JP2023137277A - Photosensitive resin composition and cured film - Google Patents

Abstract

To provide a photosensitive resin composition which can form a pattern having excellent resolution even with a thick film having a film thickness of 10 μm or more, has high transparency and low film stress and has high adhesion to a metal layer containing molybdenum, aluminum or nickel.SOLUTION: There is provided a photosensitive resin composition which comprises (A) a siloxane resin containing 30 mol% or more and 85 mol% or less of an organosilane unit (D unit) represented by (R)2SiO2/2 (R is a hydrogen atom or an organic group) with respect to the total organosilane units and having a radical polymerizable group, (B) an N-substituted (meth)acrylamide derivative and (C) a photo-radical polymerization initiator.SELECTED DRAWING: None

Description

The present invention relates to a photosensitive resin composition, a transparent medium layer, and a light emitting device, a solid-state image sensor, and a fingerprint authentication device including the same.

Biometric authentication is essential for various mobile display terminals such as smartphones and tablet PCs (personal computers) for unlocking and other personal authentication purposes. Fingerprint authentication in particular is installed in many terminals because it is cheap, compact, and highly convenient.
Conventionally, it has been common to mount a capacitive fingerprint authentication device on the bezel portion of the display (around the display). However, in smartphones, the trend is toward full-screen displays, and the bezel that traditionally houses the fingerprint authentication device is becoming obsolete. Therefore, it has become necessary to install the fingerprint authentication device below the display (this configuration is called an ``under-display type'').
Authentication methods for under-display type fingerprint authentication devices include optical and ultrasonic methods, but optical methods are particularly suitable for use with not only organic light emitting diode (hereinafter abbreviated as OLED) displays but also liquid crystal displays, etc. It has become mainstream due to its versatility and ease of introduction.
Regarding such under-display type fingerprint authentication devices, a thin optical under-display type fingerprint authentication device that has high authentication accuracy and can be installed in a very narrow area between the battery and the screen has been proposed (for example, Patent Document 1, see Patent Document 2).

An optical under-display type fingerprint authentication device as described in Patent Document 2 includes a substrate, a sensor, a light shielding layer, a transparent medium layer, and a microlens. The transparent medium layer can be formed by screen printing or photolithography using a photosensitive material, but the latter method has excellent positional and dimensional accuracy, which is important for improving authentication accuracy. This method is attracting attention.
Compared to microlenses applied to CMOS image sensors, etc., the diameter of microlenses applied to fingerprint authentication devices is generally larger, so the focal length, which is the distance from the center point of the microlens to the image sensor, is also larger. become longer. Therefore, the transparent medium layer formed between the microlens and the image sensor needs to have a thickness of about 10 μm to 100 μm, which is excellent for forming patterns with thick films of 10 μm or more and suppresses warping of the substrate. Therefore, there is a need for materials with low film stress in the cured film.
In addition, TFT production lines are often used as production lines for manufacturing fingerprint authentication devices, and metal layers containing molybdenum, aluminum, or nickel are used as light-shielding layers and sensor lead-out wiring in fingerprint authentication devices. Therefore, excellent adhesion to the metal layer is also required.

A photosensitive resin composition containing a specific alkali-soluble silicone resin, etc. (see, for example, Patent Document 3) is disclosed as a photosensitive material having heat-resistant transparency, crack resistance, and thermal shock test resistance in a thick film. However, it has poor adhesion to metal layers containing molybdenum, aluminum, or nickel, and with thick films exceeding 10 μm used in fingerprint authentication devices, the substrate may warp due to the film stress of the cured film. There was an issue that I had to do.
A photosensitive resin composition containing polysiloxane, a photosensitizer, a polymerizable compound having a phosphorus atom, and a silane compound having a ureido group is used as a photosensitive material with excellent adhesion to glass substrates and metal substrates and chemical resistance. For example, see Patent Document 4), but a thick film exceeding 10 μm has a similar problem in that the substrate warps due to film stress of the cured film.

Japanese Patent Application Publication No. 2020-35327 WO2020/038408 WO2013/031985 WO2019/102655

The present invention was devised in view of the problems of the prior art, and it is possible to form a pattern with excellent resolution even with a thick film of 10 μm or more, has high transparency, low film stress, and uses molybdenum. An object of the present invention is to provide a photosensitive resin composition that has high adhesion to metal layers containing nickel, aluminum, or nickel.

The object of the present invention is achieved by the following configuration. A photosensitive resin composition containing the following (A) to (C). Contains organosilane units (D units) represented by (A) (R) ₂ SiO _2/2 (R is a hydrogen atom or an organic group), and the proportion of D units is 30 mol% or more 85 mol with respect to all organosilane units % or less, a siloxane resin having a radically polymerizable group, (B) an N-substituted (meth)acrylamide derivative, and (C) a photoradical polymerization initiator.

According to the photosensitive resin composition of the present invention, it is possible to form a pattern with excellent resolution even in a thick film of 10 μm or more, and it has high transparency and low film stress. It is possible to provide a cured film having high adhesion to a metal layer containing.

The present invention will be explained in more detail below.
The photosensitive resin composition of the present invention is a photosensitive resin composition containing the following (A) to (C).
Contains organosilane units (D units) represented by (A) (R) ₂ SiO _2/2 (R is a hydrogen atom or an organic group), and the proportion of D units is 30 mol% or more 85 mol with respect to all organosilane units % or less and has a radically polymerizable group (hereinafter sometimes simply abbreviated as (A) siloxane resin),
(B) N-substituted (meth)acrylamide derivative,
(C) Radical photopolymerization initiator.

By containing (A) siloxane resin, (B) N-substituted (meth)acrylamide derivative, and (C) photopolymerization initiator, radically polymerizable groups of (A) siloxane resin and (B) N-substituted Radical polymerization of the (meth)acrylamide derivative progresses, making it possible to perform negative pattern processing in which the light irradiated area becomes insolubilized.
(A) By containing the siloxane resin, a cured film with high transparency and excellent heat resistance and weather resistance can be formed. This is because the siloxane resin (A) has a siloxane skeleton in its main chain. Furthermore, since the proportion of D units is 30 mol% or more and 85 mol% or less of all organosilane units, it is possible to moderately suppress three-dimensional crosslinking while maintaining sufficient chemical resistance against acids and alkalis, and reduce membrane stress. It is possible to form a low cured film.

(B) By containing the N-substituted (meth)acrylamide derivative, a cured film having high adhesiveness to a metal layer containing molybdenum, aluminum, or nickel can be formed. This is because the lone electron of the nitrogen atom in the N-substituted (meth)acrylamide derivative has a strong interaction with the d orbital of the metal.
The photosensitive resin composition of the present invention contains (A) a siloxane resin. Siloxane resin refers to a polymer having repeating units having a siloxane skeleton. The siloxane resin (A) in the present invention has a radically polymerizable group, and is preferably a hydrolyzed condensate of an organosilane compound having a radically polymerizable group.

(A) The weight average molecular weight (Mw) of the siloxane resin is preferably 500 or more, more preferably 1,000 or more from the viewpoint of further improving chemical resistance. On the other hand, the Mw of the siloxane resin (A) is preferably 10,000 or less, more preferably 5,000 or less, from the viewpoint of improving solubility in a developer during pattern formation. Here, the Mw of the siloxane resin (A) refers to a polystyrene equivalent value measured by gel permeation chromatography (GPC).

Examples of the radically polymerizable group include a vinyl group, an α-methylvinyl group, an allyl group, a styryl group, and a (meth)acryloyl group. From the viewpoint of further improving the pencil hardness of the cured film and the sensitivity during pattern processing, a (meth)acryloyl group is preferred.

Examples of the organosilane compound having a radically polymerizable group include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltri(methoxyethoxy)silane, vinylmethyldimethoxysilane, vinylmethyldiethoxysilane, vinylmethyldi(methoxyethoxy)silane, and allyl. Trimethoxysilane, allyltriethoxysilane, allyltri(methoxyethoxy)silane, allylmethyldimethoxysilane, allylmethyldiethoxysilane, allylmethyldi(methoxyethoxy)silane, styryltrimethoxysilane, styryltriethoxysilane, styryltri(methoxyethoxy)silane , styrylmethyldimethoxysilane, styrylmethyldiethoxysilane, styrylmethyldi(methoxyethoxy)silane, 3-acryloxypropyltrimethoxysilane, 3-acryloxypropyltriethoxysilane, 3-acryloxypropyltri(methoxyethoxy)silane , 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-methacryloxypropyltri(methoxyethoxy)silane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, Examples include 3-acryloxypropylmethyldimethoxysilane, 3-acryloxypropylmethyldiethoxysilane, and 3-methacryloxypropyl(methoxyethoxy)silane. Two or more types of these may be used. Among these, from the viewpoint of further improving the pencil hardness of the cured film and the sensitivity during pattern processing, 3-acryloxypropyltrimethoxysilane, 3-acryloxypropyltriethoxysilane, 3-methacryloxypropyltrimethoxysilane, -Methacryloxypropyltriethoxysilane is preferred.

