CN114114839A

CN114114839A - Photosensitive resin composition, patterning method and application of photosensitive resin composition

Info

Publication number: CN114114839A
Application number: CN202010906176.9A
Authority: CN
Inventors: 钱晓春; 龚艳; 姜超; 徐丽萍
Original assignee: Changzhou Tronly New Electronic Materials Co Ltd; Changzhou Tronly Advanced Electronic Materials Co Ltd
Current assignee: Changzhou Tronly New Electronic Materials Co Ltd; Changzhou Tronly Advanced Electronic Materials Co Ltd
Priority date: 2020-09-01
Filing date: 2020-09-01
Publication date: 2022-03-01

Abstract

The invention provides a photosensitive resin composition, a patterning method and application of the photosensitive resin composition. The photosensitive resin composition comprises a resin component and an acid generator, wherein the acid generator is a sulfimide photo-acid generator, and the sulfimide photo-acid generator has a structure shown in the following general formula (A):

Description

Photosensitive resin composition, patterning method and application of photosensitive resin composition

Technical Field

The invention relates to the technical field of photosensitive materials, in particular to a photosensitive resin composition, a patterning method and application of the photosensitive resin composition.

Background

The photolithography technique refers to a technique of forming a resist film made of a resist material, coating and molding the resist film on a substrate, selectively exposing the resist film to radiation of light or electron beams through a mask on which a predetermined pattern is formed, and then performing a developing process to form a resist pattern having a predetermined shape on the resist film. A resist material in which an exposed portion is changed to be dissolved in a developer is referred to as a positive resist material, and a resist material in which an exposed portion is changed to be insoluble in a developer is referred to as a negative resist material.

With the demand for high integration and high speed of LSIs, the miniaturization of pattern feature sizes is rapidly progressing. As a refinement technique, it is generally required to shorten the wavelength (high-energy radiation) of an exposure light source, for example, ultraviolet rays which have been represented by g-line and i-line, and to gradually convert them into KrF excimer laser or ArF excimer laser for mass production of semiconductor devices. In addition, there are F2 excimer lasers, electron beams, EUV (extreme ultraviolet) and X-rays, which have shorter wavelengths than these excimer lasers. As the exposure light source is shortened, the resist composition is required to have high sensitivity to the exposure light source and resolution capable of reproducing the formation of a fine-sized pattern, in order to improve the lithographic characteristics. Therefore, the resist material must have lithographic characteristics such as sensitivity to the exposure light source and resolution capable of reproducing a pattern having a fine size. As a resist material that satisfies such a requirement, a chemically amplified resist containing a basic resin whose alkali solubility can be changed by the action of an acid can be used, for example, a chemically amplified positive resist contains a base resin of an acid generator, the alkali solubility is increased by the acid generated by the acid generator, and when a resist pattern is formed, the acid is generated from the acid generator by exposure, and the exposed region becomes soluble in an alkali developer.

However, such positive resist compositions are still required to be further improved in terms of the miniaturization technique, such as adjustment of sensitivity, resolution, and contrast of a formed pattern in resist pattern formation.

Disclosure of Invention

The invention mainly aims to provide a photosensitive resin composition, a patterning method and application of the photosensitive resin composition, so as to solve the problem of insufficient sensitivity of a positive type resist composition in the prior art when a fine pattern is formed.

In order to achieve the above object, according to one aspect of the present invention, there is provided a photosensitive resin composition comprising a resin component and an acid generator, the acid generator being a sulfimide-based photoacid generator having a structure represented by the following general formula (a):

wherein R is₁Is represented by C₁-C₂₀Alkyl of (C)₁-C₂₀Fluoroalkyl of, C₆-C₁₈And wherein the alkyl group is a straight-chain alkyl group or a branched-chain alkyl group; r₂-R₇Each independently represents the following group: hydrogen; halogen; c₁-C₂₀Optionally, -CH therein₂-may be substituted by-O-and alkyl is straight or branched alkyl; phenyl, optionally, in which at least one hydrogen atom may be replaced by C₁-C₈Alkyl or alkoxy of (a); c₇-C₂₀Optionally, at least one hydrogen atom on the phenyl group may be replaced by C₁-C₈Substituted by alkyl or alkoxy groups, -CH in alkyl₂-may be substituted by-O-or-S-and alkyl is straight or branched alkyl; r₁' -CO-, wherein R₁' represents C₁-C₁₀Alkyl of (C)₃-C₁₀And optionally, at least one hydrogen atom in the phenyl group may be replaced by C₁-C₈And alkyl is straight chain alkyl or branched chain alkyl; r₂’-CO-O-R₃' -, wherein R₂' represents C₁-C₁₀Alkyl, phenyl, R₃' represents null, C₁-C₈Alkoxy of, or C₃-C₈Optionally, at least one hydrogen atom in the phenyl group may be replaced by C₁-C₈And alkyl is straight chain alkyl or branched alkyl; r₄’-O-CO-R₅' -, wherein R₄' represents C₁-C₁₀Alkyl of R₅' represents C₁-C₁₀And optionally, R₄' and R₅' of-CH₂-may be substituted by-O-and alkyl is straight or branched alkyl; c₂-C₁₀Linear or branched alkenyl of (a); with C₃-C₁₀Cycloalkyl or C₆-C₂₀Aryl of (A) is end-capped C₂-C₈Alkenyl of (a); c₂-C₁₀Straight or branched alkynyl of (a); c₁-C₁₀Optionally, the hydrogen on the alkyl group may be substituted by a fluorine atom; or C₆-C₂₀Arylsulfonyloxy of (a); provided that R is₂-R₇Not hydrogen at the same time.

Further, the above-mentioned R₁Is C₁-C₆Linear or branched perfluoroalkyl, perfluorophenyl, at least one hydrogen atom being replaced by C₁-C₆Phenyl or camphoryl substituted by alkyl or fluoroalkyl of (A), preferably R₁Is perfluoromethyl, perfluoroethyl, perfluoropropyl, perfluorobutyl, perfluoropentyl, perfluorophenyl, camphoryl, p-methylphenyl or perfluoromethylphenyl.

Further, the above-mentioned R₂、R₄-R₇Is hydrogen, R₃Selected from the following groups: halogen; c₁-C₁₀An alkyl group or a halogenated alkyl group of (a),optionally, wherein-CH₂-may be substituted by-O-; phenyl, optionally, in which at least one hydrogen atom may be replaced by C₁-C₄Alkyl or alkoxy of (a); c₇-C₁₀Optionally, at least one hydrogen atom on the phenyl group may be replaced by C₁-C₄Substituted by alkyl or alkoxy groups, -CH in alkyl₂-may be substituted by-O-or-S-; r₁' -CO-, wherein R₁' represents C₁-C₆Alkyl of (C)₃-C₆And optionally, at least one hydrogen atom in the phenyl group may be replaced by C₁-C₄Alkyl or alkoxy of (a); r₂’-CO-O-R₃' -, wherein R₂' represents C₁-C₈Alkyl, phenyl, R₃' represents null, C₁-C₄Alkoxy of, or C₃-C₄Optionally, at least one hydrogen atom in the phenyl group may be replaced by C₁-C₄Alkyl of (a); r₄’-O-CO-R₅' -, wherein R₄' represents C₁-C₆Alkyl of R₅' represents C₁-C₆And optionally, R₄' and R₅' of-CH₂-may be substituted by-O-; c₂-C₆Linear or branched alkenyl of (a); with C₃-C₆Cycloalkyl or C₆-C₁₀Aryl of (A) is end-capped C₂-C₄Alkenyl of (a); c₂-C₆Straight or branched alkynyl of (a); c₁-C₆Optionally, the hydrogen on the alkyl group may be substituted by a fluorine atom; or C₆-C₁₀Arylsulfonyloxy of (a).

Further, the above-mentioned R₂-R₇One of the groups is selected from any one of methyl, ethyl, propyl, butyl and amyl, and the rest is H; or R₂、R₄-R₇Is hydrogen, R₃Any one selected from the following groups: halogen, halomethyl, haloethyl; or R₂、R₄-R₇Is a hydrogen atom, and is,R₃any one selected from the following groups: methyl, ethyl, propyl, butyl, pentyl, and one of them-CH₂-is substituted by-O-; or R₂、R₄-R₇Is hydrogen, R₃Any one selected from the following groups: c₇-C₁₀Optionally, a hydrogen atom on the phenyl group may be replaced by a methyl group, and/or a-CH group in the alkyl group₂-may be substituted by-O-or-S-; or R₂、R₄-R₇Is hydrogen, R₃Any one selected from the following groups: r₁' -CO-, wherein R₁' represents a methyl group, an ethyl group, a propyl group, a cyclohexyl group, a phenyl group, a methylphenyl group, an ethylphenyl group, a tert-butylphenyl group, an alkoxymethylphenyl group or an alkoxyethylphenyl group; or R₂、R₄-R₇Is hydrogen, R₃Any one selected from the following groups: r₂’-CO-O-R₃' -, wherein R₂' represents methyl, ethyl, propyl or phenyl, one of the hydrogen atoms of which may be replaced by methyl, R₃' represents a null or propynyl group; or R₂、R₄-R₇Is hydrogen, R₃Any one selected from the following groups: r₄’-O-CO-R₅' -, wherein R₄' represents methyl, ethyl, propyl, butyl, pentyl or hexyl, R₅' represents a methylene group or an ethylene group, and R₄' and R₅One of ` -CH₂-may be substituted by-O-; or R₂、R₄-R₇Is hydrogen, R₃Any one selected from the following groups: a straight chain butenyl group, a branched butenyl group, a phenyl terminated propenyl group, or a cyclohexyl terminated propenyl group; or R₂、R₄-R₇Is hydrogen, R₃Any one selected from the following groups: ethynyl, propynyl, butynyl or pentynyl; or R₂、R₄-R₇Is hydrogen, R₃Any one selected from the following groups: c₁-C₆A methylsulfonyloxy group, a trifluoromethylsulfonyloxy group, a butylsulfonyloxy group, a phenylsulfonyloxy group or a p-methylphenylsulfonyloxy group.

