JP7826767B2 - Photosensitive resin composition and cured film - Google Patents

Description

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

Biometric authentication is essential for unlocking and other identity authentication purposes on various mobile display devices such as smartphones and tablet PCs (personal computers). Fingerprint authentication, in particular, is installed on many devices because it is inexpensive, compact, and highly convenient.
Traditionally, it was common for a capacitive fingerprint authentication device to be mounted on the bezel of a display (around the periphery of the display). However, with the trend toward full-screen displays in smartphones, the bezel where the fingerprint authentication device was previously mounted tends to disappear. This has made it necessary to install the fingerprint authentication device below the display (this configuration is called the "under-display type").
The authentication methods for under-display fingerprint authentication devices include optical and ultrasonic methods, but the optical method in particular is becoming mainstream due to its versatility, as it can be applied not only to organic light-emitting diode (hereinafter abbreviated as OLED) displays but also to liquid crystal displays and the like.
Regarding such under-display fingerprint authentication devices, a thin optical under-display fingerprint authentication device has been proposed that has high authentication accuracy and can be installed in a very narrow space between the battery and the screen (see, for example, Patent Documents 1 and 2).

The optical under-display fingerprint authentication device described in Patent Document 2 is composed of a substrate, a sensor, a light-shielding layer, a transparent medium layer, and a microlens. Methods for forming the transparent medium layer include a method of forming it by screen printing and a method of forming it by photolithography using a photosensitive material, but the latter method has attracted attention because it excels in positional accuracy and dimensional accuracy, which are important for improving authentication accuracy.
Compared to microlenses used in CMOS image sensors, etc., the diameter of microlenses used in fingerprint authentication devices is generally larger, and therefore the focal length, which is the distance from the center of the microlens to the image sensor, is also longer. Therefore, the transparent medium layer formed between the microlens and the image sensor needs to be approximately 10 μm to 100 μm thick, and there is a demand for a material that is excellent for pattern formation of thick films with a thickness of 10 μm or more, and that also has low film stress in the cured film to suppress warping of the substrate.
Furthermore, TFT production lines are often used as production lines for manufacturing fingerprint authentication devices, and metal layers containing molybdenum, aluminum, or nickel are generally used as light-shielding layers or sensor lead wiring in fingerprint authentication devices, so excellent adhesion to the metal layers is also required.

A photosensitive resin composition containing a specific alkali-soluble silicone resin or the like has been disclosed as a photosensitive material that has heat resistance, transparency, crack resistance, and thermal shock test resistance in a thick film (see, for example, Patent Document 3). However, this composition has poor adhesion to metal layers containing molybdenum, aluminum, or nickel, and in the case of thick films exceeding 10 μm in thickness used in fingerprint authentication devices, there is a problem that warping occurs in the substrate due to film stress of the cured film.
As a photosensitive material having excellent adhesion to glass substrates and metal substrates and excellent chemical resistance, a photosensitive resin composition containing polysiloxane, a photosensitizer, a polymerizable compound having a phosphorus atom, and a silane compound having a ureido group (see, for example, Patent Document 4) has been disclosed. However, in the case of a thick film having a thickness exceeding 10 μm, there is a similar problem in that the film stress of the cured film causes warping of the substrate.

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

The present invention was devised in light of these problems with the prior art, and aims to provide a photosensitive resin composition that is capable of forming patterns with excellent resolution even in thick films with a thickness of 10 μm or more, and that has high transparency, low film stress, and high adhesion to metal layers containing molybdenum, aluminum, or nickel.

The object of the present invention is achieved by the following constitution: A photosensitive resin composition comprising the following (A) to (C): (A) a siloxane resin containing organosilane units (D units) represented by (R) ₂ SiO _2/2 (R is a hydrogen atom or an organic group), in which the proportion of the D units is 30 mol % to 85 mol % based on the total organosilane units, and having a radical polymerizable group; (B) an N-substituted (meth)acrylamide derivative; and (C) a photoradical polymerization initiator.

The photosensitive resin composition of the present invention makes it possible to form patterns with excellent resolution even in thick films with a thickness of 10 μm or more, and to provide cured films that have high transparency, low film stress, and high adhesion to metal layers containing molybdenum, aluminum, or nickel.

The present invention will be described in further detail below.
The photosensitive resin composition of the present invention is a photosensitive resin composition containing the following (A) to (C):
(A) a siloxane resin containing organosilane units (D units) represented by (R)2SiO2 _{/ 2} (R is a hydrogen atom or an organic group), in which the proportion of D units is 30 mol% or more and 85 mol% or less based on the total organosilane units, and having a radical polymerizable group (hereinafter, this may be simply abbreviated as (A) siloxane resin);
(B) N-substituted (meth)acrylamide derivatives,
(C) a photoradical polymerization initiator.

By containing (A) a siloxane resin, (B) an N-substituted (meth)acrylamide derivative, and (C) a photopolymerization initiator, radical polymerization of the radically polymerizable groups of the (A) siloxane resin and the (B) N-substituted (meth)acrylamide derivative proceeds in the light-irradiated areas, thereby enabling negative pattern processing in which the light-irradiated areas become insolubilized.
By including the (A) siloxane resin, it is possible to form a cured film with high transparency and excellent heat resistance and weather resistance. This is because the (A) siloxane resin has a siloxane skeleton in the main chain. Furthermore, since the proportion of D units is 30 mol% or more and 85 mol% or less relative to the total organosilane units, it is possible to moderately suppress three-dimensional crosslinking while maintaining sufficient chemical resistance to acids and alkalis, and it is possible to form a cured film with low film stress.

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

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

Examples of radically polymerizable groups include vinyl groups, α-methylvinyl groups, allyl groups, styryl groups, and (meth)acryloyl groups. From the perspective of further improving the pencil hardness of the cured film and the sensitivity during pattern processing, (meth)acryloyl groups are preferred.