(A) The siloxane resin may be a hydrolyzed condensate of the above-mentioned organosilane compound having a radically polymerizable group and another organosilane compound. Examples of other organosilane compounds include methyltrimethoxysilane, methyltriethoxysilane, methyltri(methoxyethoxy)silane, methyltripropoxysilane, methyltriisopropoxysilane, methyltributoxysilane, ethyltrimethoxysilane, and ethyltrimethoxysilane. Ethoxysilane, hexyltrimethoxysilane, octadecyltrimethoxysilane, octadecyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, 3-aminopropyltriethoxysilane, N-(2-aminoethyl)-3-aminopropyltriethoxysilane Methoxysilane, 3-chloropropyltrimethoxysilane, 3-(N,N-diglycidyl)aminopropyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxy Silane, N-2-(aminoethyl)-3-aminopropyltrimethoxysilane, 2-cyanoethyltriethoxysilane, glycidoxymethyltrimethoxysilane, glycidoxymethyltriethoxysilane, 1-glycidoxyethyltrimethoxy Silane, 1-glycidoxyethyltriethoxysilane, 2-glycidoxyethyltrimethoxysilane, 2-glycidoxyethyltriethoxysilane, 1-glycidoxypropyltrimethoxysilane, 1-glycidoxypropyltriethoxy Silane, 2-glycidoxypropyltrimethoxysilane, 2-glycidoxypropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropyltripropoxy Sisilane, 3-glycidoxypropyltriisopropoxysilane, 3-glycidoxypropyltributoxysilane, 3-glycidoxypropyltri(methoxyethoxy)silane, 1-glycidoxybutyltrimethoxysilane, 1- Glycidoxybutyltriethoxysilane, 2-glycidoxybutyltrimethoxysilane, 2-glycidoxybutyltriethoxysilane, 3-glycidoxybutyltrimethoxysilane, 3-glycidoxybutyltriethoxysilane, 4- Glycidoxybutyltrimethoxysilane, 4-glycidoxybutyltriethoxysilane, (3,4-epoxycyclohexyl)methyltrimethoxysilane, (3,4-epoxycyclohexyl)methyltriethoxysilane, 2-(3,4 -Epoxycyclohexyl)ethyltripropoxysilane, 2-(3,4-epoxycyclohexyl)ethyltributoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 2-(3,4-epoxycyclohexyl)ethyl Triethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltriphenoxysilane, 3-(3,4-epoxycyclohexyl)propyltrimethoxysilane, 3-(3,4-epoxycyclohexyl)propyltriethoxysilane, 4 -(3,4-epoxycyclohexyl)butyltrimethoxysilane, 4-(3,4-epoxycyclohexyl)butyltriethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, diphenylsilanediol, dimethoxydiphenylsilane, 3-glyside Xypropylmethyldimethoxysilane, 3-aminopropylmethyldimethoxysilane, 3-aminopropylmethyldiethoxysilane, N-(2-aminoethyl)-3-aminopropylmethyldimethoxysilane, glycidoxymethyldimethoxysilane, glycidoxy Methylmethyldiethoxysilane, 1-glycidoxyethylmethyldimethoxysilane, 1-glycidoxyethylmethyldiethoxysilane, 2-glycidoxyethylmethyldimethoxysilane, 2-glycidoxyethylmethyldiethoxysilane, 1- Glycidoxypropylmethyldimethoxysilane, 1-glycidoxypropylmethyldiethoxysilane, 2-glycidoxypropylmethyldimethoxysilane, 2-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropylmethyldipropoxysilane, 2-glycidoxypropylmethyldibutoxysilane, 3-glycidoxypropylmethyldi(methoxyethoxy)silane, 3-glycidoxypropylmethyldipropoxysilane Sidoxypropylethyldimethoxysilane, 3-glycidoxypropylethyldiethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropylmethyldiethoxysilane, cyclohexylmethyldimethoxysilane, octadecylmethyldimethoxysilane, tetramethoxysilane, tetra Ethoxysilane, trifluoromethyltrimethoxysilane, trifluoromethyltriethoxysilane, trifluoropropyltrimethoxysilane, trifluoropropyltriethoxysilane, perfluoropropyltrimethoxysilane, perfluoropropyltriethoxysilane, perfluoropentyltrimethoxy Silane, perfluoropentyltriethoxysilane, tridecafluorooctyltrimethoxysilane, tridecafluorooctyltriethoxysilane, tridecafluorooctyltripropoxysilane, tridecafluorooctyltriisopropoxysilane, heptadecafluorodecyltrimethoxysilane, Heptadecafluorodecyltriethoxysilane, bis(trifluoromethyl)dimethoxysilane, bis(trifluoropropyl)dimethoxysilane, bis(trifluoropropyl)diethoxysilane, trifluoropropylmethyldimethoxysilane, trifluoropropylmethyldiethoxysilane , trifluoropropylethyldimethoxysilane, trifluoropropylethyldiethoxysilane, heptadecafluorodecylmethyldimethoxysilane, 3-trimethoxysilylpropylsuccinic anhydride, 3-triethoxysilylpropylsuccinic anhydride, 3-triphenoxy Silylpropylsuccinic anhydride, 3-trimethoxysilylpropylcyclohexyldicarboxylic anhydride, 3-trimethoxysilylpropyl phthalic anhydride, 1-naphthyltrimethoxysilane, 1-naphthyltriethoxysilane, 1-naphthyltri- n-propoxysilane, 2-naphthyltrimethoxysilane, 1-anthracenyltrimethoxysilane, 9-anthracenyltrimethoxysilane, 9-phenanthrenyltrimethoxysilane, 9-fluorenyltrimethoxysilane, 2-fluorene Examples include nyltrimethoxysilane, 2-fluorenonyltrimethoxysilane, 1-pyrenyltrimethoxysilane, 2-indenyltrimethoxysilane, and 5-acenaphthenyltrimethoxysilane. Two or more types of these may be used. Among these, from the viewpoint of improving the crack resistance of the cured film, it is preferable that the siloxane resin (A) contains 15 mol% or more of organosilane units having diphenyl groups, suppressing residues during development and improving resolution. It is preferable that the siloxane resin (A) contains 65 mol % or less of an organosilane unit having a diphenyl group, from the viewpoint of improving the adhesion with the substrate, metal layer, and resin layer.

In addition, from the viewpoint of suppressing residues during development, improving resolution, and improving adhesion to the substrate, metal layer, and resin layer, 3-trimethoxysilylpropyl succinic anhydride, 3-triethoxysilylpropyl Carboxyl groups and/or dicarboxylic acids such as succinic anhydride, 3-triphenoxysilylpropylsuccinic anhydride, 3-trimethoxysilylpropylcyclohexyldicarboxylic anhydride, 3-trimethoxysilylpropylphthalic anhydride Organosilane compounds having an anhydride structure are preferred.

(A) Siloxane resin can be obtained by hydrolyzing and condensing an organosilane compound. For example, it can be obtained by hydrolyzing an organosilane compound and then subjecting the resulting silanol compound to a condensation reaction in the presence of an organic solvent or in the absence of a solvent.
Various conditions for the hydrolysis reaction can be appropriately set in consideration of the reaction scale, the size and shape of the reaction container, etc. For example, it is preferable to add an acid catalyst and water to an organosilane compound in a solvent over a period of 1 to 180 minutes, and then react at room temperature to 110° C. for 1 to 180 minutes. By carrying out the hydrolysis reaction under such conditions, rapid reaction can be suppressed. The reaction temperature is more preferably 30 to 105°C.

The hydrolysis reaction is preferably carried out in the presence of an acid catalyst. As the acid catalyst, an acidic aqueous solution containing formic acid, acetic acid, phosphoric acid, or nitric acid is preferable. The amount of the acid catalyst added is preferably 0.05 to 5 parts by weight based on 100 parts by weight of the total organosilane compound used during the hydrolysis reaction. By controlling the amount of the acid catalyst within the above range, the hydrolysis reaction can proceed more efficiently.
After obtaining a silanol compound by a hydrolysis reaction of an organosilane compound, the reaction solution is preferably heated as it is at 50° C. or higher and below the boiling point of the solvent for 1 to 100 hours to perform a condensation reaction. Further, in order to increase the degree of polymerization of the siloxane resin, reheating or addition of a base catalyst may be performed.

Examples of organic solvents used in the hydrolysis reaction of organosilane compounds and the condensation reaction of silanol compounds include methanol, ethanol, propanol, isopropanol, butanol, isobutanol, t-butanol, pentanol, and 4-methyl-2-pene. Alcohols such as tanol, 3-methyl-2-butanol, 3-methyl-3-methoxy-1-butanol, 1-t-butoxy-2-propanol, diacetone alcohol; Glycols such as ethylene glycol and propylene glycol; Ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol dibutyl ether, diethyl ether, etc. ethers; ketones such as methyl ethyl ketone, acetylacetone, methyl propyl ketone, methyl butyl ketone, methyl isobutyl ketone, diisobutyl ketone, cyclopentanone, 2-heptanone; amides such as dimethylformamide, dimethyl acetamide; ethyl acetate, propyl acetate , butyl acetate, isobutyl acetate, ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, methyl lactate, ethyl lactate, butyl lactate, and other acetates; toluene , aromatic or aliphatic hydrocarbons such as xylene, hexane, and cyclohexane, γ-butyrolactone, N-methyl-2-pyrrolidone, and dimethyl sulfoxide. Two or more types of these may be used. From the viewpoint of cured film transmittance, crack resistance, etc., diacetone alcohol, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether, propylene glycol mono-t-butyl ether, propylene glycol monopropyl ether, propylene glycol Monobutyl ether, γ-butyrolactone and the like are preferred.

When a solvent is generated by the hydrolysis reaction, it is also possible to carry out the hydrolysis without a solvent. It is also preferable to adjust the concentration to an appropriate level as a resin composition by further adding a solvent after the reaction is completed. Further, depending on the purpose, after the hydrolysis, an appropriate amount of the produced alcohol and the like may be distilled off and removed under heating and/or reduced pressure, and then a suitable solvent may be added.
The amount of the solvent used in the hydrolysis reaction is preferably 80 parts by weight or more and 500 parts by weight or less based on 100 parts by weight of the total organosilane compound. By controlling the amount of the solvent within the above range, the hydrolysis reaction can proceed more efficiently.
Furthermore, the water used in the hydrolysis reaction is preferably ion-exchanged water. The amount of water is preferably 1.0 to 4.0 moles per mole of silane atoms.

The photosensitive resin composition of the present invention contains (B) an N-substituted (meth)acrylamide derivative. N-substituted (meth)acrylamide derivatives include N-alkylacrylamide, N-allylacrylamide, acryloylmorpholine, N-alkylmethacrylamide, N-allylmethacrylamide, N,N-dialkylacrylamide, N,N-diallylacrylamide, -Alkyl, N-allyl acrylamide, N,N-dialkyl methacrylamide, N,N-diallyl methacrylamide, N-alkyl, N-allyl methacrylamide, and their derivatives.
Specifically, for example, N-methylacrylamide, N-ethylacrylamide, N-n propylacrylamide, N-isopropylacrylamide, N-cyclopropylacrylamide, N-hydroxyethylacrylamide, N-methylolacrylamide methyl ether, N-methylol Acrylamide ethyl ether, N-methylolacrylamide propyl ether, N-methylolacrylamide butyl ether, N-methoxymethylacrylamide, N-butoxymethylacrylamide, N,N'-methylenebisacrylamide, acryloylmorpholine, diacetone acrylamide, N-methylmethacrylamide , N-ethylmethacrylamide, Nn-propylmethacrylamide, N-isopropylmethacrylamide, N-cyclopropylmethacrylamide, N-methoxymethylmethacrylamide, N-butoxymethylmethacrylamide, N,N'-methylenebismethacrylamide , diacetone methacrylamide, N,N-dimethylacrylamide, N,N-diethylacrylamide, N-methyl,N-ethylacrylamide, N,N-dimethylmethacrylamide, N,N-diethylmethacrylamide, N,N-dimethyl Examples include aminopropylacrylamide, N-methyl, N-ethylmethacrylamide, and the like. Two or more types of these may be contained.
Among these, N-monosubstituted (meth)acrylamide derivatives are preferred from the viewpoint of improving adhesion to metal layers containing molybdenum, aluminum, or nickel. More preferred are N-alkoxyalkyl acrylamide and N-alkoxyalkyl methacrylamide, such as those mentioned above.

