JP2015069161A - Photosensitive resin composition, production method of resin pattern, and display device - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a negative photosensitive resin composition from which a resin pattern having a normally tapered opening can be easily formed, a production method of a resin pattern using the photosensitive resin composition, and a display device including a resin pattern produced by the above production method.SOLUTION: The photosensitive resin composition comprises (A) an alkali-soluble resin, (B) a photopolymerization initiator, and (C) a photopolymerizable compound. The (C) photopolymerizable compound contains a monofunctional monomer that shows a glass transition temperature of -10°C or lower when the monomer is prepared into a homopolymer having a mass average molecular weight of 10000 or more.

Description

  The present invention relates to a photosensitive resin composition, a method for producing a resin pattern using the photosensitive resin composition, and a display device including the resin pattern produced by the production method.

  2. Description of the Related Art In recent years, a configuration in which a driving element such as a thin film transistor (TFT) element is provided in each pixel of a liquid crystal display element has been widely adopted in order to improve response speed, increase luminance, improve image quality, and the like. In the liquid crystal display element having such a configuration, for example, the drain electrode of the TFT element and the pixel electrode made of ITO (indium tin oxide) or the like are connected by a contact hole formed in the organic insulating film. The contact hole preferably has a forward tapered shape having an inner diameter that increases from the bottom surface toward the surface. Since the contact hole has a forward tapered shape, for example, when ITO is deposited, an ITO film can be appropriately formed on the inner surface of the contact hole, and the risk of disconnection can be reduced (Patent Document 1, etc.) See).

  Here, the organic insulating film having a contact hole is often formed by a lithography method using a photosensitive resin composition. The photosensitive resin composition is preferably a negative type from the viewpoint of heat resistance and the like. However, when a negative type photosensitive resin composition is used, the side wall of the contact hole becomes nearly vertical and has a forward taper. It is difficult to form a shaped contact hole. In this regard, if the photocuring reaction is made insufficient, a forward tapered contact hole can be obtained by the heat flow during post-baking, but the risk of outgassing because unreacted components remain in the insulating film. In addition, the resistance to various durability tests deteriorates.

International Publication No. 2011/004717

  The present invention has been made in view of such conventional circumstances, and is a negative photosensitive resin composition capable of easily forming a resin pattern having a forward tapered opening, and the photosensitive resin composition It aims at providing the display apparatus provided with the manufacturing method of the resin pattern using the, and the resin pattern manufactured by the manufacturing method.

  The inventors of the present invention have made extensive studies to achieve the above object. As a result, the inventors have found that the object can be achieved by using a photosensitive resin composition containing a specific monofunctional monomer, and have completed the present invention.

  The first aspect of the present invention comprises (A) an alkali-soluble resin, (B) a photopolymerization initiator, and (C) a photopolymerizable compound, and the (C) photopolymerizable compound has a mass average molecular weight of 10,000. A photosensitive resin composition containing a monofunctional monomer having a glass transition temperature of −10 ° C. or lower when the above homopolymer is obtained.

  Moreover, the 2nd aspect of this invention has the coating process which apply | coats the photosensitive resin composition which concerns on a 1st aspect on a board | substrate, and forms a coating film, The exposure process which selectively exposes the said coating film, The method for producing a resin pattern includes: a development step for developing the coating film after the exposure step to obtain a resin pattern; and a heating step for heating the resin pattern.

  Moreover, the 3rd aspect of this invention is a display apparatus provided with the resin pattern manufactured by the manufacturing method which concerns on a 2nd aspect.

  According to the present invention, a negative photosensitive resin composition capable of easily forming a resin pattern having a forward tapered opening, a method for producing a resin pattern using the photosensitive resin composition, and a method for producing the same A display device including the resin pattern manufactured by the method can be provided.

≪Photosensitive resin composition≫
The photosensitive resin composition according to the present invention contains at least (A) an alkali-soluble resin, (B) a photopolymerization initiator, and (C) a photopolymerizable compound. Hereinafter, each component contained in the photosensitive resin composition will be described.

<(A) Alkali-soluble resin>
(A) The alkali-soluble resin is a resin film having a resin concentration of 20% by mass (solvent: propylene glycol monomethyl ether acetate), and a resin film having a thickness of 1 μm is formed on the substrate, and 2.38% by mass at 23 ° C. When immersed in an aqueous tetramethylammonium hydroxide (TMAH) solution for 1 minute, it means a film that dissolves in a thickness of 0.01 μm or more.

  (A) The alkali-soluble resin is not particularly limited as long as it is a resin exhibiting alkali solubility as described above. For example, the unsaturated carboxylic acid (a1) and an alicyclic epoxy group-containing unsaturated compound (a2) are polymerized at least. The copolymer (A1) made can be used.

As the unsaturated carboxylic acid (a1), monocarboxylic acids such as (meth) acrylic acid and crotonic acid; dicarboxylic acids such as maleic acid, fumaric acid, citraconic acid, mesaconic acid and itaconic acid; anhydrides of these dicarboxylic acids; Etc. Among these, (meth) acrylic acid and maleic anhydride are preferable in terms of copolymerization reactivity, alkali solubility of the resulting resin, availability, and the like. These unsaturated carboxylic acids (a1) can be used alone or in combination of two or more.
In the present specification, “(meth) acrylic acid” means both acrylic acid and methacrylic acid. Similarly, “(meth) acrylate” means both acrylate and methacrylate.

  The proportion of the structural unit derived from the unsaturated carboxylic acid (a1) (the structural unit having a carboxyl group) in the copolymer (A1) is preferably 5 to 29% by mass, and 10 to 25% by mass. It is more preferable. By setting it as the said range, the developability of the photosensitive resin composition can be made moderate.

  The alicyclic group of the alicyclic epoxy group-containing unsaturated compound (a2) may be monocyclic or polycyclic. Examples of the monocyclic alicyclic group include a cyclopentyl group and a cyclohexyl group. Examples of the polycyclic alicyclic group include a norbornyl group, an isobornyl group, a tricyclononyl group, a tricyclodecyl group, and a tetracyclododecyl group.

  Specifically, examples of the alicyclic epoxy group-containing unsaturated compound (a2) include compounds represented by the following formulas (a2-1) to (a2-16). Among these, in order to make the developability of the photosensitive resin composition appropriate, compounds represented by the following formulas (a2-1) to (a2-6) are preferable, and the following formula (a2-1) The compound represented by (a2-4) is more preferable.

In the above formula, R ^a1 represents a hydrogen atom or a methyl group, R ^a2 represents a divalent saturated aliphatic hydrocarbon group having 1 to 6 carbon atoms, and R ^a3 represents a divalent hydrocarbon having 1 to 10 carbon atoms. Represents a group, and n represents an integer of 0 to 10. R ^a2 is preferably a linear or branched alkylene group such as a methylene group, an ethylene group, a propylene group, a tetramethylene group, an ethylethylene group, a pentamethylene group, or a hexamethylene group. As R ^a3 , for example, methylene group, ethylene group, propylene group, tetramethylene group, ethylethylene group, pentamethylene group, hexamethylene group, phenylene group, cyclohexylene group, —CH ₂ —Ph—CH ₂ — (Ph is A phenylene group) is preferred.

  These alicyclic epoxy group-containing unsaturated compounds (a2) can be used alone or in combination of two or more.

  The proportion of the structural unit derived from the alicyclic epoxy group-containing unsaturated compound (a2) in the copolymer (A1) (the structural unit having an alicyclic epoxy group) is preferably 5 to 90% by mass. More preferably, it is 15-75 mass%. By setting it as the above range, it becomes easy to form a resin pattern having a good shape.

  The copolymer (A1) is preferably obtained by further polymerizing an alicyclic group-containing unsaturated compound (a3) having no epoxy group.

  The alicyclic group of the alicyclic group-containing unsaturated compound (a3) may be monocyclic or polycyclic. Examples of the monocyclic alicyclic group include a cyclopentyl group and a cyclohexyl group. Examples of the polycyclic alicyclic group include an adamantyl group, a norbornyl group, an isobornyl group, a tricyclononyl group, a tricyclodecyl group, and a tetracyclododecyl group.

  Specifically, examples of the alicyclic group-containing unsaturated compound (a3) include compounds represented by the following formulas (a3-1) to (a3-8). Among these, in order to make the developability of the photosensitive resin composition appropriate, compounds represented by the following formulas (a3-3) to (a3-8) are preferable, and the following formula (a3-3) , (A3-4) is more preferred.

In the above formula, R ^a4 represents a hydrogen atom or a methyl group, R ^a5 represents a single bond or a divalent aliphatic saturated hydrocarbon group having 1 to ⁶ carbon atoms, and R ^a6 represents a hydrogen atom or 1 to 5 carbon atoms. Represents an alkyl group. R ^a5 is preferably a single bond or a linear or branched alkylene group such as a methylene group, an ethylene group, a propylene group, a tetramethylene group, an ethylethylene group, a pentamethylene group or a hexamethylene group. As R ^a6 , for example, a methyl group and an ethyl group are preferable.