Further, the above-mentioned sulfonyl imide photoacid generator is selected from any one of the following structural formulae:

further, the above resin component has an acid-labile group protected by a protecting group; the acid labile group comprises at least one of carboxyl and phenolic hydroxyl; and the content of the acid labile group accounts for 1-80% of the content of the resin component, preferably 3-70%.

Further, the above-mentioned protecting group includes at least one of the following groups:

wherein R is₈、R₉、R₁₀Each independently represents a group having C₁-C₆Alkyl of (C)₁-C₁₀Wherein the alkyl group is a straight-chain or branched-chain alkyl group, and R₈、R₉、R₁₀Any two of which are adapted to bond to each other to form a ring; r₁₁、R₁₂And R₁₃Each independently represents C₁-C₂₀And R is a hydrocarbon group of₁₁、R₁₂、R₁₃Are adapted to key each otherSynthesizing a ring; r₁₄Is represented by having C₁-C₆Straight chain alkyl group of (1), C₁-C₆Branched alkyl of C₁-C₆And n is 0 or 1.

Further, the weight content of the acid generator is 0.5 to 5%, preferably 1 to 3%, relative to the mass of the solid content of the photosensitive resin composition, and the resin component is preferably selected from any one of (meth) acrylic resin, polyhydroxystyrene resin and phenolic resin polymer.

Further, the resin composition further includes an aromatic carboxylic acid compound, and the aromatic carboxylic acid compound is preferably contained in an amount of 3 to 35% by weight based on the mass of the solid content of the photosensitive resin composition.

Further, the resin composition further includes a bridging compound, and the content of the bridging compound is preferably 10 to 50% by weight based on the mass of the solid content of the photosensitive resin composition.

Further, the photosensitive resin composition may further include a solvent.

According to another aspect of the present invention, there is provided a patterning method comprising mixing, film forming and patterning a photosensitive resin composition, which is any one of the photosensitive resin compositions described above.

According to another aspect of the present invention, there is provided a use of the photosensitive resin composition of any one of the above, including a use of the photosensitive composition in the preparation of a protective film, an interlayer insulating material, a pattern transfer material for an electronic component.

By applying the technical scheme of the invention, the molecules of the sulfonyl imide photo-acid generator with the general formula (A) contain sulfonate groups, the sulfonate groups are directly connected with an imide structure, and the structure has a photosensitive cracking characteristic and can be photolyzed under the irradiation of active energy rays to generate stronger sulfonic acid. When the photosensitive resin composition comprising the sulfonyl imide photoacid generator and a resin component is used for a positive photosensitive composition subjected to dissolution exposure by an alkali developing solution, a pattern having excellent sensitivity and good contrast can be formed due to the increase in sensitivity of the sulfonyl imide photoacid generator during patterning, and sufficiently high sensitivity can be obtained even when a fine pattern is formed. The active energy ray is an active energy ray having a wavelength of 300-450nm in the near ultraviolet region and the visible light region, and particularly active energy rays having a wavelength of 365nm (I line) and 405nm (H line) are preferable, thereby further improving the resolution and the sensitivity.

Detailed Description

It should be noted that the embodiments and features of the embodiments in the present application may be combined with each other without conflict. The present invention will be described in detail with reference to examples.

The positive resist composition of the prior art has insufficient sensitivity when forming a fine pattern, and in order to solve this problem, the present application provides a photosensitive resin composition, a patterning method, and an application of the photosensitive resin composition.

In one exemplary embodiment of the present application, there is provided a photosensitive resin composition including a resin component and an acid generator, the acid generator being a sulfimide photoacid generator having a structure represented by the following general formula (a):

wherein R is₁Is represented by C₁-C₂₀Alkyl of (C)₁-C₂₀Fluoroalkyl of, C₆-C₁₈And wherein the alkyl group is a straight-chain alkyl group or a branched-chain alkyl group; r₂-R₇Each independently represents the following group: hydrogen; halogen; c₁-C₂₀Optionally, -CH therein₂-may be substituted by-O-and alkyl is straight or branched alkyl; phenyl, optionally, in which at least one hydrogen atom may be replaced by C₁-C₈Alkyl or alkoxy of (a); c₇-C₂₀Phenylalkyl of (a), optionally, on phenyl toOne less hydrogen atom may be replaced by C₁-C₈Substituted by alkyl or alkoxy groups, -CH in alkyl₂-may be substituted by-O-or-S-and alkyl is straight or branched alkyl; r₁' -CO-, wherein R₁' represents C₁-C₁₀Alkyl of (C)₃-C₁₀And optionally, at least one hydrogen atom in the phenyl group may be replaced by C₁-C₈And alkyl is straight chain alkyl or branched chain alkyl; r₂’-CO-O-R₃' -, wherein R₂' represents C₁-C₁₀Alkyl, phenyl, R₃' represents null, C₁-C₈Alkoxy of, or C₃-C₈Optionally, at least one hydrogen atom in the phenyl group may be replaced by C₁-C₈And alkyl is straight chain alkyl or branched alkyl; r₄’-O-CO-R₅' -, wherein R₄' represents C₁-C₁₀Alkyl of R₅' represents C₁-C₁₀And optionally, R₄' and R₅' of-CH₂-may be substituted by-O-and alkyl is straight or branched alkyl; c₂-C₁₀Linear or branched alkenyl of (a); with C₃-C₁₀Cycloalkyl or C₆-C₂₀Aryl of (A) is end-capped C₂-C₈Alkenyl of (a); c₂-C₁₀Straight or branched alkynyl of (a); c₁-C₁₀Optionally, the hydrogen on the alkyl group may be substituted by a fluorine atom; or C₆-C₂₀Arylsulfonyloxy of (a); provided that R is₂-R₇Not hydrogen at the same time.

The molecules of the sulfonyl imide photo-acid generator with the general formula (A) contain sulfonate groups, the sulfonate groups are directly connected with an imide structure, and the structure has a photosensitive cracking characteristic and can be photolyzed under the irradiation of active energy rays to generate strong sulfonic acid. When the photosensitive resin composition comprising the sulfonyl imide photoacid generator and a resin component is used for a positive photosensitive composition subjected to dissolution exposure by an alkali developing solution, a pattern having excellent sensitivity and good contrast can be formed due to the increase in sensitivity of the sulfonyl imide photoacid generator during patterning, and sufficiently high sensitivity can be obtained even when a fine pattern is formed. The active energy ray is an active energy ray having a wavelength of 300-450nm in the near ultraviolet region and the visible light region, and particularly active energy rays having a wavelength of 365nm (I line) and 405nm (H line) are preferable, thereby further improving the resolution and the sensitivity.

In order to further improve the structural stability and performance of the above-mentioned sulfonamide photoacid generator, the above-mentioned R is preferably used₁Is C₁-C₆Linear or branched perfluoroalkyl, perfluorophenyl, at least one hydrogen atom being replaced by C₁-C₆Phenyl or camphoryl substituted by alkyl or fluoroalkyl of (A), preferably R₁Is perfluoromethyl, perfluoroethyl, perfluoropropyl, perfluorobutyl, perfluoropentyl, perfluorophenyl, camphoryl, p-methylphenyl or perfluoromethylphenyl.

Preferably, R is as defined above₂、R₄-R₇Is hydrogen, R₃Selected from the following groups: halogen; c₁-C₁₀Optionally, -CH therein₂-may be substituted by-O-; phenyl, optionally, in which at least one hydrogen atom may be replaced by C₁-C₄Alkyl or alkoxy of (a); c₇-C₁₀Optionally, at least one hydrogen atom on the phenyl group may be replaced by C₁-C₄Substituted by alkyl or alkoxy groups, -CH in alkyl₂-may be substituted by-O-or-S-; r₁' -CO-, wherein R₁' represents C₁-C₆Alkyl of (C)₃-C₆And optionally, at least one hydrogen atom in the phenyl group may be replaced by C₁-C₄Alkyl or alkoxy of (a); r₂’-CO-O-R₃' -, wherein R₂' represents C₁-C₈Alkyl, phenyl, R₃' represents null, C₁-C₄Alkoxy of, or C₃-C₄Optionally, at least one hydrogen atom in the phenyl group may be replaced by C₁-C₄Alkyl of (a); r₄’-O-CO-R₅' -, wherein R₄' represents C₁-C₆Alkyl of R₅' represents C₁-C₆And optionally, R₄' and R₅' of-CH₂-may be substituted by-O-; c₂-C₆Linear or branched alkenyl of (a); with C₃-C₆Cycloalkyl or C₆-C₁₀Aryl of (A) is end-capped C₂-C₄Alkenyl of (a); c₂-C₆Straight or branched alkynyl of (a); c₁-C₆Optionally, the hydrogen on the alkyl group may be substituted by a fluorine atom; or C₆-C₁₀Arylsulfonyloxy of (a).