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

(A) The siloxane resin may be a hydrolysis condensate of the aforementioned organosilane compound having a radical polymerizable group with another organosilane compound. Examples of other organosilane compounds include methyltrimethoxysilane, methyltriethoxysilane, methyltri(methoxyethoxy)silane, methyltripropoxysilane, methyltriisopropoxysilane, methyltributoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, hexyltrimethoxysilane, octadecyltrimethoxysilane, octadecyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, 3-aminopropyltriethoxysilane, N-(2-aminoethyl)-3-aminopropyltrimethoxysilane, 3-chloropropyltrimethoxysilane, 3-(N,N-diglycidyl)aminopropyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, and 3-aminopropyltrimethoxysilane. Silane, 3-aminopropyltriethoxysilane, N-2-(aminoethyl)-3-aminopropyltrimethoxysilane, 2-cyanoethyltriethoxysilane, glycidoxymethyltrimethoxysilane, glycidoxymethyltriethoxysilane, 1-glycidoxyethyltrimethoxysilane, 1-glycidoxyethyltriethoxysilane, 2-glycidoxyethyltrimethoxysilane, 2-glycidoxyethyltriethoxysilane, 1-glycidoxypropyltrimethoxysilane, 1-glycidoxypropyltriethoxysilane, 2-glycidoxypropyltrimethoxysilane, 2-glycidoxypropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropyltripropoxysilane , 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)ethyltripropoxysilane (3,4-epoxycyclohexyl)ethyltributoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltriethoxysilane, 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-glycidoxypropylmethyldimethoxysilane, 3-aminopropylmethyldimethoxysilane, 3-aminopropylmethyldimethoxysilane, Aminopropylmethyldiethoxysilane, N-(2-aminoethyl)-3-aminopropylmethyldimethoxysilane, glycidoxymethyldimethoxysilane, glycidoxymethylmethyldiethoxysilane, 1-glycidoxyethylmethyldimethoxysilane, 1-glycidoxyethylmethyldiethoxysilane, 2-glycidoxyethylmethyldimethoxysilane, 2-glycidoxyethylmethyldiethoxysilane, 1-glycidoxypropylmethyldimethoxysilane, 1-glycidoxypropylmethyldiethoxysilane, 2-glycidoxypropylmethyldimethoxysilane, 2-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropylmethyldipropoxysilane Silane, 2-glycidoxypropylmethyldibutoxysilane, 3-glycidoxypropylmethyldi(methoxyethoxy)silane, 3-glycidoxypropylethyldimethoxysilane, 3-glycidoxypropylethyldiethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropylmethyldiethoxysilane, cyclohexylmethyldimethoxysilane, octadecylmethyldimethoxysilane, tetramethoxysilane, tetraethoxysilane, trifluoromethyltrimethoxysilane, trifluoromethyltriethoxysilane, trifluoropropyltrimethoxysilane, trifluoropropyltriethoxysilane, perfluoropropyltrimethoxysilane, perfluoropropyltriethoxysilane, perfluoropentyltrimethoxysilane, perfluoro Pentyltriethoxysilane, tridecafluorooctyltrimethoxysilane, tridecafluorooctyltriethoxysilane, tridecafluorooctyltripropoxysilane, tridecafluorooctyltriisopropoxysilane, heptadecafluorodecyltrimethoxysilane, heptadecafluorodecyltriethoxysilane, bis(trifluoromethyl)dimethoxysilane, bis(trifluoropropyl)dimethoxysilane, bis(trifluoropropyl)diethoxysilane, trifluoropropylmethyldimethoxysilane, trifluoropropylmethyldiethoxysilane, trifluoropropylethyldimethoxysilane, trifluoropropylethyldiethoxysilane, heptadecafluorodecylmethyldimethoxysilane, 3-trimethoxysilylpropylsuccinic acid Anhydride, 3-triethoxysilylpropyl succinic anhydride, 3-triphenoxysilylpropyl succinic anhydride, 3-trimethoxysilylpropyl cyclohexyl dicarboxylic anhydride, 3-trimethoxysilylpropyl phthalic anhydride, 1-naphthyltrimethoxysilane, 1-naphthyltriethoxysilane, 1-naphthyltri-n-propoxysilane, 2-naphthyltrimethoxysilane, 1-anthracenyltrimethoxysilane, 9-anthracenyltrimethoxysilane, 9-phenanthrenyltrimethoxysilane, 9-fluorenyltrimethoxysilane, 2-fluorenyltrimethoxysilane, 2-fluorenonyltrimethoxysilane, 1-pyrenyltrimethoxysilane, 2-indenyltrimethoxysilane, 5-acenaphthenyltrimethoxysilane, etc. Two or more of these may be used. Among these, from the viewpoint of improving the crack resistance of the cured film, it is preferable that the (A) siloxane resin contain 15 mol% or more of organosilane units having a diphenyl group, and from the viewpoint of suppressing residue during development, improving resolution, and improving adhesion to the substrate, metal layer, and resin layer, it is preferable that the (A) siloxane resin contain 65 mol% or less of organosilane units having a diphenyl group.

In addition, from the viewpoints of suppressing residues during development, improving resolution, and improving adhesion to the substrate, metal layer, and resin layer, organosilane compounds having a carboxyl group and/or a dicarboxylic acid anhydride structure, such as 3-trimethoxysilylpropyl succinic anhydride, 3-triethoxysilylpropyl succinic anhydride, 3-triphenoxysilylpropyl succinic anhydride, 3-trimethoxysilylpropyl cyclohexyl dicarboxylic anhydride, and 3-trimethoxysilylpropyl phthalic anhydride, are preferred.

The siloxane resin (A) can be obtained by hydrolysis and condensation of an organosilane compound, for example, by hydrolyzing an organosilane compound and then condensing the resulting silanol compound in the presence of an organic solvent or without a solvent.
The various conditions for the hydrolysis reaction can be appropriately set taking into consideration the reaction scale, size, shape, etc. of the reaction vessel. For example, it is preferable to add an acid catalyst and water to an organosilane compound in a solvent over 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, a 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. The acid catalyst is preferably an acidic aqueous solution containing formic acid, acetic acid, phosphoric acid, or nitric acid. The amount of acid catalyst added is preferably 0.05 to 5 parts by weight per 100 parts by weight of the total organosilane compounds used in the hydrolysis reaction. By using the acid catalyst in this amount within the above range, the hydrolysis reaction can proceed more efficiently.
After obtaining the silanol compound by the hydrolysis reaction of the organosilane compound, the reaction solution is preferably heated as is at 50°C or higher and below the boiling point of the solvent for 1 to 100 hours to carry out the condensation reaction. In addition, reheating or the addition of a base catalyst may be carried out to increase the degree of polymerization of the siloxane resin.

Organic solvents used in the hydrolysis reaction of organosilane compounds and the condensation reaction of silanol compounds include, for example, alcohols such as methanol, ethanol, propanol, isopropanol, butanol, isobutanol, t-butanol, pentanol, 4-methyl-2-pentanol, 3-methyl-2-butanol, 3-methyl-3-methoxy-1-butanol, 1-t-butoxy-2-propanol, and 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, and ethylene glycol monomethyl ether. Examples of suitable solvents include ethers such as ethylene glycol dibutyl ether and diethyl ether; ketones such as methyl ethyl ketone, acetylacetone, methyl propyl ketone, methyl butyl ketone, methyl isobutyl ketone, diisobutyl ketone, cyclopentanone, and 2-heptanone; amides such as dimethylformamide and dimethylacetamide; acetates such as 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, and butyl lactate; aromatic or aliphatic hydrocarbons such as toluene, xylene, hexane, and cyclohexane; γ-butyrolactone, N-methyl-2-pyrrolidone, and dimethyl sulfoxide. Two or more of these may be used. From the standpoint of the transmittance and crack resistance of the cured film, 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, etc. are preferred.

When a solvent is produced by the hydrolysis reaction, it is possible to carry out the hydrolysis without a solvent. After the reaction is completed, it is also preferable to add a solvent to adjust the concentration to an appropriate level for the resin composition. Depending on the purpose, after the hydrolysis, an appropriate amount of the produced alcohol may be distilled and removed under heating and/or reduced pressure, and then a suitable solvent may be added.
The amount of solvent used in the hydrolysis reaction is preferably 80 parts by weight or more and 500 parts by weight or less per 100 parts by weight of the total organosilane compounds. By setting the amount of solvent within this range, the hydrolysis reaction can proceed more efficiently.
The water used in the hydrolysis reaction is preferably ion-exchanged water, and the amount of water is preferably 1.0 to 4.0 moles per mole of silane atom.

The photosensitive resin composition of the present invention contains (B) an N-substituted (meth)acrylamide derivative. The N-substituted (meth)acrylamide derivative is a general term for N-alkylacrylamide, N-allylacrylamide, acryloylmorpholine, N-alkylmethacrylamide, N-allylmethacrylamide, N,N-dialkylacrylamide, N,N-diallylacrylamide, N-alkyl,N-allylacrylamide, N,N-dialkylmethacrylamide, N,N-diallylmethacrylamide, N-alkyl,N-allylmethacrylamide, and derivatives thereof.
Specific examples include N-methylacrylamide, N-ethylacrylamide, N-n-propylacrylamide, N-isopropylacrylamide, N-cyclopropylacrylamide, N-hydroxyethylacrylamide, N-methylolacrylamide methyl ether, N-methylolacrylamide ethyl ether, N-methylolacrylamide propyl ether, N-methylolacrylamide butyl ether, N-methoxymethylacrylamide, N-butoxymethylacrylamide, N,N'-methylenebisacrylamide, acryloylmorpholine, diacetone acrylamide, N-methylmethacryl ... Examples of the acrylic acid ester include acrylamide, N-ethyl methacrylamide, N-n-propyl methacrylamide, N-isopropyl methacrylamide, N-cyclopropyl methacrylamide, N-methoxymethyl methacrylamide, N-butoxymethyl methacrylamide, N,N'-methylenebismethacrylamide, diacetone methacrylamide, N,N-dimethyl acrylamide, N,N-diethyl acrylamide, N-methyl,N-ethyl acrylamide, N,N-dimethyl methacrylamide, N,N-diethyl methacrylamide, N,N-dimethylaminopropyl acrylamide, and N-methyl,N-ethyl methacrylamide. Two or more of these may be used.
Among these, from the viewpoint of improving adhesion to a metal layer containing molybdenum, aluminum, or nickel, N-monosubstituted (meth)acrylamide derivatives are preferred, and among these, N-alkoxyalkylacrylamides and N-alkoxyalkylmethacrylamides as represented by the following general formula (1) are more preferred.