  The proportion of the structural unit derived from the alicyclic group-containing unsaturated compound (a3) in the copolymer (A1) is preferably 1 to 40% by mass, and more preferably 5 to 30% by mass. .

  Moreover, the said copolymer (A1) may further copolymerize other compounds other than the above. Examples of such other compounds include (meth) acrylic acid esters, (meth) acrylamides, allyl compounds, vinyl ethers, vinyl esters, styrenes, and the like. These compounds can be used alone or in combination of two or more.

  As (meth) acrylic acid esters, linear or branched chain such as methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, amyl (meth) acrylate, t-octyl (meth) acrylate, etc. Alkyl (meth) acrylates; chloroethyl (meth) acrylate, 2,2-dimethylhydroxypropyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, trimethylolpropane mono (meth) acrylate, benzyl (meth) acrylate, furfuryl (Meth) acrylate; etc. are mentioned.

  (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, N-hydroxyethyl-N-methyl (meth) acrylamide and the like.

  Examples of the allyl compound include allyl acetate, allyl caproate, allyl caprylate, allyl laurate, allyl palmitate, allyl stearate, allyl benzoate, allyl acetoacetate, allyl lactate, etc .; allyloxyethanol; Can be mentioned.

  As vinyl ethers, hexyl vinyl ether, octyl vinyl ether, decyl vinyl ether, ethyl hexyl 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 , Alkyl vinyl ethers such as diethylene glycol vinyl ether, dimethylaminoethyl vinyl ether, diethylaminoethyl vinyl ether, butylaminoethyl vinyl ether, benzyl vinyl ether, tetrahydrofurfuryl vinyl ether; vinyl phenyl ether, vinyl tolyl ether, vinyl chlorophenyl ether, vinyl-2,4-dichloropheny And the like; ethers, vinyl naphthyl ether, vinyl aryl ethers such as vinyl anthranyl ether.

  Vinyl esters include vinyl butyrate, vinyl isobutyrate, vinyl trimethyl acetate, vinyl diethyl acetate, vinyl valate, vinyl caproate, vinyl chloroacetate, vinyl dichloroacetate, vinyl methoxyacetate, vinyl butoxyacetate, vinyl vinyl. Examples include enyl acetate, vinyl acetoacetate, vinyl lactate, vinyl-β-phenylbutyrate, vinyl benzoate, vinyl salicylate, vinyl chlorobenzoate, vinyl tetrachlorobenzoate, vinyl naphthoate and the like.

  Styrenes include: styrene; methyl styrene, dimethyl styrene, trimethyl styrene, ethyl styrene, diethyl styrene, isopropyl styrene, butyl styrene, hexyl styrene, cyclohexyl styrene, decyl styrene, benzyl styrene, chloromethyl styrene, trifluoromethyl styrene, ethoxy Alkyl styrene such as methyl styrene and acetoxymethyl styrene; alkoxy styrene such as methoxy styrene, 4-methoxy-3-methyl styrene and dimethoxy styrene; chlorostyrene, dichlorostyrene, trichlorostyrene, tetrachlorostyrene, pentachlorostyrene, bromostyrene, Dibromostyrene, iodostyrene, fluorostyrene, trifluorostyrene, 2-bromo-4-trifluoromethyl Styrene, halostyrenes such as 4-fluoro-3-trifluoromethyl styrene; and the like.

  The mass average molecular weight of the copolymer (A1) is preferably 2000 to 50000, and more preferably 5000 to 30000. By setting it as the above range, there is a tendency that the film forming ability and developability of the photosensitive resin composition are easily balanced.

  (A) The content of the alkali-soluble resin is preferably 40 to 85% by mass and more preferably 45 to 75% by mass with respect to the solid content of the photosensitive resin composition.

<(B) Photopolymerization initiator>
It does not specifically limit as a photoinitiator, A conventionally well-known photoinitiator can be used. A photoinitiator can be used individually or in combination of 2 or more types.

  Specific examples of the photopolymerization initiator include 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, and 1- [4- (2-hydroxyethoxy) phenyl] -2- Hydroxy-2-methyl-1-propan-1-one, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, 1- (4-dodecylphenyl) -2-hydroxy-2 -Methylpropan-1-one, bis (4-dimethylaminophenyl) ketone, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 4-benzoyl-4'-methyldimethylsulfide, 4-dimethylaminobenzoic acid, 4- Methyl dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, 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, azobisisobu Tyronitrile, benzoyl peroxide, cumene peroxide, 2-mercaptobenzoimidazole, 2-mercaptobenzoxazole, 2-mercaptobenzothiazole, 2- (o-chlorophenyl) -4,5-diphenylimidazole dimer, 2- ( o-chlorophenyl) -4,5-di (methoxyphenyl) imidazole dimer, 2- (o-fluorophenyl) -4,5-diphenylimidazole dimer, 2- (o-methoxyphenyl) -4,5 -Diphenylimidazole dimer, 2- (p-methoxyphenyl) -4,5-diphenylimidazole dimer, 2,4,5-triarylimidazole dimer, benzophenone, 2-chlorobenzophenone, 4,4 ' -Bisdimethylaminobenzophenone (ie Michler's ketone), 4 4′-bisdiethylaminobenzophenone (ie, ethyl Michler's ketone), 4,4′-dichlorobenzophenone, 3,3-dimethyl-4-methoxybenzophenone, benzyl, 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-dimethylaminopropiophenone, dichloroacetophenone, trichloroacetophenone, p-tert-butylacetophenone, p -Dimethylaminoacetophenone, p-tert-butyltrichloroacetophenone, p-tert-butyldichloroaceto Enone, α, α-dichloro-4-phenoxyacetophenone, thioxanthone, 2-methylthioxanthone, 2-isopropylthioxanthone, dibenzosuberone, pentyl-4-dimethylaminobenzoate, 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) ethenyl] -4,6-bis (trichloromethyl) -s- Triazine, 2- [2- (furan-2-yl) ethenyl] -4,6-bis (trichloromethyl)- -Triazine, 2- [2- (4-diethylamino-2-methylphenyl) ethenyl] -4,6-bis (trichloromethyl) -s-triazine, 2- [2- (3,4-dimethoxyphenyl) ethenyl] -4,6-bis (trichloromethyl) -s-triazine, 2- (4-methoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4-ethoxystyryl) -4,6 -Bis (trichloromethyl) -s-triazine, 2- (4-n-butoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine, 2,4-bis-trichloromethyl-6- (3- Bromo-4-methoxy) phenyl-s-triazine, 2,4-bis-trichloromethyl-6- (2-bromo-4-methoxy) phenyl-s-triazine, 2,4-bis -Trichloromethyl-6- (3-bromo-4-methoxy) styrylphenyl-s-triazine, 2,4-bis-trichloromethyl-6- (2-bromo-4-methoxy) styrylphenyl-s-triazine, IRGACURE OXE02 "," IRGACURE OXE01 "," IRGACURE 369 "," IRGACURE 651 "," IRGACURE 907 "(trade name, manufactured by BASF)," NCI-831 "(trade name, manufactured by ADEKA), and the like. These photopolymerization initiators can be used alone or in combination of two or more.

Among these, it is particularly preferable in terms of sensitivity to use an oxime photopolymerization initiator.
A preferable example of the oxime photopolymerization initiator includes a photopolymerization initiator represented by the following formula (b-1).

In the above formula (b-1), R ^b1 represents a heterocyclic group, a condensed cyclic aromatic group, or an aromatic group, which may have a substituent. R ^{b2 to} R ^b4 each independently represent a monovalent organic group.

^Examples of the heterocyclic group for R ^b1 include 5-membered or more, preferably 5- or 6-membered heterocyclic groups containing at least one of a nitrogen atom, a sulfur atom, and an oxygen atom. Examples of heterocyclic groups include nitrogen-containing 5-membered ring groups such as pyrrolyl, imidazolyl and pyrazolyl groups; nitrogen-containing 6-membered ring groups such as pyridyl, pyrazinyl, pyrimidyl and pyridazinyl groups; thiazolyl and isothiazolyl groups Nitrogen-containing sulfur groups such as oxazolyl groups and isoxazolyl groups; sulfur-containing groups such as thienyl groups and thiopyranyl groups; oxygen-containing groups such as furyl groups and pyranyl groups; Among these, those containing one nitrogen atom or one sulfur atom are preferable. This heterocyclic ring may contain a condensed ring. Examples of the heterocyclic group containing a condensed ring include a benzothienyl group.

^Examples of the condensed cyclic aromatic group for R ^b1 include a naphthyl group, an anthryl group, and a phenanthryl group. The aromatic group represented by R ^b1, and a phenyl group.