Preferably, R is as defined above₂-R₇One of the groups is selected from any one of methyl, ethyl, propyl, butyl and amyl, and the rest is H; or R₂、R₄-R₇Is hydrogen, R₃Any one selected from the following groups: halogen, halomethyl, haloethyl; or R₂、R₄-R₇Is hydrogen, R₃Any one selected from the following groups: methyl, ethyl, propyl, butyl, pentyl, and one of them-CH₂-is substituted by-O-; or R₂、R₄-R₇Is hydrogen, R₃Any one selected from the following groups: c₇-C₁₀Optionally, a hydrogen atom on the phenyl group may be replaced by a methyl group, and/or a-CH group in the alkyl group₂-may be substituted by-O-or-S-; or R₂、R₄-R₇Is hydrogen, R₃Any one selected from the following groups: r₁' -CO-, wherein R₁' represents a methyl group, an ethyl group, a propyl group, a cyclohexyl group, a phenyl group, a methylphenyl group, an ethylphenyl group, a tert-butylphenyl group, an alkoxymethylphenyl group or an alkoxyethylphenyl group; or R₂、R₄-R₇Is hydrogen, R₃Any one selected from the following groups: r₂’-CO-O-R₃' -, wherein R₂' represents methyl, ethyl, propyl or phenyl, one of the hydrogen atoms of which may be replaced by methyl, R₃' represents a null or propynyl group; or R₂、R₄-R₇Is hydrogen, R₃Any one selected from the following groups: r₄’-O-CO-R₅' -, wherein R₄' represents methyl, ethyl, propyl, butyl, pentyl or hexyl, R₅' represents a methylene group or an ethylene group, and R₄' and R₅One of ` -CH₂-may be substituted by-O-; or R₂、R₄-R₇Is hydrogen, R₃Any one selected from the following groups: a straight chain butenyl group, a branched butenyl group, a phenyl terminated propenyl group, or a cyclohexyl terminated propenyl group; or R₂、R₄-R₇Is hydrogen, R₃Any one selected from the following groups: ethynyl, propynyl, butynyl or pentynyl; or R₂、R₄-R₇Is hydrogen, R₃Any one selected from the following groups: c₁-C₆A methylsulfonyloxy group, a trifluoromethylsulfonyloxy group, a butylsulfonyloxy group, a phenylsulfonyloxy group or a p-methylphenylsulfonyloxy group.

In one embodiment, the above-mentioned sulfonyl imide photoacid generator is selected from any one of the following structural formulas:

the resin component used in the present application may be a resin commonly used in photosensitive resin compositions, and it is preferable in the present application that the above resin component has an acid-labile group protected by a protecting group.

Wherein the acid labile group comprises at least one of a carboxyl group, a phenolic hydroxyl group, which may be derived from (meth) acrylic acid (acrylic resin), a polymer with hydroxystyrene (polyhydroxystyrene resin) and a phenolic resin polymer; the content of the acid labile group is 1 to 80%, preferably 3 to 70%, and optionally 26% or 45% of the content of the resin component, and when within this range, the photosensitive composition can have better developability.

Alternatively, the above hydroxystyrene resin is a polymer of a monomer containing a styrene compound, and may be selected from p-hydroxystyrene, α -methylhydroxystyrene, α -ethylhydroxystyrene, and the like.

The hydroxystyrene resin is preferably a copolymer of a hydroxystyrene compound and a styrene compound, and may be selected from styrene, chlorostyrene, chloromethylstyrene, vinyltoluene, α -methylstyrene, and the like. And the hydroxystyrene resin preferably has a molecular weight of 1000 to 50000. As the resin component, a resin in which at least a part of the hydroxyl groups of the hydroxystyrene resin is protected with a protecting group is used. As described above, the polyhydroxystyrene resin may be incorporated with a crosslinking group as required. A crosslinking group, i.e., a functional group that can be crosslinked thermally when a patterned film to be formed is post-baked. The group suitable for crosslinking may be selected from epoxy groups, oxetanyl groups and groups containing unsaturated double bonds (e.g., (meth) acryloyl groups in the resin component, the content of the crosslinking groups is preferably 20 to 70% (w/w), in which a film having excellent mechanical properties and chemical resistance can be formed by thermal crosslinking between the crosslinking groups during PEB (post-exposure heating).

Alternatively, the acrylic resin is preferably a resin obtained by copolymerizing (meth) acrylic acid with another monomer having an unsaturated bond. The monomer copolymerizable with (meth) acrylic acid may be selected from unsaturated carboxylic acids other than (meth) acrylic acid, (meth) acrylic acid esters, (meth) acrylamides, allyl compounds, vinyl ethers, and the like. Among them, the unsaturated carboxylic acid is preferably a monocarboxylic acid of (meth) acrylic acid, a dicarboxylic acid of maleic acid. The linear or branched (meth) acrylate may be selected from methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, pentyl (meth) acrylate, t-octyl (meth) acrylate, and the like. Among the (meth) acrylates having no epoxy group, a (meth) acrylate having an alicyclic skeleton is preferable, and in the (meth) acrylate having an alicyclic skeleton, the alicyclic group may be monocyclic or polycyclic, the monocyclic alicyclic group may be selected from cyclopentyl and cyclohexyl, and the polycyclic alicyclic group may be selected from norbornyl, isobornyl, tricyclononyl and the like.

The (meth) acrylamide includes (meth) acrylamide, (meth) N-alkyl (meth) acrylamide, (meth) N-aryl (meth) acrylamide, N-methyl-N-phenyl (meth) acrylamide, N-hydroxyethyl-N-methyl (meth) acrylamide and the like. The allyl compounds include allyl acetate, allyl caproate, allyl caprylate, allyl laurate, allyl palmitate, allyl stearate, allyl benzoate, allyl acetoacetate, allyl lactate, and the like. Vinyl ethers include hexyl vinyl ether, octyl vinyl ether, ethylhexyl vinyl ether, methoxyethyl vinyl ether, ethoxyethyl vinyl ether, chloroethyl vinyl ether, 1-methyl-2, 2-dimethylpropyl vinyl ether, 2-ethylbutyl vinyl ether, hydroxyethyl vinyl ether, diethylene glycol vinyl ether, dimethylaminoethyl vinyl ether, diethylaminoethyl vinyl ether, benzyl vinyl ether, and the like.

Alternatively, the novolak resin can be obtained by addition-condensing an aromatic compound having a phenolic hydroxyl group (hereinafter, simply referred to as "phenol") with an aldehyde under an acid catalyst. The phenol may be selected from phenol, o-cresol, m-cresol, p-cresol, o-ethylphenol, m-ethylphenol, p-ethylphenol, o-butylphenol, m-butylphenol, p-butylphenol, 2, 3-xylenol, 2, 4-xylenol, 2, 5-xylenol, 2, 6-xylenol, 3, 4-xylenol, 3, 5-xylenol, 2,3, 5-trimethylphenol, 3,4, 5-trimethylphenol, p-phenol, resorcinol, hydroquinone monomethyl ether, pyrogallol, phloroglucinol, hydroxydiphenyl, bisphenol a, gallic acid, alpha-naphthol, beta-naphthol, and the like. The aldehyde can be selected from formaldehyde, acetaldehyde, furfural, benzaldehyde, nitrobenzaldehyde, etc. The acid catalyst may be selected from hydrochloric acid, sulfuric acid, formic acid, acetic acid, oxalic acid, and the like. The molecular weight of the novolac resin is preferably 1000 to 50000, and a resin in which at least a part of the hydroxyl groups of the novolac resin is protected by a protecting group can be used as a resin component. As described above, a crosslinking group such as a carboxyl group bonded to an aromatic group, an alcoholic hydroxyl group, and a cyclic ether group can be introduced into the novolak resin as needed.

Further, it is preferable that the above-mentioned protecting group includes at least one of the following groups:

wherein R is₈、R₉、R₁₀Each independently represents a group having C₁-C₆Alkyl of (C)₁-C₁₀Wherein the alkyl group is a straight-chain or branched-chain alkyl group, and R₈、R₉、R₁₀Any two of which are adapted to bond to each other to form a ring; r₁₁、R₁₂And R₁₃Each independently represents C₁-C₂₀And R is a hydrocarbon group of₁₁、R₁₂、R₁₃Any two of which are adapted to bond to each other to form a ring; r₁₄Is represented by having C₁-C₆Straight chain alkyl group of (1), C₁-C₆Branched alkyl of C₁-C₆And n is 0 or 1.

Specifically, in the formula (a), when R is₈、R₉And R₁₀When alkyl, exemplary groups can be selected from methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butylButyl, n-pentyl, isopentyl, tert-pentyl, n-hexyl, n-heptyl, n-octyl, 2-ethyl-n-hexyl, n-nonyl, n-decyl, and the like; when R is₃、R₄And R₅When any two groups in (1) are bonded to each other to form a ring, it is preferable to have C₅-C₂₀Exemplary monocyclic or polycyclic aliphatic hydrocarbons can be selected from cyclopentane, cyclohexane, cycloheptane, cyclooctane, adamantane, norbornane, tricyclodecane, tetracyclodecane, and the like; by binding to R₃、R₄And R₅The ring formed by any two of the groups may have a substituent such as a hydroxyl group, a cyano group and an oxygen atom (═ O), and have C₁-C₄Linear or branched alkyl. Preferably, formula (a) is selected from the following formulas₁-formula a₆) A group of (a);

formula a₁：

Formula a₂：

Formula a₃：

Formula a₄：

Formula a₅：

Formula a₆：

Specifically, in the formula (b), R₁₁、R₁₂And R₁₃To have C₁-C₂₀Aliphatic or/and aromatic hydrocarbon groups. When R is₁₁、R₁₂And R₁₃When the aliphatic hydrocarbon group is used, the aliphatic hydrocarbon group may have a linear structure selected from the group consisting of methyl, ethyl, n-propyl, and iso-propyl, and a cyclic structurePropyl, n-butyl and isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, tert-pentyl, n-hexyl, n-heptyl, n-octyl, 2-ethyl-n-hexyl, n-nonyl, n-decyl, and n-undecyl groups, and the like; the cyclic structure is selected from the group consisting of cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclononyl, cyclodecyl, cycloundecyl, cyclododecyl, and polycyclic groups of the formula (formula b)₁-formula b₈)；

Formula b₁：

Formula b₂：

Formula b₃：

Formula b₄：

Formula b₅：

Formula b₆：

Formula b₇：

Formula b₈：

And, in formula (b), when R is₁₁、R₁₂And R₁₃When it is an aromatic hydrocarbon group, it may be selected from phenyl, naphthyl, anthryl, biphenyl, phenanthryl and fluorenyl groups. When R is₁₁、R₁₂And R₁₃When both aliphatic and aromatic groups are present, the aromatic group is selected from benzyl, phenethyl, 3-phenyl-n-propyl, 4-benzeneThe group-n-butyl, α -naphthylmethyl, β -naphthylmethyl, 2- (. alpha. -naphthyl) ethyl, 2- (. beta. -naphthyl) ethyl, and the like. The aromatic ring may be substituted or partially substituted, the substituent being selected from the group consisting of a halogen atom, a hydroxyl group, a C₁-C₁₀Alkyl or alkoxy of, C₂-C₁₀Alkanoyl and alkanoyloxy of (a). In the formula (b), R₁₁Preferably a hydrogen atom, R₁₂Preferably methyl, R₁₃Preferably ethyl, isobutyl, cyclohexyl, 2-ethyl-n-hexyl or octadecyl; when R is₁₂And R₁₃When they are bonded to each other to form a ring, C containing O, S or N atom is preferable₄-C₆A heterocycle; when R is₁₁And R₁₂When they are bonded to each other to form a ring, C is preferred₃-C₁₂A saturated aliphatic hydrocarbon ring.