(In the above general formula (1), ^R1 represents a hydrogen atom or a methyl group, ^R2 represents an alkylene group, and ^R3 represents an alkyl group.)
The content of the N-substituted (meth)acrylamide derivative (B) in the photosensitive resin composition of the present invention is preferably 1% by weight or more, and more preferably 2% by weight or more, of the solid content from the viewpoint of improving adhesion to a metal layer using a Mo alloy, an Al alloy, or a Ni alloy, and is preferably 30% by weight or less, and more preferably 25% by weight or less, of the solid content from the viewpoint of increasing the hydrophobicity of the cured film and further improving the chemical resistance.

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

Specific examples of the acylphosphine oxide compound include 2,4,6-trimethylbenzoylphenylphosphine oxide, bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide, bis(2,6-dimethoxybenzoyl)-(2,4,4-trimethylpentyl)-phosphine oxide, and the like.
Specific examples of the oxime ester compound 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-(O-acetyloxime), and the like.

Specific examples of benzophenone compounds having an amino group include 4,4-bis(dimethylamino)benzophenone, 4,4-bis(diethylamino)benzophenone, and the like.
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) photoradical polymerization initiator in the photosensitive resin composition of the present invention is preferably 0.01% by weight or more, and more preferably 0.1% by weight or more, of the solid content from the viewpoint of sufficiently promoting radical polymerization and improving the pencil hardness of the cured film, and is preferably 20% by weight or less, and more preferably 15% by weight or less, from the viewpoint of improving the transparency of the cured film.
The photosensitive resin composition of the present invention preferably contains (D) a monofunctional (meth)acrylate in addition to (B) the N-substituted (meth)acrylamide derivative.

Specific examples of the monofunctional (meth)acrylate (D) 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, and 2-phenoxyethyl (meth)acrylate. 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, dimethylaminoethyl(meth)acrylate, diethylaminoethyl(meth)acrylate, 2-methoxyethyl(meth)acrylate, 2-ethoxyethyl(meth)acrylate, 3-methoxybutyl(meth)acrylate, 2-(meth)acryloyloxyethyl succinate, N-(meth)acryloyloxyethylhexahydrophthalimide, trifluoroethyl(meth)acrylate, ethyl carbitol(meth)acrylate, ethoxydi Examples include ethylene 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, o-phenylphenol EO-modified (meth)acrylate, p-cumylphenol EO-modified (meth)acrylate, methoxytriethylene glycol (meth)acrylate, etc. Two or more 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 preferred, and among these, monofunctional (meth)acrylates represented by the following general formula (2) and/or (3) are more preferred.

(In the above general formula (2), ^R4 represents a hydrogen atom or a methyl group, ^R5 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), ^R6 represents a hydrogen atom or a methyl group, ^R7 represents an alkylene group, and n represents a positive integer.)
In the monofunctional (meth)acrylates represented by the general formulas (2) and (3), m and n are each preferably 2 or greater, more preferably 4 or greater, from the viewpoint of reducing the film stress of the cured film.

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

The photosensitive resin composition of the present invention may contain a polyfunctional (meth)acrylate in addition to (D) the monofunctional (meth)acrylate. A polyfunctional (meth)acrylate refers to a compound having two or more acrylate groups. For example, compounds having two acrylate groups include 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, and dimethyloltricyclode Candi(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-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, 1,10-decamethyl Examples of compounds having three or more acrylate groups include acrylic acid esters of tris(2-hydroxyethyl)isocyanuric acid, 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, and pentapentaerythritol dodeca(meth)acrylate. Two or more of these may be contained.

The photosensitive resin composition of the present invention preferably contains an adhesion improver such as a silane coupling agent, which can further improve the adhesion between the coating film and the underlying substrate. Examples of silane coupling agents include silane coupling agents having functional groups such as vinyl groups, epoxy groups, styryl groups, methacryloxy groups, acryloxy groups, and amino groups. Specific examples include 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris(2-methoxyethoxy)silane, and N-(2-aminoethyl)-3-aminopropylmethyldimethoxysilane. Preferred are hydroxysilane, N-(2-aminoethyl)-3-aminopropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-acryloxypropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N-(1,3-dimethylbutylidene)propylamine, 3-mercaptopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane, 3-isocyanatopropyltriethoxysilane, and p-thrityltrimethoxysilane.

The content of the adhesion improver in the photosensitive resin composition of the present invention is preferably 0.1% by weight or more, and more preferably 1% by weight or more, of the solids content from the viewpoint of further improving adhesion, and is preferably 10% by weight or less, and more preferably 8% by weight or less from the viewpoint of improving pattern resolution by alkaline development.

The photosensitive resin composition of the present invention preferably contains a crosslinking agent, which can promote or facilitate crosslinking of the resin. Examples of crosslinking agents include nitrogen-containing organic compounds, silicone resin curing agents, metal alkoxides, metal chelates, isocyanate compounds and polymers thereof, epoxy compounds and polymers thereof, methylolated melamine derivatives, and methylolated urea derivatives. Two or more 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, the chemical resistance of the obtained cured film, etc. The content of the crosslinking agent is preferably 0.1 wt % or more, more preferably 0.5 wt % or more, and even more preferably 1 wt % or more, of the solid content from the viewpoint of improving the chemical resistance of the cured film, and is preferably 30 wt % or less, more preferably 25 wt % or less, and even more preferably 20 wt % or less, of the solid content from the viewpoint of improving the resolution of the photosensitive resin composition.
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, and more preferably 0.05% by weight or more, of the solid content from the viewpoint of further improving the storage stability and resolution of the photosensitive resin composition, and is preferably 5% by weight or less, and more preferably 3% by weight or less, of the solid content from the viewpoint of further improving the pencil hardness of the cured film.
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-based compounds, benzophenone-based compounds, and triazine-based compounds are preferably used in terms 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, 2-(2H-benzotriazol-2-yl)-4-(1,1,3,3-tetramethylbutyl)phenol, 2(2H-benzotriazol-2-yl)-6-dodecyl-4-methylphenol, 2-(2'-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, which allows the individual components to be uniformly dissolved. Examples of solvents include aliphatic hydrocarbons, carboxylic acid esters, ketones, ethers, and alcohols. Two or more of these may be contained. From the viewpoint of uniformly dissolving the individual components 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, and tetrahydrofurfuryl alcohol.

Specific examples of cyclic compounds having a carbonyl group include γ-butyrolactone, γ-valerolactone, δ-valerolactone, propylene carbonate, N-methylpyrrolidone, cyclohexanone, cycloheptanone, etc. Among these, γ-butyrolactone is particularly preferably used.
Examples of the aliphatic hydrocarbon 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 monoethyl ether acetate, ethyl acetate, butyl acetate, isopentyl acetate, pentyl acetate, and propylene glycol monomethyl ether acetate.
Examples of ketones 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, etc. For example, when coating by spin coating, the content 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, which can improve flow properties during application. Examples of surfactants include fluorine-based surfactants; silicone-based surfactants; fluorine-containing thermally decomposable surfactants; polyether-modified siloxane-based surfactants; polyalkylene oxide-based surfactants; poly(meth)acrylate-based surfactants; anionic surfactants such as ammonium lauryl sulfate and polyoxyethylene alkyl ether triethanolamine sulfate; cationic surfactants such as stearylamine acetate and lauryl trimethylammonium chloride; amphoteric surfactants such as lauryl dimethylamine oxide and lauryl carboxymethyl hydroxyethyl imidazolium betaine; and nonionic surfactants such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, and sorbitan monostearate. Two or more of these surfactants may be used.