(In the above general formula (1), R ¹ represents a hydrogen atom or a methyl group, R ² represents an alkylene group, and R ³ represents an alkyl group.)
The content of the (B) N-substituted (meth)acrylamide derivative in the photosensitive resin composition of the present invention is set to 1% in the solid content from the viewpoint of improving the adhesion to the metal layer using Mo alloy, Al alloy, or Ni alloy. It is preferably at least 2% by weight, more preferably at least 2% by weight, and from the viewpoint of increasing the hydrophobicity of the cured film and further improving the chemical resistance, it is preferably at most 30% by weight, more preferably at most 25% by weight based on the solid content.

The photosensitive resin composition of the present invention contains (C) a photoradical polymerization initiator. A photoradical polymerization initiator refers to a substance that decomposes and/or reacts with light (including ultraviolet rays and electron beams) to generate radicals. (C) As the photoradical polymerization initiator, α-aminoalkylphenone compounds, acylphosphine oxide compounds, oxime ester compounds, benzophenone compounds having an amino group, and benzoic acid ester compounds having an amino group are preferable, and they are effective in improving the cured film. can be improved. Two or more types of these compounds may be contained.
Specific examples of α-aminoalkylphenone compounds include 2-methyl-[4-(methylthio)phenyl]-2-morpholinopropan-1-one, 2-dimethylamino-2-(4-methylbenzyl)-1 -(4-morpholin-4-yl-phenyl)-butan-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone-1, and the like.

Specific examples of acylphosphine oxide compounds include 2,4,6-trimethylbenzoylphenylphosphine oxide, bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide, bis(2,6-dimethoxybenzoyl)-( Examples include 2,4,4-trimethylpentyl)-phosphine oxide.
Specific examples of oxime ester compounds include 1-phenyl-1,2-propanedione-2-(o-ethoxycarbonyl)oxime, 1,2-octanedione, 1-[4-(phenylthio)-2-(O -benzoyloxime)], 1-phenyl-1,2-butadione-2-(o-methoxycarbonyl)oxime, 1,3-diphenylpropanetrione-2-(o-ethoxycarbonyl)oxime, ethanone, 1-[9 -ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-, 1-(0-acetyloxime) and the like.

Specific examples of the benzophenone compound having an amino group include 4,4-bis(dimethylamino)benzophenone and 4,4-bis(diethylamino)benzophenone.
Specific examples of benzoic acid ester compounds having an amino group include ethyl p-dimethylaminobenzoate, 2-ethylhexyl-p-dimethylaminobenzoate, and ethyl p-diethylaminobenzoate.
The content of the (C) radical photopolymerization initiator in the photosensitive resin composition of the present invention is 0.01% by weight or more based on the solid content, from the viewpoint of sufficiently promoting radical polymerization and improving the pencil hardness of the cured film. The content is preferably 0.1% by weight or more, more preferably 0.1% by weight or more, and from the viewpoint of improving the transparency of the cured film, the content is preferably 20% by weight or less, and more preferably 15% by weight or less.
The photosensitive resin composition of the present invention preferably contains (D) monofunctional (meth)acrylate in addition to (B) the N-substituted (meth)acrylamide derivative.

(D) Specific examples of monofunctional (meth)acrylate include n-butyl (meth)acrylate, n-hexyl (meth)acrylate, isobutyl (meth)acrylate, isoamyl (meth)acrylate, isooctyl (meth)acrylate, isodecyl (meth)acrylate, isostearyl (meth)acrylate, lauryl (meth)acrylate, cyclohexyl (meth)acrylate, benzyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, 2-phenoxyethyl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, dicyclopentenyloxyethyl (meth)acrylate, 2-cyanoethyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate , 2-hydroxy-3-phenoxypropyl (meth)acrylate, 2-hydroxy-3-butyloxypropyl (meth)acrylate, 2-hydroxy-3-(2-ethylhexyloxy)propyl (meth)acrylate, amino (meth)acrylate Acrylate, dimethylaminoethyl (meth)acrylate, diethylaminoethyl (meth)acrylate, 2-methoxyethyl (meth)acrylate, 2-ethoxyethyl (meth)acrylate, 3-methoxybutyl (meth)acrylate, 2-(meth)acrylate Royloxyethyl succinic acid, N-(meth)acryloyloxyethylhexahydrophthalimide, trifluoroethyl (meth)acrylate, ethyl carbitol (meth)acrylate, ethoxydiethylene glycol (meth)acrylate, methoxytripropylene glycol (meth)acrylate, 2-ethylhexyl EO modified (meth)acrylate, phenol EO modified (meth)acrylate, p-nonylphenol EO modified (meth)acrylate, p-nonylphenol PO modified (meth)acrylate, о-phenylphenol EO modified (meth)acrylate, p -cumylphenol EO modified (meth)acrylate, methoxytriethylene glycol (meth)acrylate, etc. Two or more types of these may be contained.
Among these, from the viewpoint of improving the crack resistance of the cured film, monofunctional (meth)acrylates containing a phenol structure are preferable, and among them, monofunctional (meth)acrylates represented by the following general formulas (2) and/or (3) are preferable. It is more preferable to use monofunctional (meth)acrylates such as those mentioned above.

(In the above general formula (2), R ⁴ represents a hydrogen atom or a methyl group, R ⁵ represents an alkylene group, X represents a hydrogen atom, an alkyl group or a phenyl group, and m represents a positive integer. .)

(In the above general formula (3), R ⁶ represents a hydrogen atom or a methyl group, R ⁷ represents an alkylene group, and n represents a positive integer.)
Regarding the monofunctional (meth)acrylates represented by the above general formulas (2) and (3), from the viewpoint of reducing the film stress of the cured film, m and n are each preferably 2 or more, and 4 or more. It is more preferable.

The content of monofunctional (meth)acrylate (D) in the photosensitive resin composition of the present invention is preferably 3% by weight or more, more preferably 5% by weight or more based on the solid content, from the viewpoint of reducing film stress of the cured film. Preferably, from the viewpoint of improving the pencil hardness of the cured film, the amount is preferably 40% by weight or less, more preferably 35% by weight or less in the solid content.

The photosensitive resin composition of the present invention may contain polyfunctional (meth)acrylate in addition to (D) monofunctional (meth)acrylate. Polyfunctional (meth)acrylate refers to a compound having two or more acrylate groups. For example, as a compound having two acrylate groups, 2,2-[9H-fluorene-9,9-diylbis(1, 4-phenylene)bisoxy]diethanol di(meth)acrylate, ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, dimethyloltricyclodecane di(meth)acrylate, ethoxylated Bisphenol A di(meth)acrylate, glycerin di(meth)acrylate, tripropylene glycol di(meth)acrylate, 1,3-butanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, 1,4-butane Diol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, 1,10-decanediol di(meth)acrylate, three or more acrylate groups Compounds include tris(2-hydroxyethyl)isocyanuric acid acrylic ester, glycerin tri(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, pentaerythritol tri(meth)acrylate , pentaerythritol tetra(meth)acrylate, ethoxylated pentaerythritol tetra(meth)acrylate, dipentaerythritol hexa(meth)acrylate, tripentaerythritol hepta(meth)acrylate, tripentaerythritol octa(meth)acrylate, tetrapentaerythritol nona (meth)acrylate, tetrapentaerythritol deca(meth)acrylate, pentapentaerythritol undeca(meth)acrylate, pentapentaerythritol dodeca(meth)acrylate, and the like. Two or more types of these may be contained.

The photosensitive resin composition of the present invention preferably contains an adhesion improver such as a silane coupling agent, and can further improve the adhesion between the coating film and the underlying substrate. Examples of the silane coupling agent include those having functional groups such as vinyl group, epoxy group, styryl group, methacryloxy group, acryloxy group, and amino group. Specifically, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 2-(3 ,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris(2-methoxyethoxy)silane, N-(2 -aminoethyl)-3-aminopropylmethyldimethoxysilane, N-(2-aminoethyl)-3-aminopropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-acryloxypropyltrimethoxysilane, 3- Aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N-(1,3-dimethyl-butylidene)propylamine, 3-mercaptopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane, 3-Isocyanatepropyltriethoxysilane, p-sulytyltrimethoxysilane and the like are preferred.

The content of the adhesion improver in the photosensitive resin composition of the present invention is preferably 0.1% by weight or more, more preferably 1% by weight or more based on the solid content, from the viewpoint of further improving the adhesion. From the viewpoint of improving resolution, the content is preferably 10% by weight or less, more preferably 8% by weight or less.

The photosensitive resin composition of the present invention preferably contains a crosslinking agent, which can promote or facilitate crosslinking of the resin. Examples of the crosslinking agent include nitrogen-containing organic substances, silicone resin curing agents, metal alkoxides, metal chelates, isocyanate compounds and polymers thereof, epoxy compounds and polymers thereof, methylolated melamine derivatives, methylolated urea derivatives, and the like. Two or more types of these may be contained.
Among these, metal chelate compounds and epoxy compounds are preferably used in view of the reactivity of the crosslinking agent and the chemical resistance of the obtained cured film. The content of the crosslinking agent is preferably 0.1% by weight or more in the solid content, more preferably 0.5% by weight or more, even more preferably 1% by weight or more, from the viewpoint of improving the chemical resistance of the cured film. From the viewpoint of improving the resolution of the polyurethane resin composition, the solid content is preferably 30% by weight or less, more preferably 25% by weight or less, and even more preferably 20% by weight or less.
The photosensitive resin composition of the present invention preferably contains a polymerization inhibitor, which can further improve the storage stability and resolution of the photosensitive resin composition. Examples of the polymerization inhibitor include phenol, catechol, resorcinol, hydroquinone, 4-t-butylcatechol, 2,6-di(t-butyl)-p-cresol, phenothiazine, and 4-methoxyphenol.

