the resulting dye-coated carbon black (D1) cannot be fully ensured, making it difficult to form a high-resistance cured film.

[0475] Examples of the oxidation treatment include methods using ozone gas, nitric acid, sodium hypochlorite, hydrogen peroxide, nitrogen monoxide gas, nitrogen dioxide gas, anhydrous sulfuric acid, fluorine gas, concentrated sulfuric acid, nitric acid, and various peroxides.

[0476] Examples of the functional groups generated by the oxidation treatment include a hydroxyl group, an oxo group, a hydroperoxy group, a carbonyl group, a carboxyl group, a peroxycarboxylic acid group, an aldehyde group, a ketone group, a nitro group, a nitroso group, an amide group, an imide group, a sulfonic acid group, a sulfinic acid group, a sulfenic acid group, a thiocarboxylic acid group, a monochlorooxy group, a dichlorooxy group, a perchlorooxy group, an iodosyl group, and an iodoyl group.

[0477] The dye used in the production of the dye-coated carbon black (D1) is not particularly limited as long as it can be adsorbed on the surface of carbon black, and known basic dyes, acid dyes, direct dyes, reactive dyes, etc. can be used.

[0478] Anionic or nonionic dyes are more preferably used from the viewpoints of interaction between sulfonic and carboxyl groups and functional groups on carbon black, reaction between amino groups and alkali-soluble resins, and ability to be insolubilized by aluminum sulfate or the like.

[0479] From the viewpoint of easily forming a cured film with high light-shielding properties, it is preferred to use a dark-colored dye close to black.

[0480] Specific examples of such dyes include food coloring dyes such as Food Black No. 1, Food Black No. 2, Food Red No. 40, Food Blue No. 1, and Food Yellow No. 7; acid dyes of various colors such as Bernacid Red 2BMN, Basacid Black X34 (BASF X-34) (manufactured by BASF), Kayanol Red 3BL (manufactured by Nippon Kayaku Company), Dermacarbon 2GT (manufactured by Sandoz), Telon Fast Yellow 4GL-175, BASF Basacid Black SE 0228, Basacid Black X34 (BASF X-34) (manufactured by BASF), Basacid Blue 750 (manufactured by BASF), Bernacid Red (manufactured by Bemcolors, Poughkeepsie, NY), and BASF Basacid Black SE 0228 (manufactured by BASF); and Pontamine Brilliant Bond Blue A and other Pontamine Brilliant Bond Blues. A and other Pontamine (registered trademark) dyes (Bayer Chemicals Corporation, Pittsburgh, PA), Cartasol Yellow GTF Presscake (Sandoz, Inc.); Cartasol Yellow GTF Liquid Special 110 (Sandoz, Inc.); Yellow Shade 16948 (Tricon Corporation), Direct Brilliant Pink B (Crompton & Knowles), Direct Black 154, Direct Deep Black, Carta Black 2GT (Sandoz, Inc.), Sirius Supra Yellow GD 167, Cartasol Brilliant Yellow 4GF (Sandoz); Pergasol Yellow CGP (BASF), Pyrazol Black BG (JCI), Diazol Black RN Quad (JCJ), Pontamine Brilliant Bond Blue, Berncolor AYDirect dyes of various colors such as Cibacron Brilliant Red 3B-A (Reactive Red 4) (manufactured by Aldrich Chemical, Milwaukee, WI), Drimarene Brilliant Red X-2B (Reactive Red 56) (manufactured by Pylam Products, Inc., Tempe, AZ), LevafiX Brilliant Red E-4B, LevafiX Brilliant Red F-6BA, and similar LevafiX (registered trademark) dyes manufactured by Dystar LP (manufactured by Charlotte, NC), Procion Red H8B (Reactive Red 31) (manufactured by JCI America); Reactive dyes of various colors such as Neozapon Red 492 (manufactured by BASF), Orasol Red G (manufactured by BASF), Aizen Spilon Red C-BH (manufactured by Hodogaya Chemical Company), Spirit Fast Yellow 3G, Aizen Spilon Yellow C-GNH (manufactured by Hodogaya Chemical Company), Orasol Black Oil-soluble dyes such as RL (manufactured by BASF), Orasol Black RLP (manufactured by BASF), Savinyl Black RLS (manufactured by Sandoz), Orasol Blue GN (manufactured by BASF), Luxol Blue MBSN (manufactured by Morton-Thiokol), and Morfast Black Concentrate A (manufactured by Morton-Thiokol). These may be used alone or in combination of two or more.

[0481] The dye content in the dye-coated carbon black (D1) is preferably from 0.5% to 10% by mass, more preferably from 1% to 7% by mass, and particularly preferably from 1% to 5% by mass, relative to the total mass of the coated carbon black. If the dye content is too low, the carbon black will be insufficiently coated, making it difficult to form a high-resistance cured film. If the dye content is too high, the excess dye will hinder the dispersion of the dye-coated carbon black, making it more likely that the photosensitive composition will thicken and the dye-coated carbon black (D1) will aggregate.