The heterocyclic group, the condensed cyclic aromatic group, or the aromatic group may have a substituent. In particular, when R ^b1 is an aromatic group, it preferably has a substituent. Examples of such _{^{substituents, -NO 2, -CN, -SO 2}} R b5, -COR b5, -NR b6 R b7, -R b8, -OR b8, -O-R b9 -O-R b10 , etc. Is mentioned.

R ^b5 independently represents an alkyl group, which may be substituted with a halogen atom, and is an ether bond (—O—), a thioether bond (—S—), an ester bond (—COO—, —OCO—). ) May be interrupted. The alkyl group for R ^b5 preferably has 1 to 5 carbon atoms, and examples thereof include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, and an isobutyl group.

R ^b6 and R ^b7 each independently represent a hydrogen atom, an alkyl group, or an alkoxy group, which may be substituted with a halogen atom, and among these, the alkylene part of the alkyl group and the alkoxy group is an ether bond, It may be interrupted by a thioether bond or an ester bond. R ^b6 and R ^b7 may be bonded to form a ring structure. The alkyl group or alkoxy group in R ^b6 and R ^b7 preferably has 1 to 5 carbon atoms. For example, methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, methoxy group, ethoxy group, A propoxy group etc. are mentioned.

A ring structure that can be formed by combining R ^b6 and R ^b7 includes a heterocyclic ring. Examples of the heterocyclic ring include 5-membered or more, preferably 5 to 7-membered heterocyclic rings containing at least a nitrogen atom. This heterocyclic ring may contain a condensed ring. Examples of the heterocyclic ring include piperidine ring, morpholine ring, thiomorpholine ring and the like. Among these, a morpholine ring is preferable.

R ^b8 represents an alkyl group in which part or all of the hydrogen atoms may be substituted with a halogen atom. The alkyl group for R ^b8 preferably has 1 to 6 carbon atoms, and examples thereof include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, and an isobutyl group.

R ^b9 and R ^b10 each independently represent an alkyl group, which may be substituted with a halogen atom, and may be interrupted by an ether bond, a thioether bond, or an ester bond. Preferred carbon numbers and specific examples thereof are the same as those described above for R ^b1 .

Among these, preferred examples of R ^b1 include a pyrrolyl group, a pyridyl group, a thienyl group, a thiopyralyl group, a benzothienyl group, a naphthyl group, and a phenyl group having a substituent.

In the above formula (b-1), R ^b2 represents a monovalent organic group. As ^the organic ^{group, -R b11, -OR b11, -COR} b11, -SR b11, preferably a group represented by -NR ^{b11 R b12.} R ^b11 and R ^b12 each independently represent an alkyl group, an alkenyl group, an aryl group, an aralkyl group, or a heterocyclic group, which may be substituted with a halogen atom, an alkyl group, or a heterocyclic group, Among them, the alkylene part of the alkyl group and the aralkyl group may be interrupted by an unsaturated bond, an ether bond, a thioether bond, or an ester bond. R ^b11 and R ^b12 may be bonded to form a ring structure with the nitrogen atom.

The alkyl group in R ^b11 and ^{R b12,} preferably those having 1 to 20 carbon atoms, more preferably from 1 to 5 carbon atoms. Examples of alkyl groups include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, sec-pentyl. Group, tert-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, isooctyl group, sec-octyl group, tert-octyl group, n-nonyl group, isononyl group, n-decyl group, isodecyl group And a straight chain or branched chain group such as Moreover, this alkyl group may have a substituent. Examples of those having a substituent include a methoxyethoxyethyl group, an ethoxyethoxyethyl group, a propyloxyethoxyethyl group, and a methoxypropyl group.

The alkenyl group for R ^b11 and ^{R b12,} preferably those having 1 to 20 carbon atoms, more preferably from 1 to 5 carbon atoms. Examples of alkenyl groups include linear or branched groups such as vinyl, allyl, butenyl, ethenyl, and propynyl groups. Moreover, this alkenyl group may have a substituent. Examples of those having a substituent include 2- (benzoxazol-2-yl) ethenyl group and the like.

The aryl group for R ^b11 and ^{R b12,} preferably has 6 to 20 carbon atoms, more preferably from 6 to 10 carbon atoms. Examples of the aryl group include phenyl group, tolyl group, xylyl group, ethylphenyl group, naphthyl group, anthryl group, phenanthryl group and the like.

The aralkyl group in R ^b11 and ^{R b12,} preferably has 7 to 20 carbon atoms, more preferably has 7 to 12 carbon atoms. Examples of the aralkyl group include benzyl group, α-methylbenzyl group, α, α-dimethylbenzyl group, phenylethyl group, phenylethenyl group and the like.

^Examples of the heterocyclic group for R ^b11 and R ^b12 include a 5- or more-membered heterocyclic group containing at least one of a nitrogen atom, a sulfur atom, and an oxygen atom, and preferably a 5- to 7-membered heterocyclic group. This heterocyclic group may contain a condensed ring. Examples of the heterocyclic group include pyrrolyl, pyridyl, pyrimidyl, furyl, and thienyl groups.

Among these R ^b11 and R ^b12 , the alkylene part of the alkyl group and the aralkyl group may be interrupted by an unsaturated bond, an ether bond, a thioether bond, or an ester bond.

A ring structure that can be formed by combining R ^b11 and R ^b12 includes a heterocyclic ring. Examples of the heterocyclic ring include 5-membered or more, preferably 5 to 7-membered heterocyclic rings containing at least a nitrogen atom. This heterocyclic ring may contain a condensed ring. Examples of the heterocyclic ring include piperidine ring, morpholine ring, thiomorpholine ring and the like.

Among these, R ^b2 is most preferably a methyl group, an ethyl group, a propyl group, or a phenyl group.

In the formula (b-1), R ^b3 represents a monovalent organic group. Examples of the organic group include an alkyl group having 1 to 6 carbon atoms, an aryl group having 6 to 12 carbon atoms which may have a substituent, a group represented by the following formula (b-2), or a substituent. The heterocyclic group which may have is preferable. Examples of the substituent include the same groups as in R ^b1 above. Examples of the aryl group having 6 to 12 carbon atoms include a phenyl group, a naphthyl group, an anthryl group, and a phenanthryl group.

In the above formula (b-2), R ^b13 represents an alkylene group having 1 to 5 carbon atoms which may be interrupted by an oxygen atom. Examples of such an alkylene group include methylene group, ethylene group, n-propylene group, isopropylene group, n-butylene group, isobutylene group, sec-butylene group, n-pentylene group, isopentylene group, sec-pentylene group and the like. A linear or branched group is mentioned. Among these, R ^b13 is most preferably an isopropylene group.

In the formula (b-2), R ^b14 represents a monovalent organic group represented by —NR ^b15 R ^b16 (R ^b15 and R ^b16 each independently represents a monovalent organic group). Among such organic groups, if the structure of R ^b14 is represented by the following formula (b-3), it is preferable in that the solubility of the photopolymerization initiator can be improved.

In the formula (b-3), R ^b17 and R ^b18 each independently represent an alkyl group having 1 to 5 carbon atoms. Examples of such an alkyl group include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, n-pentyl group, isopentyl group, sec- Examples thereof include a pentyl group and a tert-pentyl group. Among these, R ^b17 and R ^b18 are most preferably methyl groups.

^Examples of the heterocyclic group for R ^b3 include 5-membered or more, preferably 5-membered or 6-membered heterocyclic groups containing at least one atom of a nitrogen atom, a sulfur atom, and an oxygen atom. Examples of heterocyclic groups include nitrogen-containing 5-membered ring groups such as pyrrolyl, imidazolyl and pyrazolyl groups; nitrogen-containing 6-membered ring groups such as pyridyl, pyrazinyl, pyrimidyl and pyridazinyl groups; thiazolyl and isothiazolyl groups Nitrogen-containing sulfur groups such as oxazolyl groups and isoxazolyl groups; sulfur-containing groups such as thienyl groups and thiopyranyl groups; oxygen-containing groups such as furyl groups and pyranyl groups; Among these, those containing one nitrogen atom or one sulfur atom are preferable. This heterocyclic ring may contain a condensed ring. Examples of the heterocyclic group containing a condensed ring include a benzothienyl group.

Moreover, the heterocyclic group may have a substituent. Examples of the substituent include the same groups as in R ^b1 above.

In the formula (b-1), R ^b4 represents a monovalent organic group. Among these, it is preferable that it is a C1-C5 alkyl group. Examples of such an alkyl group include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, n-pentyl group, isopentyl group, sec- Examples thereof include a pentyl group and a tert-pentyl group. Among these, R ^b4 is most preferably a methyl group.

  Another preferred example of the oxime photopolymerization initiator is a photopolymerization initiator represented by the following formula (b-4) proposed in JP 2010-15025 A.

In the formula (b-4), R ^b21 and R ^b22 each independently represent R ^b31 , OR ^b31 , COR ^b31 , SR ^b31 , CONR ^b32 R ^b33 , or CN.