Commercially available fluorine-based surfactants include, for example, Megafac (registered trademark) F142D, F172, F173, F183, F445, F470, F475, and F477 (all manufactured by DIC Corporation), NBX-15, and FTX-218 (manufactured by Neos Corporation). Commercially available silicone-based surfactants include, for example, BYK (registered trademark)-333, BYK-301, BYK-331, BYK-345, and BYK-307 (manufactured by BYK Japan KK). Commercially available fluorine-containing thermally decomposable surfactants include, for example, 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, and BYK-349 (all manufactured by BYK Japan K.K.), and 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 liquid-repellent compounds include compounds having a fluoroalkyl or fluoroalkylene group at the end, main chain, and/or side chain.

The photosensitive resin composition of the present invention may contain a dispersant, such as a polyacrylic acid-based dispersant, a polycarboxylic acid-based dispersant, a phosphoric acid-based dispersant, or a silicone-based dispersant.
A method for producing a cured film using the photosensitive resin composition of the present invention will be described below with examples. The method for producing a cured film of the present invention preferably includes a step of curing by light and/or heat without a step of removing all of the alkali-soluble resin component (A) by baking or treatment with a stripping solution. Specifically, a method of applying the photosensitive resin composition of the present invention, exposing and developing it, and heating it is preferred.

In the step of applying the photosensitive resin composition of the present invention, it is preferable to apply the photosensitive resin composition of the present invention to a base substrate and prebake it. Examples of application methods include microgravure coating, spin coating, dip coating, curtain flow coating, roll coating, spray coating, and slit coating. Examples of heating devices used for prebaking include hot plates and ovens. The prebaking temperature 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 pre-baking, it is preferable to pattern the film by exposure and development. Examples of exposure devices include a mask aligner (LA) and a mirror projection mask aligner (MPA). The exposure intensity is preferably approximately 10 to 4000 J/m2 (equivalent to an exposure dose at a wavelength of 365 nm). To form a pattern, it is preferable to expose through a desired mask, but if the entire surface is to be cured, exposure may be performed without 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, yielding a negative pattern. Development methods include immersion in a developer by showering, dipping, puddling, or other methods. The development time is preferably 5 seconds to 10 minutes. Examples of developers include known alkaline developers, such as inorganic alkalis such as alkali metal hydroxides, carbonates, phosphates, silicates, and borates; amines such as 2-diethylaminoethanol, monoethanolamine, and diethanolamine; and aqueous solutions containing one or more quaternary ammonium salts such as tetramethylammonium hydroxide and choline. After development, the film is preferably rinsed with water, and can then be dry-baked at a temperature of 50 to 150°C.

The film after exposure and development is preferably heated using the heating device described above. 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 contain, if necessary, additives 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.

The photosensitive resin composition of the present invention is suitable for use in light-emitting elements such as organic EL light-emitting elements and display elements. More specifically, examples include cured films and transparent medium layers formed on organic EL elements to improve light extraction efficiency.

Of these, this material is particularly suitable for use as a transparent medium layer formed between a microlens and an imaging element in a fingerprint authentication device, as it is excellent for forming thick film patterns with a film thickness of 10 μm or more, and the low film stress of the cured film makes it possible to suppress warping of the substrate. From the perspective of suppressing substrate warping, 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. In view of the focal length of the microlens formed on the transparent medium layer, the film thickness of the cured film formed as the transparent medium layer is preferably approximately 10 μm to 100 μm. From the perspective of improving optical properties, the transmittance of the cured film formed as the transparent medium layer at a wavelength of 550 nm is preferably 90% or more and 100% or less.

The photosensitive resin composition of the present invention has high adhesion to metal layers containing molybdenum, aluminum, or nickel, making it particularly suitable for use in fingerprint authentication devices that use metal layers containing molybdenum, aluminum, or nickel as light-shielding layers or sensor lead wiring.

The present invention will be described in more detail below 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, those for which abbreviations are used are shown below.
PGMEA: Propylene glycol monomethyl ether acetate. In the evaluation methods, if the evaluation number n is not specified, it is an evaluation where n=1. If the temperature is not specified in the evaluation and synthesis conditions, the evaluation was performed at room temperature.

<Evaluation method>
"Crack resistance"
The photosensitive resin compositions obtained in each Example and Comparative Example were spin-coated onto alkali-free glass substrates (glass thickness 0.55 mm) using a spin coater (MS-A150, manufactured by Mikasa Co., Ltd.) and then prebaked for 2 minutes at 100°C using a hot plate (HHP-230SQ, manufactured by AS ONE Corporation) to produce prebaked films with film thicknesses of 15 μm, 60 μm, and 115 μm, respectively. The resulting prebaked films were exposed to light using a mask aligner (LA-610, manufactured by Minaga Electric Mfg. Co., Ltd.) with an ultra-high pressure mercury lamp as the light source at an exposure dose of 200 mJ/cm ² (i-line). Subsequently, the films were shower-developed for 60 seconds using a 2.38 wt % TMAH aqueous solution using an automatic developing apparatus (AD-1200, manufactured by Takizawa Sangyo Co., Ltd.), followed by rinsing with water for 30 seconds. Finally, the coating was cured in air at 230°C for 30 minutes using an oven (DHS-42 manufactured by Espec Corp.) to produce cured films with thicknesses of 10 μm, 50 μm, and 100 μm. The cured films on the alkali-free glass substrates thus obtained were visually inspected for cracks, and grades AA, A, and B were deemed acceptable from the standpoint of industrial application.
AA: No cracks were observed at any film thickness of 10 μm, 30 μm, 50 μm, or 100 μm.
A: No cracks at film thicknesses of 10 μm, 30 μm, and 50 μm. Cracks present at film thickness of 100 μm.
B: No cracks at film thicknesses of 10 μm and 30 μm. Cracks at film thicknesses of 50 μm and 100 μm.
C: No cracks at a film thickness of 10 μm. Cracks were observed at film thicknesses of 30 μm, 50 μm, and 100 μm.
D: Cracks were observed at film thicknesses of 10 μm, 30 μm, 50 μm, and 100 μm.

"Membrane stress"
The photosensitive resin compositions obtained in each of the Examples and Comparative Examples were spin-coated onto a 6-inch silicon wafer using a spin coater (MS-A150, manufactured by Mikasa Co., Ltd.), and then pre-baked for 2 minutes at 100°C using a hot plate (HHP-230SQ, manufactured by AS ONE Corporation) to produce pre-baked films with a thickness of 15 μm. The resulting pre-baked films were exposed to light using a mask aligner (LA-610, manufactured by Minaga Electric Mfg. Co., Ltd.) with an ultra-high pressure mercury lamp as the light source at an exposure dose of 200 mJ/cm ² (i-line). Subsequently, using an automatic developing apparatus (AD-1200, manufactured by Takizawa Sangyo Co., Ltd.), the films were shower-developed for 60 seconds using a 2.38 wt % TMAH aqueous solution, followed by rinsing with water for 30 seconds. Finally, the film was cured in air at 230°C for 30 minutes using an oven (DHS-42, manufactured by Espec Corp.) to produce a cured film with a thickness of 10 µm. The film stress of the resulting 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 scores of A and B were determined to be acceptable from the viewpoint of industrial use.
A: Film stress less than 5 MPa.
B: Film stress is 5 MPa or more and less than 10 MPa.
C: Film stress is 10 MPa or more and less than 15 MPa.
D: Film stress is 15 MPa or more.