[0482] In the dye-coated carbon black (D1), it is preferred that the dye present on the surface of the dye-coated carbon black (D1) is laked by a metal or a metal salt.

[0483] By the above-mentioned laking, the dye is fixed to the surface of the carbon black or to the functional groups generated by the oxidation treatment via the metal or metal salt, and the dye is not easily detached from the surface of the carbon black.

[0484] Therefore, when the dye is laked, the dye is less likely to be eluted and a cured film having a high OD is easily formed.

[0485] Examples of the metal or metal salt used for the lake formation include aluminum, magnesium, calcium, strontium, barium, and manganese, or hydrochlorides and sulfates thereof. These metals or metal salts may be used alone or in combination of two or more.

[0486] The amount of the metal or metal salt used for laking is preferably 0.3 times the mole of the dye or more, more preferably 0.5 times the mole or more, particularly preferably 0.8 times the mole or more.

[0487] When the amount of the metal or metal salt added is too small, the dye is not sufficiently fixed and is easily detached from the carbon black surface, resulting in poor stability of the color paste and a decrease in the resistance value, which is not preferred.

[0488] Next, the method for producing dye-coated carbon black (D1) is described. First, the raw carbon black is mixed with water (carbon black prepared by appropriately mixing ion exchange water into tap water in a manner that the electrical conductivity becomes constant. The same applies hereinafter.) to form a slurry, and the carbon black is washed by heating and stirring for a predetermined time. After cooling, it is washed with water again. Next, water is added to the obtained carbon black to form a slurry again, and the above-mentioned oxidant is added. The surface of the carbon black is oxidized and washed with water after stirring at a predetermined temperature for a predetermined time. As for the oxidation treatment, the type of oxidant is changed as needed and the treatment is performed multiple times. Next, the obtained carbon black that has completed the oxidation treatment is mixed with water to form a slurry again, and the dye is added in a manner that becomes the aforementioned predetermined content relative to the target dye-coated carbon black (D1). The mixture is stirred at 40 to 90°C for 1 to 5 hours to allow the dye to be adsorbed and coated on the surface of the carbon black. Furthermore, an equimolar amount of the aforementioned metal or metal salt is added to the dye, and the mixture is stirred at 30-70°C for 1-5 hours to lake the dye with the metal or metal salt, thereby fixing the dye on the surface of the carbon black. The mixture is then cooled, washed with water, and filtered and dried to obtain the desired dye-coated carbon black (D1).

[0489] The acidic group introduced into carbon black (D1) by the treatment for introducing an acidic group is a functional group that exhibits acidity according to the Bronsted definition. Specific examples of the acidic group include a carboxyl group, a sulfonic acid group, and a phosphoric acid group. The acidic group introduced into carbon black may form a salt. The cation that forms a salt with the acidic group is not particularly limited as long as it does not hinder the purpose of the present invention. Examples of the cation include various metal ions, cations of nitrogen-containing compounds, and ammonium ions, preferably alkali metal ions such as sodium ions, potassium ions, and lithium ions, and ammonium ions.

[0490] Among the carbon blacks (D1) described above that have been treated to introduce acidic groups, from the viewpoint of achieving high resistance of a light-shielding cured film formed using a photosensitive composition, carbon black (D1) having one or more functional groups selected from the group consisting of a carboxylic acid group, a carboxylate group, a sulfonic acid group, and a sulfonate group is preferred.

[0491] The method for introducing acidic groups into untreated carbon black is not particularly limited. Examples of the method for introducing acidic groups include the following methods.

[0492] Method 1): Sulfonic acid groups are introduced into untreated carbon black by a direct substitution method (using concentrated sulfuric acid, fuming sulfuric acid, chlorosulfonic acid, etc.) or an indirect substitution method (using sulfite, bisulfite, etc.).

[0493] Method 2): An organic compound having an amino group and an acidic group is subjected to diazo coupling with untreated carbon black.

[0494] Method 3): Using the Williamson etherification method, an organic compound having a halogen atom and an acidic group is reacted with untreated carbon black having a hydroxyl group.

[0495] Method 4): An organic compound having a halogenated carbonyl group and an acidic group protected by a protecting group is reacted with untreated carbon black having a hydroxyl group.

[0496] Method 5): Using an organic compound having a halogenated carbonyl group and an acidic group protected by a protecting group, untreated carbon black is subjected to a Friedel-Crafts reaction, followed by deprotection.

[0497] Method 6): Perform the aforementioned oxidation treatment.

[0498] Of the above methods, method 2 is preferred because the treatment for introducing an acidic group is easy and safe. The organic compound having an amino group and an acidic group used in method 2) is preferably a compound in which an amino group and an acidic group are bonded to an aromatic group. Examples of such compounds include aminobenzenesulfonic acid such as p-aminobenzenesulfonic acid and aminobenzoic acid such as 4-aminobenzoic acid.