Preferably, formula (b) may preferably be represented by the following formula (formula b)₉-formula b₁₄) The group of (a):

formula b₉：

Formula b₁₀：

Formula b₁₁：

Formula b₁₂：

Formula b₁₃：

Formula b₁₄：

Specifically, the formula (c) can be selected from tert-butoxycarbonyl and tert-butoxycarbonylmethyl.

The amount of the acid generator can be referred to the amount of the acid generator conventionally used in the prior art, and in one embodiment, the weight content of the acid generator is 0.5 to 5%, preferably 1 to 3%, relative to the mass of the solid content of the photosensitive resin composition, and preferably the resin component is any one selected from (meth) acrylic resin, polyhydroxystyrene resin and phenolic resin polymer.

In another embodiment of the present application, the resin composition further comprises an aromatic carboxylic acid compound, i.e., at least one carboxyl group is bonded to an aromatic group, and the aromatic group may be an aromatic hydrocarbon group or an aromatic heterocyclic group. The aromatic carboxylic acid compound can promote deprotection reaction after exposure of the acid labile group protected by the protecting group in the resin component in the composition. When an aromatic carboxylic acid compound is used in combination with the above-described resin component and acid generator of the present application, the resolution of the pattern can be further improved. The aromatic carboxylic acid compound is preferably contained in an amount of 3 to 35% by weight based on the mass of the solid content of the photosensitive resin composition.

The aromatic carboxylic acid compound may be at least one selected from low molecular aromatic carboxylic acid compounds and high molecular aromatic carboxylic acid compounds; wherein the low molecular aromatic carboxylic acid compound comprises monocarboxylic acid compound, polycarboxylic acid compound with at least two carboxyl and/or substituent groups; the polymer aromatic carboxylic acid compound includes a polymer compound containing a carboxyl group and an unsaturated double bond bonded to an aromatic group.

In the aromatic carboxylic acid compound, 1 or more substituents may be present in addition to the carboxyl group, and may be selected from the group consisting of halogen, hydroxyl group, mercapto group, sulfide group, silyl group, silanol group, nitro group, nitroso group, sulfonate group, phosphono group, and phosphonate group; when the substituent on the aromatic group is an organic group, it may be selected from alkyl, alkenyl, cycloalkyl, cycloalkenyl, aryl and aralkyl; the organic group may contain a bond or substituent other than the hydrocarbon group, such as heteroatoms like O, Si, N, etc., and the bond of the heteroatom may include ether, thioether, carbonyl, thiocarbonyl, ester, amide, carbamate and imino, carbonate, sulfonyl, sulfinyl and azo bonds, etc. The organic group may be linear, branched or cyclic. As on aromatic groupsSubstituent, preferably having C₁-C₁₂Alkyl, aryl, alkoxy and halogen.

The aromatic carboxylic acid compound may be a low molecular compound such as benzoic acid or naphthoic acid, or a high molecular compound having a carboxyl group bonded to an aromatic group, and specifically, the following may be mentioned:

the low molecular weight aromatic carboxylic acid compound may be a monocarboxylic acid compound or a polyvalent carboxylic acid compound having two or more carboxyl groups. The aromatic group contained in the low-molecular weight aromatic carboxylic acid compound may have a substituent other than a carboxyl group. The low molecular weight aromatic carboxylic acid compound may be selected from the following carboxylic acids: benzoic acid; hydroxybenzoic acids such as salicylic acid, m-hydroxybenzoic acid and p-hydroxybenzoic acid, etc.; alkylbenzoic acids such as o-methylbenzoic acid, m-methylbenzoic acid and p-methylbenzoic acid; halogenated benzoic acids such as o-chlorobenzoic acid, m-chlorobenzoic acid, p-chlorobenzoic acid, o-bromobenzoic acid, m-bromobenzoic acid and p-bromobenzoic acid; alkoxybenzoic acids such as o-methoxybenzoic acid, m-methoxybenzoic acid, p-methoxybenzoic acid, o-ethoxybenzoic acid, m-ethoxybenzoic acid and p-ethoxybenzoic acid; aminobenzoic acids such as anthranilic acid, m-aminobenzoic acid and p-aminobenzoic acid; acyloxybenzoic acids such as o-acetoxybenzoic acid, m-acetoxybenzoic acid and p-acetoxybenzoic acid; naphthoic acids such as 1-naphthoic acid and 2-naphthoic acid; hydroxynaphthoic acids such as 1-hydroxy-2-naphthoic acid, 1-hydroxy-3-naphthoic acid, 1-hydroxy-4-naphthoic acid, 1-hydroxy-5-naphthoic acid, 1-hydroxy-6-naphthoic acid, 1-hydroxy-7-naphthoic acid, 1-hydroxy-8-naphthoic acid, 2-hydroxy-1-naphthoic acid, 2-hydroxy-3-naphthoic acid, 2-hydroxy-4-naphthoic acid, 2-hydroxy-5-naphthoic acid, 2-hydroxy-6-naphthoic acid, 2-hydroxy-7-naphthoic acid, and 2-hydroxy-8-naphthoic acid; aminonaphthoic acids such as 1-amino-2-naphthoic acid, 1-amino-3-naphthoic acid, 1-amino-4-naphthoic acid, 1-amino-5-naphthoic acid, 1-amino-6-naphthoic acid, 1-amino-7-naphthoic acid, 1-amino-8-naphthoic acid, 2-amino-1-naphthoic acid, 2-amino-3-naphthoic acid, 2-amino-4-naphthoic acid, 2-amino-5-naphthoic acid, 2-amino-6-naphthoic acid, 2-amino-7-naphthoic acid and 2-amino-8-naphthoic acid; alkoxy naphthoic acids such as 1-methoxy-2-naphthoic acid, 1-methoxy-3-naphthoic acid, 1-methoxy-4-naphthoic acid, 1-methoxy-5-naphthoic acid, 1-methoxy-6-naphthoic acid, 1-methoxy-7-naphthoic acid, 1-methoxy-8-naphthoic acid, 2-methoxy-1-naphthoic acid, 2-methoxy-3-naphthoic acid, 2-methoxy-4-naphthoic acid, 2-methoxy-5-naphthoic acid, 2-methoxy-6-naphthoic acid, 2-methoxy-7-naphthoic acid, 2-methoxy-8-naphthoic acid, 1-ethoxy-2-naphthoic acid, 1-methoxy-3-naphthoic acid, 1-methoxy-2-naphthoic acid, 1-methoxy-4-naphthoic acid, 2-methoxy-5-naphthoic acid, 2-methoxy-6-naphthoic acid, 1-methoxy-8-naphthoic acid, 2-methoxy-4-naphthoic acid, 1-methoxy-4-naphthoic acid, 2-naphthoic acid, 1-methoxy-4-naphthoic acid, 1-methoxy-4-naphthoic acid, 2-methoxy-naphthoic acid, 2-methoxy-8-naphthoic acid, and 1-naphthoic acid, 1-ethoxy-3-naphthoic acid, 1-ethoxy-4-naphthoic acid, 1-ethoxy-5-naphthoic acid, 1-ethoxy-6-naphthoic acid, 1-ethoxy-7-naphthoic acid, 1-ethoxy-8-naphthoic acid, 2-ethoxy-1-naphthoic acid, 2-ethoxy-3-naphthoic acid, 2-ethoxy-4-naphthoic acid, 2-ethoxy-5-naphthoic acid, 2-ethoxy-6-naphthoic acid, 2-ethoxy-7-naphthoic acid, 2-ethoxy-8-naphthoic acid, and the like; phthalic acids such as phthalic acid, terephthalic acid and isophthalic acid; naphthalenedicarboxylic acids such as 1, 2-naphthalenedicarboxylic acid, 1, 3-naphthalenedicarboxylic acid, 1, 4-naphthalenedicarboxylic acid, 1, 5-naphthalenedicarboxylic acid, 1, 6-naphthalenedicarboxylic acid, 1, 7-naphthalenedicarboxylic acid, 1, 8-naphthalenedicarboxylic acid, 2, 3-naphthalenedicarboxylic acid, 2, 6-naphthalenedicarboxylic acid and 2, 7-naphthalenedicarboxylic acid; biphenyl carboxylic acids such as 1,1 ' -biphenyl-4-carboxylic acid, 1 ' -biphenyl-3-carboxylic acid and 1,1 ' -biphenyl-2-carboxylic acid; biphenyldicarboxylic acids such as 1,1 '-biphenyl-4, 4' -dicarboxylic acid, 1 '-biphenyl-3, 3' -dicarboxylic acid, 1 '-biphenyl-2, 2' -dicarboxylic acid, 1 '-biphenyl-3, 4' -dicarboxylic acid, 1 '-biphenyl-2, 4' -dicarboxylic acid and 1,1 '-biphenyl-2, 3' -dicarboxylic acid; trivalent or higher aromatic polycarboxylic acids such as pyromellitic acid, trimellitic acid, and trimellitic acid; hydroxybenzenedicarboxylic acids such as 5-hydroxyisophthalic acid, 4-hydroxyisophthalic acid and 2-hydroxyisophthalic acid; dihydroxybenzenedicarboxylic acids such as 2, 5-dihydroxyterephthalic acid, 2, 6-dihydroxyisophthalic acid, 4, 6-dihydroxyisophthalic acid, 2, 3-dihydroxyphthalic acid, 2, 4-dihydroxyphthalic acid, 3, 4-dihydroxyphthalic acid, and the like; pyridine carboxylic acids such as pyridine-2-carboxylic acid, pyridine-3-carboxylic acid and pyridine-4-carboxylic acid, etc.; dipicolinic acids such as pyridine-2, 5-dicarboxylic acid, pyridine-3, 5-dicarboxylic acid, pyridine-2, 6-dicarboxylic acid, pyridine-2, 4-dicarboxylic acid, and the like; pyrimidine carboxylic acids such as pyrimidine-2-carboxylic acid, pyrimidine-4-carboxylic acid, pyrimidine-5-carboxylic acid and pyrimidine-6-carboxylic acid; and pyrimidinedicarboxylic acids such as 2, 6-pyrimidinedicarboxylic acid and 2, 5-pyrimidinedicarboxylic acid. These low molecular weight aromatic carboxylic acid compounds may be used alone or in combination of two or more.