The content of the polymerization inhibitor in the photosensitive resin composition of the present invention is preferably 0.01% by weight or more in the solid content, and 0.05% by weight or more in the solid content from the viewpoint of further improving the storage stability and resolution of the photosensitive resin composition. It is more preferably at least 5% by weight, and from the viewpoint of further improving the pencil hardness of the cured film, it is preferably at most 5% by weight, more preferably at most 3% by weight based on the solid content.
The photosensitive resin composition of the present invention may contain an ultraviolet absorber. By containing an ultraviolet absorber, the resolution of the photosensitive resin composition and the weather resistance of the cured film can be further improved. As the ultraviolet absorber, benzotriazole compounds, benzophenone compounds, and triazine compounds are preferably used from the viewpoint of transparency and non-coloring properties.
Examples of benzotriazole compounds include 2-(2H benzotriazol-2-yl)phenol, 2-(2H-benzotriazol-2-yl)-4,6-t-pentylphenol, and 2-(2H benzotriazole-2-yl). -2-yl)-4-(1,1,3,3-tetramethylbutyl)phenol, 2(2H-benzotriazol-2-yl)-6-dodecyl-4-methylphenol, 2-(2'- Examples include hydroxy-5'-methacryloxyethylphenyl)-2H-benzotriazole and RUVA-93 (trade name, manufactured by Otsuka Chemical Co., Ltd.).

The photosensitive resin composition of the present invention preferably contains a solvent, so that each component can be uniformly dissolved. Examples of the solvent include aliphatic hydrocarbons, carboxylic acid esters, ketones, ethers, and alcohols. Two or more types of these may be contained. From the viewpoint of uniformly dissolving each component and improving the transparency of the resulting coating film, compounds having an alcoholic hydroxyl group and cyclic compounds having a carbonyl group are preferred.

Examples of compounds having an alcoholic hydroxyl group include acetol, 3-hydroxy-3-methyl-2-butanone, 4-hydroxy-3-methyl-2-butanone, 5-hydroxy-2-pentanone, 4-hydroxy-4 -Methyl-2-pentanone (diacetone alcohol), ethyl lactate, butyl lactate, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-n-propyl ether, propylene glycol mono-n-butyl ether, propylene glycol mono-t-butyl ether , 3-methoxy-1-butanol, 3-methyl-3-methoxy-1-butanol, tetrahydrofurfuryl alcohol and the like.

Specific examples of the cyclic compound having a carbonyl group include γ-butyrolactone, γ-valerolactone, δ-valerolactone, propylene carbonate, N-methylpyrrolidone, cyclohexanone, cycloheptanone, and the like. Among these, γ-butyrolactone is particularly preferably used.
Examples of aliphatic hydrocarbons include xylene, ethylbenzene, and solvent naphtha.
Examples of carboxylic acid esters include benzyl acetate, ethyl benzoate, γ-butyrolactone, methyl benzoate, diethyl malonate, 2-ethylhexyl acetate, 2-butoxyethyl acetate, 3-methoxy-3-methyl-butyl acetate, diethyl oxalate. , ethyl acetoacetate, cyclohexyl acetate, 3-methoxy-butyl acetate, methyl acetoacetate, ethyl-3-ethoxypropionate, 2-ethylbutyl acetate, isopentyl propionate, propylene glycol monomethyl ether propionate, propylene glycol Examples include monoethyl ether acetate, ethyl acetate, butyl acetate, isopentyl acetate, pentyl acetate, propylene glycol monomethyl ether acetate, and the like.
Examples of the ketone include cyclopentanone and cyclohexanone.
Examples of the ether include aliphatic ethers such as propylene glycol derivatives such as propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol tertiary butyl ether, and dipropylene glycol monomethyl ether.
Among these, diacetone alcohol and tetrahydrofurfuryl alcohol are preferred from the viewpoint of storage stability, and propylene glycol monomethyl ether acetate is preferred from the viewpoint of step coverage.
The content of the solvent in the photosensitive resin composition of the present invention can be adjusted depending on the coating method and the like. For example, when applying by spin coating, the amount is generally 50 to 95% by weight of the entire photosensitive resin composition.

The photosensitive resin composition of the present invention preferably contains a surfactant, and can improve flowability during application. Examples of the surfactant include fluorine-based surfactants; silicone-based surfactants; fluorine-containing thermally decomposable surfactants; polyether-modified siloxane-based surfactants; polyalkylene oxide-based surfactants; poly(meth) Acrylate surfactants; Anionic surfactants such as ammonium lauryl sulfate and polyoxyethylene alkyl ether sulfate triethanolamine; Cationic surfactants such as stearylamine acetate and lauryl trimethylammonium chloride; Lauryl dimethylamine oxide and lauryl carboxymethyl Examples include amphoteric surfactants such as hydroxyethylimidazolium betaine; nonionic surfactants such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, and sorbitan monostearate. Two or more types of these may be contained.

Commercially available fluorosurfactants include, for example, "Megafac" (registered trademark) F142D, F172, F173, F183, F445, F470, F475, and F477 (all of which are manufactured by DIC Corporation). (manufactured by NEOS Co., Ltd.), NBX-15, FTX-218 (manufactured by NEOS Co., Ltd.). Examples of commercially available silicone surfactants include "BYK" (registered trademark)-333, BYK-301, BYK-331, BYK-345, BYK-307 (manufactured by BYK Chemie Japan Co., Ltd.). It will be done. Examples of commercially available fluorine-containing thermally decomposable surfactants include "Megafac" (registered trademark) DS-21 (manufactured by DIC Corporation). Commercially available polyether-modified siloxane surfactants include, for example, "BYK" (registered trademark)-345, BYK-346, BYK-347, BYK-348, BYK-349 (all manufactured by BYK-Chemie Japan Co., Ltd.). ), "Silface" (registered trademark) SAG002, SAG005, SAG0503A, and SAG008 (all manufactured by Nissin Chemical Industry Co., Ltd.).

The photosensitive resin composition of the present invention may contain a liquid repellent compound. Examples of the liquid-repellent compound include compounds having a fluoroalkyl or fluoroalkylene group at the terminal, main chain, and/or side chain.

The photosensitive resin composition of the present invention may contain a dispersant. Examples of the dispersant include polyacrylic acid dispersants, polycarboxylic acid dispersants, phosphoric acid dispersants, silicone dispersants, and the like.
The method for producing a cured film using the photosensitive resin composition of the present invention will be explained by giving examples. The method for producing a cured film of the present invention preferably includes a step of curing with light and/or heat without the step of removing all the alkali-soluble resin component (A) by baking or treatment with a stripping solution. Specifically, a method in which the photosensitive resin composition of the present invention is applied, exposed and developed, and heated is preferred.

In the step of applying the photosensitive resin composition of the present invention, it is preferred that the photosensitive resin composition of the present invention is applied onto a base substrate and prebaked. Examples of the coating method include microgravure coating, spin coating, dip coating, curtain flow coating, roll coating, spray coating, and slit coating. Examples of the heating device used for pre-baking include a hot plate and an oven. The heating temperature for pre-baking is preferably 50 to 150°C, and the heating time is preferably 30 seconds to 30 minutes. The film thickness after prebaking is preferably 0.03 to 15 μm.

After prebaking, it is preferable to perform pattern processing by exposure and development. Examples of the exposure device include a mask aligner (LA) and a mirror projection mask aligner (MPA). The exposure intensity is preferably about 10 to 4000 J/m2 (converted to the exposure amount at a wavelength of 365 nm). In order to form a pattern, it is preferable to expose to light through a desired mask, but when curing the entire surface, exposure may be performed without using a mask. A high-pressure mercury lamp is generally used as the exposure light source, and its main wavelengths include 302 nm, 312 nm, 334 nm, 365 nm, and 405 nm.

Next, the unexposed areas are dissolved by development to obtain a negative pattern. Examples of the developing method include methods of immersing the film in a developer using methods such as showering, dipping, and paddling. The development time is preferably 5 seconds to 10 minutes. Examples of the developer include known alkaline developers, and specific examples include inorganic alkalis such as alkali metal hydroxides, carbonates, phosphates, silicates, and borates, 2-diethylaminoethanol, Examples include aqueous solutions containing one or more of amines such as monoethanolamine and diethanolamine, and quaternary ammonium salts such as tetramethylammonium hydroxide and choline. After development, it is preferable to rinse with water, followed by dry baking at a temperature in the range of 50 to 150°C.

It is preferable to heat the film after exposure and development using the above-mentioned heating device. The heating temperature is preferably 150 to 450°C, and the heating time is preferably 20 minutes to 1 hour.
Furthermore, the photosensitive resin composition of the present invention may optionally contain components other than those listed above, such as a crosslinking accelerator, a sensitizer, a thermal radical generator, a dissolution inhibitor, a stabilizer, and an antifoaming agent. It may also contain additives.

The photosensitive resin composition of the present invention is suitably used for light emitting devices such as organic EL light emitting devices and display devices. More specifically, examples include a cured film, a transparent medium layer, etc., which are formed in an organic EL element for the purpose of improving light extraction efficiency.

Among these, it is excellent for patterning thick films with a thickness of 10 μm or more, and the cured film has low film stress, which makes it possible to suppress substrate warping. It is particularly suitable for use as a transparent medium layer formed in From the viewpoint of suppressing warpage of the substrate, the film stress of the cured film formed as the transparent medium layer is preferably 0.01 MPa or more and 10 MPa or less. Considering the focal length of the microlenses formed on the transparent medium layer, the thickness of the cured film formed as the transparent medium layer is preferably about 10 μm to 100 μm. From the viewpoint of improving optical properties, it is preferable that the cured film formed as the transparent medium layer has a transmittance of 90% or more and 100% or less at a wavelength of 550 nm.

Since the photosensitive resin composition of the present invention has high adhesion to a metal layer containing molybdenum, aluminum, or nickel, the metal layer containing molybdenum, aluminum, or nickel can be used as a light-shielding layer or an extraction wiring of a sensor. It can be particularly suitably used in a fingerprint authentication device using.

Hereinafter, the present invention will be explained in more detail using Examples and Comparative Examples, but the present invention is not limited to the following Examples. Among the compounds used in the synthesis examples and examples, the abbreviations used are shown below.
PGMEA: Propylene glycol monomethyl ether acetate Also, in the evaluation method, if the number of evaluation n is not stated, it is an evaluation of n = 1, and if the temperature is not specified in each condition such as evaluation and synthesis, it is evaluated at room temperature. This is the implementation of

<Evaluation method>
"Crack resistance"
After spin-coating the molded photosensitive resin compositions obtained in each example and comparative example on a non-alkali glass substrate (glass thickness 0.55 mm) using a spin coater (MS-A150 manufactured by Mikasa Co., Ltd.) Prebaking was performed at 100° C. for 2 minutes using a hot plate (HHP-230SQ manufactured by As One Corporation) to produce prebaked films with thicknesses of 15 μm, 60 μm, and 115 μm, respectively. The obtained prebaked film was exposed to light using a mask aligner (LA-610 manufactured by San-ei Denki Seisakusho Co., Ltd.) using an ultra-high pressure mercury lamp as a light source at an exposure dose of 200 mJ/cm ² (i-line). Thereafter, using an automatic developing device (AD-1200 manufactured by Takizawa Sangyo Co., Ltd.), shower development was performed using a 2.38% by weight TMAH aqueous solution for 60 seconds, followed by rinsing with water for 30 seconds. Finally, the mixture was cured in air at 230° C. for 30 minutes using an oven (DHS-42 manufactured by ESPEC Co., Ltd.) to produce cured films with thicknesses of 10 μm, 50 μm, and 100 μm, respectively. The obtained cured film on the alkali-free glass substrate was visually checked for the presence of cracks, and from the viewpoint of industrial use, AA, A, and B were determined to be acceptable.
AA: No cracks at film thicknesses of 10 μm, 30 μm, 50 μm, and 100 μm.
A: No cracks at film thicknesses of 10 μm, 30 μm, and 50 μm. There were cracks at a film thickness of 100 μm.
B: No cracks at film thicknesses of 10 μm and 30 μm. There were cracks at film thicknesses of 50 μm and 100 μm.
C: No cracks at a film thickness of 10 μm. Cracks were found at film thicknesses of 30 μm, 50 μm, and 100 μm.
D: Cracks were present at all film thicknesses of 10 μm, 30 μm, 50 μm, and 100 μm.

