CN114516863A - Imide sulfonate photo-acid generator with high acid yield, composition and application - Google Patents

Imide sulfonate photo-acid generator with high acid yield, composition and application Download PDF

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CN114516863A
CN114516863A CN202011299973.1A CN202011299973A CN114516863A CN 114516863 A CN114516863 A CN 114516863A CN 202011299973 A CN202011299973 A CN 202011299973A CN 114516863 A CN114516863 A CN 114516863A
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alkyl
hydrogen
acid
substituted
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钱晓春
张学龙
龚艳
徐丽萍
姜超
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Changzhou Qiangli Photoelectric Material Co ltd
Changzhou Tronly New Electronic Materials Co Ltd
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Changzhou Qiangli Photoelectric Material Co ltd
Changzhou Tronly New Electronic Materials Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D409/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms
    • C07D409/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing two hetero rings
    • C07D409/04—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing two hetero rings directly linked by a ring-member-to-ring-member bond
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D409/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms
    • C07D409/14—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing three or more hetero rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D495/00—Heterocyclic compounds containing in the condensed system at least one hetero ring having sulfur atoms as the only ring hetero atoms
    • C07D495/02—Heterocyclic compounds containing in the condensed system at least one hetero ring having sulfur atoms as the only ring hetero atoms in which the condensed system contains two hetero rings
    • C07D495/04—Ortho-condensed systems
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic System
    • C07F7/02—Silicon compounds
    • C07F7/08—Compounds having one or more C—Si linkages
    • C07F7/0803—Compounds with Si-C or Si-Si linkages
    • C07F7/081—Compounds with Si-C or Si-Si linkages comprising at least one atom selected from the elements N, O, halogen, S, Se or Te
    • C07F7/0812—Compounds with Si-C or Si-Si linkages comprising at least one atom selected from the elements N, O, halogen, S, Se or Te comprising a heterocyclic ring
    • C07F7/0814—Compounds with Si-C or Si-Si linkages comprising at least one atom selected from the elements N, O, halogen, S, Se or Te comprising a heterocyclic ring said ring is substituted at a C ring atom by Si
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic System
    • C07F7/02—Silicon compounds
    • C07F7/08—Compounds having one or more C—Si linkages
    • C07F7/0803—Compounds with Si-C or Si-Si linkages
    • C07F7/0825—Preparations of compounds not comprising Si-Si or Si-cyano linkages
    • C07F7/083—Syntheses without formation of a Si-C bond
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/0045—Photosensitive materials with organic non-macromolecular light-sensitive compounds not otherwise provided for, e.g. dissolution inhibitors

Abstract

The invention discloses a photoacid generator which has high sensitivity to active energy rays with the wavelength of 300-450nm, particularly 365nm (I line), 385nm and 405nm (H line), and has good solubility, thermal stability and storage stability, a photosensitive resin composition containing the photoacid generator and application thereof. The imide sulfonate photoacid generator has a structure represented by general formula (A1) or (A2).

