Photosensitive resin composition, cured product, and photospacer

Abstract

To provide a photospacer that does not easily change in height even when in contact with chemicals such as organic solvents, and a photosensitive resin composition that does not easily gel during storage, a cured product of the aforementioned photosensitive resin composition, and a photospacer made from the aforementioned cured product. [Solution] In a photosensitive resin composition comprising an alkali-soluble resin (A), a photopolymerizable monomer (B), and a photopolymerization initiator (C), the alkali-soluble resin (A) is a resin comprising a structural unit having an alkali-soluble group (a1) and a structural unit having an alicyclic epoxy group (a2), and a fluorine atom-free silicon-based surfactant (D) is used.

Description

[Technical Field]

[0001] The present invention relates to a negative-type photosensitive resin composition that hardens upon exposure, a cured product of the aforementioned photosensitive resin composition, and a photospacer made from the aforementioned cured product. [Background technology]

[0002] When forming panels for display devices such as liquid crystal displays, various patterns with different functions are formed on the substrate for the panel. One example of such a pattern is a photospacer, which is formed to maintain a constant gap (cell gap) between two substrates.

[0003] As a method for forming photospacers, for example, a method has been proposed in which a photosensitive resin composition containing an alkali-soluble resin (A), a photopolymerizable monomer (B), and a photopolymerization initiator (C) is used to form photospacers by photolithography (see Patent Document 1).

[0004] The photosensitive resin composition described in Patent Document 1 includes an alkali-soluble resin (A) having a constituent unit (a1) derived from an unsaturated carboxylic acid, a constituent unit (a2) derived from an epoxy group-containing unsaturated compound that does not have an alicyclic group, and a constituent unit (a3) ​​derived from an alicyclic epoxy group-containing unsaturated compound, wherein the sum of the proportions of constituent unit (a2) and constituent unit (a3) ​​is 71% by mass or more. [Prior art documents] [Patent Documents]

[0005] [Patent Document 1] Japanese Patent Publication No. 2010-256848 [Overview of the project] [Problems that the invention aims to solve]

[0006] However, conventional photosensitive resin compositions, such as those described in Patent Document 1, which have been used to form photospacers, often suffer from the problem of gelation occurring when the photosensitive resin composition is stored for a long period of time. Furthermore, when manufacturing a panel for a display device using a substrate equipped with a photospacer, the photospacer may come into contact with chemicals such as organic solvents. In terms of the function required of a photospacer, which is to maintain a constant distance (cell gap) between two substrates, it is necessary that the height of the photospacer does not change even when it comes into contact with chemicals such as organic solvents. However, the photospacer formed using the photosensitive resin composition described in Patent Document 1 is prone to changes in height when it comes into contact with chemicals.

[0007] The present invention has been made in view of the above problems, and aims to provide a photospacer that does not easily change in height even when in contact with chemical solutions such as organic solvents, and a photosensitive resin composition that does not easily gel during storage, a cured product of the aforementioned photosensitive resin composition, and a photospacer made from the aforementioned cured product. [Means for solving the problem]

[0008] The present inventors have found that the above problems can be solved by using a photosensitive resin composition comprising an alkali-soluble resin (A), a photopolymerizable monomer (B), and a photopolymerization initiator (C), in which the alkali-soluble resin (A) includes a structural unit having an alkali-soluble group (a1) and a structural unit having an alicyclic epoxy group (a2), and by using a silicon-based surfactant (D) that does not contain fluorine atoms, and have completed the present invention. Specifically, the present invention provides the following.

[0009] A first aspect of the present invention comprises an alkali-soluble resin (A), a photopolymerizable monomer (B), a photopolymerization initiator (C), and a silicone-based surfactant (D). The alkali-soluble resin (A) comprises a constituent unit (a1) having an alkali-soluble group and a constituent unit (a2) having an alicyclic epoxy group. The silicone-based surfactant (D) is a photosensitive resin composition that does not contain fluorine atoms.

[0010] A second aspect of the present invention is a cured product of a photosensitive resin composition according to the first aspect.

[0011] A third aspect of the present invention is a photospacer made of a cured product according to the second aspect. [Effects of the Invention]

[0012] According to the present invention, it is possible to provide a photosensitive resin composition containing a surfactant that does not contain fluorine atoms, a cured product formed using the aforementioned photosensitive resin composition, and a photospacer made of the aforementioned cured product. [Modes for carrying out the invention]

[0013] ≪Photosensitive resin composition≫ The photosensitive resin composition comprises an alkali-soluble resin (A), a photopolymerizable monomer (B), a photopolymerization initiator (C), and a silicone-based surfactant (D). The alkali-soluble resin (A) comprises a constituent unit (a1) having an alkali-soluble group and a constituent unit (a2) having an alicyclic epoxy group. The silicone-based surfactant (D) does not contain fluorine atoms. The above photosensitive resin composition is less likely to gel during storage. Furthermore, by using the above photosensitive resin composition, it is possible to form a photospacer whose height does not change easily even when in contact with chemical solutions such as organic solvents.

[0014] In this specification, the surface tension (surface free energy) of the photosensitive resin composition is the surface tension obtained by measuring the contact angle of various droplets on the surface of the resin film formed from the photosensitive resin composition. The surface tension ([mN / m]) of the resin film is equal to the surface free energy [mJ / m] of the resin film. 2 It has the same absolute value as ]). Furthermore, in this specification, the contact angle of a liquid (e.g., pure water, methylene iodide, etc.) is the static contact angle. In this specification, unless otherwise specified, the static contact angle of a liquid can be measured, for example, using a contact angle meter (LAUDA TVT-2, manufactured by Lauda) at a temperature of 25°C and a relative humidity of 50%, by dropping a 2.0 μL liquid droplet onto the surface of the resin film and measuring the contact angle 1 second after dropping (suspended droplet method). From each of the obtained contact angles, the surface tension (surface free energy) is calculated according to the Owens-Wendt method.

[0015] The surface tension of the photosensitive resin composition at a temperature of 25°C and a relative humidity of 50% is preferably 25 mN / m to 35 mN / m, and more preferably 25 mN / m to 30 mN / m. The surface tension can be adjusted by appropriately changing the type or amount of silicone-based surfactant (D), or by appropriately changing the type or ratio of constituent units that make up the alkali-soluble resin (A).

[0016] The following describes the essential and optional components of the photosensitive resin composition, as well as the method for preparing the photosensitive resin composition.

[0017] <Alkali-soluble resin (A)> The alkali-soluble resin (A) is not particularly limited as long as it includes a constituent unit (a1) having an alkali-soluble group and a constituent unit (a2) having an alicyclic epoxy group, and can be appropriately selected from alkali-soluble resins that have been conventionally incorporated into various photosensitive resin compositions. As such alkali-soluble resins, acrylic resins containing constituent units derived from (meth)acrylic acid derivatives such as (meth)acrylic acid esters, or constituent units derived from (meth)acrylic acid, are preferred.

[0018] The constituent unit (a1) having an alkali-soluble group is not particularly limited, and examples include units having a carboxyl group, a sulfonic acid group, a phosphoric acid group, and a phenolic hydroxyl group. Among these, units having a carboxyl group are preferred. In other words, it is preferable that the constituent unit (a1) having an alkali-soluble group includes units derived from an unsaturated carboxylic acid.

[0019] Examples of unsaturated carboxylic acids include (meth)acrylic acid; (meth)acrylamide; crotonic acid, fumaric acid, citraconic acid, mesaconic acid, itaconic acid, and their dicarboxylic acid anhydrides. Of these, (meth)acrylic acid is preferred.

[0020] As a compound that gives a structural unit (a2) having an alicyclic epoxy group, an unsaturated compound having an alicyclic epoxy group is preferred, and a compound derived from an unsaturated carboxylic acid that has an alicyclic epoxy group is more preferred. Suitable examples of compounds derived from unsaturated carboxylic acids that have an alicyclic epoxy group include (meth)acrylic acid esters having an alicyclic epoxy group and (meth)acrylamide having an alicyclic epoxy group. Among these, (meth)acrylic acid esters having an alicyclic epoxy group are preferred.

[0021] The alicyclic groups constituting the alicyclic epoxy group may be monocyclic or polycyclic. Examples of monocyclic alicyclic groups include cyclopentyl and cyclohexyl groups. Examples of polycyclic alicyclic groups include norbornyl, isobornyl, tricyclononyl, tricyclodecyl, and tetracyclododecyl groups. Specifically, examples of compounds that give a structural unit (a2) having an alicyclic epoxy group include those represented by the following formulas (a2-1) to (a2-15).

[0022] [ka]

[0023] [ka]

[0024] [ka]

[0025] [Chemical formula]

[0026] [[ID=​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​The aliphatic hydrocarbon group may be linear, branched, or cyclic. The number of carbon atoms in the aliphatic hydrocarbon group is preferably 1 to 20, more preferably 1 to 15, and particularly preferably 1 to 10. The aliphatic hydrocarbon group preferably includes a saturated aliphatic hydrocarbon ring group.

[0032] When the aliphatic hydrocarbon group is linear or branched, preferred examples of the aliphatic hydrocarbon 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-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, and isodecyl group.

[0033] When the aliphatic hydrocarbon group is an aliphatic hydrocarbon ring group or a group containing an aliphatic hydrocarbon ring group, examples of aliphatic hydrocarbon ring groups include monocyclic saturated aliphatic hydrocarbon ring groups such as cyclopentyl and cyclohexyl groups, and polycyclic saturated aliphatic hydrocarbon ring groups such as adamantyl, norbornyl, isobornyl, tricyclononyl, tricyclodecyl, and tetracyclododecyl groups.

[0034] The alkali-soluble resin (A) may have other structural units besides the above-mentioned structural units (a1), (a2), and (a3). Examples of other structural units include structural units (a4) derived from compounds such as allyl compounds, vinyl ethers, vinyl esters, styrenes, and epoxy group-containing unsaturated compounds that do not have alicyclic epoxy groups. These compounds can be used individually or in combination of two or more.

[0035] Examples of allyl compounds include allyl esters such as allyl acetate, allyl caproate, allyl caprylate, allyl laurate, allyl palmitate, allyl stearate, allyl benzoate, allyl acetoacetate, and allyl lactate; and allyloxyethanol.

[0036] Examples of 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; vinyl aryl ethers such as vinyl phenyl ether, vinyl tolyl ether, vinyl chlorophenyl ether, vinyl-2,4-dichlorophenyl ether, vinyl naphthyl ether, and vinyl anthranyl ether; and the like.

[0037] Examples of vinyl esters include vinyl butyrate, vinyl isobutyrate, vinyl trimethyl acetate, vinyl diethyl acetate, vinyl barate, vinyl caproate, vinyl chlor acetate, vinyl dichlor acetate, vinyl methoxy acetate, vinyl butoxy acetate, vinyl phenyl acetate, vinyl acetoacetate, vinyl lactate, vinyl-β-phenyl butyrate, vinyl benzoate, vinyl salicylate, vinyl chlorbenzoate, vinyl tetrachlorbenzoate, vinyl naphthoate, and others.

[0038] Examples of styrenes include styrene; alkylstyrenes 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; and halostyrenes such as chlorostyrene, dichlorostyrene, trichlorostyrene, tetrachlorostyrene, pentachlorostyrene, bromostyrene, dibromostyrene, iodostyrene, fluorostyrene, trifluorostyrene, 2-bromo-4-trifluoromethylstyrene, and 4-fluoro-3-trifluoromethylstyrene.