R ^b31 , R ^b32 , and R ^b33 each independently represent a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an arylalkyl group having 7 to 30 carbon atoms, or 2 to 2 carbon atoms. 20 heterocyclic groups are shown. The hydrogen atoms of the alkyl group, aryl group, arylalkyl group, and heterocyclic group are further represented by OR ^b41 , COR ^b41 , SR ^b41 , NR ^b42 R ^b43 , CONR ^b42 R ^b43 , —NR ^b42 —OR ^b43 , —NCOR ^b42 − OCOR ^b43 , -C (= N-OR ^b41 ) -R ^b42 , -C (= N-OCOR ^b41 ) -R ^b42 , CN, halogen atom, -CR ^b41 = CR ^b42 R ^b43 , -CO-CR ^b41 = CR ^b42 R ^b43 , a carboxyl group, or an epoxy group may be substituted. R ^b41 , R ^b42 , and R ^b43 each independently represent a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an arylalkyl group having 7 to 30 carbon atoms, or 2 to 2 carbon atoms. 20 heterocyclic groups are shown.

The methylene group of the alkylene part of the substituent in R ^b31 , R ^b32 , R ^b33 , R ^b41 , R ^b42 , and R ^b43 is an unsaturated bond, ether bond, thioether bond, ester bond, thioester bond, amide bond, or urethane It may be interrupted 1 to 5 times by bonding, and the alkyl part of the substituent may be branched or cyclic alkyl, and the alkyl terminal of the substituent may be an unsaturated bond. In addition, R ^b32 and R ^b33 , and R ^b42 and R ^b43 may be bonded to each other to form a ring structure.

In the formula (b-4), R ^b23 and R ^b24 are each independently R ^b31 , OR ^b31 , COR ^b31 , SR ^b31 , CONR ^b32 R ^b33 , NR ^b31 COR ^b32 , OCOR ^b31 , COOR ^b31 , SCOR ^b31. , OCSR ^b31 , COSR ^b31 , CSOR ^b31 , CN, a halogen atom, or a hydroxyl group. a and b each independently represent an integer of 0 to 4.
R ^b23 may be bonded to one of the carbon atoms of the adjacent benzene ring via —X ^b2 — to form a ring structure, and R ^b23 and R ^b24 are bonded to form a ring structure. May be.

In the above formula (b-4), ^Xb1 represents a single bond or CO.

In the formula (b-4), X ^b2 represents an oxygen atom, a sulfur atom, a selenium atom, CR ^b51 R ^b52 , CO, NR ^b53 , or PR ^b54 . R ^b51 , R ^b52 , R ^b53 , and R ^b54 each independently represent R ^b31 , OR ^b31 , COR ^b31 , SR ^b31 , CONR ^b32 R ^b33 , or CN. R ^b51 , R ^b53 , and R ^b54 may each independently form a ring structure together with one of the adjacent benzene rings.

In the above formula (b-4), the alkyl groups in R ^b31 , R ^b32 , R ^b33 , R ^b41 , R ^b42 , and R ^b43 include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, and n-butyl. Group, isobutyl group, sec-butyl group, tert-butyl group, n-pentyl group, isopentyl group, sec-pentyl group, tert-pentyl group and the like.

In the above formula (b-4), the aryl groups in R ^b31 , R ^b32 , R ^b33 , R ^b41 , R ^b42 , and R ^b43 include a phenyl group, a tolyl group, a xylyl group, an ethylphenyl group, a chlorophenyl group, a naphthyl group Group, anthryl group, phenanthrenyl group and the like.

In the above formula (b-4), the arylalkyl group in R ^b31 , R ^b32 , R ^b33 , R ^b41 , R ^b42 , and R ^b43 includes a benzyl group, a chlorobenzyl group, an α-methylbenzyl group, α, α -A dimethylbenzyl group, a phenylethyl group, a phenylethenyl group, etc. are mentioned.

In the above formula (b-4), as the heterocyclic group in R ^b31 , R ^b32 , R ^b33 , R ^b41 , R ^b42 , and R ^b43 , a pyridyl group, a pyrimidyl group, a furyl group, a thienyl group, a tetrahydrofuryl group, Dioxolanyl group, benzoxazol-2-yl group, tetrahydropyranyl group, pyrrolidyl group, imidazolidyl group, pyrazolidyl group, thiazolidyl group, isothiazolidyl group, oxazolidyl group, isoxazolidyl group, piperidyl group, piperazyl group, morpholinyl group, etc. A 5- to 7-membered ring is preferable.

In the formula (b-4), a ring formed by combining R ^b32 and R ^b33 , a ring formed by combining R ^b42 and R ^b43 , and R ^b23 together with an adjacent benzene ring Examples of the ring that can be formed include 5- to 7-membered rings such as cyclopentane ring, cyclohexane ring, cyclopentene ring, benzene ring, piperidine ring, morpholine ring, lactone ring, and lactam ring.
When X ^b2 is NR ^b53 and R ^b23 is bonded to one of the adjacent carbon atoms of the benzene ring to form a 5-membered ring structure together with X ^b2 , the photopolymerization initiator has a carbazole skeleton. Become.

In the formula ^(b-4), as the halogen atom in ^{R b31, R b32, R b33} , R b41, R b42, and ^{R b43} which may be substituted halogen atoms, and ^{R b24, R b25,} fluorine atom , Chlorine atom, bromine atom and iodine atom.

  The methylene group of the alkylene part of the substituent may be interrupted 1 to 5 times by an unsaturated bond, an ether bond, a thioether bond, an ester bond, a thioester bond, an amide bond, or a urethane bond. In this case, the linking group to be interrupted may be one type or two or more groups, and in the case of a group that can be interrupted continuously, two or more groups may be interrupted continuously. In addition, the alkyl part of the substituent may have a branched chain or may be a cyclic alkyl, and the alkyl terminal of the substituent may be an unsaturated bond.

  Another preferred example of the oxime photopolymerization initiator is a photopolymerization initiator represented by the following formula (b-5).

In the above formula (b-5), R ^b61 represents a group selected from the group consisting of a monovalent organic group, amino group, halogen, nitro group, and cyano group, p represents an integer of 0 to 4, q represents 0 or 1, R ^b62 represents a phenyl group which may have a substituent, or a carbazolyl group which may have a substituent, R ^b63 represents a hydrogen atom, or a carbon number of 1 to 6 Represents an alkyl group.

In the above formula (b-5), when R ^b61 is a monovalent organic group, R ^b61 is not particularly limited as long as the object of the present invention is not ^{impaired, and} is appropriately selected from various organic groups. Preferable examples when R ^b61 is an organic group include an alkyl group, an alkoxy group, a saturated aliphatic acyl group, an alkoxycarbonyl group, a saturated aliphatic acyloxy group, an optionally substituted phenyl group, a substituted group A phenoxy group which may have a group, 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 substituent A phenylalkyl group which may have a group, a naphthyl group which may have a substituent, a naphthoxy group which may have a substituent, a naphthoyl group which may have a substituent, a substituent A naphthoxycarbonyl group which may have a substituent, a naphthoyloxy group which may have a substituent, a naphthylalkyl group which may have a substituent, and a hete which may have a substituent. A cyclyl group, an amino group substituted with one or two organic groups, a morpholin-1-yl group, a piperazin-1-yl group, and the like can be given. When p is an integer of 2 to 4, R ^b61 may be the same or different. Moreover, the carbon number of the substituent does not include the carbon number of the substituent that the substituent further has.

When ^Rb61 is an alkyl group, the carbon number thereof is preferably 1-20, and more preferably 1-6. When R ^b61 is an alkyl group, the alkyl group may be linear, branched, or cyclic. Specific examples when R ^b61 is an alkyl group include 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, and an n-pentyl group. , Isopentyl group, sec-pentyl group, tert-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, isooctyl group, sec-octyl group, tert-octyl group, n-nonyl group, isononyl group, An n-decyl group, an isodecyl group, etc. are mentioned. When R ^b61 is an alkyl group, the alkyl group may contain an ether bond in the carbon chain. Specific examples of the alkyl group having an ether bond in the carbon chain include methoxyethyl group, ethoxyethyl group, methoxyethoxyethyl group, ethoxyethoxyethyl group, propyloxyethoxyethyl group, methoxypropyl group and the like.

When ^Rb61 is an alkoxy group, the carbon number thereof is preferably 1-20, and more preferably 1-6. When R ^b61 is an alkoxy group, the alkyl portion of the alkoxy group may be linear, branched or cyclic. Specific examples when R ^b61 is an alkoxy group include methoxy group, ethoxy group, n-propyloxy group, isopropyloxy group, n-butyloxy group, isobutyloxy group, sec-butyloxy group, tert-butyloxy group, n -Pentyloxy group, isopentyloxy group, sec-pentyloxy group, tert-pentyloxy group, n-hexyloxy group, n-heptyloxy group, n-octyloxy group, isooctyloxy group, sec-octoxyl group, Examples thereof include a tert-octyloxy group, an n-nonyloxy group, an isononyloxy group, an n-decyloxy group, and an isodecyloxy group. When R ^b61 is an alkoxy group, the alkoxy group may include an ether bond in the carbon chain. Specific examples of the alkoxy group having an ether bond in the carbon chain include a methoxyethoxy group, an ethoxyethoxy group, a methoxyethoxyethoxy group, an ethoxyethoxyethoxy group, a propyloxyethoxyethoxy group, and a methoxypropyloxy group.