[0499] The number of moles of acidic groups introduced into the untreated carbon black is not particularly limited within the range not hindering the purpose of the present invention. The number of moles of acidic groups introduced into the untreated carbon black is preferably from 1 mmol to 200 mmol, and more preferably from 5 mmol to 100 mmol, relative to 100 g of carbon black.

[0500] [Lactam pigment (D2)]

[0501] The lactam pigment (D2) is not particularly limited as long as it is a pigment recognized as a lactam compound by those skilled in the art. Examples of the lactam pigment (D2) include compounds represented by the following formula (d-1).

[0502] [Chemical Formula 53]

[0503]

[0504] In formula (d-1), X d represents a double bond, and as geometric isomers, each is independently E or Z, R d1 Each independently represents a hydrogen atom, a methyl group, a nitro group, a methoxy group, a bromine atom, a chlorine atom, a fluorine atom, a carboxyl group, or a sulfo group. d2 Each independently represents a hydrogen atom, a methyl group, or a phenyl group. d3 Each independently represents a hydrogen atom, a methyl group, or a chlorine atom.

[0505] The compound represented by formula (d-1) can be used alone or in combination of two or more.

[0506] Just R d1 In terms of ease of producing the compound represented by formula (d-1), it is preferred to bond to the 6-position of the indolinone ring, R d3 It is preferably bonded to the 4-position of the indolinone ring. d1 、R d2 , and R d3 Preferred is a hydrogen atom.

[0507] The compound represented by formula (d-1) has EE isomer, ZZ isomer, and EZ isomer as geometric isomers, and may be a single compound of any of these or a mixture of these geometric isomers.

[0508] The compound represented by formula (d-1) can be produced by the methods described in, for example, International Publication No. 2000 / 24736 and International Publication No. 2010 / 081624.

[0509] In order to disperse the lactam pigment well in the photosensitive composition, the average particle size of the lactam pigment is preferably 10 nm or more and 1000 nm or less.

[0510] The ratio of the total mass of the carbon black (D1) and the lactam pigment (D2) to the total mass of the light-shielding agent (D) is not particularly limited as long as the purpose of the present invention is not impaired. The ratio of the total mass of the carbon black (D1) and the lactam pigment (D2) to the total mass of the light-shielding agent (D) is preferably 80% by mass or more, more preferably 90% by mass or more, further preferably 95% by mass or more, and particularly preferably 100% by mass.

[0511] When the sunscreen (D) contains another sunscreen other than carbon black (D1) and lactam pigment (D2), examples of the other sunscreen include untreated carbon black, perylene pigments, fine particles containing silver-tin (AgSn) alloy as a main component, titanium black, and various pigments, both organic and inorganic, such as metal oxides, composite oxides, metal sulfides, metal sulfates, and metal carbonates of copper, iron, manganese, cobalt, chromium, nickel, zinc, calcium, and silver.

[0512] In the photosensitive composition, the light-shielding agent (D) may contain a dye within a range not hindering the purpose of the present invention. The dye may be appropriately selected from known materials.

[0513] Examples of dyes that can be used in the photosensitive composition include azo dyes, metal complex azo dyes, anthraquinone dyes, triphenylmethane dyes, xanthene dyes, cyanine dyes, naphthoquinone dyes, quinoneimine dyes, methine dyes, and phthalocyanine dyes.

[0514] These dyes can be used as light-shielding agents (D) by laking (salification) and dispersing them in an organic solvent or the like.

[0515] In addition to these dyes, for example, dyes described in JP-A-2013-225132, JP-A-2014-178477, JP-A-2013-137543, JP-A-2011-38085, and JP-A-2014-197206 can also be preferably used.

[0516] From the perspective of easily forming a fine line pattern with good adhesion to the substrate, it is preferred that the ratio of the mass of carbon black (D1) to the total mass of the light-shielding agent (D) is 30% by mass or more and 90% by mass or less, and the ratio of the mass of the lactam pigment (D2) to the total mass of the light-shielding agent (D) is 10% by mass or more and 70% by mass or less.

[0517] Furthermore, it is more preferred that the ratio of the mass of the carbon black (D1) to the total mass of the light-shielding agent (D) is 40% by mass or more and 90% by mass or less, and the ratio of the mass of the lactam pigment (D2) to the total mass of the light-shielding agent (D) is 10% by mass or more and 60% by mass or less.

[0518] More preferably, the mass ratio of carbon black (D1) is 50 mass% to 90 mass%, and the mass ratio of lactam pigment (D2) is 10 mass% to 50 mass% relative to the total mass of light-shielding agent (D).

[0519] The form of the light-shielding agent (D), such as carbon black (D1) subjected to a prescribed treatment and a lactam pigment (D2), used in the preparation of the photosensitive composition is not particularly limited. The light-shielding agent (D) may be used in the form of a powder or a dispersion. The light-shielding agent (D) is preferably used in the form of a dispersion in the preparation of the photosensitive composition.