[0039] Examples of epoxy group-containing unsaturated compounds that do not have an alicyclic group include epoxyalkyl esters of (meth)acrylates such as glycidyl methacrylate, 2-methylglycidyl (meth)acrylate, 3,4-epoxybutyl (meth)acrylate, and 6,7-epoxyheptyl (meth)acrylate; and epoxyalkyl esters of α-alkylacrylates such as glycidyl α-ethylacrylate, glycidyl α-n-propylacrylate, glycidyl α-n-butylacrylate, and 6,7-epoxyheptyl α-ethylacrylate.

[0040] The content of the above-mentioned constituent unit (a1), constituent unit (a2), constituent unit (a3), and other constituent unit (a4) in the alkali-soluble resin (A) is not particularly limited as long as it does not hinder the objective of the present invention. The content of the above-mentioned constituent unit (a1) is preferably 1% by mass or more and 25% by mass or less, preferably 3% by mass or more and 20% by mass or less, and more preferably 5% by mass or more and 15% by mass or less, based on the mass of the alkali-soluble resin (A). The content of the above-mentioned constituent unit (a2) is 71% by mass or more, preferably 71% by mass or more and 95% by mass or less, and more preferably 75% by mass or more and 90% by mass or less, based on the mass of the alkali-soluble resin (A). The content of the above-mentioned constituent unit (a3) ​​is preferably 3% by mass or more and 25% by mass or less, and more preferably 5% by mass or more and 25% by mass or less, based on the mass of the alkali-soluble resin (A). The content of the above-mentioned other constituent units (a4) is preferably 0% by mass or more and 10% by mass or less, and more preferably 0% by mass or more and 5% by mass or less, relative to the mass of the alkali-soluble resin (A). When the content of each constituent unit of the alkali-soluble resin (A) is within the above range, the developability of the photosensitive resin composition can be made appropriate, and the shape, fracture strength, and adhesion to the substrate of the cured product can be made good.

[0041] The weight-average molecular weight of the alkali-soluble resin (A) is preferably between 2,000 and 50,000, and more preferably between 5,000 and 30,000. This range tends to facilitate a balance between the film-forming ability and developability after exposure of the photosensitive resin composition.

[0042] The content of alkali-soluble resin (A) is preferably 40% to 85% by mass, and more preferably 45% to 75% by mass, relative to the mass of solids in the photosensitive resin composition. Setting the content of alkali-soluble resin (A) within the above range tends to facilitate a balance of developability.

[0043] <Photopolymerizable monomer (B)> As the photopolymerizable monomer (B), monomers having an ethylenically unsaturated group can be preferably used. These monomers having an ethylenically unsaturated group include monofunctional monomers and polyfunctional monomers.

[0044] Examples of monofunctional monomers include (meth)acrylamide, methylol(meth)acrylamide, methoxymethyl(meth)acrylamide, ethoxymethyl(meth)acrylamide, propoxymethyl(meth)acrylamide, butoxymethoxymethyl(meth)acrylamide, N-methylol(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-acrylamide-2-methylpropanesulfonic acid, tert-butylacrylamidesulfonic acid, methyl(meth)acrylate, ethyl(meth)acrylate, butyl(meth)acrylate, 2-ethyl Examples include hexyl (meth)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, glycerin mono(meth)acrylate, tetrahydrofurfuryl (meth)acrylate, dimethylaminoethyl (meth)acrylate, glycidyl (meth)acrylate, 2,2,2-trifluoroethyl (meth)acrylate, 2,2,3,3-tetrafluoropropyl (meth)acrylate, and half (meth)acrylates of phthalic acid derivatives. These monofunctional monomers can be used individually or in combination of two or more.

[0045] On the other hand, polyfunctional monomers include 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, butylene glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate, 1,6-hexane glycol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, glycerin 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)acryloxydiethoxyphenyl)propane, 2,2-Bis(4-(meth)acryloxypolyethoxyphenyl)propane, 2-Hydroxy-3-(meth)acryloyloxypropyl (meth)acrylate, Ethylene glycol diglycidyl ether di(meth)acrylate, Diethylene glycol diglycidyl ether di(meth)acrylate, Diglycidyl phthalate diglycidyl ester di(meth)acrylate, Glycerin triacrylate, Glycerin polyglycerin Examples include polyfunctional monomers such as sidyl ether poly(meth)acrylate, urethane (meth)acrylate (i.e., reaction products of tolylene diisocyanate, trimethylhexamethylene diisocyanate, or hexamethylene diisocyanate, etc., with 2-hydroxyethyl (meth)acrylate), methylenebis(meth)acrylamide, (meth)acrylamide methylene ether, condensates of polyhydric alcohols with N-methylol(meth)acrylamide, and triacrylic formal. These polyfunctional monomers can be used individually or in combination of two or more.

[0046] Among these monomers having ethylenically unsaturated groups, polyfunctional monomers with three or more functions are preferred, polyfunctional monomers with four or more functions are more preferred, polyfunctional monomers with five or more functions are even more preferred, and polyfunctional monomers with six or more functions are particularly preferred, as they tend to improve the adhesion of the photosensitive resin composition to the substrate and the strength of the photosensitive resin composition after curing.

[0047] The content of the photopolymerizable monomer (B) in the composition is preferably 5% to 50% by mass, and more preferably 10% to 40% by mass, relative to the mass of the photosensitive resin composition excluding the mass of the organic solvent (S) described later. This range tends to facilitate a balance between sensitivity, developability, and resolution.

[0048] <Photopolymerization initiator (C)> The photopolymerization initiator (C) is not particularly limited, and conventionally known photopolymerization initiators can be used.

[0049] Specifically, the photopolymerization initiator (C) includes 1-hydroxycyclohexylphenyl ketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 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, 2,2-dimethoxy-1,2-diphenylethane-1-one, and bis(4-dimethic (Diaminophenyl)ketone, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butan-1-one, etanone, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl], 1-(O-acetyloxime), (9-ethyl-6-nitro-9H-carbazol-3-yl)[4-(2-methoxy-1-methylethoxy)-2-methylphenyl]methanone O-acetyloxime, 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, o-methyl 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, 2-mercaptobenzimidazole, 2-mercaptobenzoxazole, 2-mercaptobenzothiazole, 2-(o-chlorophenyl)-4,5-di(m-methoxyphenyl)-imidazolyl dimer, benzophenone, 2-chlorobenzophenone, p,p'-bisdimethylaminobenzophenone, 4,4'-bisdiethylaminobenzophenone, 4,4'-dichlorobenzophenone, 3,3-dimethyl-4-methoxy Benzophenone, 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 n, p-tert-butyldichloroacetophenone, α,α-dichloro-4-phenoxyacetophenone, thioxanthone, 2-methylthioxanthone, 2-isopropylthioxanthone, dibenzosverone, pentyl-4-dimethylaminobenzoate, 9-phenylacridin, 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)-s-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,Examples include 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, and 2,4-bis-trichloromethyl-6-(2-bromo-4-methoxy)styrylphenyl-s-triazine. These photopolymerization initiators can be used individually or in combination of two or more.

[0050] Among the photopolymerization initiators (C), oxime ester compounds are preferred in terms of the sensitivity of the photosensitive composition. As the oxime ester compound, a compound having a substructure represented by the following formula (c1) is preferred.

[0051] [ka]

[0052] In equation (c1), n1 is either 0 or 1. c2 R is a monovalent organic group. c3 This is a hydrogen atom, an aliphatic hydrocarbon group having 1 to 20 carbon atoms (which may have substituents), or an aryl group (which may have substituents). * indicates a bond.

[0053] Compounds having a substructure represented by formula (c1) preferably have a carbazole skeleton, a fluorene skeleton, a diphenyl ether skeleton, or a phenyl sulfide skeleton. A compound having a substructure represented by formula (c1) preferably has one or two substructures represented by formula (c1).

[0054] Examples of compounds having a substructure represented by formula (c1) include the compound represented by the following formula (c2).

[0055] [ka]

[0056] In formula (c2), R c1 R is a group represented by the following formulas (c3), (c4), or (c5). n1 is 0 or 1. c2 R is a monovalent organic group. c3 This is a hydrogen atom, an aliphatic hydrocarbon group having 1 to 20 carbon atoms (which may have substituents), or an aryl group (which may have substituents).

[0057] [ka]

[0058] In formula (c3), R c4 R is a monovalent organic group. c5 R is a monovalent organic group, a halogen atom, or a nitro group. n2 is an integer between 0 and 3. If n2 is 2 or 3, multiple R c5 They may be the same or different, and multiple R c5 These elements may join together to form a ring. * represents a bonding hand.

[0059] [ka]

[0060] In formula (c4), R c6 and R c7 Each of these is independently a substituted linear alkyl group, a substituted linear alkoxy group, a substituted cyclic organic group, or a hydrogen atom. c6 and R c7 These may be joined together to form a ring. c7 The benzene ring in the fluorene skeleton may bond to each other to form a ring.c8 n3 is a nitro group or a monovalent organic group. n3 is an integer between 0 and 4 (inclusive). * represents a bond.

[0061] [ka]

[0062] In formula (c5), R c9 is a monovalent organic group, halogen atom, nitro group, or cyano group. A is S or O. n4 is an integer between 0 and 4 (inclusive). * is a bond.

[0063] In formula (c3), R c4 R is a monovalent organic group. c4 The organic group can be selected from a variety of organic groups, as long as it does not hinder the objective of the present invention. Preferably, the organic group is a carbon-carbon-containing group, and more preferably, a group consisting of one or more carbon atoms and one or more atoms selected from the group consisting of H, O, S, Se, N, B, P, Si, and halogen atoms. The number of carbon atoms in the carbon-carbon-containing group is not particularly limited, but is preferably 1 to 50, and more preferably 1 to 20. R c4 Preferred examples include alkyl groups having 1 to 20 substituents, cycloalkyl groups having 3 to 20 substituents, saturated aliphatic acyl groups having 2 to 20 substituents, alkoxycarbonyl groups having 2 to 20 substituents, phenyl groups having substituted elements, benzoyl groups having substituted elements, phenoxycarbonyl groups having substituted elements, phenylalkyl groups having 7 to 20 substituents, naphthyl groups having substituted elements, naphthoyl groups having substituted elements, naphthoxycarbonyl groups having substituted elements, naphthylalkyl groups having 11 to 20 substituents, heterocyclyl groups having substituted elements, and heterocyclylcarbonyl groups having substituted elements.

[0064] R c4Among these, alkyl groups having 1 to 20 carbon atoms are preferred. The alkyl group may be linear or branched. From the viewpoint of good solubility in photosensitive compositions of the compound represented by formula (c3), R c4 The number of carbon atoms in the alkyl group is preferably 2 or more, more preferably 5 or more, and particularly preferably 7 or more. Furthermore, in the photosensitive composition, the compound represented by formula (c3) has good compatibility with other components, so R c4 The number of carbon atoms in the alkyl group is preferably 15 or less, and more preferably 10 or less.

[0065] R c4 If the substituent has substituents, preferred examples of such substituents include hydroxyl groups, alkyl groups having 1 to 20 carbon atoms, alkoxy groups having 1 to 20 carbon atoms, aliphatic acyl groups having 2 to 20 carbon atoms, aliphatic acyloxy groups having 2 to 20 carbon atoms, phenoxy groups, benzoyl groups, benzoyloxy groups, groups represented by -PO(OR)2 (where R is an alkyl group having 1 to 6 carbon atoms), halogen atoms, cyano groups, heterocyclyl groups, and the like.