"Transmittance"
The photosensitive resin compositions obtained in each of the Examples and Comparative Examples were spin-coated onto a Tempax glass substrate (AGC Technoglass Co., Ltd.) using a spin coater (MS-A150, Mikasa Co., Ltd.) and then prebaked for 2 minutes at 100°C using a hot plate (HHP-230SQ, AS ONE Corporation) to produce prebaked films with a thickness of 15 μm. The resulting prebaked films were exposed to light using a mask aligner (LA-610, Minaga Electric Mfg. Co., Ltd.) with an ultra-high pressure mercury lamp as the light source at an exposure dose of 200 mJ/cm ² (i-line). The films were then shower-developed for 60 seconds using a 2.38 wt % TMAH aqueous solution using an automatic developing apparatus (AD-1200, Takizawa Sangyo Co., Ltd.), followed by rinsing with water for 30 seconds. Finally, the film was cured in air at 230°C for 30 minutes using an oven (DHS-42, manufactured by Espec Corporation) 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 the Tempax glass substrate alone was measured and used as a reference. Next, the UV-visible absorption spectrum of the resulting laminate of the cured film and Tempax glass was measured using a single beam to determine the light transmittance at 400 nm, and the difference from the reference was used as the transmittance of the cured film. From the viewpoint of industrial use, A and B were deemed acceptable.
A: Transmittance is 95% or more and less than 100%.
B: Transmittance is 90% or more and less than 95%.
C: Transmittance less than 90%.

"resolution"
The photosensitive resin compositions obtained in each Example and Comparative Example were spin-coated onto alkali-free glass substrates (glass thickness 0.55 mm) using a spin coater (MS-A150, manufactured by Mikasa Co., Ltd.) and then prebaked at 100°C for 2 minutes using a hot plate (HHP-230SQ, manufactured by AS ONE Corporation) to produce prebaked films with a thickness of 15 μm. The resulting prebaked films were exposed to light using a mask aligner (LA-610, manufactured by Minei Electric Mfg. Co., Ltd.) with an ultra-high pressure mercury lamp as the light source and masks with 1:1 widths of 10, 20, 30, 40, and 50 μm, with a mask gap of 200 μm. The films were then shower-developed using an automatic developing apparatus (AD-1200, manufactured by Takizawa Sangyo Co., Ltd.) with a 2.38 wt % TMAH aqueous solution for 60 seconds, followed by rinsing with water for 30 seconds. The optimum exposure dose was the exposure dose required to form a 50 μm line-and-space pattern with a 1:1 width after development. The exposure dose was measured with an i-line illuminometer. The minimum pattern dimension after development at the optimum exposure dose was measured and used as the resolution. From the viewpoint of industrial application, A, B, and C were deemed acceptable.
A: Resolution is 10 μm or more and less than 20 μm.
B: Resolution is 20 μm or more and less than 30 μm.
C: Resolution is 30 μm or more and less than 40 μm.
D: Resolution of 50 μm or more.

"Adhesion to metal layers"
A substrate (hereinafter referred to as a "metal laminate substrate") was prepared by depositing molybdenum-nickel alloy/aluminum/molybdenum-nickel alloy (film thickness: 20 nm/300 nm/20 nm) in this order on an alkali-free glass substrate (glass thickness 0.55 mm). The photosensitive resin compositions obtained in each example and comparative example were spin-coated onto the metal laminate substrate using a spin coater (MS-A150 manufactured by Mikasa Co., Ltd.) and then prebaked at 100°C for 2 minutes using a hot plate (HHP-230SQ manufactured by AS ONE Corporation) to produce a prebaked film with a film thickness of 15 μm. The resulting prebaked film was exposed to 200 mJ/cm2 (i-line) using a mask aligner (LA-610 manufactured by Minei Electric Mfg. Co., Ltd.) with an ultra-high pressure mercury lamp as the light source. Thereafter, using an automatic developing apparatus (AD-1200 manufactured by Takizawa Sangyo Co., Ltd.), shower development was performed using a 2.38 wt % TMAH aqueous solution for 60 seconds, followed by rinsing with water for 30 seconds. Finally, using an oven (DHS-42 manufactured by Espec Corp.), the film was cured in air at 230°C for 30 minutes to produce a cured film with a film thickness of 10 μm, and the adhesion of the cured film formed on the metal laminate substrate was evaluated. That is, on the surface of the cured film on the metal laminate substrate, 11 parallel lines intersecting each other were drawn at 1 mm intervals using a cutter knife so as to reach the base of the metal laminate substrate, creating 100 1 mm x 1 mm grids. A cellophane adhesive tape (width = 18 mm, adhesive strength = 3.7 N/10 mm) was attached to the surface of the cut cured film, and rubbed with an eraser (compliant with JIS S6050) to make it adhere, and one end of the tape was held perpendicular to the plate and instantly peeled off, and the number of remaining squares was counted visually. The peeled area of the squares was judged as follows, and from the viewpoint of industrial use, 3B, 4B, and 5B were considered acceptable.
5B: Peeling area = 0%
4B: Peeled area = more than 0% but less than 5%.
3B: Peeled area = 5% or more and less than 15%.
2B: Peeled area = 15% or more and less than 35%.
1B: Peeled area = 35% or more and less than 65%.
0B: Peeled area = 65% or more but less than 100%.

Synthesis Example 1
A 500 mL three-neck flask was charged with 78.05 g of PGMEA, 34.05 g (0.25 mol) of methyltrimethoxysilane, 46.47 g (0.20 mol) of 3-methacryloxypropylmethyldimethoxysilane, 12.32 g (0.05 mol) of 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 26.23 g (0.10 mol) of 3-trimethoxysilylpropylsuccinic acid, and 86.52 g (0.40 mol) of diphenylsilanediol, and the flask was immersed in a 40°C oil bath and stirred. An aqueous phosphoric acid solution prepared by dissolving 2.06 g of phosphoric acid (1.0 wt % based on the charged monomers) in 30.60 g of water was added thereto using a dropping funnel over 10 minutes. After stirring at 40°C for 1 hour, the oil bath temperature was set to 70°C and stirring was continued for 1 hour. The oil bath was then heated to 115°C over 30 minutes. One hour after the start of the temperature increase, the internal temperature of the solution reached 100°C, and the mixture was then heated and stirred for 2 hours (internal temperature: 100-110°C). A total of 78 g of by-products, methanol and water, were distilled off during the reaction. PGMEA was added to the resulting polysiloxane PGMEA solution to a solids concentration of 65 wt%, yielding a siloxane resin solution (PS-1). The weight-average molecular weight (hereinafter, "Mw") of the resulting siloxane resin was measured by GPC and found to be 1,000 (polystyrene equivalent).

Synthesis Example 2
A 500 mL three-neck flask was charged with 92.50 g of PGMEA, 13.62 g (0.10 mol) of methyltrimethoxysilane, 46.47 g (0.20 mol) of 3-methacryloxypropylmethyldimethoxysilane, 12.32 g (0.05 mol) of 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 26.23 g (0.10 mol) of 3-trimethoxysilylpropylsuccinic acid, and 118.97 g (0.55 mol) of diphenylsilanediol, and the flask was immersed in a 40°C oil bath and stirred. An aqueous phosphoric acid solution prepared by dissolving 2.18 g of phosphoric acid (1.0 wt % based on the charged monomers) in 22.50 g of water was added thereto using a dropping funnel over 10 minutes. After stirring at 40°C for 1 hour, the oil bath temperature was set to 70°C and stirring was continued for 1 hour. The oil bath was then heated to 115°C over 30 minutes. One hour after the start of the temperature increase, the internal temperature of the solution reached 100°C, and the mixture was then heated and stirred for 2 hours (internal temperature: 100-110°C). A total of 62 g of by-products, methanol and water, were distilled off during the reaction. PGMEA was added to the resulting polysiloxane PGMEA solution to a solids concentration of 65 wt%, yielding a siloxane resin solution (PS-2). The Mw of the resulting siloxane resin was measured by GPC and found to be 1,000 (polystyrene equivalent).

Synthesis Example 3
A 500 mL three-necked flask was charged with 102.13 g of PGMEA, 46.47 g (0.20 mol) of 3-methacryloxypropylmethyldimethoxysilane, 12.32 g (0.05 mol) of 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 26.23 g (0.10 mol) of 3-trimethoxysilylpropylsuccinic acid, and 140.60 g (0.65 mol) of diphenylsilanediol. The flask was immersed in a 40 ° C. oil bath and stirred. An aqueous solution of phosphoric acid (1.0 wt% based on the charged monomer) dissolved in 17.10 g of water was added over 10 minutes using a dropping funnel. After stirring at 40 ° C. for 1 hour, the oil bath temperature was set to 70 ° C. and stirred for 1 hour. The oil bath was then heated to 115 ° C. over 30 minutes. One hour after the start of the temperature increase, the internal temperature of the solution reached 100°C, and the mixture was then heated and stirred for 2 hours (internal temperature: 100-110°C). A total of 52 g of by-products, methanol and water, were distilled off during the reaction. PGMEA was added to the resulting PGMEA solution of polysiloxane to give a solids concentration of 65 wt%, yielding a siloxane resin solution (PS-3). The Mw of the resulting siloxane resin was measured by GPC and found to be 800 (polystyrene equivalent).