When R ^b61 is a saturated aliphatic acyl group or a saturated aliphatic acyloxy group, the carbon number thereof is preferably 2 to 20, and more preferably 2 to 7. Specific examples when R ^b61 is a saturated aliphatic acyl group include acetyl group, propanoyl group, n-butanoyl group, 2-methylpropanoyl group, n-pentanoyl group, 2,2-dimethylpropanoyl group, n -Hexanoyl group, n-heptanoyl group, n-octanoyl group, n-nonanoyl group, n-decanoyl group, n-undecanoyl group, n-dodecanoyl group, n-tridecanoyl group, n-tetradecanoyl group, n-pentadecane A noyl group, n-hexadecanoyl group, etc. are mentioned. Specific examples when R ^b61 is a saturated aliphatic acyloxy group include acetyloxy group, propanoyloxy group, n-butanoyloxy group, 2-methylpropanoyloxy group, n-pentanoyloxy group, 2, 2-dimethylpropanoyloxy group, n-hexanoyloxy group, n-heptanoyloxy group, n-octanoyloxy group, n-nonanoyloxy group, n-decanoyloxy group, n-undecanoyloxy group, n -Dodecanoyloxy group, n-tridecanoyloxy group, n-tetradecanoyloxy group, n-pentadecanoyloxy group, n-hexadecanoyloxy group and the like.

When R ^b61 is an alkoxycarbonyl group, the carbon number thereof is preferably 2-20, and more preferably 2-7. Specific examples when R ^b61 is an alkoxycarbonyl group include methoxycarbonyl group, ethoxycarbonyl group, n-propyloxycarbonyl group, isopropyloxycarbonyl group, n-butyloxycarbonyl group, isobutyloxycarbonyl group, sec-butyl. Oxycarbonyl group, tert-butyloxycarbonyl group, n-pentyloxycarbonyl group, isopentyloxycarbonyl group, sec-pentyloxycarbonyl group, tert-pentyloxycarbonyl group, n-hexyloxycarbonyl group, n-heptyloxycarbonyl Group, n-octyloxycarbonyl group, isooctyloxycarbonyl group, sec-octyloxycarbonyl group, tert-octyloxycarbonyl group, n-nonyloxycarbonyl group , Isononyloxycarbonyl group, n-decyloxycarbonyl group, isodecyloxycarbonyl group and the like.

When R ^b61 is a phenylalkyl group, the carbon number is preferably 7 to 20, and more preferably 7 to 10. When R ^b61 is a naphthylalkyl group, the carbon number thereof is preferably 11-20, and more preferably 11-14. Specific examples when R ^b61 is a phenylalkyl group include a benzyl group, a 2-phenylethyl group, a 3-phenylpropyl group, a 4-phenylbutyl group, and the like. Specific examples in the case where R ^b61 is a naphthylalkyl group include an α-naphthylmethyl group, a β-naphthylmethyl group, a 2- (α-naphthyl) ethyl group, a 2- (β-naphthyl) ethyl group, and the like. . When R ^b61 is a phenylalkyl group or a naphthylalkyl group, R ^b61 may further have a substituent on the phenyl group or naphthyl group.

When R ^b61 is a heterocyclyl group, the heterocyclyl group is a 5-membered or 6-membered monocycle containing one or more N, S, or O, or such monocycles are fused with each other, or such monocycle and a benzene ring are condensed. Heterocyclyl group. When the heterocyclyl group is a condensed ring, the ring number is up to 3. Examples of the heterocyclic ring constituting the heterocyclyl group include furan, thiophene, pyrrole, oxazole, isoxazole, thiazole, thiadiazole, isothiazole, imidazole, pyrazole, triazole, pyridine, pyrazine, pyrimidine, pyridazine, benzofuran, benzothiophene, indole, Examples include isoindole, indolizine, benzimidazole, benzotriazole, benzoxazole, benzothiazole, carbazole, purine, quinoline, isoquinoline, quinazoline, phthalazine, cinnoline, quinoxaline and the like. When R ^b61 is a heterocyclyl group, the heterocyclyl group may further have a substituent.

When R ^b61 is an amino group substituted with one or two organic groups, suitable examples of the organic group include alkyl groups having 1 to 20 carbon atoms, saturated aliphatic acyl groups having 2 to 20 carbon atoms, and substitution. A phenyl group which may have a group, a benzoyl group which may have a substituent, a phenylalkyl group having 7 to 20 carbon atoms which may have a substituent, and a substituent. Examples thereof include a good naphthyl group, an optionally substituted naphthoyl group, an optionally substituted naphthylalkyl group having 11 to 20 carbon atoms, and a heterocyclyl group. Specific examples of these suitable organic groups are the same as described above. Specific examples of the amino group substituted with one or two organic groups include methylamino group, ethylamino group, diethylamino group, n-propylamino group, di-n-propylamino group, isopropylamino group, n- Butylamino group, di-n-butylamino group, n-pentylamino group, n-hexylamino group, n-heptylamino group, n-octylamino group, n-nonylamino group, n-decylamino group, phenylamino group, Naphthylamino group, acetylamino group, propanoylamino group, n-butanoylamino group, n-pentanoylamino group, n-hexanoylamino group, n-heptanoylamino group, n-octanoylamino group, n- Examples include decanoylamino group, benzoylamino group, α-naphthoylamino group, β-naphthoylamino group and the like.

^Examples of the substituent in the case where the phenyl group, naphthyl group, and heterocyclyl group included in R ^b61 further have a substituent include an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, and 2 to 2 carbon atoms. A saturated aliphatic acyl group having 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, and 1 to 6 carbon atoms And a dialkylamino group having an alkyl group, morpholin-1-yl group, piperazin-1-yl group, halogen, nitro group, cyano group and the like. When the phenyl group, naphthyl group, and heterocyclyl group included in R ^b61 further have a substituent, the number of the substituent is not limited as long as the object of the present invention is not impaired, but 1 to 4 is preferable. When the phenyl group, naphthyl group, and heterocyclyl group included in R ^b61 have a plurality of substituents, the plurality of substituents may be the same or different.

Among R ^b61 , a nitro group, an alkyl having 1 to 6 carbon atoms, because it is chemically stable, has few steric hindrances, is easy to synthesize, and has high solubility in a solvent. A group selected from the group consisting of a group, an alkoxy group having 1 to 6 carbon atoms, and a saturated aliphatic acyl group having 2 to 7 carbon atoms, more preferably a nitro group or an alkyl having 1 to 6 carbon atoms, A group or a methyl group is particularly preferred.

Position R ^b61 is attached to the phenyl group, the phenyl group R ^b61 are attached the position of the bond to the main chain of the phenyl group and the oxime ester compound as a 1-position, if the 2-position of the position of the methyl group 4th or 5th is preferable, and 5th is more preferable. Moreover, p is preferably an integer of 0 to 3, more preferably an integer of 0 to 2, and particularly preferably 0 or 1.

R ^b62 is a phenyl group which may have a substituent, or a carbazolyl group which may have a substituent. In addition, when R ^b62 is a carbazolyl group which may have a substituent, the nitrogen atom on the carbazolyl group may be substituted with an alkyl group having 1 to 6 carbon atoms.

In R ^b62 , the substituent that the phenyl group or carbazolyl group has is not particularly limited as long as the object of the present invention is not impaired. Examples of suitable substituents that the phenyl group or carbazolyl group may have on the carbon atom include alkyl groups having 1 to 20 carbon atoms, alkoxy groups having 1 to 20 carbon atoms, and saturation having 2 to 20 carbon atoms. An aliphatic acyl group, an alkoxycarbonyl group having 2 to 20 carbon atoms, a saturated aliphatic acyloxy group having 2 to 20 carbon atoms, an optionally substituted phenyl group, and an optionally substituted phenoxy group A phenylthio 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 having 7 to 20 carbon atoms which may have a substituent, a naphthyl group which may have a substituent, a naphthoxy group which may have a substituent, and a substituent. Naphtho A naphthoxycarbonyl group which may have a substituent, a naphthoyloxy group which may have a substituent, a naphthylalkyl group having 11 to 20 carbon atoms which may have a substituent, Heterocyclyl group optionally having substituent, heterocyclylcarbonyl group optionally having substituent, amino group, amino group substituted by one or two organic groups, morpholin-1-yl group, piperazine A -1-yl group, a halogen, a nitro group, a cyano group, etc. are mentioned.