The high molecular weight aromatic carboxylic acid compound may be a high molecular weight compound having a carboxyl group bonded to an aromatic group. The monomer has a carboxyl group and an unsaturated double bond bonded to an aromatic group, and does not include an acid-labile group protected by a protecting group. The polymer can be used as a polymeric aromatic carboxylic acid compound. As a preferable copolymerization component, together with the monomer having a carboxyl group and an unsaturated double bond bonded to the aromatic group, the above-mentioned (meth) acrylic acid as a monomer for producing the acrylic resin, such as unsaturated carboxylic acids other than (meth) acrylic acid, (meth) acrylic acid esters, (meth) acrylamides, allyl compounds, vinyl ethers, vinyl esters and styrene, can be used.

In another embodiment of the present invention, the resin composition further comprises a bridging compound, and the content of the bridging compound is preferably 10 to 50% by weight based on the mass of the solid content of the photosensitive resin composition.

As the name implies, the bridging compound contains at least one crosslinking group that undergoes thermal crosslinking in the presence of PEB. Preferably, the above-mentioned crosslinking group includes an epoxy group, an oxetanyl group and a group containing an unsaturated double bond (e.g., vinyl group). The bridging group compound comprises: bridging group low molecular compound and bridging group high molecular compound.

The bridging group low-molecular compound comprises: at least one of a bifunctional or higher polyfunctional epoxy compound, a polyoxetane compound, a vinyl group-containing polymerizable monomer.

Alternatively, the polyfunctional epoxy compound may be selected from difunctional epoxy resins such as dialdehyde a type epoxy resin and bisphenol S type epoxy resin, etc.; glycidyl ester type epoxy resins such as dimer acid glycidyl ester, triglycidyl ester and the like; glycidyl amine type epoxy resins such as tetraglycidyl aminodiphenylmethane, tetraglycidyl bisaminomethylcyclohexane, and the like; heterocyclic epoxy resins such as triglycidyl isocyanurate and the like; polyfunctional epoxy resins such as phloroglucinol triglycidyl ether, tetrahydroxyphenylethane tetraglycidyl ether and the like. The alicyclic epoxy compound is also preferable as a polyfunctional epoxy compound, and a highly transparent film can be easily formed. Alternatively, the polyfunctional oxetane compound may be selected from 3, 3' - (oxybis-methylene) bis (3-ethyloxetane), 4-bis [ (3-ethyl-3-oxetanyl) methyl ] biphenyl, 3, 7-bis (3-oxetanyl) -5-oxanonane, and the like.

Alternatively, the polymerizable monomer includes monofunctional monomers and multifunctional monomers. The monofunctional monomer may be selected from the group consisting of (meth) acrylamide, methylol (meth) acrylamide, methoxymethyl (meth) acrylamide, ethoxymethyl (meth) acrylamide, propoxymethyl (meth) acrylamide, N-methylol (meth) acrylamide, (meth) acrylic acid, maleic acid, crotonic acid, 2-acrylamido-2-methylpropanesulfonic acid, t-butylacrylamide sulfonic acid, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate and glycerol mono (meth) acrylate, and these monofunctional monomers may be used alone or in combination of two or more. The polyfunctional monomer may be selected from the group consisting of propylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, 1, 6-hexanediol di (meth) acrylate, glycerol di (meth) acrylate, pentaerythritol triacrylate, pentaerythritol di (meth) acrylate, 2-bis (4- (meth) acryloyloxydiethoxyphenyl) propane, 2-hydroxy-3- (meth) acryloyloxypropyl (meth) acrylate, ethylene glycol diglycidyl ether di (meth) acrylate, diethylene glycol diglycidyl ether di (meth) acrylate, diglycidyl phthalate di (meth) acrylate, glycerol triacrylate, glycerol polyglycidyl ether poly (meth) acrylate, urethane (meth) acrylate (i.e., toluene diisocyanate), Trimethylhexamethylene diisocyanate and hexamethylene diisocyanate with 2-hydroxyethyl (meth) acrylate, methylenebis (meth) acrylamide, (meth) acrylamidomethylene ether, and the like, and these polyfunctional monomers may be used alone or in combination of two or more.

The bridged polymeric compound includes: at least one of epoxy group-containing resin and unsaturated double bond-containing resin. The epoxy-containing resin may be polymerized by an epoxy-containing monomer or a mixture of monomers, and may be selected from novolac epoxy resins, such as phenol novolac type epoxy resins, brominated phenol novolac type epoxy resins, and the like; alicyclic epoxy resins such as epoxidized products of dicyclopentadiene type phenol resins; and epoxidized products of aromatic epoxy resins, such as naphthalene-type phenolic resins.

Among the epoxy group-containing resins, aliphatic (meth) acrylates having chain aliphatic epoxy groups and aliphatic (meth) acrylates having alicyclic epoxy groups are preferable, and aliphatic (meth) acrylates having alicyclic epoxy groups are particularly preferable. In the polymer having an epoxy group, the content of the unit derived from the (meth) acrylate having an epoxy group is preferably 100% (w/w).

When the polymer having an epoxy group is a copolymer of a (meth) acrylate having an epoxy group and another monomer, the other monomer has an unsaturated carboxylic acid such as, but not limited to, maleic acid, citraconic acid; or (meth) acrylates having no epoxy group such as, but not limited to, methyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate; (meth) acrylamides such as, but not limited to, N-alkyl (meth) acrylamide, N-hydroxyethyl-N-methyl (meth) acrylamide; propyl compounds (such as, but not limited to, allyl acetate, allyl laurate), vinyl ethers (such as, but not limited to, hexyl vinyl ether, chloroethyl vinyl ether), vinyl esters (such as, but not limited to, vinyl butyrate, vinyl chloroacetate), styrenes (such as, but not limited to, styrene, chloromethyl styrene), and the like. These compounds may be used alone or in combination of two or more. From the chemical viewpoints of storage stability of the positive type composition and alkali resistance of a film formed using the positive type composition, etc., the copolymer of the (meth) acrylate having an epoxy group and the other monomer preferably does not contain a unit derived from an unsaturated carboxylic acid. The molecular weight of the epoxy group-containing resin is preferably 5000 to 15000.

The unsaturated double bond-containing resin may be selected from (meth) acrylic acid, maleic acid, 2-hydroxyethyl (meth) acrylate, ethylene glycol monomethyl ether (meth) acrylate, ethylene glycol monoethyl ether (meth) acrylate, glycerol (meth) acrylate, meth) acrylamide, acrylonitrile, methacrylonitrile, methyl (meth) acrylate, ethyl (meth) acrylate, propylene glycol di (meth) acrylate, an oligomer obtained by polymerizing pentaerythritol tri (meth) acrylate with 1, 6-hexanediol di (meth) acrylate, a dibasic epoxy diacrylate, and the like; a polyol and a monobasic acid or a polyester (meth) acrylate obtained by reacting (meth) acrylic acid with a polyester prepolymer obtained by condensing a polybasic acid.

Further, the ethylenically unsaturated group-containing resin is a resin obtained by reacting a reaction product of an epoxy compound and an unsaturated group-containing carboxylic acid compound with a polybasic acid anhydride or an unsaturated carboxylic acid. It is obtained by reacting at least a part of carboxyl groups contained in a polymer containing units derived from an epoxyalkyl (meth) acrylate having a (meth) acrylate and/or an alicyclic epoxy group. A resin (hereinafter collectively referred to as "resin containing a structural unit having an ethylenically unsaturated group") can be suitably used. The ethylenically unsaturated group in the structural unit having an ethylenically unsaturated group is preferably a (meth) acryloyloxy group.

The mass average molecular weight of the ethylenically unsaturated group-containing resin is preferably 2000 to 30000, and good heat resistance, film strength and good developability can be obtained.

Further, the photosensitive composition preferably further contains a solvent to facilitate film formation. The solvent is used in the photosensitive composition to adjust coating properties and viscosity. The solvent preferably contains an aprotic organic solvent, and a photosensitive composition having excellent sensitivity and resolution can be obtained. Can be selected from lactones, such as gamma-butyrolactone; ketones such as acetone, butanone, cyclohexanone, methyl-n-amyl ketone, methyl isoamyl ketone, and 2-heptanone; polyhydric alcohols such as ethylene glycol, diethylene glycol, propylene glycol and dipropylene glycol; a compound having an ester bond, such as ethylene glycol monoacetate, diethylene glycol monoacetate, propylene glycol monoacetate, dipropylene glycol monoacetate, ethylene glycol monoacetate, diethylene glycol monopropionate, propylene glycol monopropionate, or dipropylene glycol monopropionate; monoalkyl ethers or monophenyl ethers of compounds having an ester bond, such as methyl ether, ethyl ether, propyl ether, butyl ether, etc.; aromatic organic solvents such as anisole, ethylbenzyl ether, cresolmethyl ether, diphenyl ether, dibenzyl ether, phenol, butylphenyl ether, ethylbenzene, diethylbenzene, pentylbenzene, isopropylbenzene, toluene, xylene, isopropylbenzene and mesitylene; nitrogen-containing polar solvents such as N, N' -tetramethylurea, N-methyl-2-pyrrolidone, N-dimethylformamide, N-dimethylacetamide and hexamethylphosphoramide, and these organic solvents can be used alone or as a mixed solvent of two or more kinds. The content of the aprotic organic solvent in the solvent is preferably 100% (w/w).