Synthesis Example 4
A 500 mL three-necked flask was charged with 103.51 g of PGMEA, 34.85 g (0.15 mol) of 3-methacryloxypropylmethyldimethoxysilane, 12.32 g (0.05 mol) of 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 26.23 g (0.10 mol) of 3-trimethoxysilylpropylsuccinic acid, and 151.42 g (0.70 mol) of diphenylsilanediol. The flask was immersed in a 40 ° C. oil bath and stirred. An aqueous solution of phosphoric acid (1.0 wt% based on the charged monomer) dissolved in 15.30 g of water was added over 10 minutes using a dropping funnel. After stirring at 40 ° C. for 1 hour, the oil bath temperature was set to 70 ° C. and stirred for 1 hour. The oil bath was then heated to 115 ° C. over 30 minutes. One hour after the start of the temperature increase, the internal temperature of the solution reached 100°C, and the mixture was then heated and stirred for 2 hours (internal temperature: 100-110°C). A total of 49 g of by-products, methanol and water, were distilled off during the reaction. PGMEA was added to the resulting PGMEA solution of polysiloxane to give a solids concentration of 65 wt%, yielding a siloxane resin solution (PS-4). The Mw of the resulting siloxane resin was measured by GPC and found to be 800 (polystyrene equivalent).

Synthesis Example 5
A 500 mL three-neck flask was charged with 68.42 g of PGMEA, 47.67 g (0.35 mol) of methyltrimethoxysilane, 46.47 g (0.20 mol) of 3-methacryloxypropylmethyldimethoxysilane, 12.32 g (0.05 mol) of 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 26.23 g (0.10 mol) of 3-trimethoxysilylpropylsuccinic acid, and 64.89 g (0.30 mol) of diphenylsilanediol, and the flask was immersed in a 40°C oil bath and stirred. An aqueous phosphoric acid solution prepared by dissolving 1.98 g of phosphoric acid (1.0 wt % based on the charged monomers) in 36.00 g of water was added thereto using a dropping funnel over 10 minutes. After stirring at 40°C for 1 hour, the oil bath temperature was set to 70°C and stirring was continued for 1 hour. The oil bath was then heated to 115°C over 30 minutes. One hour after the start of the temperature increase, the internal temperature of the solution reached 100°C, and the mixture was then heated and stirred for 2 hours (internal temperature: 100-110°C). A total of 89 g of by-products, methanol and water, were distilled off during the reaction. PGMEA was added to the resulting polysiloxane PGMEA solution to a solids concentration of 65 wt%, yielding a siloxane resin solution (PS-5). The Mw of the resulting siloxane resin was measured by GPC and found to be 1,000 (polystyrene equivalent).

Synthesis Example 6
A 500 mL three-neck flask was charged with 58.78 g of PGMEA, 61.29 g (0.45 mol) of methyltrimethoxysilane, 46.47 g (0.20 mol) of 3-methacryloxypropylmethyldimethoxysilane, 12.32 g (0.05 mol) of 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 26.23 g (0.10 mol) of 3-trimethoxysilylpropylsuccinic acid, and 43.26 g (0.20 mol) of diphenylsilanediol, and the flask was immersed in a 40°C oil bath and stirred. An aqueous phosphoric acid solution prepared by dissolving 1.90 g of phosphoric acid (1.0 wt % based on the charged monomers) in 41.40 g of water was added thereto using a dropping funnel over 10 minutes. After stirring at 40°C for 1 hour, the oil bath temperature was set to 70°C and stirring was continued for 1 hour. The oil bath was then heated to 115°C over 30 minutes. One hour after the start of the temperature increase, the internal temperature of the solution reached 100°C, and the mixture was then heated and stirred for 2 hours (internal temperature: 100-110°C). A total of 99 g of by-products, methanol and water, were distilled off during the reaction. PGMEA was added to the resulting polysiloxane PGMEA solution to a solids concentration of 65 wt%, yielding a siloxane resin solution (PS-6). The Mw of the resulting siloxane resin was measured by GPC and found to be 1,200 (polystyrene equivalent).

Synthesis Example 7
A 500 mL three-neck flask was charged with 50.53 g of PGMEA, 74.91 g (0.55 mol) of methyltrimethoxysilane, 34.85 g (0.15 mol) of 3-methacryloxypropylmethyldimethoxysilane, 12.32 g (0.05 mol) of 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 26.23 g (0.10 mol) of 3-trimethoxysilylpropylsuccinic acid, and 32.45 g (0.15 mol) of diphenylsilanediol, and the flask was immersed in a 40°C oil bath and stirred. An aqueous phosphoric acid solution prepared by dissolving 1.81 g of phosphoric acid (1.0 wt % based on the charged monomers) in 45.00 g of water was added thereto using a dropping funnel over 10 minutes. After stirring at 40°C for 1 hour, the oil bath temperature was set to 70°C and stirring was continued for 1 hour. The oil bath was then heated to 115°C over 30 minutes. One hour after the start of the temperature increase, the internal temperature of the solution reached 100°C, and the mixture was then heated and stirred for 2 hours (internal temperature: 100-110°C). A total of 107 g of by-products, methanol and water, were distilled off during the reaction. PGMEA was added to the resulting polysiloxane PGMEA solution to a solids concentration of 65 wt%, yielding a siloxane resin solution (PS-7). The Mw of the resulting siloxane resin was measured by GPC and found to be 1,500 (polystyrene equivalent).

Synthesis Example 8
A 500 mL three-neck flask was charged with 56.36 g of PGMEA, 34.05 g (0.25 mol) of methyltrimethoxysilane, 46.47 g (0.20 mol) of 3-methacryloxypropylmethyldimethoxysilane, 12.32 g (0.05 mol) of 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 26.23 g (0.10 mol) of 3-trimethoxysilylpropylsuccinic acid, 32.45 g (0.15 mol) of diphenylsilanediol, and 30.06 g (0.25 mol) of dimethyldimethoxysilane, and the flask was immersed in a 40°C oil bath and stirred. An aqueous phosphoric acid solution prepared by dissolving 1.82 g of phosphoric acid (1.0 wt % relative to the charged monomers) in 39.60 g of water was added thereto using a dropping funnel over 10 minutes. After stirring at 40°C for 1 hour, the oil bath temperature was set to 70°C and stirring was continued for 1 hour. The oil bath was then heated to 115°C over 30 minutes. One hour after the start of the temperature increase, the internal temperature of the solution reached 100°C, and the mixture was then heated and stirred for 2 hours (internal temperature: 100-110°C). A total of 94 g of by-products, methanol and water, were distilled off during the reaction. PGMEA was added to the resulting polysiloxane PGMEA solution to a solids concentration of 65 wt%, yielding a siloxane resin solution (PS-8). The Mw of the resulting siloxane resin was measured by GPC and found to be 1,400 (polystyrene equivalent).