When R ^b62 is a carbazolyl group, specific examples of a suitable substituent that the carbazolyl group may have on the nitrogen atom include an alkyl group having 1 to 20 carbon atoms and a saturated aliphatic acyl having 2 to 20 carbon atoms. Group, an alkoxycarbonyl group having 2 to 20 carbon atoms, 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 substituent A phenylalkyl group having 7 to 20 carbon atoms which may have a group, a naphthyl group which may have a substituent, a naphthoyl group which may have a substituent, or a substituent. A good naphthoxycarbonyl group, an optionally substituted naphthylalkyl group having 11 to 20 carbon atoms, an optionally substituted heterocyclyl group, and an optionally substituted heterocyclylcarbo Nyl group etc. are mentioned. Among these substituents, an alkyl group having 1 to 20 carbon atoms is preferable, an alkyl group having 1 to 6 carbon atoms is more preferable, and an ethyl group is particularly preferable.

Specific examples of the substituent that the phenyl group or carbazolyl group may have include an alkyl group, an alkoxy group, a saturated aliphatic acyl group, an alkoxycarbonyl group, a saturated aliphatic acyloxy group, and an optionally substituted phenyl. The alkyl group, the naphthylalkyl group which may have a substituent, the heterocyclyl group which may have a substituent, and the amino group substituted with one or two organic groups are the same as R ^b61 . is there.

In R ^b62 , specific examples of the substituent when the phenyl group, naphthyl group, and heterocyclyl group included in the substituent of the phenyl group or carbazolyl group further have a substituent include alkyl groups 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 phenyl group; a naphthyl group; A benzoyl group substituted with a group selected from the group consisting of an alkyl group having 1 to 6 carbon atoms, a morpholin-1-yl group, a piperazin-1-yl group, and a phenyl group; Monoalkylamino group having 6 alkyl groups; dialkylamino group having 1 to 6 carbon atoms; morpholin-1-yl group; piperazi N-1-yl group; halogen; nitro group; cyano group. When the phenyl group, the naphthyl group, and the heterocyclyl group included in the substituent that the phenyl group or carbazolyl group has further have a substituent, the number of the substituent is not limited as long as the object of the present invention is not impaired. ~ 4 is preferred. When the phenyl group, naphthyl group, and heterocyclyl group have a plurality of substituents, the plurality of substituents may be the same or different.

Among R ^b62 , groups represented by the following formulas (b-6) and (b-7) are preferable from the viewpoint of excellent sensitivity of the photosensitive resin composition, and represented by the following formula (b-6). A group is more preferable, and a group represented by the following formula (b-6), in which A is S, is particularly preferable.

（式中、Ｒ^ｂ６４は１価の有機基、アミノ基、ハロゲン、ニトロ基、及びシアノ基からなる群より選択される基を示し、ＡはＳ又はＯを示し、ｒは０〜４の整数を示す。）

(In the formula, R ^b64 represents a group selected from the group consisting of a monovalent organic group, amino group, halogen, nitro group, and cyano group, A represents S or O, and r represents an integer of 0-4. Is shown.)

（式中、Ｒ^ｂ６５及びＲ^ｂ６６はそれぞれ１価の有機基を示す。）

(In the formula, R ^b65 and R ^b66 each represent a monovalent organic group.)

When R ^b64 in the above formula (b-6) is an organic group, it can be selected from various organic groups as long as the object of the present invention is not ^impaired . In the above formula (b-6), when R ^b64 is an organic group, preferred examples include an alkyl group having 1 to 6 carbon atoms; an alkoxy group having 1 to 6 carbon atoms; a saturated fat having 2 to 7 carbon atoms. C2-C7 alkoxycarbonyl group; C2-C7 saturated aliphatic acyloxy group; phenyl group; naphthyl group; benzoyl group; naphthoyl group; C1-C6 alkyl group, morpholine-1 A benzoyl group substituted by a group selected from the group consisting of -yl group, piperazin-1-yl group, and phenyl group; a monoalkylamino group having an alkyl group having 1 to 6 carbon atoms; A dialkylamino group having an alkyl group; a morpholin-1-yl group; a piperazin-1-yl group; a halogen; a nitro group; and a cyano group.

In R ^b64 , substituted by a group selected from the group consisting of a benzoyl group; a naphthoyl group; an alkyl group having 1 to 6 carbon atoms, a morpholin-1-yl group, a piperazin-1-yl group, and a phenyl group Benzoyl group; nitro group is preferred, benzoyl group; naphthoyl group; 2-methylphenylcarbonyl group; 4- (piperazin-1-yl) phenylcarbonyl group; 4- (phenyl) phenylcarbonyl group is more preferred.

In the formula (b-6), r is preferably an integer of 0 to 3, more preferably an integer of 0 to 2, and particularly preferably 0 or 1. When r is 1, the binding position of R ^b64, relative bond which the phenyl group R ^b64 are bonded is bonded to the sulfur atom is preferably in the para position.

R ^b65 in the above formula (b-7) can be selected from various organic groups as long as the object of the present invention is not ^impaired . Preferable specific examples of R ^b65 include an alkyl group having 1 to 20 carbon atoms, a saturated aliphatic acyl group having 2 to 20 carbon atoms, an alkoxycarbonyl group having 2 to 20 carbon atoms, and a substituent. A phenyl group, 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 substituent; A naphthyl group which may have, a naphthoyl group which may have a substituent, a naphthoxycarbonyl group which may have a substituent, and a carbon group having 11 to 20 carbon atoms which may have a substituent Examples thereof include a naphthylalkyl group, a heterocyclyl group which may have a substituent, and a heterocyclylcarbonyl group which may have a substituent.

In ^Rb65 , a C1-C20 alkyl group is preferable, a C1-C6 alkyl group is more preferable, and an ethyl group is especially preferable.

R ^b66 in the above formula (b-7) is not particularly limited as long as the object of the present invention is not ^impaired , and can be selected from various organic groups. Specific examples of the group suitable as R ^b66 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 substituent. And a heterocyclyl group which may be present. Among these groups, R ^b66 is more preferably a phenyl group which may have a substituent, and particularly preferably a 2-methylphenyl group.

^Examples of the substituent in the case where the phenyl group, naphthyl group, and heterocyclyl group contained in R ^b64 , R ^b65 , or R ^b66 further have a substituent include an alkyl group having 1 to 6 carbon atoms and a carbon number having 1 to 6 carbon atoms. Monoalkylamino having an alkoxy group, 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, and an alkyl group having 1 to 6 carbon atoms Group, a dialkylamino group having an alkyl group having 1 to 6 carbon atoms, morpholin-1-yl group, piperazin-1-yl group, halogen, nitro group, cyano group and the like. When the phenyl group, naphthyl group, and heterocyclyl group contained in R ^b64 , R ^b65 , or R ^b66 further have a substituent, the number of substituents is not limited as long as the object of the present invention is not ^impaired , 1-4 are preferable. When the phenyl group, naphthyl group, and heterocyclyl group contained in R ^b64 , R ^b65 , or R ^b66 have a plurality of substituents, the plurality of substituents may be the same or different.

R ^b63 in the above formula (b-5) is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. R ^b63 is preferably a methyl group or an ethyl group, and more preferably a methyl group. When R ^b63 is a methyl group, the photopolymerization initiator represented by the above formula (b-5) is particularly excellent in sensitivity.

  Among the photopolymerization initiators represented by the above formula (b-5), particularly preferred are compounds represented by the following formulas.

  (B) The content of the photopolymerization initiator is preferably 0.1 to 50% by mass and more preferably 0.5 to 10% by mass with respect to the solid content of the photosensitive resin composition.

<(C) Photopolymerizable compound>
(C) As a photopolymerizable compound, a monofunctional monomer having a glass transition temperature (Tg) of −10 ° C. or lower when a homopolymer having a mass average molecular weight of 10,000 or more (for example, a homopolymer having a mass average molecular weight of 10,000) is essential. Contained. By containing such a monofunctional monomer, the resin pattern can easily flow in the heating (post-baking) step after exposing and developing the coating film of the photosensitive resin composition, and the opening portion with a forward taper shape is formed. It becomes possible to form the resin pattern which has it easily. Thereby, the risk of disconnection when forming a conductive film on the surface of the resin pattern can be reduced.
In this specification, “monofunctional” means having one polymerizable ethylenic double bond. The same applies to two or more functional groups.

  An example of such a monofunctional monomer is a compound represented by the following formula (c-1).

（式中、Ｒ^ｃ１は水素原子又はメチル基を示し、Ｒ^ｃ２は炭素数４〜１２のアルキル基を示す。該アルキル基は、置換基を有していてもよく、エーテル結合又はエステル結合を有していてもよい。）

(In the formula, R ^c1 represents a hydrogen atom or a methyl group, and R ^c2 represents an alkyl group having 4 to 12 carbon atoms. The alkyl group may have a substituent, and may have an ether bond or an ester bond. (You may have it.)