"Membrane stress"
A 6-inch silicon wafer was spin-coated with the mold photosensitive resin composition obtained in each Example and Comparative Example using a spin coater (MS-A150 manufactured by Mikasa Co., Ltd.), and then coated on a hot plate (As One Co., Ltd.). Prebaking was performed at 100° C. for 2 minutes using HHP-230SQ (manufactured by ) to prepare prebaked films with a thickness of 15 μm. The obtained prebaked film was exposed to light using a mask aligner (LA-610 manufactured by San-ei Denki Seisakusho Co., Ltd.) using an ultra-high pressure mercury lamp as a light source at an exposure dose of 200 mJ/cm ² (i-line). Thereafter, using an automatic developing device (AD-1200 manufactured by Takizawa Sangyo Co., Ltd.), shower development was performed using a 2.38% by weight TMAH aqueous solution for 60 seconds, followed by rinsing with water for 30 seconds. Finally, it was cured in air at 230° C. for 30 minutes using an oven (DHS-42 manufactured by ESPEC Co., Ltd.) to produce a cured film with a thickness of 10 μm. The film stress of the obtained cured film on the 6-inch silicon wafer was measured at room temperature of 23°C using a thin film stress measurement device (manufactured by Toho Technology Co., Ltd.), and from the viewpoint of industrial use, A and B was passed.
A: Membrane stress less than 5 MPa.
B: Membrane stress of 5 MPa or more and less than 10 MPa.
C: Membrane stress of 10 MPa or more and less than 15 MPa.
D: Membrane stress of 15 MPa or more.

"Transmittance"
The molded photosensitive resin compositions obtained in each example and comparative example were spun on a Tempax glass substrate (manufactured by AGC Techno Glass Co., Ltd.) using a spin coater (MS-A150, manufactured by Mikasa Co., Ltd.). After coating, prebaking was performed at 100° C. for 2 minutes using a hot plate (HHP-230SQ manufactured by As One Co., Ltd.) to produce prebaked films each having a thickness of 15 μm. The obtained prebaked film was exposed to light using a mask aligner (LA-610 manufactured by San-ei Denki Seisakusho Co., Ltd.) using an ultra-high pressure mercury lamp as a light source at an exposure dose of 200 mJ/cm ² (i-line). Thereafter, using an automatic developing device (AD-1200 manufactured by Takizawa Sangyo Co., Ltd.), shower development was performed using a 2.38% by weight TMAH aqueous solution for 60 seconds, followed by rinsing with water for 30 seconds. Finally, it was cured in air at 230° C. for 30 minutes using an oven (DHS-42 manufactured by ESPEC Co., Ltd.) to produce a cured film with a thickness of 10 μm. Using a UV-visible photodiode array spectrophotometer MultiSpec-1500 (manufactured by Shimadzu Corporation), the UV-visible absorption spectrum of only the Tempax glass substrate was measured, and this was used as a reference. Next, the ultraviolet-visible absorption spectrum of the resulting laminate of the cured film and Tempax glass was measured with a single beam, the light transmittance at 400 nm was determined, and the difference from the reference was taken as the transmittance of the cured film. From the viewpoint of industrial use, A and B were judged to be acceptable.
A: Transmittance of 95% or more and less than 100%.
B: Transmittance of 90% or more and less than 95%.
C: Transmittance less than 90%.

"resolution"
After spin-coating the molded photosensitive resin compositions obtained in each example and comparative example on a non-alkali glass substrate (glass thickness 0.55 mm) using a spin coater (MS-A150 manufactured by Mikasa Co., Ltd.) , and prebaked for 2 minutes at 100° C. using a hot plate (HHP-230SQ manufactured by As One Corporation) to produce prebaked films with a thickness of 15 μm. Using a mask aligner (LA-610 manufactured by Sanei Denki Seisakusho Co., Ltd.) and using an ultra-high pressure mercury lamp as a light source, the obtained prebaked film was divided into 1:1 widths of 10, 20, 30, 40, and 50 μm. Exposure was carried out using a mask with a mask gap of 200 μm. Thereafter, using an automatic developing device (AD-1200 manufactured by Takizawa Sangyo Co., Ltd.), shower development was performed using a 2.38% by weight TMAH aqueous solution for 60 seconds, followed by rinsing with water for 30 seconds. After development, the exposure amount to form a 50 μm line-and-space pattern with a width of 1:1 was determined as the optimum exposure amount. The exposure amount was measured with an i-ray luminometer. The minimum pattern size after development at the optimum exposure amount was measured, and this was taken as the resolution. From the viewpoint of industrial use, A, B, and C were considered to be acceptable.
A: Resolution of 10 μm or more and less than 20 μm.
B: Resolution of 20 μm or more and less than 30 μm.
C: Resolution of 30 μm or more and less than 40 μm.
D: Resolution of 50 μm or more.

"Adhesion to metal layer"
A substrate in which molybdenum-nickel alloy/aluminum/molybdenum-nickel alloy (film thickness: 20 nm/300 nm/20 nm) was fabricated in this order on a non-alkali glass substrate (glass thickness 0.55 mm) (hereinafter referred to as "metal laminated substrate") ) was prepared. The molded photosensitive resin compositions obtained in each of the Examples and Comparative Examples were spin-coated onto a metal laminated substrate using a spin coater (MS-A150 manufactured by Mikasa Co., Ltd.), and then coated on a hot plate (As One Co., Ltd.). Prebaking was performed at 100° C. for 2 minutes using HHP-230SQ (manufactured by ) to prepare prebaked films with a thickness of 15 μm. The obtained prebaked film was exposed to light using a mask aligner (LA-610 manufactured by Sanei Denki Seisakusho Co., Ltd.) using an ultra-high pressure mercury lamp as a light source at an exposure dose of 200 mJ/cm 2 (i-line). Thereafter, using an automatic developing device (AD-1200 manufactured by Takizawa Sangyo Co., Ltd.), shower development was performed using a 2.38% by weight TMAH aqueous solution for 60 seconds, followed by rinsing with water for 30 seconds. Finally, the cured film was cured in air at 230°C for 30 minutes using an oven (DHS-42 manufactured by ESPEC Co., Ltd.) to produce a cured film with a thickness of 10 μm, and then the cured film was formed on the metal laminated substrate. The adhesion was evaluated. That is, on the surface of the cured film on the metal laminate board, use a cutter knife to draw 11 parallel straight lines at 1 mm intervals, each vertically and horizontally perpendicular to each other, to form a 1 mm x 1 mm square. 100 pieces were made. Paste cellophane adhesive tape (width = 18 mm, adhesive force = 3.7 N/10 mm) on the surface of the cut cured film, rub it with an eraser (JIS S6050 passed product) to make it adhere, hold one end of the tape, and hold it at right angles to the board. The number of remaining squares was visually counted when the sample was kept and instantly peeled off. Judgment was made as follows based on the peeled area of the grid, and from the viewpoint of industrial use, 3B, 4B and 5B were passed.
5B: Peeling area = 0%
4B: Peeling area = more than 0% and less than 5%.
3B: Peeling area = 5% or more and less than 15%.
2B: Peeling area = 15% or more and less than 35%.
1B: Peeling area = 35% or more and less than 65%.
0B: Peeling area = 65% or more and less than 100%.

[Synthesis example 1]
In a 500 mL three-necked flask, 78.05 g of PGMEA, 34.05 g (0.25 mol) of methyltrimethoxysilane, 46.47 g (0.20 mol) of 3-methacryloxypropylmethyldimethoxysilane, 2-(3,4- Prepare 12.32 g (0.05 mol) of epoxycyclohexyl ethyltrimethoxysilane, 26.23 g (0.10 mol) of 3-trimethoxysilylpropylsuccinic acid, and 86.52 g (0.40 mol) of diphenylsilane diol, While stirring in an oil bath at 0.degree. C., a phosphoric acid aqueous solution prepared by dissolving 2.06 g of phosphoric acid (1.0% by weight based on the monomers charged) in 30.60 g of water was added using a dropping funnel over 10 minutes. After stirring at 40°C for 1 hour, the oil bath temperature was set to 70°C, stirring was continued for 1 hour, and the temperature of the oil bath was further raised to 115°C over 30 minutes. One hour after the start of heating, the internal temperature of the solution reached 100°C, and from there it was heated and stirred for 2 hours (internal temperature was 100 to 110°C). During the reaction, a total of 78 g of by-products methanol and water were distilled out. PGMEA was added to the obtained PGMEA solution of polysiloxane so that the solid content concentration was 65% by weight to obtain a siloxane resin solution (PS-1). The weight average molecular weight (hereinafter referred to as "Mw") of the obtained siloxane resin was measured by GPC and found to be 1,000 (in terms of polystyrene).

[Synthesis example 2]
In a 500 mL three-necked flask, 92.50 g of PGMEA, 13.62 g (0.10 mol) of methyltrimethoxysilane, 46.47 g (0.20 mol) of 3-methacryloxypropylmethyldimethoxysilane, 2-(3,4- Prepare 12.32g (0.05mol) of epoxycyclohexyl)ethyltrimethoxysilane, 26.23g (0.10mol) of 3-trimethoxysilylpropylsuccinic acid, and 118.97g (0.55mol) of diphenylsilanediol, While stirring in an oil bath at 0.degree. C., a phosphoric acid aqueous solution prepared by dissolving 2.18 g of phosphoric acid (1.0% by weight based on the monomers charged) in 22.50 g of water was added using a dropping funnel over 10 minutes. After stirring at 40°C for 1 hour, the oil bath temperature was set to 70°C, stirring was continued for 1 hour, and the temperature of the oil bath was further raised to 115°C over 30 minutes. One hour after the start of heating, the internal temperature of the solution reached 100°C, and from there it was heated and stirred for 2 hours (internal temperature was 100 to 110°C). During the reaction, a total of 62 g of by-products methanol and water were distilled out. PGMEA was added to the obtained polysiloxane PGMEA solution so that the solid content concentration was 65% by weight to obtain a siloxane resin solution (PS-2). In addition, when Mw of the obtained siloxane resin was measured by GPC, it was 1,000 (polystyrene equivalent).