Synthesis Example 9
A 500 mL three-neck flask was charged with 52.02 g of PGMEA, 34.05 g (0.25 mol) of methyltrimethoxysilane, 46.47 g (0.20 mol) of 3-methacryloxypropylmethyldimethoxysilane, 12.32 g (0.05 mol) of 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 26.23 g (0.10 mol) of 3-trimethoxysilylpropylsuccinic acid, 21.63 g (0.10 mol) of diphenylsilanediol, and 36.07 g (0.30 mol) of dimethyldimethoxysilane, and the flask was immersed in a 40°C oil bath and stirred. An aqueous phosphoric acid solution prepared by dissolving 1.77 g of phosphoric acid (1.0 wt % relative to the charged monomers) in 41.40 g of water was added thereto using a dropping funnel over 10 minutes. After stirring at 40°C for 1 hour, the oil bath temperature was set to 70°C and stirring was continued for 1 hour. The oil bath was then heated to 115°C over 30 minutes. One hour after the start of the temperature increase, the internal temperature of the solution reached 100°C, and the mixture was then heated and stirred for 2 hours (internal temperature: 100-110°C). A total of 97 g of by-products, methanol and water, were distilled off during the reaction. PGMEA was added to the resulting polysiloxane PGMEA solution to a solids concentration of 65 wt%, yielding a siloxane resin solution (PS-9). The Mw of the resulting siloxane resin was measured by GPC and found to be 1,500 (polystyrene equivalent).

Synthesis Example 10
A 500 mL three-necked flask was charged with 76.10 g of PGMEA, 40.86 g (0.30 mol) of methyltrimethoxysilane, 46.47 g (0.20 mol) of 3-methacryloxypropylmethyldimethoxysilane, 24.64 g (0.10 mol) of 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, and 86.52 g (0.40 mol) of diphenylsilanediol. The flask was immersed in a 40 ° C. oil bath and stirred. An aqueous solution of phosphoric acid (1.98 g of phosphoric acid (1.0 wt% relative to the charged monomer) dissolved in 28.80 g of water was added over 10 minutes using a dropping funnel. After stirring at 40 ° C. for 1 hour, the oil bath temperature was set to 70 ° C. and stirred for 1 hour. The oil bath was then heated to 115 ° C. over 30 minutes. One hour after the start of the temperature increase, the internal temperature of the solution reached 100°C, and the mixture was then heated and stirred for 2 hours (internal temperature: 100-110°C). A total of 73 g of by-products, methanol and water, were distilled off during the reaction. PGMEA was added to the resulting PGMEA solution of polysiloxane to give a solids concentration of 65% by weight, yielding a siloxane resin solution (PS-10). The Mw of the resulting siloxane resin was measured by GPC and found to be 900 (polystyrene equivalent).

Synthesis Example 11
A 500 mL three-necked flask was charged with 104.52 g of PGMEA, 46.47 g (0.20 mol) of 3-methacryloxypropylmethyldimethoxysilane, 12.32 g (0.05 mol) of 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 13.12 g (0.05 mol) of 3-trimethoxysilylpropylsuccinic acid, and 151.42 g (0.70 mol) of diphenylsilanediol. The flask was immersed in a 40 ° C. oil bath and stirred. An aqueous solution of phosphoric acid (1.0 wt% based on the charged monomer) dissolved in 13.50 g of water was added over 10 minutes using a dropping funnel. After stirring at 40 ° C. for 1 hour, the oil bath temperature was set to 70 ° C. and stirred for 1 hour. The oil bath was then heated to 115 ° C. over 30 minutes. One hour after the start of the temperature increase, the internal temperature of the solution reached 100°C, and the mixture was then heated and stirred for 2 hours (internal temperature: 100-110°C). A total of 44 g of by-products, methanol and water, were distilled off during the reaction. PGMEA was added to the resulting PGMEA solution of polysiloxane to give a solids concentration of 65% by weight, yielding a siloxane resin solution (PS-11). The Mw of the resulting siloxane resin was measured by GPC and found to be 600 (polystyrene equivalent).

Synthesis Example 12
A 500 mL three-neck flask was charged with 42.27 g of PGMEA, 88.53 g (0.65 mol) of methyltrimethoxysilane, 23.24 g (0.10 mol) of 3-methacryloxypropylmethyldimethoxysilane, 12.32 g (0.05 mol) of 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 26.23 g (0.10 mol) of 3-trimethoxysilylpropylsuccinic acid, and 21.63 g (0.10 mol) of diphenylsilanediol, and the flask was immersed in a 40°C oil bath and stirred. An aqueous phosphoric acid solution prepared by dissolving 1.72 g of phosphoric acid (1.0 wt % based on the charged monomers) in 48.60 g of water was added thereto using a dropping funnel over 10 minutes. After stirring at 40°C for 1 hour, the oil bath temperature was set to 70°C and stirring was continued for 1 hour. The oil bath was then heated to 115°C over 30 minutes. One hour after the start of the temperature increase, the internal temperature of the solution reached 100°C, and the mixture was then heated and stirred for 2 hours (internal temperature: 100-110°C). A total of 114 g of by-products, methanol and water, were distilled off during the reaction. PGMEA was added to the resulting polysiloxane PGMEA solution to a solids concentration of 65 wt%, yielding a siloxane resin solution (PS-12). The Mw of the resulting siloxane resin was measured by GPC and found to be 3,000 (polystyrene equivalent).

Synthesis Example 13
A 500 mL three-necked flask was charged with 32.63 g of PGMEA, 102.15 g (0.75 mol) of methyltrimethoxysilane, 23.24 g (0.10 mol) of 3-methacryloxypropylmethyldimethoxysilane, 12.32 g (0.05 mol) of 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, and 26.23 g (0.10 mol) of 3-trimethoxysilylpropylsuccinic acid. The flask was immersed in a 40 ° C. oil bath and stirred. An aqueous solution of phosphoric acid obtained by dissolving 1.64 g of phosphoric acid (1.0 wt% relative to the charged monomer) in 54.00 g of water was added over 10 minutes using a dropping funnel. After stirring at 40 ° C. for 1 hour, the oil bath temperature was set to 70 ° C. and stirred for 1 hour. The oil bath was then heated to 115 ° C. over 30 minutes. One hour after the start of the temperature increase, the internal temperature of the solution reached 100°C, and the mixture was then heated and stirred for 2 hours (internal temperature: 100-110°C). A total of 114 g of by-products, methanol and water, were distilled off during the reaction. PGMEA was added to the resulting PGMEA solution of polysiloxane to give a solids concentration of 65% by weight, yielding a siloxane resin solution (PS-13). The Mw of the resulting siloxane resin was measured by GPC and found to be 5,000 (polystyrene equivalent).

Synthesis Example 14
A 500 mL three-necked flask was charged with 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, 26.23 g (0.10 mol) of 3-trimethoxysilylpropylsuccinic acid, and 86.52 g (0.40 mol) of diphenylsilanediol. The flask was immersed in a 40 ° C. oil bath and stirred. An aqueous solution of phosphoric acid (1.0 wt% relative to the charged monomer) dissolved in 34.20 g of water was added over 10 minutes using a dropping funnel. After stirring at 40 ° C. for 1 hour, the oil bath temperature was set to 70 ° C. and stirred for 1 hour. The oil bath was then heated to 115 ° C. over 30 minutes. One hour after the start of the temperature increase, the internal temperature of the solution reached 100°C, and the mixture was then heated and stirred for 2 hours (internal temperature: 100-110°C). A total of 86 g of by-products, methanol and water, were distilled off during the reaction. PGMEA was added to the resulting PGMEA solution of polysiloxane to give a solids concentration of 65% by weight, yielding a siloxane resin solution (PS-14). The Mw of the resulting siloxane resin was measured by GPC and found to be 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. Then, 30 g of methacrylic acid, 35 g of benzyl methacrylate, and 35 g of tricyclo[5.2.1.02,6]decan-8-yl methacrylate were charged and stirred at room temperature for a while. The atmosphere in the flask was replaced with nitrogen, and the mixture was heated and stirred at 70 °C 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 resulting solution, and the mixture was heated and stirred at 90 °C for 4 hours. PGMEA was added to the resulting PGMEA solution of acrylic resin to achieve a solids concentration of 50 wt%, yielding an acrylic resin solution (PA-1). The Mw of the resulting acrylic resin was measured by GPC and found to be 10,000. The acid value of the resulting acrylic resin was 118 mgKOH/g.