[0520] As the dispersion liquid, a dispersion liquid containing two or more light-shielding agents (D) may be used. Alternatively, two or more dispersion liquids each containing a different type of light-shielding agent may be used.

[0521] As the dispersion medium, for example, organic solvents such as propylene glycol monomethyl ether acetate, cellosolve acetate, 3-methoxybutyl acetate, methoxypropyl acetate, 2-methoxyethyl acetate, ethyl 3-ethoxypropionate, and propylene glycol monomethyl ether propionate, and water can be used.

[0522] A dispersant may be added to the light-shielding agent (D) in order to stabilize the dispersion of the light-shielding agent (D) in the dispersion liquid and improve the dispersibility of the light-shielding agent (D) in the photosensitive composition.

[0523] As the dispersant, preferably used are polyethyleneimine-based, polyurethane resin-based, or acrylic resin-based polymer dispersants. Since the light-shielding agent (D) contains carbon black (D1), it is preferable to use an acrylic resin-based dispersant or a polyurethane resin-based dispersant suitable for dispersing carbon black as the dispersant.

[0524] In addition, corrosive gas may be generated from the cured film due to the dispersant. Therefore, dispersing the light-shielding agent (D) without using a dispersant is also an example of a preferred embodiment.

[0525] The viscosity of the dispersion of the light-shielding agent (D) is not particularly limited, but is preferably 3 mPa·s or more and 200 mPa·s or less as a value measured at 25° C. using a cone-plate viscometer.

[0526] The particle size of the light-shielding agent (D) in the dispersion is preferably 80 nm or more and 300 nm or less as a dispersed average particle size. The dispersed average particle size can be measured using a laser diffraction particle size distribution system.

[0527] The total content of the light-shielding agent (D) in the photosensitive composition can be appropriately selected within the scope of not hindering the purpose of the present invention. Typically, the total content of the light-shielding agent (D) in the photosensitive composition is preferably less than 45% by mass relative to the mass of the entire photosensitive composition, preferably more than 0.1% by mass and less than 30% by mass, more preferably more than 1% by mass and less than 20% by mass. It should be noted that, as long as a cured film with sufficiently high light-shielding properties can be formed using the photosensitive composition, the upper limit of the total content of the light-shielding agent (D) relative to the mass of the entire solid component of the photosensitive composition can be less than 90% by mass, can be less than 85% by mass, or can be less than 75% by mass. The lower limit is, for example, more than 15% by mass, preferably more than 20% by mass, and more preferably more than 40% by mass.

[0528] In addition, in this specification, the amount of the light-shielding agent (D) mentioned above can be defined as a value including the amount of the dispersant present together with the light-shielding agent (D).

[0529] <Other ingredients (E)>

[0530] Hereinafter, optional components will be described as other components. There is no particular limitation on the amount of other components (E) added. Other components (E) can be used in an amount that does not hinder the purpose of the present invention.

[0531] (Surface Conditioner)

[0532] Surface conditioners reduce the surface tension of the photosensitive composition, thereby suppressing the occurrence of surface defects and poor appearance caused by uneven distribution of pigments (uneven distribution of pigments). Specifically, polydimethylsiloxane, polyether-modified polysiloxane, polymethylalkylsiloxane, and polysiloxane modified with aralkyl or polyester chains are preferably used.

[0533] (Adhesion Improver)

[0534] Known coupling agents such as silane coupling agents, titanate coupling agents, and aluminate coupling agents can be used. Among them, silane coupling agents are preferably used from the viewpoint of improving adhesion to a glass substrate.

[0535] The photosensitive composition may contain various additives other than those listed above as needed. Specifically, examples include sensitizers, curing accelerators, photocrosslinking agents, photosensitizers, dispersing aids, fillers, antioxidants, ultraviolet absorbers, anti-aggregating agents, thermal polymerization inhibitors, defoaming agents, surfactants, chain transfer agents, photoinitiator aids, and solvents. Any of the additives may be conventionally known additives.

[0536] Examples of the surfactant include anionic compounds, cationic compounds, and nonionic compounds.

[0537] Examples of the thermal polymerization inhibitor include hydroquinone and hydroquinone monoethyl ether.

[0538] Examples of the defoaming agent include silicone compounds and fluorine compounds.

[0539] Examples of chain transfer agents include thiol compounds, halogen compounds, quinone compounds, and α-methylstyrene dimer. The inclusion of a chain transfer agent allows for good control of pattern shape (particularly, CD variation and exposure margin of the hole pattern). Among these, 2,4-diphenyl-4-methyl-1-pentene (α-methylstyrene dimer) is preferred for its ability to reduce sublimates, coloration, and odor in addition to the aforementioned effects.

[0540] Examples of the photoinitiator aid 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.