[0066] R c4 However, if it is a heterocyclyl group, the heterocyclyl group may be an aliphatic heterocyclic group or an aromatic heterocyclic group. c4When the group is a heterocyclyl group, the heterocyclyl group is a 5-membered or 6-membered monoring containing one or more N, S, and O atoms, or a heterocyclyl group formed by the fusion of such monorings with each other, or with a benzene ring. If the heterocyclyl group is a fused ring, it shall have up to 3 rings. Examples of heterocyclic rings constituting such a heterocyclyl group include furan, thiophene, pyrrole, oxazole, isoxazole, thiazole, thiadiazole, isothiazole, imidazole, pyrazole, triazole, pyridine, pyrazine, pyrimidine, pyridazine, benzofuran, benzothiophene, indole, isoindole, indidine, benzimidazole, benzotriazole, benzoxazole, benzothiazole, carbazole, purine, quinoline, isoquinoline, quinazoline, phthalazine, cinnoline, quinoxaline, piperidine, piperazine, morpholine, piperidine, tetrahydropyran, and tetrahydrofuran. R c4 If the group is a heterocyclyl group, examples of substituents that the heterocyclyl group may have include a hydroxyl group, an alkoxy group having 1 to 6 carbon atoms, a halogen atom, a cyano group, a nitro group, and the like.

[0067] R explained above c4 Preferred specific examples 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, neopentyl group, pentan-3-yl group, sec-pentyl group, tert-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, and 2-ethylhexyl group. Furthermore, the n-octyl group and the 2-ethylhexyl group are preferred, and the 2-ethylhexyl group is more preferred, given the good solubility of the compound represented by formula (c3) in the photosensitive composition.

[0068] In formula (c3), R c5 R is a monovalent organic group, a halogen atom, or a nitro group. c5The monovalent organic group can be selected from a variety of organic groups, as long as it does not hinder the objectives of the present invention. Preferably, the organic group is a carbon-carbon-containing group, and more preferably, a group consisting of one or more carbon atoms and one or more atoms selected from the group consisting of H, O, S, Se, N, B, P, Si, and halogen atoms. The number of carbon atoms in the carbon-carbon-containing group is not particularly limited, but is preferably 1 to 50, and more preferably 1 to 20. R c5 Suitable examples of monovalent organic groups include alkyl groups, alkoxy groups, cycloalkyl groups, cycloalkoxy groups, saturated aliphatic acyl groups, alkoxycarbonyl groups, saturated aliphatic acyloxy groups, optionally substituted phenyl groups, optionally substituted phenoxy groups, optionally substituted benzoyl groups, optionally substituted phenoxycarbonyl groups, optionally substituted benzoyloxy groups, optionally substituted phenylalkyl groups, optionally substituted naphthyl groups, optionally substituted naphthoxy groups, optionally substituted naphthoyl groups, optionally substituted naphthoxycarbonyl groups, optionally substituted naphthoyloxy groups, optionally substituted naphthylalkyl groups, optionally substituted heterocyclyl groups, optionally substituted heterocyclylcarbonyl groups, amino groups substituted with 1 or 2 organic groups, morpholine-1-yl group, piperazine-1-yl group, cyano groups, substituents containing groups represented by HX2C- or H2XC- (where X is independently a halogen atom), etc.

[0069] R c5 When is an alkyl group, the number of carbon atoms in the alkyl group is preferably 1 to 20, and more preferably 1 to 6. c5 If R is an alkyl group, it may be a straight chain or a branched chain. c5Specific examples of cases where is 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-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, and isodecyl group. c5 If the alkyl group is an alkyl group, the alkyl group may contain an ether bond (-O-) in its carbon chain. Examples of alkyl groups having an ether bond in their carbon chain include methoxyethyl group, ethoxyethyl group, methoxyethoxyethyl group, ethoxyethoxyethyl group, propyloxyethoxyethyl group, and methoxypropyl group.

[0070] R c5 If R is an alkoxy group, the number of carbon atoms in the alkoxy group is preferably 1 to 20, and more preferably 1 to 6. c5 If R is an alkoxy group, it may be a linear or branched chain. c5 Specific examples of cases where 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-octyloxy group, tert-octyloxy group, n-nonyloxy group, isononyloxy group, n-decyloxy group, and isodecyloxy group. c5 If the group is an alkoxy group, the alkoxy group may contain an ether bond (-O-) in its carbon chain. Examples of alkoxy groups having an ether bond in their carbon chain include methoxyethoxy group, ethoxyethoxy group, methoxyethoxyethoxy group, ethoxyethoxyethoxy group, propyloxyethoxyethoxy group, and methoxypropyloxy group.

[0071] R c5 When is a cycloalkyl group or cycloalkoxy group, the number of carbon atoms in the cycloalkyl group or cycloalkoxy group is preferably 3 to 10, and more preferably 3 to 6. c5 Specific examples of cases where is a cycloalkyl group include cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, and cyclooctyl group. c5 Specific examples of groups that are cycloalkoxy groups include cyclopropyloxy, cyclobutyloxy, cyclopentyloxy, cyclohexyloxy, cycloheptyloxy, and cyclooctyloxy groups.

[0072] R c5 When is a saturated aliphatic acyl group or a saturated aliphatic acyloxy group, the number of carbon atoms in the saturated aliphatic acyl group or saturated aliphatic acyloxy group is preferably 2 or more and 21 or less, and more preferably 2 or more and 7 or less. c5 Specific examples of cases where 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-pentadecanoyl group, and n-hexadecanoyl group. c5 Specific examples of cases where 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, and n-hexadecanoyloxy group.

[0073] R c5 When is an alkoxycarbonyl group, the number of carbon atoms in the alkoxycarbonyl group is preferably 2 to 20, and more preferably 2 to 7. c5 Specific examples of cases where is an alkoxycarbonyl group include methoxycarbonyl group, ethoxycarbonyl group, n-propyloxycarbonyl group, isopropyloxycarbonyl group, n-butyloxycarbonyl group, isobutyloxycarbonyl group, sec-butyloxycarbonyl 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, and isodecyloxycarbonyl group.

[0074] R c5 When is a phenylalkyl group, the number of carbon atoms in the phenylalkyl group is preferably 7 to 20, and more preferably 7 to 10. Also, R c5 When is a naphthylalkyl group, the number of carbon atoms in the naphthylalkyl group is preferably 11 to 20, and more preferably 11 to 14. c5 Specific examples of cases where is a phenylalkyl group include the benzyl group, 2-phenylethyl group, 3-phenylpropyl group, and 4-phenylbutyl group. c5 Specific examples of cases where is a naphthylalkyl group include α-naphthylmethyl group, β-naphthylmethyl group, 2-(α-naphthyl)ethyl group, and 2-(β-naphthyl)ethyl group. c5 However, if it is a phenylalkyl group or a naphthylalkyl group, R c5 It may have further substituents on the phenyl group or naphthyl group.

[0075] R c5 If is a heterocyclyl group, the heterocyclyl group is R in formula (c3). c4 This is similar to the case where the group is a heterocyclyl group, and the heterocyclyl group may have further substituents. R c5 If it is a heterocyclylcarbonyl group, the heterocyclyl group contained in the heterocyclylcarbonyl group is R c5 This is similar to the case where it is a heterocyclyl group.

[0076] R c5 When R is an amino group substituted with one or two organic groups, preferred examples of organic groups include alkyl groups having 1 to 20 carbon atoms, cycloalkyl groups having 3 to 10 carbon atoms, saturated aliphatic acyl groups having 2 to 21 carbon atoms, optionally substituted phenyl groups, optionally substituted benzoyl groups, optionally substituted phenylalkyl groups having 7 to 20 carbon atoms, optionally substituted naphthyl groups, optionally substituted naphthoyl groups, optionally substituted naphthylalkyl groups having 11 to 20 carbon atoms, and heterocyclyl groups. Specific examples of these preferred organic groups are shown in R. c5 The same applies. Specific examples of amino groups substituted with organic groups 1 or 2 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-decanoylamino group, benzoylamino group, α-naphthoylamino group, and β-naphthoylamino group.

[0077] R c5Examples of substituents when the phenyl group, naphthyl group, and heterocyclyl group contained in have further substituents include substituents containing groups represented by HX2C- or H2XC-, alkyl groups having 1 to 6 carbon atoms, alkoxy groups having 1 to 6 carbon atoms, saturated aliphatic acyl groups having 2 to 7 carbon atoms, alkoxycarbonyl groups having 2 to 7 carbon atoms, saturated aliphatic acyloxy groups having 2 to 7 carbon atoms, monoalkylamino groups having an alkyl group having 1 to 6 carbon atoms, dialkylamino groups having an alkyl group having 1 to 6 carbon atoms, morpholine-1-yl group, piperazine-1-yl group, benzoyl group, halogen, nitro group, and cyano group. c5 If the phenyl group, naphthyl group, and heterocyclyl group contained in have further substituents, the number of substituents is not limited as long as it does not hinder the objective of the present invention, but is preferably 1 to 4. c5 If the phenyl group, naphthyl group, and heterocyclyl group contained in have multiple substituents, the substituents may be the same or different.

[0078] R c5 Examples of substituents that may be found in the benzoyl group include alkyl groups having 1 to 6 carbon atoms, morpholine-1-yl group, piperazine-1-yl group, 2-tenoyl group (thiophene-2-ylcarbonyl group), furan-3-ylcarbonyl group, and phenyl group.

[0079] Examples of halogen atoms represented by X include fluorine atoms, chlorine atoms, and bromine atoms, with fluorine atoms being preferred.

[0080] Substituents containing a group represented by HX2C- or H2XC- include halogenated alkoxy groups containing a group represented by HX2C- or H2XC-, groups having halogenated alkoxy groups containing a group represented by HX2C- or H2XC-, halogenated alkyl groups containing a group represented by HX2C- or H2XC-, and groups having halogenated alkyl groups containing a group represented by HX2C- or H2XC-. It is more preferable that the substituent contains a halogenated alkoxy group containing a group represented by HX2C- or H2XC-, or a group having a halogenated alkoxy group containing a group represented by HX2C- or H2XC-.

[0081] Groups having a halogenated alkyl group containing a group represented by HX2C- or H2XC- include aromatic groups substituted with a halogenated alkyl group containing a group represented by HX2C- or H2XC- (e.g., phenyl group, naphthyl group, etc.) and cycloalkyl groups substituted with a halogenated alkyl group containing a group represented by HX2C- or H2XC- (e.g., cyclopentyl group, cyclohexyl group, etc.). It is preferable that the aromatic group is substituted with a halogenated alkyl group containing a group represented by HX2C- or H2XC-.

[0082] Groups having a halogenated alkoxy group containing a group represented by HX2C- or H2XC- include aromatic groups substituted with a halogenated alkoxy group containing a group represented by HX2C- or H2XC- (e.g., phenyl group, naphthyl group, etc.), alkyl groups substituted with a halogenated alkoxy group containing a group represented by HX2C- or H2XC- (e.g., methyl group, ethyl group, n-propyl group, i-propyl group, etc.), and cycloalkyl groups substituted with a halogenated alkoxy group containing a group represented by HX2C- or H2XC- (e.g., cyclopentyl group, cyclohexyl group, etc.). It is preferable that the aromatic group is substituted with a halogenated alkoxy group containing a group represented by HX2C- or H2XC-.