Example 1
First, the following raw materials were mixed and stirred under a yellow light.
A solution obtained by dissolving 0.96 g of 1,2-octanedione, 1-[4-(phenylthio)-2-(O-benzoyloxime)] (trade name "Irgacure" (registered trademark) OXE01, manufactured by BASF (hereinafter referred to as OXE-01)) in 31.62 g of PGMEA as an organic solvent.
0.30 g of a 10 wt % solution of a fluorochemical surfactant (trade name "F-477" manufactured by DIC Corporation) in PGMEA as a surfactant.
0.96 g of a silane coupling agent (trade name "KBM-303" manufactured by Shin-Etsu Chemical Co., Ltd.) as an adhesion improver.
p-Nonylphenol EO-modified acrylate (trade name "M-113" manufactured by Toagosei Co., Ltd.) 9.61 g
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.
The mixture was then filtered through a 1.0 μm filter to prepare a photosensitive resin composition A-1 having a solid content of 50% by weight.
A cured film was prepared from the obtained photosensitive resin composition A-1 by the method described above, and evaluated by the methods 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). The obtained photosensitive resin composition A-2 was evaluated in the same manner as in Example 1.

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). The obtained photosensitive resin composition A-3 was evaluated in the same manner as in Example 1.

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). The obtained photosensitive resin composition A-4 was evaluated in the same manner as in Example 1.

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). The obtained photosensitive resin composition A-5 was evaluated in the same manner as in Example 1.

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). The obtained photosensitive resin composition A-6 was evaluated in the same manner as in Example 1.

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). The obtained photosensitive resin composition A-7 was evaluated in the same manner as in Example 1.

Example 8
Photosensitive resin composition A-8 was prepared in the same manner as in Example 1, except that siloxane resin solution (PS-8) was used instead of siloxane resin solution (PS-1). The obtained photosensitive resin composition A-8 was evaluated in the same manner as in Example 1.

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). The obtained photosensitive resin composition A-9 was evaluated in the same manner as in Example 1.

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). The obtained photosensitive resin composition A-10 was evaluated in the same manner as in Example 1.

Example 11
A photosensitive resin composition A-11 was prepared in the same manner as in Example 1, except that N-n-butoxymethylacrylamide (trade name "Wasmer A" manufactured by Kasano Kosan Co., Ltd.) was used instead of N-methoxymethylacrylamide. The obtained photosensitive resin composition A-11 was evaluated in the same manner as in Example 1.

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. The obtained photosensitive resin composition A-12 was evaluated in the same manner as in Example 1.

Example 13
A 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. The obtained photosensitive resin composition A-13 was evaluated in the same manner as in Example 1.

Example 14
A photosensitive resin composition A-14 was prepared in the same manner as in Example 1, except that N-n-butoxymethyl methacrylamide (trade name "Wasmer NBMM" manufactured by Kasano Kosan Co., Ltd.) was used instead of N-methoxymethyl acrylamide. The obtained photosensitive resin composition A-14 was evaluated in the same manner as in Example 1.

Example 15
Photosensitive resin composition A-15 was prepared in the same manner as in Example 1, 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.). Evaluations were performed in the same manner as in Example 1 using the obtained photosensitive resin composition A-15.

Example 16
Photosensitive resin composition A-16 was prepared in the same manner as in Example 1, except that p-nonylphenol EO-modified acrylate (trade name "FA-318A" manufactured by Hitachi Chemical Co., Ltd.) was used instead of p-nonylphenol EO-modified acrylate (trade name "M-113" manufactured by Toagosei Co., Ltd.). The obtained photosensitive resin composition A-16 was used to perform evaluations in the same manner as in Example 1.

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). The obtained photosensitive resin composition A-17 was evaluated in the same manner as in Example 1.

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). The obtained photosensitive resin composition A-18 was evaluated in the same manner as in Example 1.

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). The obtained photosensitive resin composition A-19 was evaluated in the same manner as in Example 1.

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). The obtained photosensitive resin composition A-20 was evaluated in the same manner as in Example 1.

Comparative Example 5
Photosensitive resin composition A-21 was prepared 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.) added was increased to 14.41 g instead of N-methoxymethylacrylamide. Using the obtained photosensitive resin composition A-21, evaluations were carried out in the same manner as in Example 1.

Comparative Example 6
A photosensitive resin composition A-22 was prepared in the same manner as in Example 1, except that N-acryloyloxyethylhexahydrophthalimide (trade name "M-140" manufactured by Toagosei Co., Ltd.) was used instead of N-methoxymethylacrylamide. The obtained photosensitive resin composition A-22 was evaluated in the same manner as in Example 1.

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. The obtained photosensitive resin composition A-23 was evaluated in the same manner as in Example 1.

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. The obtained photosensitive resin composition A-24 was evaluated in the same manner as in Example 1.

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. The obtained photosensitive resin composition A-25 was evaluated in the same manner as in Example 1.

Comparative Example 10
A photosensitive resin composition A-26 was prepared in the same manner as in Example 1, except that an isocyanuric acid EO-modified triacrylate (product name "M-315" manufactured by Toagosei Co., Ltd.) was used instead of N-methoxymethylacrylamide. The obtained photosensitive resin composition A-26 was evaluated in the same manner as in Example 1.

Comparative Example 11
Photosensitive resin composition A-27 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. The obtained photosensitive resin composition A-27 was evaluated in the same manner as in Example 1.

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). The obtained photosensitive resin composition A-28 was evaluated in the same manner as in Example 1.

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.

The photosensitive resin compositions prepared in the examples are capable of forming patterns with excellent resolution even in thick films with a thickness of 10 μm or more, and are also capable of providing photosensitive resin compositions that have high transparency, low film stress, and high adhesion to metal layers containing molybdenum, aluminum, or nickel.

The photosensitive resin composition of the present invention is capable of forming patterns with excellent resolution even in thick films with a film thickness of 10 μm or more. It also provides a photosensitive resin composition that has high transparency, low film stress, and high adhesion to metal layers containing molybdenum, aluminum, or nickel. Therefore, it is particularly suitable for use in fingerprint authentication devices that use metal layers containing molybdenum, aluminum, or nickel as light-shielding layers or sensor lead wiring.

Claims (13)

(A) a siloxane resin containing organosilane units (D units) represented by (R) ₂ SiO ₂ / ₂ (R is a hydrogen atom or an organic group) in an amount of 30 mol % to 85 mol % based on all organosilane units, and having a radical polymerizable group;
(B) an N-substituted (meth)acrylamide derivative represented by the following general formula (1) :
(C) a photoradical polymerization initiator,
A photosensitive resin composition comprising:
(In the above general formula (1), R1 ^represents a hydrogen atom or a methyl group, ^R2 represents CH2 , _and ^R3 represents an alkyl group.) The photosensitive resin composition according to claim 1, wherein the (A) siloxane resin contains 15 mol % or more and 65 mol % or less of organosilane units having a diphenyl group. 3. The photosensitive resin composition according to claim 1, wherein the siloxane resin (A) has a radical polymerizable group and a carboxyl group and/or a dicarboxylic acid anhydride group. 4. The photosensitive resin composition according to claim 1 , further comprising (D) a monofunctional (meth)acrylate in addition to (B) the N-substituted (meth)acrylamide derivative. The photosensitive resin composition according to claim 4, wherein the monofunctional (meth)acrylate (D) contains a phenol structure. 6. The photosensitive resin composition according to claim 4 , wherein the monofunctional (meth)acrylate (D) is represented by the following general formula (2) and/or (3):
(In the above general formula (2), ^R4 represents a hydrogen atom or a methyl group, ^R5 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), ^R6 represents a hydrogen atom or a methyl group, ^R7 represents an alkylene group, and n represents a positive integer.) 7. The photosensitive resin composition according to claim 6 , wherein m and n in 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 7 . The cured film according to claim 8 , having a film stress of 0.01 MPa or more and 10 MPa or less. The cured film according to claim 8 , having a film stress of 0.01 MPa or more and 10 MPa or less and a film thickness of 10 μm or more and 100 μm or less. The cured film according to claim 8 , which has 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 imaging device or a fingerprint authentication device, comprising the cured film according to any one of claims 8 to 11 . 13. The solid-state imaging device or fingerprint authentication device according to claim 12 , wherein the wiring and/or the light-shielding layer is a metal layer containing molybdenum, aluminum, or nickel.