[0541] <Solvent (S)>

[0542] The photosensitive composition preferably contains a solvent (S) for dilution. Examples of the 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, and dipropylene glycol mono-n-propyl ether. , dipropylene glycol mono-n-butyl ether, tripropylene glycol monomethyl ether, tripropylene glycol monoethyl ether and other (poly) alkylene glycol monoalkyl ethers; ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate and other (poly) alkylene glycol monoalkyl ether acetates; diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol diethyl ether, tetrahydrofuran and other ethers methyl ethyl ketone, cyclohexanone, 2-heptanone, 3-heptanone and other ketones; 2-hydroxypropionic acid methyl ester, 2-hydroxypropionic acid ethyl ester and other lactic acid alkyl esters; 2-hydroxy-2-methylpropionic acid ethyl ester, 3-methoxypropionic acid methyl ester, 3-methoxypropionic acid ethyl ester, 3-ethoxypropionic acid methyl ester, 3-ethoxypropionic acid ethyl ester, ethyl ethoxyacetate, hydroxyethyl ester, 2-hydroxy-3-methylbutanoic acid methyl ester, 3-methyl-3-methoxybutyl acetate, 3-methyl-3-methoxybutyl propionate, ethyl Other esters such as ethyl formate, 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 acetoacetate, ethyl acetoacetate, and ethyl 2-oxobutyrate; aromatic hydrocarbons such as toluene and xylene; and amides such as N-methylpyrrolidone, N,N-dimethylformamide, and N,N-dimethylacetamide. These solvents may be used alone or in combination of two or more.

[0543] Among the above solvents, propylene glycol monomethyl ether, ethylene glycol monomethyl ether acetate, propylene glycol monomethyl ether acetate (GPMEA), propylene glycol monoethyl ether acetate, diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether (MEDG), cyclohexanone, and 3-methoxybutyl acetate (MBA) are preferred because they exhibit excellent solubility for the above-mentioned photopolymerization initiator (C). Propylene glycol monomethyl ether acetate and 3-methoxybutyl acetate are particularly preferred.

[0544] The content of the solvent (S) is preferably an amount such that the solid content concentration of the photosensitive composition is 1% by mass or more and 50% by mass or less, and more preferably 5% by mass or more and 40% by mass or less.

[0545] 《Method for preparing photosensitive composition》

[0546] The above ingredients are uniformly stirred, mixed, dissolved, and dispersed to prepare a photosensitive composition. Mixing can be performed using a mixer such as a roll mill, ball mill, or sand mill. If necessary, the composition can be filtered through a filter such as a 2 μm membrane filter.

[0547] 《Method for forming a solidified product, and solidified product》

[0548] The method for forming a cured product is the same as the conventional method for forming a cured product using a photosensitive composition, except that the above-mentioned photosensitive composition is used.

[0549] The method for forming a cured product using the above-mentioned photosensitive composition is not particularly limited and can be appropriately selected from the methods that have been used. For the cured product, a molded body of a desired shape can be formed by controlling the shape of the coating film when applying the photosensitive composition, and combining position-selective exposure and development. As a preferred method for forming a cured product, a method comprising the following steps can be mentioned: a coating film forming step of forming a coating film using the above-mentioned photosensitive composition; and an exposure step of exposing the above-mentioned coating film. When the exposure is performed in a position-selective manner, the exposed coating film can be developed using a developer to obtain a patterned cured product.

[0550] First, in the coating film forming step, the photosensitive composition is applied to a substrate on which a cured product is to be formed using, for example, a contact transfer coating apparatus such as a roll coater, reverse coater, or bar coater, or a non-contact coating apparatus such as a spin coater or curtain flow coater. If necessary, the solvent is removed by drying (pre-baking) to form a coating film.

[0551] For convenience, droplets placed on a substrate, photosensitive compositions filled in recesses of a substrate having irregularities, and photosensitive compositions filled in recesses of a mold are also referred to as "coating films."

[0552] The film thickness of the photosensitive composition cured product formed using the photosensitive composition and the layer thickness of the light-shielding layer (black matrix, black bank) are not particularly limited, but are preferably 0.2 μm or more, more preferably 0.3 μm or more and 5 μm or less, more preferably 0.4 μm or more and 3 μm or less, and most preferably 0.5 μm or more and 2 μm or less.

[0553] Next, the formed coating film is subjected to an exposure step. In the exposure step, the coating film is irradiated with radiation or electromagnetic waves such as ArF excimer laser, KrF excimer laser, F2 excimer laser, extreme ultraviolet (EUV), vacuum ultraviolet (VUV), electron beam, X-ray, soft X-ray, i-line, g-line, h-line, etc. to expose the coating film. The exposure of the coating film can be performed in a position-selective manner through a negative mask. The exposure amount varies depending on the composition of the photosensitive composition, and is preferably 10 mJ / cm 2 Above and 600mJ / cm 2 Below left and right.