[0083] Also, R c5Preferred alternatives include cycloalkylalkyl groups, phenoxyalkyl groups which may have substituents on the aromatic ring, and phenylthioalkyl groups which may have substituents on the aromatic ring. The substituents which phenoxyalkyl groups and phenylthioalkyl groups may have are R c5 These substituents may be present on the phenyl group contained within.

[0084] Among monovalent organic groups, R c5 Preferred elements include alkyl groups, cycloalkyl groups, optionally substituted phenyl groups, or cycloalkylalkyl groups and optionally substituted phenylthioalkyl groups on the aromatic ring. Among alkyl groups, alkyl groups having 1 to 20 carbon atoms are preferred, alkyl groups having 1 to 8 carbon atoms are more preferred, alkyl groups having 1 to 4 carbon atoms are particularly preferred, and the methyl group is most preferred. Among optionally substituted phenyl groups, the methylphenyl group is preferred, and the 2-methylphenyl group is more preferred. The number of carbon atoms in the cycloalkyl group included in the cycloalkylalkyl group is preferably 5 to 10, more preferably 5 to 8, and particularly preferred as 5 or 6. The number of carbon atoms in the alkylene group included in the cycloalkylalkyl group is preferably 1 to 8, more preferably 1 to 4, and particularly preferred as 2. Among cycloalkylalkyl groups, the cyclopentylethyl group is preferred. The number of carbon atoms in the alkylene group included in the optionally substituted phenylthioalkyl group is preferably 1 to 8, more preferably 1 to 4, and particularly preferred as 2. Among optionally substituted phenylthioalkyl groups on the aromatic ring, the 2-(4-chlorophenylthio)ethyl group is preferred.

[0085] In the group represented by formula (c3), R c5 There are multiple R c5 When atoms bond to each other to form a ring, examples of the formed ring include hydrocarbon rings and heterocycles. Examples of heteroatoms included in a heterocycle include N, O, and S. c5As the ring formed by bonding to each other, an aromatic ring is particularly preferred. Such an aromatic ring may be an aromatic hydrocarbon ring or an aromatic heterocyclic ring. As such an aromatic ring, an aromatic hydrocarbon ring is preferred. In formula (c3), a plurality of R c5 Specific examples when bonding to each other to form a benzene ring are shown below.

[0086]

Chemical formula

[0087] In the group represented by formula (c4), R c8 is a nitro group or a monovalent organic group. R c8 binds to a 6-membered aromatic ring different from the aromatic ring that binds to the group represented by -(CO) n1 - on the condensed ring in formula (c4). In formula (c4), the bonding position of R c8 is not particularly limited. When the group represented by formula (c4) has one or more R c8 , since the synthesis of the compound represented by formula (c4) is easy, etc., it is preferable that one of the one or more R c8 binds to the 7-position of the fluorene skeleton. That is, when the group represented by formula (c4) has one or more R c8 , the group represented by formula (c4) is preferably represented by the following formula (c6). When there are a plurality of R c8 , the plurality of R c8 may be the same or different.

[0088]

Chemical formula

[0089] In formula (c6), R c6 , R c7 , R c8 , n3 are the same as R c6 , R c7 , R c8 , n3 in formula (c4), respectively.

[0090] Rc8 When R is a monovalent organic group, c8 it is not particularly limited as long as it does not inhibit the object of the present invention. As the organic group, a carbon atom-containing group is preferable, and a group composed of one or more carbon atoms and one or more atoms selected from the group consisting of H, O, S, Se, N, B, P, Si, and a halogen atom is more preferable. The number of carbon atoms of the carbon atom-containing group is not particularly limited, preferably 1 or more and 50 or less, more preferably 1 or more and 20 or less. R c8 When R is a monovalent organic group, preferable examples include the same groups as the preferable examples of the monovalent organic group as R in formula (c3). c5

[0091] In formula (c4), R c6 and R c7 are each 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. R c6 and R c7 may be bonded to each other to form a ring. Among these groups, as R c6 and R c7 a chain alkyl group which may have a substituent is preferable. When R c6 and R c7 are a chain alkyl group which may have a substituent, the chain alkyl group may be a linear alkyl group or a branched alkyl group.

[0092] R c6 and R c7 When they are a chain alkyl group having no substituent, the number of carbon atoms of the chain alkyl group is preferably 1 or more and 20 or less, more preferably 1 or more and 10 or less, and particularly preferably 1 or more and 6 or less. R c6 and R c7 ​Specific examples of cases where is a chain 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-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, and isodecyl group. c6 and R c7 If the alkyl group is an alkyl group, the alkyl group may contain an ether bond (-O-) in its carbon chain. Examples of alkyl groups having an ether bond in their carbon chain include methoxyethyl group, ethoxyethyl group, methoxyethoxyethyl group, ethoxyethoxyethyl group, propyloxyethoxyethyl group, and methoxypropyl group.

[0093] R c6 and R c7 When the derivative is a substituted linear alkyl group, the number of carbon atoms in the linear alkyl group is preferably 1 to 20, more preferably 1 to 10, and particularly preferably 1 to 6. In this case, the number of carbon atoms in the substituent is not included in the number of carbon atoms in the linear alkyl group. The substituted linear alkyl group is preferably linear.

[0094] The substituents that the alkyl group may have are not particularly limited as long as they do not hinder the objectives of the present invention. Preferred examples of substituents include alkoxy groups, cyano groups, halogen atoms, alkyl halides, 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 heterocyclyl groups. A specific example of a cycloalkyl group is R c8 The preferred examples are similar to those when is a cycloalkyl group. Specific examples of aromatic hydrocarbon groups include phenyl, naphthyl, biphenylyl, anthryl, and phenanthryl groups. Specific examples of heterocyclyl groups include Rc8 This is similar to a preferred example when is a heterocyclyl group. c8 When the group is an alkoxycarbonyl group, the alkoxy group contained in the alkoxycarbonyl group may be linear or branched, but linear is preferred. The number of carbon atoms in the alkoxy group contained in the alkoxycarbonyl group is preferably 1 to 10, and more preferably 1 to 6.

[0095] When a linear alkyl group has substituents, the number of substituents is not particularly limited. The preferred number of substituents varies depending on the number of carbon atoms in the linear alkyl group. Typically, the number of substituents is between 1 and 20, preferably between 1 and 10, and more preferably between 1 and 6.

[0096] R c6 and R c7 When the chain alkoxy group is unsubstituted, the number of carbon atoms in the chain alkoxy group is preferably 1 to 20, more preferably 1 to 10, and particularly preferably 1 to 6. c6 and R c7 Specific examples of cases where is a chain-like 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-octyloxy group, tert-octyloxy group, n-nonyloxy group, isononyloxy group, n-decyloxy group, and isodecyloxy group. c6 and R c7 If the group is an alkoxy group, the alkoxy group may contain an ether bond (-O-) in its carbon chain. Examples of alkoxy groups having an ether bond in their carbon chain include methoxyethoxy group, ethoxyethoxy group, methoxyethoxyethoxy group, ethoxyethoxyethoxy group, propyloxyethoxyethoxy group, and methoxypropyloxy group.

[0097] R c6 and R c7 When is a substituted linear alkoxy group, the substituents that the alkoxy group may have are R c6 and R c7 This is similar to the case where it is a chain-like alkyl group.

[0098] R c6 and R c7 If the group is a cyclic organic group, the cyclic organic group may be an alicyclic group or an aromatic group. Examples of cyclic organic groups include aliphatic cyclic hydrocarbon groups, aromatic hydrocarbon groups, and heterocyclyl groups. c6 and R c7 If is a cyclic organic group, the substituents that the cyclic organic group may have are R c6 and R c7 This is similar to the case where it is a chain-like alkyl group.

[0099] R c6 and R c7 When the aromatic hydrocarbon group is an aromatic hydrocarbon group, it is preferable that the aromatic hydrocarbon group is a phenyl group, a group formed by the bonding of multiple benzene rings via carbon-carbon bonds, or a group formed by the condensation of multiple benzene rings. When the aromatic hydrocarbon group is a phenyl group or a group formed by the bonding or condensation of multiple benzene rings, the number of benzene rings included in the aromatic hydrocarbon group is not particularly limited, but is preferably 3 or less, more preferably 2 or less, and particularly preferably 1. Preferred specific examples of aromatic hydrocarbon groups include phenyl groups, naphthyl groups, biphenylyl groups, anthryl groups, and phenanthryl groups.

[0100] R c6 and R c7When is 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 to 20, and more preferably 3 to 10. Examples of monocyclic cyclic hydrocarbon groups include cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group, norbornyl group, isobornyl group, tricyclononyl group, tricyclodecyl group, tetracyclododecyl group, and adamantyl group.

[0101] R c6 and R c7 If is a heterocyclyl group, then R in formula (c3) c5 Examples of groups similar to heterocyclyl groups include those used as heterocyclyl groups.

[0102] R c6 and R c7 These may be bonded to each other to form a ring. c6 and R c7 The ring formed by the two is preferably a cycloalkylidene group. c6 and R c7 When these are bonded to form a cycloalkylidene group, the ring constituting the cycloalkylidene group is preferably a 5-membered to 6-membered ring, and more preferably a 5-membered ring.

[0103] R c7 When forming a ring with a benzene ring of the fluorene skeleton, the ring may be an aromatic ring or an aliphatic ring.

[0104] R c6 and R c7 When the group formed by bonding is a cycloalkylidene group, the cycloalkylidene group may be fused with one or more other rings. Examples of rings that may be fused with a cycloalkylidene group include benzene rings, naphthalene rings, cyclobutane rings, cyclopentane rings, cyclohexane rings, cycloheptane rings, cyclooctane rings, furan rings, thiophene rings, pyrrole rings, pyridine rings, pyrazine rings, and pyrimidine rings.

[0105] R explained above c6 and R c7 Among the suitable bases, example of formula -A 1 -A 2 A group represented by the formula is shown below. 1 A is a linear alkylene group, 2 Examples include alkoxy groups, cyano groups, halogen atoms, alkyl halides, cyclic organic groups, or alkoxycarbonyl groups.

[0106] A 1 The number of carbon atoms in the linear alkylene group is preferably 1 to 10, and more preferably 1 to 6. 2 When the compound is an alkoxy group, the alkoxy group may be linear or branched, but linear is preferred. The number of carbon atoms in the alkoxy group is preferably 1 to 10, and more preferably 1 to 6. 2 When the atom is a halogen atom, fluorine, chlorine, bromine, and iodine atoms are preferred, and fluorine, chlorine, and bromine atoms are more preferred. 2 When is an alkyl halide, the halogen atoms contained in the alkyl halide are preferably fluorine, chlorine, bromine, and iodine atoms, and more preferably fluorine, chlorine, and bromine atoms. The alkyl halide may be linear or branched, but linear is preferred. 2 If it is a cyclic organic group, an example of a cyclic organic group is R c6 and R c7 It is similar to the cyclic organic group that has as a substituent. 2 If it is an alkoxycarbonyl group, an example of an alkoxycarbonyl group is R c6 and R c7 This is similar to the alkoxycarbonyl group that has as a substituent.