[Synthesis example 3]
In a 500 mL three-neck flask, put 102.13 g of PGMEA, 46.47 g (0.20 mol) of 3-methacryloxypropylmethyldimethoxysilane, and 12.32 g (0.20 mol) of 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane. 05 mol), 26.23 g (0.10 mol) of 3-trimethoxysilylpropylsuccinic acid, and 140.60 g (0.65 mol) of diphenylsilanediol were placed in an oil bath at 40°C, and while stirring, 17.0 g of water was added. An aqueous solution of phosphoric acid in which 2.26 g of phosphoric acid (1.0% by weight based on the monomers charged) was dissolved in 10 g was added using a dropping funnel over a period of 10 minutes. After stirring at 40°C for 1 hour, the oil bath temperature was set to 70°C, stirring was continued for 1 hour, and the temperature of the oil bath was further raised to 115°C over 30 minutes. One hour after the start of heating, the internal temperature of the solution reached 100°C, and from there it was heated and stirred for 2 hours (internal temperature was 100 to 110°C). During the reaction, a total of 52 g of by-products methanol and water were distilled out. PGMEA was added to the obtained polysiloxane PGMEA solution so that the solid content concentration was 65% by weight to obtain a siloxane resin solution (PS-3). In addition, when the Mw of the obtained siloxane resin was measured by GPC, it was 800 (in terms of polystyrene).

[Synthesis example 4]
In a 500 mL three-necked flask, put 103.51 g of PGMEA, 34.85 g (0.15 mol) of 3-methacryloxypropylmethyldimethoxysilane, and 12.32 g (0.15 mol) of 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane. 05 mol), 26.23 g (0.10 mol) of 3-trimethoxysilylpropylsuccinic acid, and 151.42 g (0.70 mol) of diphenylsilanediol were placed in an oil bath at 40°C, and while stirring, water was added to 15.0 mol). A phosphoric acid aqueous solution in which 2.25 g of phosphoric acid (1.0% by weight based on the charged monomer) was dissolved in 30 g was added using a dropping funnel over 10 minutes. After stirring at 40°C for 1 hour, the oil bath temperature was set to 70°C, stirring was continued for 1 hour, and the temperature of the oil bath was further raised to 115°C over 30 minutes. One hour after the start of heating, the internal temperature of the solution reached 100°C, and from there it was heated and stirred for 2 hours (internal temperature was 100 to 110°C). During the reaction, a total of 49 g of by-products methanol and water were distilled out. PGMEA was added to the obtained polysiloxane PGMEA solution so that the solid content concentration was 65% by weight to obtain a siloxane resin solution (PS-4). In addition, when the Mw of the obtained siloxane resin was measured by GPC, it was 800 (in terms of polystyrene).

[Synthesis example 5]
In a 500 mL three-necked flask, 68.42 g of PGMEA, 47.67 g (0.35 mol) of methyltrimethoxysilane, 46.47 g (0.20 mol) of 3-methacryloxypropylmethyldimethoxysilane, 2-(3,4- Prepare 12.32 g (0.05 mol) of epoxycyclohexyl ethyltrimethoxysilane, 26.23 g (0.10 mol) of 3-trimethoxysilylpropylsuccinic acid, and 64.89 g (0.30 mol) of diphenylsilane diol, While immersed in an oil bath at .degree. C. and stirred, a phosphoric acid aqueous solution prepared by dissolving 1.98 g of phosphoric acid (1.0% by weight based on the monomers charged) in 36.00 g of water was added using a dropping funnel over 10 minutes. After stirring at 40°C for 1 hour, the oil bath temperature was set to 70°C, stirring was continued for 1 hour, and the temperature of the oil bath was further raised to 115°C over 30 minutes. One hour after the start of heating, the internal temperature of the solution reached 100°C, and from there it was heated and stirred for 2 hours (internal temperature was 100 to 110°C). During the reaction, a total of 89 g of by-products methanol and water were distilled out. PGMEA was added to the obtained polysiloxane PGMEA solution so that the solid content concentration was 65% by weight to obtain a siloxane resin solution (PS-5). In addition, when Mw of the obtained siloxane resin was measured by GPC, it was 1,000 (polystyrene equivalent).

[Synthesis example 6]
In a 500 mL three-necked flask, 58.78 g of PGMEA, 61.29 g (0.45 mol) of methyltrimethoxysilane, 46.47 g (0.20 mol) of 3-methacryloxypropylmethyldimethoxysilane, 2-(3,4- Prepare 12.32g (0.05mol) of epoxycyclohexyl)ethyltrimethoxysilane, 26.23g (0.10mol) of 3-trimethoxysilylpropylsuccinic acid, and 43.26g (0.20mol) of diphenylsilanediol, While stirring the mixture in an oil bath at .degree. C., a phosphoric acid aqueous solution prepared by dissolving 1.90 g of phosphoric acid (1.0% by weight based on the monomers charged) in 41.40 g of water was added using a dropping funnel over 10 minutes. After stirring at 40°C for 1 hour, the oil bath temperature was set to 70°C, stirring was continued for 1 hour, and the temperature of the oil bath was further raised to 115°C over 30 minutes. One hour after the start of heating, the internal temperature of the solution reached 100°C, and from there it was heated and stirred for 2 hours (internal temperature was 100 to 110°C). During the reaction, a total of 99 g of by-products methanol and water were distilled out. PGMEA was added to the obtained polysiloxane PGMEA solution so that the solid content concentration was 65% by weight to obtain a siloxane resin solution (PS-6). In addition, when the Mw of the obtained siloxane resin was measured by GPC, it was 1,200 (polystyrene equivalent).

[Synthesis example 7]
In a 500 mL three-necked flask, 50.53 g of PGMEA, 74.91 g (0.55 mol) of methyltrimethoxysilane, 34.85 g (0.15 mol) of 3-methacryloxypropylmethyldimethoxysilane, 2-(3,4- Prepare 12.32 g (0.05 mol) of epoxycyclohexyl)ethyltrimethoxysilane, 26.23 g (0.10 mol) of 3-trimethoxysilylpropylsuccinic acid, and 32.45 g (0.15 mol) of diphenylsilane diol, While stirring the mixture in an oil bath at 0.degree. C., a phosphoric acid aqueous solution prepared by dissolving 1.81 g of phosphoric acid (1.0% by weight based on the monomers charged) in 45.00 g of water was added using a dropping funnel over 10 minutes. After stirring at 40°C for 1 hour, the oil bath temperature was set to 70°C, stirring was continued for 1 hour, and the temperature of the oil bath was further raised to 115°C over 30 minutes. One hour after the start of heating, the internal temperature of the solution reached 100°C, and from there it was heated and stirred for 2 hours (internal temperature was 100 to 110°C). During the reaction, a total of 107 g of by-products methanol and water were distilled out. PGMEA was added to the obtained polysiloxane PGMEA solution so that the solid content concentration was 65% by weight to obtain a siloxane resin solution (PS-7). In addition, when the Mw of the obtained siloxane resin was measured by GPC, it was 1,500 (polystyrene equivalent).

[Synthesis example 8]
In a 500 mL three-necked flask, 56.36 g of PGMEA, 34.05 g (0.25 mol) of methyltrimethoxysilane, 46.47 g (0.20 mol) of 3-methacryloxypropylmethyldimethoxysilane, 2-(3,4- 12.32g (0.05mol) of epoxycyclohexyl)ethyltrimethoxysilane, 26.23g (0.10mol) of 3-trimethoxysilylpropylsuccinic acid, 32.45g (0.15mol) of diphenylsilanediol, and dimethyldimethoxy 30.06 g (0.25 mol) of silane was prepared, and 1.82 g of phosphoric acid (1.0% by weight based on the monomers used) was dissolved in 39.60 g of water while stirring in an oil bath at 40°C. The aqueous acid solution was added via dropping funnel over a period of 10 minutes. After stirring at 40°C for 1 hour, the oil bath temperature was set to 70°C, stirring was continued for 1 hour, and the temperature of the oil bath was further raised to 115°C over 30 minutes. One hour after the start of heating, the internal temperature of the solution reached 100°C, and from there it was heated and stirred for 2 hours (internal temperature was 100 to 110°C). During the reaction, a total of 94 g of by-products methanol and water were distilled out. PGMEA was added to the obtained polysiloxane PGMEA solution so that the solid content concentration was 65% by weight to obtain a siloxane resin solution (PS-8). In addition, when Mw of the obtained siloxane resin was measured by GPC, it was 1,400 (polystyrene equivalent).

[Synthesis example 9]
In a 500 mL three-necked flask, 52.02 g of PGMEA, 34.05 g (0.25 mol) of methyltrimethoxysilane, 46.47 g (0.20 mol) of 3-methacryloxypropylmethyldimethoxysilane, 2-(3,4- 12.32g (0.05mol) of epoxycyclohexyl)ethyltrimethoxysilane, 26.23g (0.10mol) of 3-trimethoxysilylpropylsuccinic acid, 21.63g (0.10mol) of diphenylsilane diol, dimethyldimethoxy 36.07 g (0.30 mol) of silane was prepared, and 1.77 g of phosphoric acid (1.0% by weight based on the monomers used) was dissolved in 41.40 g of water while stirring in an oil bath at 40°C. The aqueous acid solution was added via dropping funnel over a period of 10 minutes. After stirring at 40°C for 1 hour, the oil bath temperature was set to 70°C, stirring was continued for 1 hour, and the temperature of the oil bath was further raised to 115°C over 30 minutes. One hour after the start of heating, the internal temperature of the solution reached 100°C, and from there it was heated and stirred for 2 hours (internal temperature was 100 to 110°C). During the reaction, a total of 97 g of by-products methanol and water were distilled out. PGMEA was added to the obtained PGMEA solution of polysiloxane so that the solid content concentration was 65% by weight to obtain a siloxane resin solution (PS-9). The Mw of the obtained siloxane resin was measured by GPC and was found to be 1,500 (in terms of polystyrene).