[0554] The exposed coating film is developed as needed.

[0555] The photosensitive composition described above is unlikely to dissolve excessively in an alkaline developer after exposure. Therefore, by using the photosensitive composition described above, a well-shaped patterned cured product with exposed areas as convex portions and unexposed areas as concave portions can be easily formed.

[0556] In particular, when using the aforementioned photosensitive composition, a pattern with a relatively fine line width can be formed while ensuring good adhesion between the patterned cured product and the substrate. The line width of the pattern is, for example, preferably 10 μm or less, more preferably 7 μm or less, further preferably 5 μm or less, and particularly preferably 3 μm or less.

[0557] In the development step, the exposed coating film is developed with a developer to form a patterned cured product in the desired shape. The development method is not particularly limited, and immersion methods, spray methods, etc. can be used. Specific examples of the developer include aqueous solutions of sodium hydroxide, potassium hydroxide, sodium carbonate, ammonia, and quaternary ammonium salts.

[0558] Furthermore, if necessary, the cured product after exposure or the cured product after development and patterning can be subjected to post-baking for further heat curing. The post-baking temperature is preferably 150° C. or higher and 270° C. or lower.

[0559] The cured product is formed using the aforementioned photosensitive composition. The purpose of the cured product is not particularly limited. The cured product is particularly preferably used as a black matrix or black bank used in various image display device color filters. A color filter having a black matrix or black bank formed by a cured product formed using the aforementioned photosensitive composition can be suitably used in an image display panel. The image display panel can be suitably used in various image display devices such as liquid crystal display devices, organic EL display devices, and inorganic EL display devices. In addition, in a touch panel having both an image display panel and a surface sensor (the surface sensor includes an electrostatic capacitance electrode, a resistance electrode, etc.), it can also be suitably used.

[0560] Example

[0561] Hereinafter, the present invention will be described in further detail with reference to Examples, but the present invention is not limited to these Examples.

[0562] [Examples 1 to 4 and Comparative Examples 1 to 4]

[0563] In the Examples and Comparative Examples, the Cardo resin obtained in the following Preparation Example 1 was used as the alkali-soluble resin (A).

[0564] [Preparation Example 1]

[0565] To a 500mL four-necked flask, 235g of bisphenol fluorene epoxy resin (epoxy equivalent of 235), 110mg of tetramethylammonium chloride, 100mg of 2,6-di-tert-butyl-4-methylphenol, and 72.0g of acrylic acid were added, and air was blown into it at a rate of 25mL / min while heating it to above 90°C and below 100°C to dissolve it. Then, the solution was slowly heated while maintaining a turbid state, and heated to 120°C to completely dissolve it. At this point, the solution gradually became transparent and viscous, and this state was maintained and stirred continuously. During this period, the acid value was measured, and heating and stirring were continued until the acid value was less than 1.0mgKOH / g. It took 12 hours until the acid value reached the target value. Then, it was cooled to room temperature to obtain a colorless, transparent, solid bisphenol fluorene epoxy acrylate represented by the following formula.

[0566] [Chemical Formula 54]

[0567]

[0568] Next, 600 g of 3-methoxybutyl acetate was added to 307.0 g of the bisphenol fluorene epoxy acrylate obtained above and dissolved. Then, 80.5 g of biphenyltetracarboxylic dianhydride and 1 g of tetraethylammonium bromide were mixed and the temperature was gradually raised to react at 110-115°C for 4 hours. After confirming the disappearance of the anhydride groups, 38.0 g of 1,2,3,6-tetrahydrophthalic anhydride was added and reacted at 90°C for 6 hours to obtain a cardo resin (R-1) as the alkali-soluble resin (A). The disappearance of the anhydride groups was confirmed by IR spectroscopy.

[0569] [Preparation Example 2]

[0570] A Cardo resin (R-2) was obtained as the alkali-soluble resin (A) in the same manner as in Preparation Example 1 except that the biphenyltetracarboxylic dianhydride in Preparation Example 1 was replaced with pyromellitic dianhydride.

[0571] In Examples and Comparative Examples, dipentaerythritol hexaacrylate (B-1) was used as the photopolymerizable monomer (B).

[0572] In Examples and Comparative Examples, oxime ester compounds (P-1) to (P-3) represented by the following formulae were used as the photopolymerization initiator (C).

[0573] [Chemical Formula 55]

[0574]

[0575] As the resin-coated carbon black (D1), D-1a, an epoxy resin-coated carbon black dispersion, was used. The dispersion medium was propylene glycol monomethyl ether acetate (PM). The average dispersed particle size of D-1a's resin-coated carbon black was 130 nm, and the powder resistivity was 5 Ω·cm.

[0576] As the dye-coated carbon black (D1), carbon black D-1b, which is a dye-coated carbon coated with a black direct dye, was used. Carbon black D-1b was prepared according to Preparation Example 3 below.