[0107] R c6 and R c7Suitable specific examples include alkyl groups such as ethyl group, n-propyl group, n-butyl group, n-hexyl group, n-heptyl group, and n-octyl group; 2-methoxyethyl group, 3-methoxy-n-propyl group, 4-methoxy-n-butyl group, 5-methoxy-n-pentyl group, 6-methoxy-n-hexyl group, 7-methoxy-n-heptyl group, 8-methoxy-n-octyl group, 2-ethoxyethyl group, 3-ethoxy-n-propyl group Alkoxyalkyl groups such as 4-ethoxy-n-butyl group, 5-ethoxy-n-pentyl group, 6-ethoxy-n-hexyl group, 7-ethoxy-n-heptyl group, and 8-ethoxy-n-octyl group; cyanoethyl group, 3-cyano-n-propyl group, 4-cyano-n-butyl group, 5-cyano-n-pentyl group, 6-cyano-n-hexyl group, 7-cyano-n-heptyl group, and 8-cyano-n-octyl group. Phenylalkyl groups such as 2-phenylethyl group, 3-phenyl-n-propyl group, 4-phenyl-n-butyl group, 5-phenyl-n-pentyl group, 6-phenyl-n-hexyl group, 7-phenyl-n-heptyl group, and 8-phenyl-n-octyl group; 2-cyclohexylethyl group, 3-cyclohexyl-n-propyl group, 4-cyclohexyl-n-butyl group, 5-cyclohexyl-n-pentyl group, 6- Cycloalkylalkyl groups such as cyclohexyl-n-hexyl group, 7-cyclohexyl-n-heptyl group, 8-cyclohexyl-n-octyl group, 2-cyclopentylethyl group, 3-cyclopentyl-n-propyl group, 4-cyclopentyl-n-butyl group, 5-cyclopentyl-n-pentyl group, 6-cyclopentyl-n-hexyl group, 7-cyclopentyl-n-heptyl group, and 8-cyclopentyl-n-octyl group;2-Methoxycarbonylethyl group, 3-Methoxycarbonyl-n-propyl group, 4-Methoxycarbonyl-n-butyl group, 5-Methoxycarbonyl-n-pentyl group, 6-Methoxycarbonyl-n-hexyl group, 7-Methoxycarbonyl-n-heptyl group, 8-Methoxycarbonyl-n-octyl group, 2-Ethoxycarbonylethyl group, 3-Ethoxycarbonyl-n-propyl group, 4-Ethoxycarbonyl-n-butyl group, 5-Ethoxycarbonyl-n-pentyl group, 6-Ethoxycarbonyl-n-hexyl group, 7-Ethoxycarbonyl-n-heptyl group, and 8-Ethoxycarbonyl-n-octyl group Examples include alkoxycarbonyl alkyl groups such as 2-chloroethyl group, 3-chloro-n-propyl group, 4-chloro-n-butyl group, 5-chloro-n-pentyl group, 6-chloro-n-hexyl group, 7-chloro-n-heptyl group, 8-chloro-n-octyl group, 2-bromoethyl group, 3-bromo-n-propyl group, 4-bromo-n-butyl group, 5-bromo-n-pentyl group, 6-bromo-n-hexyl group, 7-bromo-n-heptyl group, 8-bromo-n-octyl group, 3,3,3-trifluoropropyl group, and 3,3,4,4,5,5,5-heptafluoro-n-pentyl group.

[0108] R c6 and R c7 Among the above, preferred groups are the ethyl group, n-propyl group, n-butyl group, n-pentyl group, 2-methoxyethyl group, 2-cyanoethyl group, 2-phenylethyl group, 2-cyclohexylethyl group, 2-methoxycarbonylethyl group, 2-chloroethyl group, 2-bromoethyl group, 3,3,3-trifluoropropyl group, and 3,3,4,4,5,5,5-heptafluoro-n-pentyl group.

[0109] In formula (c5), it is particularly preferable that A is S, as this makes it easier to obtain a photopolymerization initiator with excellent sensitivity.

[0110] In formula (c5), R c9 This is a monovalent organic group, a halogen atom, a nitro group, or a cyano group. R in equation (c5) c9When is a monovalent organic group, it can be selected from a variety of organic groups, as long as it does not hinder the objective of the present invention. Preferably, the organic group is a carbon-carbon-containing group, and more preferably a group consisting of one or more carbon atoms and one or more atoms selected from the group consisting of H, O, S, Se, N, B, P, Si, and halogen atoms. The number of carbon atoms in the carbon-carbon-containing group is not particularly limited, but is preferably 1 to 50, and more preferably 1 to 20. In equation (c5), R c9 A preferred example of when is an organic group is R in formula (c3). c5 Examples of monovalent organic groups include those similar to monovalent organic groups.

[0111] R c9 Among these, benzoyl groups; naphthoyl groups; benzoyl groups substituted with groups selected from the group consisting of alkyl groups having 1 to 6 carbon atoms, morpholine-1-yl groups, piperazine-1-yl groups, and phenyl groups; nitro groups; and optionally substituted benzofuranylcarbonyl groups are preferred, with benzoyl groups; naphthoyl groups; 2-methylphenylcarbonyl groups; 4-(piperazine-1-yl)phenylcarbonyl groups; and 4-(phenyl)phenylcarbonyl groups being more preferred.

[0112] Furthermore, in equation (c5), n4 is preferably an integer between 0 and 3, more preferably an integer between 0 and 2, and particularly preferably 0 or 1. When n4 is 1, R c9 The bonding position is R c9 It is preferable that the phenyl group to which it is bonded is in the para position relative to the bond that connects to the oxygen atom or sulfur atom.

[0113] In equations (c1) and (c2), R c2 The monovalent organic group is not particularly limited as long as it does not hinder the objectives of the present invention. The organic group is preferably a carbon-carbon-containing group, more preferably a group consisting of one or more carbon atoms and one or more atoms selected from the group consisting of H, O, S, Se, N, B, P, Si, and halogen atoms. The number of carbon atoms in the carbon-carbon-containing group is not particularly limited, but is preferably 1 to 50, and more preferably 1 to 20. R c2 A suitable example of a monovalent organic group is R in formula (c3). c5 Examples of such groups include monovalent organic groups and similar groups. Specific examples of these groups include R in formula (c3). c5 This is similar to the basis explained earlier. Also, R c2 Preferred alternatives include cycloalkylalkyl groups, phenoxyalkyl groups which may have substituents on the aromatic ring, and phenylthioalkyl groups which may have substituents on the aromatic ring. The substituents which phenoxyalkyl groups and phenylthioalkyl groups may have are R in formula (c3). c5 The substituents are similar to those found when the phenyl group, naphthyl group, and heterocyclyl group contained in the compound have further substituents.

[0114] Among organic groups, R c2 Preferred as is a substituent containing the group represented by HX2C- or H2XC-, an alkyl group, a cycloalkyl group, a optionally substituted phenyl group, or a cycloalkylalkyl group or a phenylthioalkyl group which may have substituents on the aromatic ring. For alkyl groups, optionally substituted phenyl groups, the number of carbon atoms in the cycloalkyl group contained in the cycloalkylalkyl group, the number of carbon atoms in the alkylene group contained in the cycloalkylalkyl group, the number of carbon atoms in the alkylene group contained in the cycloalkylalkyl group or a phenylthioalkyl group which may have substituents on the aromatic ring, or a phenylthioalkyl group which may have substituents on the aromatic ring, the R of formula (c3) c5 It is similar to that.

[0115] Also, R c2 As for -A 3 -CO-OA 4 The group represented by A is also preferred. 3 This is a divalent organic group, preferably a divalent hydrocarbon group, and preferably an alkylene group. 4 It is a monovalent organic group, preferably a monovalent hydrocarbon group.

[0116] A 3When is an alkylene group, the alkylene group may be linear or branched, but linear is preferred. 3 If the alkylene group is an alkylene group, the number of carbon atoms in the alkylene group is preferably 1 to 10, more preferably 1 to 6, and particularly preferably 1 to 4.

[0117] A 4 Preferred examples include alkyl groups having 1 to 10 carbon atoms, aralkyl groups having 7 to 20 carbon atoms, and aromatic hydrocarbon groups having 6 to 20 carbon atoms. 4 Suitable specific examples include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, n-pentyl group, n-hexyl group, phenyl group, naphthyl group, benzyl group, phenethyl group, α-naphthylmethyl group, and β-naphthylmethyl group.

[0118] -A 3 -CO-OA 4 Preferred specific examples of the group represented by include 2-methoxycarbonylethyl group, 2-ethoxycarbonylethyl group, 2-n-propyloxycarbonylethyl group, 2-n-butyloxycarbonylethyl group, 2-n-pentyloxycarbonylethyl group, 2-n-hexyloxycarbonylethyl group, 2-benzyloxycarbonylethyl group, 2-phenoxycarbonylethyl group, 3-methoxycarbonyl-n-propyl group, 3-ethoxycarbonyl-n-propyl group, 3-n-propyloxycarbonyl-n-propyl group, 3-n-butyloxycarbonyl-n-propyl group, 3-n-pentyloxycarbonyl-n-propyl group, 3-n-hexyloxycarbonyl-n-propyl group, 3-benzyloxycarbonyl-n-propyl group, and 3-phenoxycarbonyl-n-propyl group.

[0119] Also, R c2 As an alternative, a group represented by the following formula (c7) or (c8) is also preferred. [ka]

[0120] In equations (c7) and (c8), R c10 and R c11 Each of these is an independent monovalent organic group. n5 is an integer between 0 and 4 (inclusive). c10 and R c11 If R is located at an adjacent position on the benzene ring, c10 and R c11 They may be joined to each other to form a ring. c12 n is a monovalent organic group. n6 is an integer between 1 and 8. n7 is an integer between 1 and 5. n8 is an integer between 0 and (n7+3).

[0121] R in equation (c7) c10 and R c11 The organic group as is R in formula (c4). c8 It is similar to R. c10 Preferably, the group is a halogenated alkoxy group containing a group represented by HX2C- or H2XC-, a halogenated alkyl group containing a group represented by HX2C- or H2XC-, an alkyl group, or a phenyl group. c10 and R c11 When and are bonded to form a ring, the ring may be an aromatic ring or an aliphatic ring. The group is represented by formula (c7), and R c10 and R c11 Suitable examples of groups that form a ring include the naphthalen-1-yl group and the 1,2,3,4-tetrahydronaphthalen-5-yl group. In the above formula (c7), n7 is an integer between 0 and 4, preferably 0 or 1, and more preferably 0.

[0122] In the above formula (c8), R c12 R is an organic group. As an organic group, R in formula (c4) is an organic group. c8 Examples of organic groups similar to those described above include alkyl groups. Among 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 to 10, more preferably 1 to 5, and particularly preferred to be 1 to 3. c12Examples of preferred groups include methyl, ethyl, propyl, isopropyl, and butyl groups, with methyl groups being more preferred among these.

[0123] In the above formula (c8), n7 is an integer between 1 and 5, preferably between 1 and 3, and more preferably 1 or 2. In the above formula (c8), n8 is between 0 and (n7+3), preferably between 0 and 3, more preferably between 0 and 2, and particularly preferably 0. In the above formula (c8), n6 is an integer between 1 and 8, preferably between 1 and 5, more preferably between 1 and 3, and particularly preferably 1 or 2.

[0124] In formula (c2), R c3 R is a hydrogen atom, an aliphatic hydrocarbon group having 1 to 20 carbon atoms (which may have substituents), or an aryl group (which may have substituents). c3 When the group is an aliphatic hydrocarbon group, preferred substituents that may be present include phenyl groups, naphthyl groups, and the like.