^Examples of the alkyl group as R ^c2 include an n-butyl group, an n-pentyl group, an isoamyl group, an n-hexyl group, an n-octyl group, a 2-ethylhexyl group, an n-decyl group, an isodecyl group, and an n-lauryl group. Is mentioned.
Examples of the substituent that the alkyl group represented by R ^c2 may have include a hydroxy group, a carboxy group, a group containing a hetero atom (such as a sulfur atom and a nitrogen atom), and a halogen atom. Bulky substituents such as aryl groups tend to increase the glass transition temperature and are not preferred as substituents. The alkyl group as R ^c2 may have an ether bond or an ester bond, and may have a repeating structure such as ethylene oxide and propylene oxide.
In particular, when the carbon number of the alkyl group as R ^c2 is 4 to 12, the solubility of the monomer is improved, and a uniform photosensitive resin composition is easily produced.

  Specific examples of such monofunctional monomers include isoamyl acrylate, 2-ethylhexyl (meth) acrylate, isodecyl (meth) acrylate, n-lauryl (meth) acrylate, ethoxydiethylene glycol (meth) acrylate, methoxytriethylene glycol (meth) ) Acrylate, 2- (meth) acryloyloxyethyl succinate, 2- (meth) acryloyloxyethyl succinic acid, phenoxyethyl (meth) acrylate, and the like. These monofunctional monomers can be used alone or in combination of two or more. Among these, n-lauryl (meth) acrylate and methoxytriethylene glycol (meth) acrylate are preferable.

  In addition, (C) the photopolymerizable compound preferably further contains a trifunctional or higher polyfunctional monomer. By containing such a polyfunctional monomer, the sensitivity of the photosensitive resin composition can be improved.

  Specific examples of the polyfunctional monomer include pentaerythritol tri (meth) acrylate, dipentaerythritol tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, ethylene oxide modified trimethylolpropane tri (meth) acrylate, propylene oxide modified tri Methylolpropane tri (meth) acrylate, ethylene oxide and propylene oxide modified trimethylolpropane tri (meth) acrylate, ethoxylated isocyanuric acid tri (meth) acrylate, caprolactone modified tris- (2- (meth) acryloxyethyl) isocyanurate, glycerin Tri (meth) acrylate, ethoxylated glycerin tri (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dimethyl Roll propane tetra (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, pentaerythritol tetra (meth) acrylate, ethoxylated pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) ) Acrylate, caprolactone-modified dipentaerythritol hexa (meth) acrylate, and the like. These polyfunctional monomers can be used alone or in combination of two or more. Among these, a polyfunctional monomer having 4 or more functional groups is preferable, a polyfunctional monomer having 6 or more functional groups is more preferable, and dipentaerythritol hexa (meth) acrylate is particularly preferable.

  Moreover, it is preferable that the (C) photopolymerizable compound further contains a bifunctional monomer. By containing such a bifunctional monomer, the boundary portion between the bottom surface and the inner surface of the opening of the resin pattern becomes a skirt shape, and there is a risk of disconnection when a conductive film is formed on the surface of the resin pattern. It can be further reduced.

  Specific examples of the bifunctional monomer include 1,3-butanediol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, and 1,9-nonane. Diol 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, tetraethylene glycol di ( Meta) Acu Rate, dipropylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, ethoxylated neopentyl glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, polyethylene glycol Di (meth) acrylate, poly (ethylene-propylene) glycol di (meth) acrylate, polytetramethylene glycol di (meth) acrylate, ethoxylated bisphenol A di (meth) acrylate, propoxylated bisphenol A di (meth) acrylate, propoxy Ethoxylated bisphenol A di (meth) acrylate, glycerin di (meth) acrylate, and the like. These bifunctional monomers can be used alone or in combination of two or more. Among these, 1,6-hexanediol di (meth) acrylate is preferable.

  (C) It is preferable that content of a photopolymerizable compound is 20-50 mass% with respect to solid content of the photosensitive resin composition, and it is more preferable that it is 25-40 mass%. In particular, the content of the monofunctional monomer having a Tg of −10 ° C. or less when the homopolymer having a mass average molecular weight of 10,000 or more is 1 to 40% by mass relative to the solid content of the photosensitive resin composition. Preferably, it is 5-30 mass%. Moreover, when it contains a polyfunctional monomer, it is preferable that the content is 1-40 mass% with respect to solid content of the photosensitive resin composition, and it is more preferable that it is 5-20 mass%. Furthermore, when it contains a bifunctional monomer, the content thereof is preferably 1 to 40% by mass, and more preferably 3 to 15% by mass with respect to the solid content of the photosensitive resin composition.

<(S) Organic solvent>
The photosensitive resin composition according to the present invention preferably contains (S) an organic solvent for improving coatability and adjusting viscosity.

  Specific examples of the organic solvent include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono-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, (Poly) alkylene glycol monoalkyl ethers such as propylene glycol monoethyl ether, dipropylene glycol mono-n-propyl ether, dipropylene glycol mono-n-butyl ether, tripropylene glycol monomethyl ether, tripropylene glycol monoethyl ether; ethylene (Poly) alkylene glycol monoalkyl ether acetates such as glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monoethyl ether acetate Diethylene Other ethers such as recall dimethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol diethyl ether, tetrahydrofuran; ketones such as methyl ethyl ketone, cyclohexanone, 2-heptanone, 3-heptanone; methyl 2-hydroxypropionate, ethyl 2-hydroxypropionate, etc. Alkyl 2-lactic acid esters; ethyl 2-hydroxy-2-methylpropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl ethoxyacetate, hydroxy Ethyl acetate, methyl 2-hydroxy-3-methylbutanoate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, 3-methyl-3- Methoxybutyl propionate, ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, n-pentyl formate, isopentyl acetate, n-butyl propionate, ethyl butyrate, n-propyl butyrate, isopropyl butyrate, Other esters such as n-butyl butyrate, methyl pyruvate, ethyl pyruvate, n-propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, ethyl 2-oxobutanoate; aromatic hydrocarbons such as toluene, xylene; Amides such as N-methylpyrrolidone, N, N-dimethylformamide, N, N-dimethylacetamide; and the like. Among these, alkylene glycol monoalkyl ethers, alkylene glycol monoalkyl ether acetates, other ethers described above, alkyl lactate esters, and other esters described above are preferable, alkylene glycol monoalkyl ether acetates described above. Other ethers and other esters described above are more preferred. These solvents can be used alone or in combination of two or more.

  (S) Content of the organic solvent is not specifically limited, It is the quantity within the range which can apply | coat the photosensitive resin composition to a board | substrate etc., and is suitably set according to a coating film thickness. The viscosity of the photosensitive resin composition is preferably 0.9 to 500 cp, more preferably 1 to 50 cp, and further preferably 1 to 30 cp. Moreover, 1-80 mass% is preferable and, as for the solid content density | concentration of the photosensitive resin composition, 5-50 mass% is more preferable.

<Other ingredients>
The photosensitive resin composition according to the present invention may contain additives such as a surface tension adjuster, an adhesion improver, a thermal polymerization inhibitor, and an antifoaming agent as necessary. Any additive can be used as the additive. Examples of the surface tension adjusting agent include anionic, cationic, and nonionic compounds. Examples of the adhesion improver include conventionally known silane coupling agents. Examples of the thermal polymerization inhibitor include hydroquinone and hydroquinone. Examples thereof include monoethyl ether, and examples of the antifoaming agent include silicone compounds and fluorine compounds.

<Method for preparing photosensitive resin composition>
The photosensitive resin composition according to the present invention is prepared by stirring, mixing and dissolving the above components using a stirrer such as a magnetic stirrer and, if necessary, filtering through a filter such as a 0.2 μm membrane filter. Can do.

≪Resin pattern manufacturing method≫
The method for producing a resin pattern according to the present invention includes a coating step of coating the photosensitive resin composition according to the present invention on a substrate to form a coating film, an exposure step of selectively exposing the coating film, The development process which develops the said coating film after an exposure process and obtains a resin pattern, and the heating process which heats the said resin pattern are included at least. Hereinafter, each process of the manufacturing method of a resin pattern is demonstrated.

  First, in the coating process, a contact transfer type coating device such as a roll coater, reverse coater, and bar coater, or a non-contact type coating device such as a spinner (rotary coating device) or a curtain flow coater is used in the present invention. The photosensitive resin composition is applied, and if necessary, the solvent is removed by drying to form a coating film. Examples of the substrate include a glass substrate and a silicon substrate, and a wiring pattern, a TFT element, or the like may be formed.

Next, in the exposure step, the coating film formed in the coating step is selectively exposed according to the shape of the resin pattern to be formed. The selective exposure method is not particularly limited, but it is preferable to expose the coating film through a negative mask. The coating film is exposed using radiation such as ArF excimer laser, KrF excimer laser, F ₂ excimer laser, extreme ultraviolet (EUV), vacuum ultraviolet (VUV), electron beam, X-ray, and soft X-ray. . Although the exposure amount varies depending on the composition of the photosensitive resin composition, for example, about 10 to 600 mJ / cm ² is preferable.