[0577] [Preparation Example 3]

[0578] 1000 g of carbon black (Regal 250R, manufactured by Cabot Corporation) was mixed with water to prepare 10 L of slurry. The slurry was stirred at 95°C for 1 hour and allowed to cool. Then, the carbon black was filtered out and the obtained carbon black was washed with water. The washed carbon black was mixed with water again to prepare 10 L of slurry. Next, 42.9 g of nitric acid with a concentration of 70% by mass was added to the slurry, and the slurry was stirred at 40°C for 4 hours. After the slurry was allowed to cool, the carbon black was filtered out and the obtained carbon black was washed with water. The washed carbon black was mixed with water again to prepare 10 L of slurry. Next, 769.2 g of an aqueous sodium hypochlorite solution with a concentration of 13% by mass was added to the slurry, and the slurry was stirred at 40°C for 6 hours. After the slurry was allowed to cool, the carbon black was filtered out and the obtained carbon black was washed with water. The washed carbon black was mixed with water again to prepare 10 L of slurry. Next, 38.1 g of a dye (Direct Deep BLACK) with a purity of 38.4% by mass was added to the slurry, and the slurry was stirred at 40°C for 1 hour. Then, 10.1 g of aluminum sulfate was further added to the slurry, and the slurry was stirred at 40°C for 1 hour. After the slurry was allowed to cool, the carbon black was filtered out, washed with water, filtered, and dried to obtain dye-coated carbon black D-1b.

[0579] As the carbon black (D1) subjected to a treatment for introducing an acidic group, the carbon black D-1c obtained in the following Preparation Example 2 was used.

[0580] [Preparation Example 4]

[0581] 550 g of carbon black (Regal 250R, manufactured by Cabot Corporation), 31.5 g of sulfanilic acid, and 1000 g of ion exchange water were added to a reaction vessel with a cover and a stirring device, the cover temperature of which was set to 60°C. A solution obtained by dissolving 12.6 g of sodium nitrite in 100 g of deionized water was added to a Braun mixer, and then the mixture in the mixer was stirred at 60°C and 50 rpm for 2 hours to carry out a diazo coupling reaction. After stirring, the contents of the mixer were cooled to room temperature. Next, the carbon black contained in the contents of the mixer was purified by diafiltration using deionized water. No benzenesulfonic acid from sulfanilic acid was detected in the rinse water, indicating that benzenesulfonic acid groups were introduced into the carbon black by diazo coupling reaction. The purified carbon black was dried at 75°C overnight and then crushed to obtain carbon black (D-1c) into which benzenesulfonic acid groups were introduced.

[0582] As the lactam pigment (D2), D-2, a compound represented by the following formula, was used.

[0583] [Chemical Formula 56]

[0584]

[0585] As the perylene pigment, D-3, which is Perylene (3,4,9,10-perylenetetracarboxylic acid diimide), was used.

[0586] In addition, in Table 1, description about the usage-amount of each light-shielding agent is described as the mass of each solid content.

[0587] In the Examples and Comparative Examples, the following solvents (S) were mixed and used as a mixed solvent. The mixing ratio (mass ratio) of each solvent was S-1:S-2:S-3 = 50:30:20.

[0588] S-1: 3-Methoxybutyl acetate (MA)

[0589] S-2: Propylene glycol monomethyl ether acetate (PM)

[0590] S-3: Cyclohexanone (AN)

[0591] Here, when the light-shielding agent (D) contains a solvent as a dispersion medium, the solvent (S) includes the dispersion medium contained in the light-shielding agent (D).

[0592] The amounts and types of alkali-soluble resin (A) (component (A)) listed in Table 1, photopolymerizable monomer (B) (component (B)), photopolymerization initiator (C) (component (C)) listed in Table 1, light-shielding agent (D) (component (D)), 0.1 parts by mass of BYK-310 (manufactured by BYK-Chemie Japan Co., Ltd.), a polyester-modified polydimethylsiloxane, as a surface conditioner, and 0.5 parts by mass of 3-phenylamino-n-propyl (trimethoxy)silane as an adhesion enhancer were dissolved and dispersed in the aforementioned solvent (S) to a solids concentration of 15% by mass to obtain photosensitive compositions for each of the Examples and Comparative Examples. In each of the Examples except Comparative Example 4, the light-shielding agent (D) contained 7.9 parts by mass of a dispersant. Table 1 only lists the types of pigments used. In Comparative Example 4, a photosensitive composition containing only component (D) D-2 was prepared. However, even when the amount of component (D) was increased, the OD value could not be made equivalent to that of the photosensitive compositions of other examples in the evaluation described below, and the OD value was 2.8.

[0593] Evaluation was performed by the following method using the photosensitive compositions of Examples 1 to 6 and Comparative Examples 1 to 4.

[0594] <Optical density (OD value) of cured film>

[0595] The photosensitive composition obtained in each of Examples and Comparative Examples was applied onto a 100×100 mm, 0.7 mm thick glass substrate using a spin coater, and the coating was pre-baked at 100° C. for 120 seconds.