[0125] In equations (c1) and (c2), R c3 Examples of preferred groups include hydrogen atoms, methyl groups, ethyl groups, n-propyl groups, isopropyl groups, n-butyl groups, 2-cyclopentylethyl groups, 2-cyclobutylethyl groups, cyclohexylmethyl groups, phenyl groups, benzyl groups, methylphenyl groups, and naphthyl groups, with methyl groups or phenyl groups being more preferred among these.

[0126] It is expressed by equation (c2), and R c1 The following compounds are suitable examples of compounds having a group represented by formula (c3). [ka]

[0127] [ka]

[0128] [ka]

[0129] [ka]

[0130] It is expressed by equation (c2), and R c1 The following are some suitable examples of compounds having a group represented by formula (c4). [ka]

[0131] [ka]

[0132] [ka]

[0133] [ka]

[0134] [ka]

[0135] It is expressed by equation (c2), and R c1 The following compounds are suitable examples of compounds having a group represented by formula (c5). [ka]

[0136] As the photopolymerization initiator (C), phosphine oxide compounds are also preferred because they exhibit good deep curing properties of the photosensitive composition. Among the phosphine oxide compounds, phosphine oxide compounds containing a substructure represented by the following formula (c9) are preferred. [ka]

[0137] In formula (c9), R c21 and R c22 Each of these is independently an alkyl group, a cycloalkyl group, an aryl group, an aliphatic acyl group having 2 to 20 carbon atoms, or an aromatic acyl group having 7 to 20 carbon atoms. However, R c21 and R c22 Neither of them is an aliphatic acyl group or an aromatic acyl group.

[0138] R c21 and R c22 The number of carbon atoms in the alkyl group is preferably 1 to 12, more preferably 1 to 8, and even more preferably 1 to 4. c21 and R c22 The alkyl group may be linear or branched. Specific examples of alkyl groups 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, tert-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, 2,4,4-trimethylpentyl group, 2-ethylhexyl group, n-nonyl group, n-decyl group, n-undecyl group, and n-dodecyl group.

[0139] R c21 and R c22 The number of carbon atoms in the cycloalkyl group is preferably 5 to 12. Specific examples of cycloalkyl groups include cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl, cycloundecyl, and cyclododecyl groups.

[0140] R c21 and R c22 The aryl group preferably has 6 to 12 carbon atoms. The aryl group may have substituents. Examples of substituents include halogen atoms, alkyl groups with 1 to 4 carbon atoms, and alkoxy groups with 1 to 4 carbon atoms. Specific examples of aryl groups include phenyl and naphthyl groups.

[0141] R c21 and R c22 The number of carbon atoms in the aliphatic acyl group is 2 to 20, preferably 2 to 12, more preferably 2 to 8, and even more preferably 2 to 6. The aliphatic acyl group may be linear or branched. Specific examples of aliphatic acyl groups include acetyl, propionyl, butanoyl, pentanoyl, hexanoyl, heptanyl, octanoyl, nonanoyl, decanoyl, undecanoyl, dodecanoyl, tridecanoyl, tetradecanoyl, pentadecanoyl, hexadecanoyl, heptadecanoyl, octadecanoyl, nonadecanoyl, and eicosanoyl.

[0142] R c21 and R c22 The aromatic acyl group has 7 to 20 carbon atoms. The aromatic acyl group may have substituents. Examples of substituents include halogen atoms, alkyl groups with 1 to 4 carbon atoms, and alkoxy groups with 1 to 4 carbon atoms. Specific examples of aromatic acyl groups include benzoyl, o-tolyl, m-tolyl, p-tolyl, 2,6-dimethylbenzoyl, 2,6-dimethoxybenzoyl, 2,4,6-trimethylbenzoyl, α-naphthoyl, and β-naphthoyl groups.

[0143] Preferred examples of phosphine oxide compounds containing the structural moiety represented by formula (c9) include 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide, and bis(2,6-dimethoxybenzoyl)-2,4,4-trimethylpentylphosphine oxide. From the viewpoint of deep curing of the photosensitive composition, it is also preferable to use the phosphine oxide compound containing the structural moiety represented by formula (c9) together with an α-hydroxyalkylphenone-based initiator such as 2-hydroxy-2-methylpropiophenone. When a phosphine oxide compound containing the structural moiety represented by formula (c9) is used in combination with an α-hydroxyalkylphenone-based initiator such as 2-hydroxy-2-methylpropiophenone, the ratio of the mass of the phosphine oxide compound containing the structural moiety represented by formula (c9) to the total mass of both is preferably 20% by mass or more and 80% by mass or less, more preferably 30% by mass or more and 70% by mass or less, and even more preferably 40% by mass or more and 60% by mass or less.

[0144] The content of the photopolymerization initiator (C) is preferably 0.5% to 30% by mass, and more preferably 1% to 20% by mass, relative to the mass of the photosensitive resin composition excluding the mass of the organic solvent (S) described later. By setting the content of the photopolymerization initiator (C) within the above range, a photosensitive resin composition that is less prone to defects in pattern shape can be obtained.

[0145] In addition, a photoinitiator (C) may be combined with a photoinitiator aid. Examples of photoinitiators include triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, 2-ethylhexyl 4-dimethylaminobenzoate, 2-dimethylaminoethyl benzoate, N,N-dimethylparatoluidine, 4,4'-bis(dimethylamino)benzophenone, 9,10-dimethoxyanthracene, and 2-ethyl-9,10- Examples include thiol compounds such as dimethoxyanthracene, 9,10-diethoxyanthracene, 2-ethyl-9,10-diethoxyanthracene, 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, 2-mercaptobenzimidazole, 2-mercapto-5-methoxybenzothiazole, 3-mercaptopropionic acid, methyl 3-mercaptopropionate, pentaerythritol tetramercaptoacetate, and 3-mercaptopropionate. These photoinitiators can be used alone or in combination of two or more.

[0146] <Silicone-based surfactant (D)> Silicone-based surfactant (D) does not contain fluorine atoms. Furthermore, the structure of silicone-based surfactant (D) is not particularly limited, but it is usually chain-like, and linear is preferred. The main chain of silicone-based surfactant (D) typically contains linear siloxane moieties in which two or more silicon atoms are linked via siloxane bonds (Si-O-Si).

[0147] The structure of the linear siloxane moiety in the main chain of the silicone-based surfactant (D) is preferably represented by the following formula (D-1). -(SiR d1 R d2 O 2 / 2 )-···(D-1) In formula (D-1), R d1 , and R d2 Each of these is independently a linear or branched alkyl group having 1 to 4 carbon atoms, or a phenyl group. R d1, and R d2 Examples of alkyl groups having 1 to 4 carbon atoms include methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, and tert-butyl groups. Among these alkyl groups, the methyl group is preferred.

[0148] As the silicone-based surfactant (D), unmodified silicone-based surfactants, polyether-modified silicone-based surfactants, polyester-modified silicone-based surfactants, alkyl-modified silicone-based surfactants, aralkyl-modified silicone-based surfactants, and reactive silicone-based surfactants can be preferably used. Modified silicone-based surfactants (D) are typically compounds in which the above-mentioned polymer chain or functional group is bonded to one or both ends of a linear siloxane moiety. As the silicone-based surfactant (D), a polyester-modified silicone-based surfactant is particularly preferred.

[0149] As the silicone-based surfactant, commercially available silicone-based surfactants can be used. Specific examples of commercially available silicone-based surfactants include Paintad M (manufactured by Toray Dow Corning), Topica K1000, Topica K2000, Topica K5000 (all manufactured by Takachiho Sangyo Co., Ltd.), XL-121 (polyether-modified silicone-based surfactant, manufactured by Clariant), BYK-088 (silicone-based defoamer, manufactured by Bic Chemie), BYK-210 (polyester-modified silicone-based surfactant, manufactured by Bic Chemie), BYK-310, BYK-370, BYK-313, BYK-3570, BYK-315N (polyester-modified silicone-based surfactants, all manufactured by Bic Chemie), and others.

[0150] The content of the silicone-based surfactant (D) is preferably 0.001% by mass or more and 10% by mass or less, and more preferably 0.003% by mass or more and 5% by mass or less, relative to the total solid components of the photosensitive resin composition.

[0151] <Adhesion enhancer (E)> Examples of adhesion enhancers (E) include conventionally known silane coupling agents, which can prevent the pattern of the photospacer from peeling off during development.

[0152] As the adhesion enhancer (E), known coupling agents such as silane coupling agents, titanate coupling agents, and aluminate coupling agents can be used. Of these, silane coupling agents can be suitably used from the viewpoint of improving adhesion to the substrate.

[0153] Examples of silane coupling agents include 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 2-(epoxycyclohexyl)ethyltrimethoxysilane, 2-(epoxycyclohexyl)triethoxysilane, tris(3-trimethoxysilylpropyl)isocyanurate, tris(3-triethoxysilylpropyl)isocyanurate, N-phenyl-3-aminopropyltrimethoxysilane, reaction products of 3-aminopropyltrimethoxysilane and acid anhydrides, and reaction products of 3-aminopropyltriethoxysilane and acid anhydrides. Examples of acid anhydrides to be reacted with 3-aminopropyltrimethoxysilane or 3-aminopropyltriethoxysilane include succinic anhydride, maleic anhydride, nadic anhydride, 3-hydroxyphthalic anhydride, pyromellitic dianhydride, 3,3',4,4'-biphenyltetracarboxylic dianhydride, 2,2',3,3'-benzophenonetetracarboxylic dianhydride, and 4,4'-oxydiphthalic dianhydride.

[0154] The amount of adhesion enhancer (E) used is preferably 0.01% by mass or more and 10% by mass or less, relative to the mass of the alkali-soluble resin (A).

[0155] <Organic solvent (S)> The photosensitive resin composition preferably contains an organic solvent (S) to improve its applicability and adjust its viscosity.

[0156] Specifically, the organic solvent (S) includes 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, dipropylene glycol monoethyl ether, dipropylene glycol mono-n-propyl ether, dipropylene glycol mono-n-butyl ether, and tripropylene glycol (Poly)alkylene glycol monoalkyl ethers such as monomethyl ether and tripropylene glycol monoethyl ether; (Poly)alkylene glycol monoalkyl ether acetates such as ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate (PGMEA), and propylene glycol monoethyl ether acetate; other ethers such as diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether (MEDG), diethylene glycol diethyl ether, and tetrahydrofuran; ketones such as methyl ethyl ketone, cyclohexanone, 2-heptanone, and 3-heptanone; alkyl lactate esters such as methyl 2-hydroxypropionate and ethyl 2-hydroxypropionate;Ethyl 2-hydroxy-2-methylpropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl ethoxyacetate, ethyl hydroxyacetate, methyl 2-hydroxy-3-methylbutanoate, 3-methoxybutyl acetate (MBA), 3-methyl-3-methoxybutyl acetate, 3-methyl-3-methoxybutyl propionate, ethyl acetate, n-propyl acetate, i-propyl acetate, n-butyl acetate, i-butyl acetate, n-pentyl formate, i-pentyl acetate, n-butyl propionate, ethyl butyrate, n-propyl butyrate Examples include other esters such as i-propyl butyrate, n-butyl butyrate, methyl pyruvate, ethyl pyruvate, n-propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, and ethyl 2-oxobutanoate; aromatic hydrocarbons such as toluene and xylene; nitrogen-containing polar organic solvents such as N-methyl-2-pyrrolidone, N,N-dimethylformamide, N,N-dimethylacetamide, N,N-dimethylisobutylamide, N,N-diethylacetamide, N,N-diethylformamide, N-methylcaprolactam, 1,3-dimethyl-2-imidazolidinone, pyridine, and N,N,N',N'-tetramethylurea; etc.