Further, the solvent is preferably one or a mixture of two or more of Propylene Glycol Monomethyl Ether Acetate (PGMEA), cyclohexanone, γ -butyrolactone, and N, N-dimethylacetamide. In general, the amount of the solvent is selected so that the solid content concentration of the photosensitive composition is preferably 5 to 30% (w/w).

In addition, the photosensitive resin composition of the present application may further include the following auxiliary raw materials, as required for the function: any one or more of a dissolution control agent, a dissolution inhibitor, a basic compound, a surfactant, a dye, a pigment, a plasticizer, a photosensitizer, a light absorber, an antihalation agent, a storage stabilizer, a defoaming agent, an adhesion promoter, a phosphor, and a magnetic material.

Optionally, the photosensitizer is contained in an amount of 0.1 to 100% based on the sulfonate photoacid generator, and may be selected from compounds having at least one of an alkoxy group, a substituted carbonyloxy group, an oxo group (═ O) and a thiophene ring as a substituent, preferably a condensed polycyclic aromatic hydrocarbon compound or a condensed polycyclic aromatic heterocyclic compound (i.e. anthracene ring, tetra-benzene ring), and the substituent preferably has C₁-C₆Alkoxy of (C)₆-C₁₀Aryloxy of having C₂-C₇Alkanoyl of having C₇-C₁₁Aroyl, cyano, nitro, nitroso, halogen, hydroxy and mercapto.

Anthracycline-containing compounds suitable for use as photosensitizers include, but are not limited to: 9, 10-bis (acetoxy) anthracene, 9, 10-bis (propionyloxy) anthracene, 9, 10-bis (n-propylcarbonyloxy) anthracene, 9, 10-bis (n-butylcarbonyloxy) anthracene, 9, 10-bis (n-pentylcarbonyloxy) anthracene, 9, 10-bis (n-hexylcarbonyloxy) anthracene, 9, 10-bis (benzoyloxy) anthracene, 9, 10-bis (4-methylbenzoyloxy) anthracene, 9, 10-bis (2-naphthylmethoxy) anthracene, 2-methyl-9, 10-bis (acetoxy) anthracene, 2-methyl-9, 10-bis (propionyloxy) anthracene, 2-methyl-9, 10-bis (n-propylcarbonyloxy) anthracene, 2-methyl-9, 10-bis (n-butylcarbonyloxy) anthracene, 2-methyl-9, 10-bis (n-pentylcarbonyloxy) anthracene, 2-methyl-9, 10-bis (n-hexylcarbonyloxy) anthracene, 2-methyl-9, 10-bis (benzoyloxy) anthracene, 1-methyl-9, 10-bis (acetoxy) anthracene, 1-methyl-9, 10-bis (propionyloxy) anthracene, 1-methyl-9, 10-bis (n-propylcarbonyloxy) anthracene, 1-methyl-9, 10-bis (n-butylcarbonyloxy) anthracene, 1-methyl-9, 10-bis (n-pentylcarbonyloxy) anthracene, 1-methyl-9, 10-bis (n-hexylcarbonyloxy) anthracene, 1-methyl-9, 10-bis (benzoyloxy) anthracene, 1-methyl-9, 10-bis (2-naphthylmethoxy) anthracene, 2-ethyl-9, 10-bis (acetoxy) anthracene, 2-ethane-9, 10-bis (propionyloxy) anthracene, 2-ethyl-9, 10-bis (n-propylcarbonyloxy) anthracene, 2-ethyl-9, 10-bis (n-butylcarbonyloxy) anthracene, 2-ethyl-9, 10-bis (benzoyloxy) anthracene, 1-ethyl-9, 10-bis (acetoxy) anthracene, 1-ethyl-9, 10-bis (propionyloxy) anthracene, 1-ethyl-9, 10-bis (n-propylcarbonyloxy) anthracene, 1-ethyl-9, 10-bis (n-butylcarbonyloxy) anthracene, 1-ethyl-9, 10-bis (n-pentylcarbonyloxy) anthracene, 1-ethyl 9, 10-bis (benzoyloxy) anthracene, 1-ethyl-9, 10-bis (2-naphthoyloxy) anthracene, 1- (tert-butyl) -9, 10-bis (n-propylcarbonyloxy) anthracene, 1- (tert-butyl) -9, 10-bis (n-butylcarbonyloxy) anthracene, 1- (tert-butyl) -9, 10-bis (n-pentylcarbonyloxy) anthracene, - (tert-butyl) -9, 10-bis (n-hexylcarbonyl) oxy) anthracene, 1- (tert-butyl) -9, 10-bis (benzoyloxy) anthracene, 1- (tert-butyl) -9, 10-bis (4- (tert-butyl) -benzoyloxy) anthracene, 1- (tert-butyl) -9, 10-bis (2-naphthoxy) anthracene, 2- (tert-butyl) -9, 10-bis (n-propylcarbonyloxy) anthracene, 2- (tert-butyl) -9, 10-bis (n-butylcarbonyloxy) anthracene, 2- (tert-butyl) -9, 10-bis (n-pentylcarbonyloxy) anthracene, 2- (t-butyl) -9, 10-bis (n-hexylcarbonyloxy) anthracene, 2- (t-butyl) -9, 10-bis (2-naphthylmethoxy) anthracene, 2-pentyl-9, 10-bis (n-propylcarbonyloxy) anthracene, 2-pentyl-9, 10-bis (n-butylcarbonyl) oxy) anthracene, 2-pentyl-9, 10-bis (n-pentylcarbonyloxy) anthracene, 2-pentyl-9, 10-bis (benzoyloxy) anthracene, and 2-pentyl-9, 10-bis (2-naphthoyloxy) anthracene, and the like.

Compounds containing tetracene rings and suitable for use as photosensitizers include, but are not limited to: alkylcarbonyloxy-substituted tetracene compounds such as 2-methyl-5, 11-dioxo-6, 12-bis (acetoxy) tetracene, 2-ethyl-5, 11-dioxo-6, 12-bis (n-hexylcarbonyloxy) naphthalene and the like; aryloxy-substituted tetracene compounds such as 2-methyl-5, 11-dioxo-6, 12-bis (benzoyloxy) tetracene, 2-methyl-5, 11-dioxo-6, 12-bis (o-tolyloxy) tetracene and the like; aryloxycarbonyloxy substituted tetranaphthalene compounds such as 2-methyl-5, 11-dioxo-6, 12-bis (phenoxycarbonyloxy) naphthacene, and 2-ethyl-5, 11-dioxo-6, 12-bis (. alpha. -naphthyloxycarbonyloxy) naphthalene, and the like.

Other types of auxiliary agents can be selected by those skilled in the art from those commonly used in photosensitive resin compositions, and will not be described in detail herein.

In another exemplary embodiment of the present application, there is also provided a patterning method including mixing, film forming, and patterning a photosensitive resin composition, the photosensitive resin composition being any one of the photosensitive resin compositions described above.

The patterning method may specifically include: coating the photosensitive composition on a carrier, and pre-baking to form a coating film; selectively exposing the coating film; heating after exposure; and developing the exposed coating film with an alkaline developer. The specific operation is as follows:

the photosensitive composition is mixed and coated on a substrate (silicon substrate, metal substrate, glass substrate, inorganic and/or organic film), preferably by using a spinner; the formed coating film is subjected to prebaking at 80 to 120 ℃ for 40 to 120 seconds as required.

After a resist is formed on a substrate, a wiring pattern shape is irradiated with light. Actinic rays include low-pressure mercury lamps, medium-pressure mercury lamps, high-pressure mercury lamps, ultrahigh-pressure mercury lamps, xenon lamps, metal halide lamps, electron beam irradiation devices, X-ray irradiation devices, lasers (argon lasers, dye lasers, nitrogen lasers, LEDs, helium cadmium lasers), preferably high-pressure mercury lamps and LED lamps.

The post-exposure heating (PEB) temperature is 80-150 ℃, preferably 95-110 ℃, and the heating time is preferably 0.5-30 min. The deprotection reaction or the crosslinking reaction does not sufficiently proceed at a temperature lower than 40 ℃, and therefore there is not a sufficient difference in solubility between the ultraviolet irradiated portion and the ultraviolet unirradiated portion, and a pattern cannot be formed.

The development is performed with an alkali developer, and the alkali development method includes dissolving and removing the wiring pattern shape using an alkali developer. The alkaline developer is selected from 0.1-10% (w/w) aqueous solution of tetramethylammonium hydroxide, sodium hydroxide, potassium hydroxide, and sodium bicarbonate, and the alkaline developer may comprise water-soluble organic solvent such as methanol, ethanol, isopropanol, tetrahydrofuran, and N-methylpyrrolidone. The developing method may be selected from the group consisting of a dipping method, a spraying method and a spraying method, preferably a spraying method; the temperature of the developer is preferably 25 to 40 ℃, and the developing time is appropriately determined according to the thickness of the resist, so as to obtain a resist pattern faithful to the mask pattern.

Among them, the wavelength for exposure may be selected from g, h, i line, ArF excimer laser (wavelength 193nm), KrF excimer laser (wavelength 248nm), F2 excimer laser, EUV (extreme ultraviolet), VUV (vacuum ultraviolet), EB (electron beam), X-ray, and exposure may be performed using soft X-ray or the like. Among them, g, h, i lines, ArF excimer laser, KrF excimer laser, EUV and EB are preferable. Further, since a favorable pattern can be formed even when a photosensitive composition containing no compound which generates an acid or a radical by the action of light is used, ArF excimer laser (wavelength of 193nm) can be used, and EB (electron beam) is preferable.