[Synthesis example 10]
In a 500 mL three-neck flask, 76.10 g of PGMEA, 40.86 g (0.30 mol) of methyltrimethoxysilane, 46.47 g (0.20 mol) of 3-methacryloxypropylmethyldimethoxysilane, 2-(3,4- 24.64 g (0.10 mol) of epoxycyclohexyl ethyltrimethoxysilane and 86.52 g (0.40 mol) of diphenylsilanediol were placed in an oil bath at 40°C, and while stirring, phosphoric acid was added to 28.80 g of water. An aqueous solution of phosphoric acid containing 1.98 g (1.0% by weight based on the monomers charged) was added using a dropping funnel over a period of 10 minutes. After stirring at 40°C for 1 hour, the oil bath temperature was set to 70°C, stirring was continued for 1 hour, and the temperature of the oil bath was further raised to 115°C over 30 minutes. One hour after the start of heating, the internal temperature of the solution reached 100°C, and from there it was heated and stirred for 2 hours (internal temperature was 100 to 110°C). A total of 73 g of methanol and water as by-products were distilled out during the reaction. PGMEA was added to the obtained PGMEA solution of polysiloxane so that the solid content concentration was 65% by weight to obtain a siloxane resin solution (PS-10). In addition, when the Mw of the obtained siloxane resin was measured by GPC, it was 900 (polystyrene equivalent).

[Synthesis example 11]
In a 500 mL three-neck flask, add 104.52 g of PGMEA, 46.47 g (0.20 mol) of 3-methacryloxypropylmethyldimethoxysilane, and 12.32 g (0.20 mol) of 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane. 05 mol), 13.12 g (0.05 mol) of 3-trimethoxysilylpropylsuccinic acid, and 151.42 g (0.70 mol) of diphenylsilanediol were placed in an oil bath at 40°C, and while stirring, water was added to 13.12 g (0.05 mol). An aqueous solution of phosphoric acid in which 2.23 g of phosphoric acid (1.0% by weight based on the charged monomer) was dissolved in 50 g was added using a dropping funnel over a period of 10 minutes. After stirring at 40°C for 1 hour, the oil bath temperature was set to 70°C, stirring was continued for 1 hour, and the temperature of the oil bath was further raised to 115°C over 30 minutes. One hour after the start of heating, the internal temperature of the solution reached 100°C, and from there it was heated and stirred for 2 hours (internal temperature was 100 to 110°C). During the reaction, a total of 44 g of by-products methanol and water were distilled out. PGMEA was added to the obtained PGMEA solution of polysiloxane so that the solid content concentration was 65% by weight to obtain a siloxane resin solution (PS-11). In addition, when the Mw of the obtained siloxane resin was measured by GPC, it was 600 (polystyrene equivalent).

[Synthesis example 12]
In a 500 mL three-neck flask, 42.27 g of PGMEA, 88.53 g (0.65 mol) of methyltrimethoxysilane, 23.24 g (0.10 mol) of 3-methacryloxypropylmethyldimethoxysilane, 2-(3,4- Prepare 12.32 g (0.05 mol) of epoxycyclohexyl ethyltrimethoxysilane, 26.23 g (0.10 mol) of 3-trimethoxysilylpropylsuccinic acid, and 21.63 g (0.10 mol) of diphenylsilane diol, While stirring in an oil bath at 0.degree. C., a phosphoric acid aqueous solution prepared by dissolving 1.72 g of phosphoric acid (1.0% by weight based on the monomers charged) in 48.60 g of water was added using a dropping funnel over 10 minutes. After stirring at 40°C for 1 hour, the oil bath temperature was set to 70°C, stirring was continued for 1 hour, and the temperature of the oil bath was further raised to 115°C over 30 minutes. One hour after the start of heating, the internal temperature of the solution reached 100°C, and from there it was heated and stirred for 2 hours (internal temperature was 100 to 110°C). During the reaction, a total of 114 g of by-products methanol and water were distilled out. PGMEA was added to the obtained polysiloxane PGMEA solution so that the solid content concentration was 65% by weight to obtain a siloxane resin solution (PS-12). In addition, when Mw of the obtained siloxane resin was measured by GPC, it was 3,000 (polystyrene equivalent).

[Synthesis example 13]
In a 500 mL three-necked flask, 32.63 g of PGMEA, 102.15 g (0.75 mol) of methyltrimethoxysilane, 23.24 g (0.10 mol) of 3-methacryloxypropylmethyldimethoxysilane, 2-(3,4- 12.32 g (0.05 mol) of epoxycyclohexyl)ethyltrimethoxysilane and 26.23 g (0.10 mol) of 3-trimethoxysilylpropylsuccinic acid were placed in an oil bath at 40°C, and while stirring, 54 g of water was added. A phosphoric acid aqueous solution in which 1.64 g of phosphoric acid (1.0% by weight based on the monomers charged) was dissolved in 1.00 g of the monomer was added using a dropping funnel over a period of 10 minutes. After stirring at 40°C for 1 hour, the oil bath temperature was set to 70°C, stirring was continued for 1 hour, and the temperature of the oil bath was further raised to 115°C over 30 minutes. One hour after the start of heating, the internal temperature of the solution reached 100°C, and from there it was heated and stirred for 2 hours (internal temperature was 100 to 110°C). During the reaction, a total of 114 g of by-products methanol and water were distilled out. PGMEA was added to the obtained PGMEA solution of polysiloxane so that the solid content concentration was 65% by weight to obtain a siloxane resin solution (PS-13). In addition, when Mw of the obtained siloxane resin was measured by GPC, it was 5,000 (polystyrene equivalent).

[Synthesis example 14]
In a 500 mL three-necked flask, 64.29 g of PGMEA, 61.29 g (0.45 mol) of methyltrimethoxysilane, 12.32 g (0.05 mol) of 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3 - Prepare 26.23 g (0.10 mol) of trimethoxysilylpropylsuccinic acid and 86.52 g (0.40 mol) of diphenylsilanediol, and add phosphoric acid to 34.20 g of water while stirring in an oil bath at 40°C. An aqueous solution of phosphoric acid in which 1.86 g (1.0% by weight based on the monomers charged) was dissolved was added using a dropping funnel over a period of 10 minutes. After stirring at 40°C for 1 hour, the oil bath temperature was set to 70°C, stirring was continued for 1 hour, and the temperature of the oil bath was further raised to 115°C over 30 minutes. One hour after the start of heating, the internal temperature of the solution reached 100°C, and from there it was heated and stirred for 2 hours (internal temperature was 100 to 110°C). During the reaction, a total of 86 g of by-products methanol and water were distilled out. PGMEA was added to the obtained polysiloxane PGMEA solution so that the solid content concentration was 65% by weight to obtain a siloxane resin solution (PS-14). In addition, when the Mw of the obtained siloxane resin was measured by GPC, it was 1,200 (polystyrene equivalent).

[Synthesis example 15]
A 500 ml flask was charged with 3 g of 2,2'-azobis(isobutyronitrile) and 50 g of PGMEA. Thereafter, 30 g of methacrylic acid, 35 g of benzyl methacrylate, and 35 g of tricyclo[5.2.1.02,6]decane-8-yl methacrylate were charged, stirred for a while at room temperature, and after purging the inside of the flask with nitrogen, 70°C The mixture was heated and stirred for 5 hours. Next, 15 g of glycidyl methacrylate, 1 g of dimethylbenzylamine, 0.2 g of p-methoxyphenol, and 100 g of PGMEA were added to the obtained solution, and the mixture was heated and stirred at 90° C. for 4 hours. PGMEA was added to the obtained PGMEA solution of the acrylic resin so that the solid content concentration was 50% by weight to obtain an acrylic resin solution (PA-1). The Mw of the obtained acrylic resin was measured by GPC and was found to be 10,000. Moreover, the acid value of the obtained acrylic resin was 118 mgKOH/g.

[Example 1]
First, the following raw materials were mixed and stirred under a yellow light.
1,2-octanedione, 1-[4-(phenylthio)-2-(O-benzoyloxime)] (trade name: "Irgacure" (registered trademark) OXE01, manufactured by BASF (hereinafter referred to as OXE-01). )) 0.96 g was dissolved in 31.62 g of PGMEA as an organic solvent.
As a surfactant, 0.30 g of a 10% by weight PGMEA solution of a fluorine-based surfactant (trade name "F-477" manufactured by DIC Corporation) was used.
0.96 g of a silane coupling agent (trade name "KBM-303" manufactured by Shin-Etsu Chemical Co., Ltd.) as an adhesion improver.
9.61 g of p-nonylphenol EO modified acrylate (trade name "M-113" manufactured by Toagosei Co., Ltd.).
4.80 g of N-methoxymethylacrylamide (trade name "Wasmer 2MA" manufactured by Kasano Kosan Co., Ltd.).
51.74 g of the siloxane resin solution (PS-1) obtained in Synthesis Example 1.
Next, filtration was performed using a 1.0 μm filter to prepare a photosensitive resin composition A-1 having a solid content concentration of 50% by weight.
A cured film of the obtained photosensitive resin composition A-1 was prepared by the method described above, and evaluated by the method described above.

[Example 2]
Photosensitive resin composition A-2 was prepared in the same manner as in Example 1 except that siloxane resin solution (PS-2) was used instead of siloxane resin solution (PS-1). Evaluation was performed in the same manner as in Example 1 using the obtained photosensitive resin composition A-2.

[Example 3]
Photosensitive resin composition A-3 was prepared in the same manner as in Example 1 except that siloxane resin solution (PS-3) was used instead of siloxane resin solution (PS-1). Evaluation was performed in the same manner as in Example 1 using the obtained photosensitive resin composition A-3.

[Example 4]
Photosensitive resin composition A-4 was prepared in the same manner as in Example 1 except that siloxane resin solution (PS-4) was used instead of siloxane resin solution (PS-1). Evaluation was performed in the same manner as in Example 1 using the obtained photosensitive resin composition A-4.

[Example 5]
Photosensitive resin composition A-5 was prepared in the same manner as in Example 1 except that siloxane resin solution (PS-5) was used instead of siloxane resin solution (PS-1). Evaluation was performed in the same manner as in Example 1 using the obtained photosensitive resin composition A-5.

[Example 6]
Photosensitive resin composition A-6 was prepared in the same manner as in Example 1 except that siloxane resin solution (PS-6) was used instead of siloxane resin solution (PS-1). Evaluation was performed in the same manner as in Example 1 using the obtained photosensitive resin composition A-6.

[Example 7]
Photosensitive resin composition A-7 was prepared in the same manner as in Example 1 except that siloxane resin solution (PS-7) was used instead of siloxane resin solution (PS-1). Evaluation was performed in the same manner as in Example 1 using the obtained photosensitive resin composition A-7.