[0157] Among these, alkylene glycol monoalkyl ethers, alkylene glycol monoalkyl ether acetates, the other ethers mentioned above, alkyl lactate esters, and the other esters mentioned above are preferred, and alkylene glycol monoalkyl ether acetates, the other ethers mentioned above, and the other esters mentioned above are more preferred. These solvents can be used individually or in combination of two or more.

[0158] The content of the organic solvent (S) is not particularly limited and is appropriately set according to the coating film thickness at a concentration that can be applied to a substrate or the like. The viscosity of the photosensitive resin composition is preferably 1 cp or more and 500 cp or less, and more preferably 2 cp or more and 50 cp or less. Also, the solid content concentration is preferably 1% by mass or more and 99% by mass or less, and more preferably 10% by mass or more and 50% by mass or less.

[0159] <Other components> The photosensitive resin composition can contain additives such as a thermal polymerization inhibitor and an antifoaming agent as required. Any of these additives can be those conventionally known. Examples of the thermal polymerization inhibitor include hydroquinone and hydroquinone monoethyl ether. Examples of the antifoaming agent include silicone-based and fluorine-based compounds.

[0160] <Method for preparing the photosensitive resin composition> The photosensitive resin composition described above can be obtained by mixing the above components in respective predetermined amounts and then uniformly mixing them with a stirrer. Note that it may be filtered using a filter so that the obtained mixture becomes more uniform.

[0161] ≪Method for producing a cured product≫ The photosensitive resin composition described above typically becomes a cured product by a method including shaping the photosensitive resin composition according to the shape of the cured product and exposing the shaped photosensitive resin composition.

[0162] Since the cured product produced by the above method has high transparency, it is useful for applications such as display devices such as OLEDs, organic ELs, or liquid crystals, and can be suitably used for a planarization film, an interlayer insulating film, a protective film for a color filter, a photospacer for keeping the thickness of the liquid crystal layer constant in a liquid crystal display device, or a microlens in a solid-state imaging device.

[0163] The method for molding the photosensitive resin composition is not particularly limited and is appropriately selected depending on the shape of the cured product. The shape of the cured product is not limited to these, but examples include film shape, lens shape, line shape, prism shape, etc. Among these shapes, the film shape is preferred. The method for molding the photosensitive resin composition is not particularly limited. If the shape of the cured product is a lens shape, a prism shape, etc., the photosensitive resin composition may be filled into a mold corresponding to the shape of the cured product using a squeegee or the like. If the cured product has a line shape or the like, the photosensitive resin composition can be applied to the substrate according to the shape of the cured product. Examples of application methods include printing methods such as inkjet printing. Methods for applying a photosensitive resin composition to form a film include using contact transfer type coating devices such as roll coaters, reverse coaters, and bar coaters, as well as non-contact type coating devices such as spinners (rotary coating devices) and curtain flow coaters. Alternatively, the photosensitive resin composition can be applied to form a film by printing methods such as inkjet printing.

[0164] When using the aforementioned photosensitive resin composition, even if there are steps on the surface of the substrate to be coated, a coating film with a uniform thickness can be formed that follows the steps.

[0165] There are no particular restrictions on the thickness of the coating film. A coating film thickness of 0.05 μm or more is preferred, and 1 μm or more is more preferred. For example, the coating film thickness may be 7 μm or more, or 10 μm or more. There is no particular upper limit to the thickness of the coating film, but for example, it may be 50 μm or less, or 20 μm or less. A coating film thickness of 10 μm or less is preferred, 5 μm or less is more preferred, and 2 μm or less is even more preferred. The thickness of the coating film is preferably between 0.05 μm and 10 μm, more preferably between 1 μm and 5 μm, and even more preferably between 1 μm and 2 μm.

[0166] Next, the coating film is dried as needed. The drying method is not particularly limited. Examples of drying methods include: (1) drying on a hot plate at a temperature of 80°C to 120°C, preferably 80°C to 100°C, for 1 minute to 30 minutes, preferably 3 minutes to 10 minutes; (2) leaving it at room temperature for several hours to several days; and (3) removing the solvent by placing it in a hot air heater or infrared heater for several tens of minutes to several hours. This allows a resin film to be obtained. The resin film differs from the coating film in that it does not contain or contains only a very small amount of volatile components such as organic solvents (S).

[0167] A cured film is formed by exposing such a coated film or resin film to light.

[0168] The light source for exposure is not particularly limited and examples include high-pressure mercury lamps, ultra-high-pressure mercury lamps, xenon lamps, carbon arc lamps, LEDs, etc. Using such a light source, the coated film can be exposed by irradiating it with radiation such as ArF excimer lasers, KrF excimer lasers, F2 excimer lasers, extreme ultraviolet (EUV), vacuum ultraviolet (VUV), electron beams, X-rays, soft X-rays, g-rays, i-rays, h-rays, j-rays, k-rays, or electromagnetic waves.

[0169] The exposure amount also varies depending on the composition of the photosensitive resin composition, but for example, 5 mJ / cm² 2 More than 2000mJ / cm 2 The following is preferable: 10 mJ / cm 2 More than 1500mJ / cm 2 The following is more preferable: 10 mJ / cm² 2 More than 1200mJ / cm 2 The following is even more preferable: The exposure intensity also varies depending on the composition of the photosensitive resin composition, but is 1 mW / cm². 2 More than 50mW / cm 2 The following range is preferable.

[0170] The cured film hardened by exposure may be heated. The temperature for heating is not particularly limited, but is preferably 180°C to 280°C, more preferably 200°C to 260°C, and particularly preferably 220°C to 250°C. The heating time is typically preferably 1 minute to 60 minutes, more preferably 10 minutes to 50 minutes, and particularly preferably 20 minutes to 40 minutes.

[0171] On the other hand, selective exposure may be performed on the coated film or resin film. In this case, the coated film or resin film is selectively exposed via a negative-type mask having a light-transmitting portion with a shape corresponding to the pattern shape of the cured film. Aside from using a negative-type mask, the exposure method is the same as the exposure method described above.

[0172] Next, the exposed coating film or resin film is developed with a developer to form a patterned cured film. The development method is not particularly limited, and for example, immersion or spray methods can be used. Examples of developers include organic ones such as monoethanolamine, diethanolamine, and triethanolamine, as well as aqueous solutions of sodium hydroxide, potassium hydroxide, sodium carbonate, ammonia, and quaternary ammonium salts.

[0173] The patterned cured film obtained after development may be heated in the same manner as the exposure method described above for the patterned coated film.

[0174] As described above, the inventors of the present invention provide the following (1) to (11). (1) comprising an alkali-soluble resin (A), a photopolymerizable monomer (B), a photopolymerization initiator (C), and a silicone-based surfactant (D), The alkali-soluble resin (A) comprises a constituent unit (a1) having an alkali-soluble group and a constituent unit (a2) having an alicyclic epoxy group. A photosensitive resin composition in which the silicone-based surfactant (D) does not contain fluorine atoms. (2) The structure of the silicone surfactant (D) is linear, and the main chain of the molecule of the silicone surfactant (D) has a polysiloxane skeleton or an oligosiloxane skeleton. The photosensitive resin composition according to (1). (3) The surface tension of the photosensitive resin composition under the conditions of a temperature of 25 °C and a relative humidity of 50% is 25 mN / m or more and 35 mN / m or less. The photosensitive resin composition according to (1) or (2). (4) The content of the silicone surfactant (D) is 0.001% by mass or more and 10% by mass or less based on the total solid content of the photosensitive resin composition. The photosensitive resin composition according to any one of (1) to (3). (5) The silicone surfactant (D) is a polyester-modified silicone surfactant (D1). The photosensitive resin composition according to any one of (1) to (4). (6) The alkali-soluble resin (A) contains, as a constitutional unit (a1), a constitutional unit derived from (meth)acrylic acid. The photosensitive resin composition according to any one of (1) to (5). (7) The alkali-soluble resin (A) contains a constitutional unit (a3) represented by the following formula (a3-1). The photosensitive resin composition according to any one of (1) to (6). [Chemical formula] (In the above formula (a3-1), R a5 represents a hydrogen atom or a methyl group, and R <00​​​​​​​​​​​​​​​The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these examples.

[0176] [Examples 1-16 and Comparative Examples 1-2] In the examples and comparative examples, acrylic resins A-1 to A-5 with the following structures were used as alkali-soluble resins (A). The weight-average molecular weight of resin A-1 on a polystyrene basis is 12,000, and the molecular weight dispersibility is 1.2. The weight-average molecular weight of resin A-2 on a polystyrene basis is 12,000, and the molecular weight dispersibility is 1.2. The weight-average molecular weight of resin A-3 on a polystyrene basis is 12,000, and the molecular weight dispersibility is 1.2. The weight-average molecular weight of resin A-4 on a polystyrene basis is 12,000, and the molecular weight dispersibility is 1.2. The weight-average molecular weight of resin A-5 on a polystyrene basis is 12,000, and the molecular weight dispersibility is 1.2. [ka]

[0177] In the examples and comparative examples, the following B-1 to B-3 were used as the photopolymerizable compound (B). B-1: Dipentaerythritol hexaacrylate B-2: Compound represented by the following formula [ka] B-3: Pentaerythritol tetraacrylate

[0178] In the examples and comparative examples, the following C-1 or C-2 was used as the photopolymerization initiator (C). [ka]

[0179] In the examples and comparative examples, the following D-1 to D-6 were used as surfactants (D). (Silicone-based surfactants) D-1: BYK-310 (made by Big Chemistry) D-3: BYK-370 (made by Big Chemistry) D-4: BYK-313 (made by Big Chemistry) D-5: BYK-3570 (Made by Big Chemie) D-6: BYK-315N (manufactured by Big Chemistry) (Fluorine-based surfactants) D-2: APX-4082B (manufactured by Kyoeisha Chemical Co., Ltd.)

[0180] In the examples and comparative examples, E-1 and E-2 were used as adhesion enhancers. [ka]

[0181] In the examples and comparative examples, a mixed solvent (S-1) consisting of 85% by mass of diethylene glycol methyl ethyl ether, 10% by mass of propylene glycol monomethyl ether acetate, and 5% by mass of 3-methoxybutyl acetate was used as the organic solvent (S).

[0182] The types and mass parts of alkali-soluble resin (A) (component (A)) listed in Table 1, the types and mass parts of photopolymerizable compound (B) (component (B)) listed in Table 1, the types and mass parts of photopolymerizable compound (C) (component (C)) listed in Table 1, the types and mass parts of surfactant (D) (component (D)) listed in Table 1, the adhesion improver (E) (component (E)), and 100 parts by mass of mixed solvent S-1 were mixed to obtain the photosensitive compositions for each example and each comparative example.

[0183] [Table 1]

[0184] The obtained photosensitive compositions were evaluated according to the following methods: elemental analysis, bottle stability, outgassing, leveling properties, residual film rate, panel reliability, thermal convection resistance, and developability. The results of these evaluations are shown in Table 1.