In still another exemplary embodiment of the present application, there is provided a use of the photosensitive resin composition of any one of the above, including a use of the photosensitive composition in a protective film, an interlayer insulating material, a pattern transfer material of an electronic component.

The above applications may specifically include forming a photosensitive composition into an interlayer insulating film for a TFT or a panel of a liquid crystal display device; can also be used as a protective film for color filters and spacing columns, and also used as PS photoresist and BCS photoresist for pattern transfer.

The electronic components include, but are not limited to, liquid crystal display devices, organic EL display devices, Micro-LED, Mini-LED, and quantum dot LED display devices.

In order to facilitate the synthesis of the above-mentioned sulfonamide photoacid generators, the method for producing the sulfonamide photoacid generators of the present application will be briefly described below:

the preparation method comprises the following steps:

(1) 4-bromo-1, 8-naphthalic anhydride and indole derivative are subjected to coupling reaction to generate an intermediate 1, wherein the reaction formula is as follows:

(2) the intermediate 1 and hydroxylamine hydrochloride are subjected to a hydroxylamination reaction to generate an intermediate 2, wherein the reaction formula is as follows:

(3) intermediate 2 with sulfonic anhydride (R)₁-SO₂)₂O or sulfonyl chloride R₁-SO₂-Cl to give compound A, of the formula:

the reactions involved in steps (1) - (3) are conventional in the art of organic synthesis, and specific reaction conditions are readily determined by those skilled in the art, given the synthetic routes disclosed herein.

Without limitation, the reaction of step (1) is carried out in an organic solvent. The organic solvent to be used is not particularly limited as long as it can dissolve the raw materials and does not adversely affect the reaction, and examples thereof include dioxane, dichloroethane, t-butanol, toluene, xylene, DMF and DMSO.

The hydroxylamination reaction in step (2) and the esterification reaction in step (3) are likewise carried out in an organic solvent. The organic solvent to be used is not particularly limited as long as it can dissolve the raw materials and does not adversely affect the reaction, and examples thereof include methylene chloride, dichloroethane, benzene, toluene, xylene, and the like.

The starting materials used in the above preparation processes are all known compounds in the art and can be prepared commercially or conveniently by known synthetic methods such as coupling, Friedel-crafts, etc.

Examples of photosensitive compositions

Each raw material of the photosensitive composition was uniformly dissolved in 100% PGMEA (propylene glycol methyl ether acetate) to obtain a photosensitive composition having a solid content concentration of 20% (w/w). Wherein the types and contents of the resin component (a), the aromatic carboxylic acid compound (B), and the sulfonyl imide photoacid generator (C) are shown in table 1.

Example 1

Wherein the resin component (A) is A₁The structural formula of each component of the resin is shown as formula A₁₁-formula A₁₅As shown, the numerical value at the lower right of each repeating unit represents the content (mass%) of the repeating unit in the resin.

Formula A₁₁：

Formula A₁₂：

Formula A₁₃：

Formula A₁₄：

Formula A₁₅：

A sulfonamide photoacid generator (C) By C₁₁(i.e., I-9 above) type of the sulfonamide photoacid generator, which has the molecular formula:

formula C₁₁：

The remaining component types and contents are shown in table 1.

Example 2

Example 2 differs from example 1 in that,

the resin component (A) adopts A₁Type A and₃mixtures of resins of the type A₁Type A and₃the mass ratio of the type of resin is 7:3, A₁Resins of the type shown in formula A₁₁-formula A₁₅As shown, the numerical value at the lower right of each repeating unit represents the content (mass%) of the repeating unit in the resin.

Formula A₁₁：

Formula A₁₂：

Formula A₁₃：

Formula A₁₄：

Formula A₁₅：

A₃Resins of the type shown in formula A₃₁-formula A₃₂As shown, the numerical value at the lower right of each structural unit represents the content (mass%) of the repeating unit in the resin.

Formula A₃₁：

Formula A₃₂：

The remaining component types and contents are shown in table 1.

Example 3

Formula A₁₁：

Formula A₁₂：

Formula A₁₃：

Formula A₁₄：

Formula A₁₅：

Aromatic carboxylic acid compound (B)₁) The molar ratio is 1: 1 with 2,3,3 ', 4' -biphenyltetracarboxylic dianhydride.

A formula B':

the sulfoimide photo-acid generator (C) is C₁₁(i.e., I-9 above) type of the sulfonamide photoacid generator, which has the molecular formula:

formula C₁₁：

Example 4

Example 4 differs from example 3 in that,

the resin component (A) adopts A₂The structural formula of each component of the resin is shown as formula A₂₁-formula A₂₄As shown, the numerical value at the lower right of each repeating unit represents the content (mass%) of the repeating unit in the resin.

Formula A₂₁：

Formula A₂₂：

Formula A₂₃：

Formula A₂₄：

The remaining component types and contents are shown in table 1.

Example 5

Example 5 differs from example 3 in that,

the resin component (A) adopts A₃The structural formula of each component of the resin is shown as formula A₃₁-formula A₃₂As shown, the numerical value at the lower right of each structural unit represents the content (mass%) of the repeating unit in the resin.

Formula A₃₁：

Formula A₃₂：

The remaining component types and contents are shown in table 1.

Example 6

Example 6 differs from example 3 in that,

(1) the sulfoimide photo-acid generator (C) is C₁₂(i.e., I-13 above) type of the sulfonamide photoacid generator, which has the molecular formula:

formula C₁₂：

(2) The remaining component types and contents are shown in table 1.

Example 7

Example 7 differs from example 3 in that,

(1) the sulfoimide photo-acid generator (C) is C₁₃(i.e., I-16 above) type of the sulfonamide photoacid generator, which has the molecular formula:

formula C₁₃：

(2) The remaining component types and contents are shown in table 1.

Example 8 differs from example 3 in that,

(1) the sulfoimide photo-acid generator (C) is C₁₄(i.e., I-28 above) type of the sulfonamide photoacid generator, which has the molecular formula:

formula C₁₄：

(2) The remaining component types and contents are shown in table 1.

Example 9 differs from example 3 in that,

(1) the sulfoimide photo-acid generator (C) is C₁₅(i.e., I-46 above) type of the sulfonamide photoacid generator, which has the molecular formula:

formula C₁₅：

(2) The remaining component types and contents are shown in table 1.

Example 10

Example 10 differs from example 3 in that,

(1) using an aromatic diol (B') and tetrahydrophthalic anhydride in a ratio of 1: 1 molar ratio of the non-aromatic carboxylic acid compound B₂。

(2) The remaining component types and contents are shown in table 1.

Example 11

Example 11 differs from example 3 in that,

(1) using a non-aromatic carboxylic acid compound polymethacrylic acid (B)₃)。

(2) 1 part by mass of 2-isopropylthioxanthone was added as a photosensitizer.

(3) The remaining component types and contents are shown in table 1.

Example 12

Example 12 differs from example 3 in that,

(1)C₁₁the content of the type of sulfonate photoacid generator varies.

(2) 1 part by mass of 9, 10-bis (n-butoxy) anthracene was added as a photosensitizer.

(3) The remaining component types and contents are shown in table 1.

Example 13

Example 13 differs from example 3 in that,

C₁₁the content of the type of the sulfonamide photoacid generator is different.

The remaining component types and contents are shown in table 1.

Comparative example 1

Comparative example 1 differs from example 1 in that C is used as the sulfonyl imide photoacid generator (C)₂The type of the sulfonyl imide photoacid generator has a molecular formula structure as follows:

formula C₂：

The remaining component types and contents are shown in table 1.

Comparative example 2

Comparative example 2 is different from example 2 in that,

(1) the sulfoimide photo-acid generator (C) is C₂The type of the sulfonyl imide photoacid generator has a molecular formula structure as follows:

formula C₂：

(2) The remaining component types and contents are shown in table 1.

Comparative example 3

Comparative example 3 differs from example 3 in that,

formula C₂：

(2) The remaining component types and contents are shown in table 1.

The photosensitive compositions prepared in examples 1 to 13 and comparative examples 1 to 3 were evaluated for sensitivity and resolution by the following methods, and the results are reported in table 1.

(1) Sensitivity evaluation method

The photosensitive compositions of examples and comparative examples were applied to respective silicon wafers in a film thickness of 3 μm, which enables pattern formation, to form coating films. The formed coating film was prebaked at 90 ℃ for 100 seconds. After the prebaking, the coating film was exposed through a mask for hole pattern formation having a diameter of 10 μm while gradually changing the exposure amount, and then developed with a 2.0% tetramethylammonium hydroxide aqueous solution at 25 ℃ for 30 seconds. The minimum exposure required to form a 10 μm diameter hole pattern was determined by the method described above. From the obtained minimum exposure value, the sensitivity was evaluated according to the following criteria. (. smallcircle. -50 mJ/cm)²X-300mJ/cm²Above)

(2) Evaluation of resolution

A mask for forming a hole pattern having a diameter of 5 μm was used except at 100mJ/cm²Is exposed to an exposure dose ofThe coating film formation, the coating film exposure and the development were performed in the same manner as in the sensitivity evaluation. The coating film after development was observed, and the resolution was evaluated according to the following criteria. (. smallcircle. -a pattern with a diameter of 5 μm can be formed, X-a pattern with a diameter of 5 μm cannot be formed)

TABLE 1

As is clear from table 1, the resin component (a) having an acid group protected by a protecting group, the aromatic carboxylic acid compound (B) having a carboxyl group bonded to an aryl group, and the naphthalimide sulfonate (C) having a predetermined structure are mixed to form a photosensitive composition containing the derivative, and a pattern having excellent sensitivity and resolution can be formed. If the resin is not protected with a protecting group, a pattern cannot be formed.