[Example 8]
A photosensitive resin composition A-8 was prepared in the same manner as in Example 1, except that a siloxane resin solution (PS-8) was used instead of the siloxane resin solution (PS-1). Evaluation was performed in the same manner as in Example 1 using the obtained photosensitive resin composition A-8.

[Example 9]
Photosensitive resin composition A-9 was prepared in the same manner as in Example 1 except that siloxane resin solution (PS-9) was used instead of siloxane resin solution (PS-1). Evaluation was performed in the same manner as in Example 1 using the obtained photosensitive resin composition A-9.

[Example 10]
Photosensitive resin composition A-10 was prepared in the same manner as in Example 1 except that siloxane resin solution (PS-10) was used instead of siloxane resin solution (PS-1). Evaluation was performed in the same manner as in Example 1 using the obtained photosensitive resin composition A-10.

[Example 11]
Photosensitive resin composition A-11 was prepared in the same manner as in Example 1 except that Nn-butoxymethylacrylamide (trade name "Wasmer A" manufactured by Kasano Kosan Co., Ltd.) was used instead of N-methoxymethylacrylamide. Prepared. Evaluation was performed in the same manner as in Example 1 using the obtained photosensitive resin composition A-11.

[Example 12]
Photosensitive resin composition A-12 was prepared in the same manner as in Example 1, except that N-i-butoxymethylacrylamide (trade name "Wasmer IBM" manufactured by Kasano Kosan Co., Ltd.) was used instead of N-methoxymethylacrylamide. Prepared. Evaluation was performed in the same manner as in Example 1 using the obtained photosensitive resin composition A-12.

[Example 13]
Photosensitive resin composition A-13 was prepared in the same manner as in Example 1, except that N-methoxymethylmethacrylamide (trade name "Wasmer 3MA" manufactured by Kasano Kosan Co., Ltd.) was used instead of N-methoxymethylacrylamide. did. Evaluation was performed in the same manner as in Example 1 using the obtained photosensitive resin composition A-13.

[Example 14]
Photosensitive resin composition A-14 was prepared in the same manner as in Example 1, except that Nn-butoxymethylmethacrylamide (trade name "Wasmer NBMM" manufactured by Kasano Kosan Co., Ltd.) was used instead of N-methoxymethylacrylamide. was prepared. Evaluation was performed in the same manner as in Example 1 using the obtained photosensitive resin composition A-14.

[Example 15]
Examples except that phenol EO modified acrylate (trade name "M-102" manufactured by Toagosei Co., Ltd.) was used instead of p-nonylphenol EO modified acrylate (trade name "M-113" manufactured by Toagosei Co., Ltd.) Photosensitive resin composition A-15 was prepared in the same manner as in Example 1. Evaluation was performed in the same manner as in Example 1 using the obtained photosensitive resin composition A-15.

[Example 16]
Except for using p-nonylphenol EO modified acrylate (trade name "FA-318A" manufactured by Hitachi Chemical Co., Ltd.) instead of p-nonylphenol EO modified acrylate (trade name "M-113" manufactured by Toagosei Co., Ltd.) A photosensitive resin composition A-16 was prepared in the same manner as in Example 1. Evaluation was performed in the same manner as in Example 1 using the obtained photosensitive resin composition A-16.

[Comparative example 1]
Photosensitive resin composition A-17 was prepared in the same manner as in Example 1 except that siloxane resin solution (PS-11) was used instead of siloxane resin solution (PS-1). Evaluation was performed in the same manner as in Example 1 using the obtained photosensitive resin composition A-17.

[Comparative example 2]
Photosensitive resin composition A-18 was prepared in the same manner as in Example 1, except that siloxane resin solution (PS-12) was used instead of siloxane resin solution (PS-1). Evaluation was performed in the same manner as in Example 1 using the obtained photosensitive resin composition A-18.

[Comparative example 3]
Photosensitive resin composition A-19 was prepared in the same manner as in Example 1 except that siloxane resin solution (PS-13) was used instead of siloxane resin solution (PS-1). Evaluation was performed in the same manner as in Example 1 using the obtained photosensitive resin composition A-19.

[Comparative example 4]
Photosensitive resin composition A-20 was prepared in the same manner as in Example 1 except that siloxane resin solution (PS-14) was used instead of siloxane resin solution (PS-1). Evaluation was performed in the same manner as in Example 1 using the obtained photosensitive resin composition A-20.

[Comparative example 5]
Photosensitization was carried out in the same manner as in Example 1, except that the amount of p-nonylphenol EO-modified acrylate (trade name "M-113" manufactured by Toagosei Co., Ltd.) was increased to 14.41 g instead of N-methoxymethylacrylamide. A resin composition A-21 was prepared. Evaluation was performed in the same manner as in Example 1 using the obtained photosensitive resin composition A-21.

[Comparative example 6]
A photosensitive resin composition A- 22 was prepared. Evaluation was performed in the same manner as in Example 1 using the obtained photosensitive resin composition A-22.

[Comparative example 7]
Photosensitive resin composition A-23 was prepared in the same manner as in Example 1 except that acrylamide was used instead of N-methoxymethylacrylamide. Evaluation was performed in the same manner as in Example 1 using the obtained photosensitive resin composition A-23.

[Comparative example 8]
Photosensitive resin composition A-24 was prepared in the same manner as in Example 1 except that N-vinylacetamide was used instead of N-methoxymethylacrylamide. Evaluation was performed in the same manner as in Example 1 using the obtained photosensitive resin composition A-24.

[Comparative Example 9]
Photosensitive resin composition A-25 was prepared in the same manner as in Example 1, except that bisallylnadimide (trade name "BANI-M" manufactured by Maruzen Petrochemical Co., Ltd.) was used instead of N-methoxymethylacrylamide. did. Evaluation was performed in the same manner as in Example 1 using the obtained photosensitive resin composition A-25.

[Comparative Example 10]
Photosensitive resin composition A-26 was prepared in the same manner as in Example 1 except that isocyanuric acid EO modified triacrylate (trade name "M-315" manufactured by Toagosei Co., Ltd.) was used instead of N-methoxymethylacrylamide. Prepared. Evaluation was performed in the same manner as in Example 1 using the obtained photosensitive resin composition A-26.

[Comparative Example 11]
A photosensitive resin composition was prepared in the same manner as in Example 1, except that dipentaerythritol hexaacrylate (trade name "Kayarad" (registered trademark) DPHA, manufactured by Nippon Kayaku Co., Ltd.) was used instead of N-methoxymethylacrylamide. Product A-27 was prepared. Evaluation was performed in the same manner as in Example 1 using the obtained photosensitive resin composition A-27.

[Comparative example 12]
Photosensitive resin composition A-28 was prepared in the same manner as in Example 1 except that the acrylic resin solution (PA-1) was used instead of the siloxane resin solution (PS-1). Evaluation was performed in the same manner as in Example 1 using the obtained photosensitive resin composition A-28.

The compositions of the resin compositions in each example and comparative example are shown in Tables 1 and 2, and the evaluation results are shown in Table 3.

According to the photosensitive resin composition prepared in the examples, a pattern with excellent resolution can be formed even in a thick film of 10 μm or more, and it has high transparency and low film stress, and has molybdenum, aluminum, Alternatively, it can be seen that a photosensitive resin composition having high adhesiveness to a metal layer containing nickel can be provided.

According to the photosensitive resin composition of the present invention, it is possible to form a pattern with excellent resolution even in a thick film of 10 μm or more, and it has high transparency and low film stress. Since it is possible to provide a photosensitive resin composition that has high adhesion to metal layers containing It can be particularly suitably used in devices.

Claims (15)

Contains an organosilane unit (D unit) represented by (A) (R) ₂ SiO ₂ / ₂ (R is a hydrogen atom or an organic group) in an amount of 30 mol% or more and 85 mol% or less based on the total organosilane units, and is capable of radical polymerization. siloxane resin having a functional group,
(B) N-substituted (meth)acrylamide derivative,
(C) radical photopolymerization initiator,
A photosensitive resin composition containing. The photosensitive resin composition according to claim 1, wherein the siloxane resin (A) contains 15 mol% or more and 65 mol% or less of organosilane units having a diphenyl group. The photosensitive resin composition according to claim 1, wherein the siloxane resin (A) has a radically polymerizable group, a carboxyl group, and/or a dicarboxylic acid anhydride group. The photosensitive resin composition according to any one of claims 1 to 3, wherein the (B) N-substituted (meth)acrylamide derivative is an N-monosubstituted (meth)acrylamide derivative. The photosensitive resin composition according to any one of claims 1 to 4, wherein the (B) N-substituted (meth)acrylamide derivative is represented by the following general formula (1).

(In the above general formula (1), R ¹ represents a hydrogen atom or a methyl group, R ² represents an alkylene group, and R ³ represents an alkyl group.) The photosensitive resin composition according to any one of claims 1 to 5, which contains (D) a monofunctional (meth)acrylate in addition to the (B) N-substituted (meth)acrylamide derivative. The photosensitive resin composition according to any one of claims 1 to 6, wherein the monofunctional (meth)acrylate (D) contains a phenol structure. The photosensitive resin composition according to any one of claims 1 to 7, wherein the monofunctional (meth)acrylate (D) is represented by the following general formula (2) and/or (3).

(In the above general formula (2), R ⁴ represents a hydrogen atom or a methyl group, R ⁵ represents an alkylene group, X represents a hydrogen atom, an alkyl group or a phenyl group, and m represents a positive integer. .)

(In the above general formula (3), R ⁶ represents a hydrogen atom or a methyl group, R ⁷ represents an alkylene group, and n represents a positive integer.) The photosensitive resin composition according to claim 8, wherein m and n of the monofunctional (meth)acrylate represented by the general formula (2) and/or (3) are each 4 or more. A cured film obtained by curing the photosensitive resin composition according to any one of claims 1 to 9. The cured film according to claim 10, wherein the film stress is 0.01 MPa or more and 10 MPa or less. The cured film according to claim 10, wherein the film stress is 0.01 MPa or more and 10 MPa or less, and the film thickness is 10 μm or more and 100 μm or less. The cured film according to claim 10, having a film stress of 0.01 MPa or more and 10 MPa or less, a film thickness of 10 μm or more and 100 μm or less, and a transmittance at a wavelength of 550 nm of 90% or more and 100% or less. A solid-state image sensor or fingerprint authentication device comprising the cured film according to any one of claims 10 to 13. The solid-state image sensor or fingerprint authentication device according to claim 14, wherein the wiring and/or the light shielding layer is a metal layer containing molybdenum, aluminum, or nickel.