[0185] <Formation of resin film> After applying the photosensitive resin compositions prepared in each of the above examples and comparative examples onto a 10cm x 10cm glass substrate (Dow Corning 1737 glass), the resin film having a thickness of 1.7 μm was dried on a hot plate at 80°C for 10 minutes.

[0186] (Elemental analysis evaluation) The photosensitive resin compositions prepared in each of the above examples and comparative examples were measured by ICP-AES multi-elemental analysis using an ICP-MS 8900 (manufactured by Agilent Technologies) and evaluated according to the following criteria. A: No fluorine detected. B: Fluorine element detected.

[0187] (Bottle stability evaluation) The photosensitive resin compositions prepared in each of the above examples and comparative examples, both immediately after preparation and after being stored at 25°C for 7 days, were visually inspected for gelation and evaluated according to the following criteria. A: No gelation B: Present as gel

[0188] (Outgassing evaluation) The resin film formed by the above resin film formation process was treated with ORC HMW-532D at a concentration of 30 mJ / cm². 2 The film was exposed to light, developed at 23°C for 80 seconds using the paddle method with a 0.5% aqueous tetramethylammonium hydroxide solution as the developer, and then post-baked on a hot plate at 100°C for 10 minutes and in an oven at 220°C for 40 minutes to obtain a patterned cured film. The portion of the hardened film-patterned glass substrate obtained was cut out to a weight of 3g and packed into a vial. The sample was maintained at 230°C for 60 minutes using a headspace gas chromatography analyzer, and the amount of outgassing in toluene equivalent was calculated. As a reference for outgassing volume, the resin film of Comparative Example 1, formed by the above resin film formation method, was cut to a weight of 3g and packed into a vial tube. The outgassing volume was calculated in toluene equivalent by holding the vial at 230°C for 60 minutes using a headspace gas chromatography analyzer. For the calculated outgassing volume, the outgassing volume of the resin film of Comparative Example 1 was set as V1, and the outgassing volume of the cured films of each of the above examples and comparative examples was set as V2. The outgassing volume was then calculated according to the following formula and evaluated according to the following criteria. Outgassing amount = V2 / V1 × 100 A: 65% or less B: More than 65%

[0189] (Leveling performance evaluation) The photosensitive resin compositions prepared in each of the above examples and comparative examples were stored at 60°C for 24 hours, and a resin film for leveling evaluation was formed using the same method as for forming the above photosensitive resin film. Using a contact angle meter (LAUDA TVT-2, manufactured by Lauda), droplets of pure water and methylene iodide were dropped onto the surface of each resin film under conditions of 25°C and 50% relative humidity. The contact angle was measured 1 second after the droplet adhered to the surface, and the surface tension (surface free energy) was calculated from the obtained contact angles according to the Owens-Wendt method. Of the calculated surface tensions, the surface tension value of the resin film formed by the above resin film formation was denoted as γ1, and the surface tension value of the resin film used for leveling evaluation was denoted as γ2. The change in surface tension was calculated according to the following formula and evaluated according to the following criteria. Change in surface tension = |γ1-γ2| A: More than 0N / m and less than 0.1N / m B: More than 0.1N / m and less than 0.2N / m C: More than 0.2N / m and less than 0.5N / m D: More than 0.5N / m

[0190] (Evaluation of residual film percentage) The resin film formed by the above resin film formation process is subjected to a Canon MPA600FA at a rate of 10 mJ / cm² via a negative mask. 2The photosensitive resin film was exposed to light, and a pattern was formed by developing it at 23°C for 80 seconds using the paddle method with a 0.5% tetramethylammonium hydroxide aqueous solution as the developer. The film thickness T1 of the photosensitive resin film and the film thickness T2 of the exposed area of ​​the patterned photosensitive resin film were measured using a stylus-type film thickness gauge (Dektak-3ST, Bruker), and the residual film percentage (%) was calculated according to the following formula. Remaining film rate (%)=T2 / T1×100

[0191] (Panel reliability evaluation) The resin film formed by the above resin film formation process was treated with ORC HMW-532D at a concentration of 30 mJ / cm². 2 The film was exposed to light, developed at 23°C for 80 seconds using the paddle method with a 0.5% aqueous tetramethylammonium hydroxide solution as the developer, and then post-baked on a hot plate at 100°C for 10 minutes and in an oven at 220°C for 40 minutes to obtain a patterned cured film. The resulting cured film pattern-forming glass substrate was cut to a width of 2.5 cm and placed in a beaker containing NMP (N-methylpyrrolidone) solvent. The beaker was heated to 80°C in a water bath. The cut glass substrate was then immersed in the NMP solvent at 80°C for 40 minutes, rinsed with pure water for 20 seconds, and dried in an oven at 220°C for 5 minutes. The film thickness T3 of the cured film formed on the glass substrate before NMP immersion and the film thickness T4 after NMP immersion were measured using a stylus-type film thickness gauge (Dektak-3ST, Bruker), and the rate of change in film thickness (%) was calculated according to the following formula and evaluated according to the following criteria. Film thickness change rate (%) = (T3 - T4) / T3 × 100 A: 1% or less B: More than 1% and less than 3% C: More than 3%

[0192] (Thermal convection resistance evaluation) The surfactant (D) listed in Table 1 for each of the above examples and comparative examples was replaced with 0.15 parts by mass of a fluorine-based surfactant (product name: APX-4082B (manufactured by Kyoeisha Chemical Co., Ltd.)), and a photosensitive resin composition for evaluating thermal convection resistance was prepared in the same manner as for each of the above examples and comparative examples. A photosensitive resin composition prepared in each of the above examples and comparative examples, as well as a photosensitive resin composition for evaluating thermal convection resistance, were applied to a 10cm x 10cm glass substrate (Dow Corning 1737 glass) to form a coating film. Two glass spacers, 5mm wide x 10cm long, were placed parallel to each other at a 5cm interval between the glass substrate and a hot plate, with the long sides of the spacers parallel. The coating film was then dried on the hot plate at 80°C for 10 minutes to obtain a resin film with a thickness of 1.7μm. By placing a 5mm wide x 10cm long glass spacer between the glass substrate and the hot plate and heating it, heat from the hot plate is locally transferred to the glass substrate via the glass spacer at the location where the glass spacer is placed. On the other hand, at locations where the glass spacer is not placed, the air gap between the glass substrate and the hot plate reduces heat transfer from the hot plate to the glass substrate. This generates Marangoni convection in the coated film due to the difference in surface tension, causing a change in the thickness of the resin film. The maximum film thickness t5a of the resin film formed from the photosensitive resin composition of each of the above examples and comparative examples was measured at a position corresponding to one of the long sides of one of the two glass spacers. Similarly, the maximum thickness t5b of the resin film was measured at a position corresponding to the other long side of the other glass spacer. Furthermore, the maximum resin film thicknesses t5a' and t5b' were measured at the positions corresponding to the two long sides of the other glass spacer, in the same manner as described above. The average value of t5a, t5b, t5a', and t5b' was defined as T5. Furthermore, the minimum thicknesses t6 and t6' of the resin film at positions directly above the center of each of the two glass spacers in the width direction were measured. The average value of t6 and t6' was defined as T6. Note that the "center in the width direction" is a position equidistant from the two long sides of the glass spacer. The resin film thickness T7 was measured at an arbitrary position corresponding to a position equidistant from the two glass spacers mentioned above. The average resin film thickness for each example and each comparative example was calculated from the film thicknesses T5 to T7. Using the film thickness of the resin film in Comparative Example 1 as a reference, the rate of change in film thickness for each example and each comparative example was calculated according to the following formula and evaluated according to the following criteria. Film thickness change rate (%) = (T5 - T6) / T7 × 100 A: Less than 150% B: 150% or more, less than 200% C: 200% or more

[0193] (Evaluation of development potential) The resin films of each example and each comparative example formed by the above resin film formation process were subjected to a Canon MPA600FA at 40 mJ / cm² via a negative mask. 2 The substrate was exposed to light, and then developed using a 0.5% tetramethylammonium hydroxide aqueous solution as the developer for 80 seconds at 23°C by the paddle method to obtain a patterned cured film. The substrate with the patterned cured film was observed with an optical microscope and evaluated according to the following criteria. A: Less than 5% of the total counted pattern peeling. B: More than 5% of the total counted pattern peeling.

[0194] [Table 2]

[0195] The fluorine-free photosensitive resin compositions of Examples 1-16 exhibit equivalent outgassing and panel reliability to the fluorine-containing photosensitive resin composition of Comparative Example 1. Furthermore, the photosensitive resin compositions of Examples 1-16 exhibit superior bottle stability compared to the photosensitive resin composition of Comparative Example 1. The photosensitive resin compositions of Examples 1-3 and 6-16 exhibit equivalent leveling properties to the photosensitive resin composition of Comparative Example 1. The photosensitive resin compositions of Examples 1-3, 6-11, 15, and 16 exhibit equivalent residual film rates to the photosensitive resin composition of Comparative Example 1. The photosensitive resin compositions of Examples 1, 2, 3, and 6-16 exhibit equivalent thermal convection resistance to the photosensitive resin composition of Comparative Example 1. The photosensitive resin compositions of Examples 1 to 16, which include an alkali-soluble resin (A) containing a saturated aliphatic hydrocarbon ring as a constituent unit, exhibit superior bottle stability compared to the photosensitive resin composition of Comparative Example 2, which includes an alkali-soluble resin (A) that does not contain a saturated aliphatic hydrocarbon ring as a constituent unit.

Claims

1. It comprises an alkali-soluble resin (A), a photopolymerizable monomer (B), a photopolymerization initiator (C), and a silicone-based surfactant (D). The alkali-soluble resin (A) comprises a constituent unit (a1) having an alkali-soluble group and a constituent unit (a2) having an alicyclic epoxy group. A photosensitive resin composition in which the aforementioned silicone-based surfactant (D) does not contain fluorine atoms.

2. The photosensitive resin composition according to claim 1, wherein the structure of the silicone-based surfactant (D) is linear, and the main chain of the molecule of the silicone-based surfactant (D) has a polysiloxane skeleton or an oligosiloxane skeleton.

3. The photosensitive resin composition according to claim 1, wherein the surface tension of the photosensitive resin composition under conditions of a temperature of 25°C and a relative humidity of 50% is 25 mN / m or more and 35 mN / m or less.

4. The photosensitive resin composition according to claim 1, wherein the content of the silicone-based surfactant (D) is 0.001% by mass or more and 10% by mass or less with respect to the total solid components of the photosensitive resin composition.

5. The photosensitive resin composition according to claim 1, wherein the silicone-based surfactant (D) is a polyester-modified silicone-based surfactant (D1).

6. The photosensitive resin composition according to claim 1, wherein the alkali-soluble resin (A) includes a constituent unit (a1) derived from (meth)acrylic acid.

7. The photosensitive resin composition according to claim 1, wherein the alkali-soluble resin (A) includes a constituent unit (a3) ​​represented by the following formula (a3-1). 【Chemistry 1】 (In the above formula (a3-1), R ａ５ R represents a hydrogen atom or a methyl group. ａ６ (This refers to an aliphatic hydrocarbon group having 1 to 20 carbon atoms.)

8. The photosensitive resin composition according to claim 7, wherein the aliphatic hydrocarbon group comprises a saturated aliphatic hydrocarbon ring.

9. The photosensitive resin composition according to claim 1, comprising an adhesion enhancer (E).

10. A cured product of the photosensitive resin composition according to any one of claims 1 to 9.

11. A photospacer comprising the cured product described in claim 10.

Images