As can be seen from example 1 and comparative example 1, when the photosensitive composition contains the sulfimide-based photoacid generator of the present invention, the photosensitive composition can obtain a desired sensitivity. As can be seen from examples 3, 10 and 11, even if the photosensitive composition contains a compound having a carboxyl group, when the compound does not have a carboxyl group bonded to an aromatic group, the resolution of the photosensitive composition cannot meet the requirements. Comparing example 2 with comparative example 2, it was found that indole derivative substituted naphthalimide sulfonates had better sensitivity and resolution. As can be seen from example 3 and comparative example 3, when the photosensitive composition contains the sulfonyl imide-based photoacid generator of the present invention, the photosensitive composition can obtain desired sensitivity and resolution.

As described above, the photosensitive composition of the present invention can be used as a positive photosensitive composition, which has a small difference between the opening width of a pattern mask and the pattern width, can form a fine pattern, can suppress the occurrence of undercut in the pattern after development, and has excellent sensitivity. Can be used as a photosensitive composition in a protective film, an interlayer insulating material or a pattern transfer material of electronic components such as a liquid crystal display device, an organic EL display device, a Micro-LED, a Mini-LED and a quantum dot LED display device.

The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.

Claims

1. A photosensitive resin composition comprises a resin component and an acid generator, and is characterized in that the acid generator is a sulfimide photoacid generator which has a structure represented by the following general formula (A):

wherein the content of the first and second substances,

R₁is represented by C₁-C₂₀Alkyl of (C)₁-C₂₀Fluoroalkyl of, C₆-C₁₈And wherein the alkyl group is a straight-chain alkyl group or a branched-chain alkyl group;

R₂-R₇each independently represents the following group:

hydrogen;

halogen;

C₁-C₂₀optionally, -CH therein₂-may be substituted by-O-and the alkyl is a straight or branched alkyl;

phenyl, optionally, in which at least one hydrogen atom may be replaced by C₁-C₈Alkyl or alkoxy of (a);

C₇-C₂₀optionally, at least one hydrogen atom on the phenyl group may be replaced by C₁-C₈Alkyl orSubstituted by alkoxy groups, -CH in alkyl₂-may be substituted by-O-or-S-and the alkyl is a straight or branched alkyl;

R₁' -CO-, wherein R₁' represents C₁-C₁₀Alkyl of (C)₃-C₁₀And optionally, at least one hydrogen atom in the phenyl group may be replaced by C₁-C₈And the alkyl group is a straight-chain alkyl group or a branched-chain alkyl group;

R₂’-CO-O-R₃' -, wherein R₂' represents C₁-C₁₀Alkyl, phenyl, R₃' represents null, C₁-C₈Alkoxy of, or C₃-C₈Optionally, at least one hydrogen atom in the phenyl group may be replaced by C₁-C₈And the alkyl is a straight chain or branched alkyl;

R₄’-O-CO-R₅' -, wherein R₄' represents C₁-C₁₀Alkyl of R₅' represents C₁-C₁₀And optionally, R₄' and R₅' of-CH₂-may be substituted by-O-and the alkyl is a straight or branched alkyl;

C₂-C₁₀linear or branched alkenyl of (a);

with C₃-C₁₀Cycloalkyl or C₆-C₂₀Aryl of (A) is end-capped C₂-C₈Alkenyl of (a);

C₂-C₁₀straight or branched alkynyl of (a);

C₁-C₁₀optionally, the hydrogen on the alkyl group may be substituted by a fluorine atom;

or C₆-C₂₀Arylsulfonyloxy of (a);

provided that R is₂-R₇Not hydrogen at the same time.

2. The photosensitive resin composition according to claim 1A compound characterized in that R is₁Is C₁-C₆Linear or branched perfluoroalkyl, perfluorophenyl, at least one hydrogen atom being replaced by C₁-C₆Phenyl or camphoryl substituted by alkyl or fluoroalkyl of (A), preferably R₁Is perfluoromethyl, perfluoroethyl, perfluoropropyl, perfluorobutyl, perfluoropentyl, perfluorophenyl, camphoryl, p-methylphenyl or perfluoromethylphenyl.

3. The photosensitive resin composition according to claim 1 or 2, wherein R is₂、R₄-R₇Is hydrogen, said R₃Selected from the following groups:

halogen;

C₁-C₁₀optionally, -CH therein₂-may be substituted by-O-;

phenyl, optionally, in which at least one hydrogen atom may be replaced by C₁-C₄Alkyl or alkoxy of (a);

C₇-C₁₀optionally, at least one hydrogen atom on the phenyl group may be replaced by C₁-C₄Substituted by alkyl or alkoxy groups, -CH in alkyl₂-may be substituted by-O-or-S-;

R₁' -CO-, wherein R₁' represents C₁-C₆Alkyl of (C)₃-C₆And optionally, at least one hydrogen atom in the phenyl group may be replaced by C₁-C₄Alkyl or alkoxy of (a);

R₂’-CO-O-R₃' -, wherein R₂' represents C₁-C₈Alkyl, phenyl, R₃' represents null, C₁-C₄Alkoxy of, or C₃-C₄Optionally, at least one hydrogen atom in the phenyl group may be replaced by C₁-C₄Alkyl of (a);

R₄’-O-CO-R₅' -, wherein R₄' represents C₁-C₆Alkyl of R₅' represents C₁-C₆And optionally, R₄' and R₅' of-CH₂-may be substituted by-O-;

C₂-C₆linear or branched alkenyl of (a);

with C₃-C₆Cycloalkyl or C₆-C₁₀Aryl of (A) is end-capped C₂-C₄Alkenyl of (a);

C₂-C₆straight or branched alkynyl of (a);

C₁-C₆optionally, the hydrogen on the alkyl group may be substituted by a fluorine atom;

or C₆-C₁₀Arylsulfonyloxy of (a).

4. The photosensitive resin composition according to claim 1 or 2, wherein R is₂-R₇One of the groups is selected from any one of methyl, ethyl, propyl, butyl and amyl, and the rest is H;

or said R is₂、R₄-R₇Is hydrogen, said R₃Any one selected from the following groups: halogen, halomethyl, haloethyl;

or said R is₂、R₄-R₇Is hydrogen, said R₃Any one selected from the following groups: methyl, ethyl, propyl, butyl, pentyl, and one of them-CH₂-is substituted by-O-;

or said R is₂、R₄-R₇Is hydrogen, said R₃Any one selected from the following groups: c₇-C₁₀Optionally, a hydrogen atom on the phenyl group may be replaced by a methyl group, and/or a-CH group in the alkyl group₂-may be substituted by-O-or-S-;

or said R is₂、R₄-R₇Is hydrogen, said R₃Any one selected from the following groups: r₁' -CO-, whereinR₁' represents a methyl group, an ethyl group, a propyl group, a cyclohexyl group, a phenyl group, a methylphenyl group, an ethylphenyl group, a tert-butylphenyl group, an alkoxymethylphenyl group or an alkoxyethylphenyl group;

or said R is₂、R₄-R₇Is hydrogen, said R₃Any one selected from the following groups: r₂’-CO-O-R₃' -, wherein R₂' represents methyl, ethyl, propyl or phenyl, one of the hydrogen atoms of which may be replaced by methyl, R₃' represents a null or propynyl group;

or said R is₂、R₄-R₇Is hydrogen, said R₃Any one selected from the following groups: r₄’-O-CO-R₅' -, wherein R₄' represents methyl, ethyl, propyl, butyl, pentyl or hexyl, R₅' represents a methylene group or an ethylene group, and R₄' and R₅One of ` -CH₂-may be substituted by-O-;

or said R is₂、R₄-R₇Is hydrogen, said R₃Any one selected from the following groups: a straight chain butenyl group, a branched butenyl group, a phenyl terminated propenyl group, or a cyclohexyl terminated propenyl group;

or said R is₂、R₄-R₇Is hydrogen, said R₃Any one selected from the following groups: ethynyl, propynyl, butynyl or pentynyl;

or said R is₂、R₄-R₇Is hydrogen, said R₃Any one selected from the following groups: c₁-C₆A methylsulfonyloxy group, a trifluoromethylsulfonyloxy group, a butylsulfonyloxy group, a phenylsulfonyloxy group or a p-methylphenylsulfonyloxy group.

5. The photosensitive resin composition according to claim 1, wherein the sulfonyl imide photoacid generator is selected from any one of the following structural formulae:

6. the photosensitive resin composition according to claim 1, wherein the resin component has an acid-labile group protected by a protecting group; the acid labile group comprises at least one of a carboxyl group and a phenolic hydroxyl group; and the content of the acid labile group accounts for 1-80% of the content of the resin component, preferably 3-70%.

7. The photosensitive resin composition according to claim 6, wherein the protecting group comprises at least one of the following groups:

8. The photosensitive resin composition according to claim 6, wherein the acid generator is contained in an amount of 0.5 to 5% by weight, preferably 1 to 3% by weight, based on the mass of the solid content of the photosensitive resin composition, and preferably the resin component is selected from any one of a (meth) acrylic resin, a polyhydroxystyrene resin and a phenol resin polymer.

9. The photosensitive resin composition according to claim 1, wherein the resin composition further comprises an aromatic carboxylic acid compound, and the aromatic carboxylic acid compound is preferably contained in an amount of 3 to 35% by weight based on the mass of the solid content of the photosensitive resin composition.

10. The photosensitive resin composition according to claim 1, wherein the resin composition further comprises a bridging compound, and the weight content of the bridging compound is preferably 10 to 50% based on the mass of the solid content of the photosensitive resin composition.

11. The photosensitive resin composition according to claim 1, further comprising a solvent.

12. A patterning method comprising mixing, film forming and patterning a photosensitive resin composition, wherein the photosensitive resin composition is the photosensitive resin composition according to any one of claims 1 to 11.

13. Use of the photosensitive resin composition according to any one of claims 1 to 11, comprising application of the photosensitive composition to the production of a protective film, an interlayer insulating material, a pattern transfer material for an electronic component.