  Next, in the development step, the exposed coating film is developed with a developer, thereby removing unexposed portions and forming a resin pattern. The development method is not particularly limited, and an immersion method, a spray method, or the like can be used. Examples of the developer include aqueous solutions of monoethanolamine, diethanolamine, triethanolamine, sodium hydroxide, potassium hydroxide, sodium carbonate, ammonia, quaternary ammonium salts and the like.

Next, in the heating step, the obtained resin pattern is heated (post-baked). The heating temperature is preferably 150 to 270 ° C., and the heating time is preferably 20 to 60 minutes.
As described above, the photosensitive resin composition according to the present invention contains a monofunctional monomer having a Tg of −10 ° C. or less when a homopolymer having a mass average molecular weight of 10,000 or more. Easy to heat flow. Therefore, when the resin pattern has an opening, the shape of the opening after the heating step can be a forward tapered shape.

  The method for producing a resin pattern according to the present invention may further include a conductive film forming step of forming a conductive film on the surface of the resin pattern after the heating step. For example, ITO may be deposited on the surface of the resin pattern to form an ITO film. As described above, according to the method for producing a resin pattern according to the present invention, a resin pattern having a forward tapered opening can be obtained, and therefore a conductive film can be appropriately formed on the inner surface of the opening. And the risk of disconnection can be reduced.

≪Display device≫
The display device according to the present invention includes a resin pattern manufactured by the method for manufacturing a resin pattern according to the present invention. Since this resin pattern has an insulating property, it is useful as an organic insulating film of a display device. In particular, according to the method for producing a resin pattern according to the present invention, a resin pattern having a forward tapered opening can be obtained, which is suitable when the opening is used as a contact hole of a display device.
In this case, the taper angle (inclination angle of the inner surface) of the opening is preferably 45 to 75 degrees, and more preferably 50 to 70 degrees. By setting the taper angle to 45 degrees or more, the inner diameter on the surface side of the opening is not excessively widened, and the inner diameter on the bottom surface side is not excessively narrowed, so that a wide viewing angle can be secured. Moreover, by setting the taper angle to 75 degrees or less, an ITO film or the like can be appropriately formed on the inner side surface of the opening, and the risk of disconnection can be reduced.

  EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, this invention is not limited to these Examples.

<Examples 1-7, Comparative Examples 1-8>
Components shown in Tables 1 and 2 below were mixed to prepare a photosensitive resin composition having a solid content concentration of 23% by mass. In addition, the numerical value in a parenthesis shows the mass part of each component.

  In Tables 1 and 2, each abbreviation indicates the following. In addition, Tg described about the monofunctional monomer of a photopolymerizable compound is a value when it is set as the homopolymer of the mass mean molecular weight 10,000.

(Alkali-soluble resin)
A-1: 3,4-epoxycyclohexane-1-ylmethyl methacrylate / tricyclo [5.2.1.0 ^2,6 ] decan-8-yl methacrylate / methacrylic acid / methyl methacrylate = 40/15/12/33 (Mass ratio) resin (mass average molecular weight 7000, dispersity 1.70)
(Photopolymerizable compound)
C-1: Lauryl methacrylate (Tg = −37.8 ° C.)
C-2: Methoxytriethylene glycol acrylate (Tg = −14.0 ° C.)
C-3: Phenoxypolyethylene glycol acrylate (Tg = −53.5 ° C.)
C-4: Dicyclopentenyl axethyl acrylate (Tg = 92.4 ° C.)
C-5: 1,6-hexanediol diacrylate C-6: propoxylated ethoxylated bisphenol A diacrylate C-7: polytetraethylene glycol # 650 diacrylate C-8: polypropylene glycol # 400 diacrylate C-9: Polypropylene glycol # 400 dimethacrylate C-10: dipentaerythritol hexaacrylate (photopolymerization initiator)
OXE02: “IRGACURE OXE02” manufactured by BASF
(Organic solvent)
PGMEA: Propylene glycol monomethyl ether acetate

<Evaluation>
(Evaluation of residual film sensitivity)
The photosensitive resin composition prepared in each of the above Examples and Comparative Examples was applied to a 6-inch silicon substrate using a spinner (Mikasa Spinner IH-360S, manufactured by Mikasa Corporation), and then the coating film was applied at 100 ° C. for 120 seconds. A coating film was formed by drying. Next, the coating film was exposed with various exposure amounts using an exposure apparatus (“MPA600FA” manufactured by Canon). Subsequently, paddle development was performed at 23 ° C. for 60 seconds using a 2.38 mass% tetramethylammonium hydroxide aqueous solution to form a resin pattern having holes with a diameter of about 10 μm. After development, the resin pattern was post-baked at 230 ° C. for 30 minutes. The film thickness of the pattern after post-baking was about 3 μm. The film thickness of the pattern was measured using a stylus type surface shape measuring instrument (“Dektak 3st” manufactured by ULVAC). Then, the film thickness after post-baking / the film thickness before exposure was calculated as the remaining film ratio, and the minimum exposure amount at which the remaining film ratio exceeded 80% was evaluated as the remaining film sensitivity. The results are shown in Table 3 below.

(Evaluation of taper angle)
A resin pattern having a hole with a diameter of about 10 μm was formed in the same manner as described above (evaluation of residual film sensitivity) except that the coating film was exposed with a minimum exposure amount with a residual film ratio exceeding 80%. And the cross section of the hole was observed with the scanning electron microscope (SEM), and the taper angle (inclination angle of the inner surface at the intermediate height between the substrate surface and the film surface) was measured. The results are shown in Table 3 below.

(Evaluation of skirt shape)
In the same manner as described above (evaluation of taper angle), a resin pattern having holes with a diameter of about 10 μm was formed. And the cross section of the hole was observed with the scanning electron microscope (SEM), and the extent of the bottoming shape was evaluated with the following evaluation criteria. In addition, when the cross section of a hole is a skirt shape, the risk of disconnection when forming a conductive film on the surface of the resin pattern can be further reduced.
・ Evaluation criteria When the taper angle is θ1 and the inclination angle of the skirt is θ2,
When 1/2 ・ θ1> θ2 ・ ・ ・ ◎
θ1> θ2 ≧ 1/2 · θ1.
When θ2 ≧ θ1 ・ ・ ・ ×

As can be seen from Table 3 above, by adding a monofunctional monomer having a Tg of −10 ° C. or less when a homopolymer having a mass average molecular weight of 10,000 is added to the photosensitive resin composition, the taper angle of the hole is greatly reduced. Is possible. Thereby, the risk of disconnection when forming a conductive film on the surface of the resin pattern can be reduced.
Moreover, it is possible to adjust the sensitivity of the photosensitive resin composition appropriately by combining such a monofunctional monomer with a bifunctional monomer or a trifunctional or higher polyfunctional monomer. In particular, when a monofunctional monomer, a bifunctional monomer, and a trifunctional or higher polyfunctional monomer are combined, the cross section of the hole becomes a trailing shape, and the risk of disconnection when a conductive film is formed on the surface of the resin pattern Can be further reduced.

Claims (8)

(A) an alkali-soluble resin, (B) a photopolymerization initiator, and (C) a photopolymerizable compound,
A photosensitive resin composition comprising a monofunctional monomer having a glass transition temperature of −10 ° C. or lower when the photopolymerizable compound (C) is a homopolymer having a mass average molecular weight of 10,000 or more. The photosensitive resin composition according to claim 1, wherein the monofunctional monomer is represented by the following formula (c-1).

(In the formula, R ^c1 represents a hydrogen atom or a methyl group, and R ^c2 represents an alkyl group having 4 to 12 carbon atoms. The alkyl group may have a substituent, and may have an ether bond or an ester bond. (You may have it.)   The photosensitive resin composition of Claim 1 or 2 in which the said (C) photopolymerizable compound further contains the polyfunctional monomer more than trifunctional.   The photosensitive resin composition according to claim 1, wherein the photopolymerizable compound (C) further contains a bifunctional monomer.   The said (A) alkali-soluble resin contains the copolymer (A1) which polymerized at least the unsaturated carboxylic acid (a1) and the alicyclic epoxy-group-containing unsaturated compound (a2). The photosensitive resin composition of Claim 1. An application step of applying the photosensitive resin composition according to any one of claims 1 to 5 on a substrate to form a coating film;
An exposure step of selectively exposing the coating film;
Developing the coating film after the exposure step to obtain a resin pattern; and
A heating step of heating the resin pattern;
The manufacturing method of the resin pattern containing this.   The method for producing a resin pattern according to claim 6, further comprising a conductive film forming step of forming a conductive film on the surface of the resin pattern after the heating step.   A display apparatus provided with the resin pattern manufactured by the manufacturing method of Claim 6 or 7.