[0596] Next, the coating film was entirely exposed to light (ultraviolet light exposure using an ultrahigh pressure mercury lamp) at an optimum exposure dose (Eop) without using a mask using an exposure apparatus TME150RTO (manufactured by TOPCON).

[0597] After the exposure, development was performed at 25° C. for 60 seconds using an aqueous solution of potassium hydroxide having a concentration of 0.05% by mass as a developer.

[0598] The exposed coating film after development was post-baked at 230° C. for 30 minutes to form a cured film with a film thickness of 1 μm.

[0599] The optical density of the formed cured film was measured using an optical density meter D-200II (manufactured by GretagMacbeth), and the unit optical density (unit: / μm) was calculated as the OD value by converting the film thickness. The results are shown in Table 1.

[0600] <Reflectivity>

[0601] A 1μm-thick cured film was formed under the same conditions as for the OD value measurement. The reflectance of the resulting cured film in the visible light region was measured using a multi-channel spectrometer, MCPD-3700 (manufactured by Otsuka Electronics), with both the incident and reflection angles set at 10°. The reflected light incident from the top of the glass substrate was detected by the detector of the measuring instrument as the total reflected light, which is a combination of the reflected light from the outermost surface and the reflected light from the bottom of the substrate. The results were evaluated according to the following criteria and are reported in Table 1.

[0602] ·Below 7%···〇

[0603] ·More than 7%···×

[0604] <Pattern Adhesion>

[0605] The photosensitive composition obtained in each of Examples and Comparative Examples was applied onto a 100×100 mm, 0.7 mm thick glass substrate using a spin coater, and the coating was pre-baked at 100° C. for 120 seconds.

[0606] Next, the coating film was exposed to light (ultraviolet light exposure using an ultrahigh pressure mercury lamp) at an optimum exposure dose (Eop) via a mask using an exposure apparatus TME150RTO (manufactured by TOPCON).

[0607] After the exposure, development was performed at 25° C. for 60 seconds using an aqueous solution of potassium hydroxide having a concentration of 0.05% by mass as a developer.

[0608] After development, post-baking was performed at 230° C. for 30 minutes to form a line pattern.

[0609] The formed line pattern was observed under a microscope, and the pattern adhesion was evaluated according to the following criteria: In Comparative Example 4, no pattern was formed.

[0610] ⊚: A line pattern with a mask size of 3 μm can be formed without pattern peeling.

[0611] ◯: A line pattern with a mask size of 5 μm could be formed without pattern peeling, but pattern peeling occurred when a line pattern with a mask size of 3 μm was formed.

[0612] ×: When forming a line pattern with a mask size of 5 μm, pattern peeling occurred.

[0613] [Table 1]

[0614]

[0615] As can be seen from Table 1, a photosensitive composition comprising an alkali-soluble resin (A), a photopolymerizable monomer (B), and a photopolymerization initiator (C), and comprising carbon black (D1) subjected to a prescribed surface treatment, and a lactam pigment (D2) as a light-shielding agent (D) can form a fine line pattern with low reflectivity and close adhesion to the substrate.

Claims

1. A photosensitive composition comprising an alkali-soluble resin (A), a photopolymerizable monomer (B), a photopolymerization initiator (C), and a light-shielding agent (D). The sunscreen (D) comprises carbon black (D1) and a lactam pigment (D2). The carbon black (D1) is subjected to a surface treatment selected from a coating treatment with an organic substance and a treatment for introducing an acidic group. The ratio of the mass of the carbon black (D1) to the total mass of the light-shielding agent (D) is 70% by mass or more and 90% by mass or less, The ratio of the mass of the lactam pigment (D2) to the total mass of the light-shielding agent (D) is 10% by mass or more and 30% by mass or less.

2. The photosensitive composition according to claim 1, wherein The organic matter is resin or dye.

3. The photosensitive composition according to claim 1 or 2, wherein The ratio of the total mass of the carbon black (D1) and the lactam pigment (D2) to the total mass of the light-shielding agent (D) is 80% by mass or more.

4. The photosensitive composition according to claim 1 or 2, wherein The alkali-soluble resin (A) includes a resin having a Cardo structure. 5 . A cured product, which is a cured product of the photosensitive composition according to claim 1 . 6 . A black matrix or a black bank formed from the cured product according to claim 5 . 7 . A color filter comprising the black matrix or the black bank according to claim 6 .

8. An image display panel comprising the color filter according to claim 7. 9 . An image display device comprising the image display panel according to claim 8 .

10. A method for producing a patterned cured film, comprising: applying the photosensitive composition according to any one of claims 1 to 4 on a substrate to form a coating film; exposing the coating film in a position-selective manner; and The exposed coating film is developed.

11. The manufacturing method according to claim 10, wherein: The patterned cured film is a black matrix or a black bank.

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