Description

Imide sulfonate photo-acid generator with high acid yield, composition and application
Technical Field
The invention belongs to the technical field of photosensitive materials, and particularly relates to an imide sulfonate photoacid generator capable of generating acid at a high rate in the wavelength range of 300-450nm, a photosensitive resin composition containing the photoacid generator and application of the photoacid generator.
Background
A resin composition containing a resin (such as tert-butyl ester of carboxylic acid or tert-butyl ester of phenol, silyl ether, etc.) and a photoacid generator is a typical resist material used in a photolithography process. Various types of photoacid generators are known and can be classified into nonionic and ionic types. Among them, the ionic photoacid generator tends to have insufficient compatibility and to cause phase separation in a resist material, and thus cannot sufficiently function. Nonionic photoacid generators generally have problems such as insufficient sensitivity at long wavelengths and poor solubility in solvents.
Therefore, the search for a novel photoacid generator having more excellent properties is a major research point in this field.
Disclosure of Invention
The invention mainly aims to provide a photo-acid generator which has high sensitivity to active energy rays with the wavelength of 300-450nm, particularly 365nm (I line), 385nm and 405nm (H line), and has good solubility, good thermal stability and good storage stability.
Specifically, the imide sulfonate photoacid generator has a structure represented by the following general formula (a1) or (a 2):
Figure BDA0002786528990000021
wherein the content of the first and second substances,
R1is represented by C1-C20Linear or branched alkyl of (2), C3-C20Cyclic alkyl of (2), C1-C20Linear or branched fluoroalkyl of (2), C3-C20Fluorinated cyclic alkyl group of6-C18Substituted or unsubstituted aryl, camphoryl, or azidonaphthalenone groups of (a);
R2、R3、R4and R4The "may be the same or different and each is independently selected from the group consisting of: hydrogen; nitro, nitro-containing alkyl, or nitro-containing aryl, optionally (optional), wherein the hydrogen on the hydrocarbon radical may be partially or partiallyAll substituted with fluorine; the amino group, the alkyl group containing the amino group or the aromatic group containing the amino group, wherein the hydrogen on the hydrocarbon group can be partially or completely replaced by fluorine; cyano, cyano-containing alkyl, or cyano-containing aryl, wherein the hydrogen on the hydrocarbon group may be partially or fully substituted by fluorine; straight or branched alkyl, or cycloalkyl, optionally, -CH therein2-may be substituted by-O-, -S-, the hydrogen on the hydrocarbon group may be partially or fully substituted by fluorine; aryl (e.g., phenyl, naphthyl, etc.), wherein the hydrogen on the aryl ring may be substituted by alkyl, alkoxy, or fluorine, and the hydrogen at other positions may be partially or fully substituted by fluorine; c7-C20Optionally, at least one hydrogen atom on the phenyl group may be replaced by C1-C8Substituted by alkyl or alkoxy groups of which-CH is2-may be substituted by-O-, -S-or-NH-; r1' -CO-, wherein R1' represents hydrogen, C1-C10Alkyl of (C)3-C10And optionally, at least one hydrogen atom in the phenyl group may be replaced by C1-C8Alkyl or alkoxy of (a); r2’-CO-O-R3' -, wherein R2' represents C1-C10Alkyl, phenyl, R3' represents null, C1-C8Alkylene oxide of, or C3-C8Optionally, at least one hydrogen atom in the phenyl group may be replaced by C1-C8Alkyl of (a); r4’-O-CO-R5' -, wherein R4' represents C1-C10Alkyl of R5' represents C1-C10An alkylene group of (a); linear or branched alkenyl, cycloalkyl or aryl containing alkenyl, optionally wherein the hydrogens on the hydrocarbon group may be partially or fully substituted with fluorine; straight or branched chain alkynyl, cycloalkyl-or aryl-containing alkynyl, optionally wherein the hydrogens on the hydrocarbon group may be partially or fully substituted with fluorine; alkylsulfonyloxy, cycloalkyl-or aryl-containing sulfonyloxy, optionally the hydrogen on the alkyl may be partially or fully substituted by fluorine; alkylsilyl group, cycloalkyl-containing silyl group, orOptionally, the hydrogen on the alkyl group may be partially or fully substituted by fluorine; a heterocyclic group containing N, S or O;
R2and R3May be linked to each other to form a five-membered ring or a six-membered ring;
provided that R in the formula (A1)2、R3And R4Not simultaneously hydrogen, R in the general formula (A2)2、R3And R4"not simultaneously hydrogen.
The compounds of the general formulas (A1) and (A2) belong to nonionic photoacid generators, have photosensitive groups and acid-generating groups, can realize long-wave absorption, have high sensitivity and strong absorption on active energy rays with the wavelengths of 300-450nm, especially 365nm (I line), 385nm and 405nm (H line), and can generate acid quickly under lower exposure. At the same time, it has good solubility, thermal stability and storage stability.
Accordingly, the present invention also provides an acid generating method of irradiating the above-mentioned photoacid generator, i.e., a compound of the general formula (a1) and/or (a2) with active energy rays.
The compounds of the general formulas (A1) and (A2) contain sulfonate groups in molecules, are directly connected with an imide structure, have photocleavage characteristics, and can be photolyzed under the irradiation of active energy rays to generate stronger sulfonic acid. The active energy rays are active energy rays with the wavelengths of 300-450nm in the near ultraviolet light region and the visible light region, and active energy rays with the wavelengths of 365nm (I rays), 385nm and 405nm (H rays) are particularly preferable.
The photoacid generator of the present invention can be used for any known uses of photoacid generators, such as resist films, liquid resists, negative resists, positive resists, resists for MEMS, materials for stereolithography and micro-stereolithography, and the like. It is most preferable to use the photoacid generator in a resist, together with an acid-dissociable resin, to prepare a resist for use in semiconductor lithography.
Compared with the prior art, the acid generator has the beneficial effects that: the photo-acid generator can realize long-wave absorption, has high sensitivity to active energy rays with the wavelength of 300-450nm, particularly 365nm (I line), 385nm and 405nm (H line), and has strong absorption; strong sulfonic acid can be generated by photolysis; and has good solubility, thermal stability and storage stability.
Another main object of the present invention is to provide a photosensitive resin composition and its application, which can solve the problem of insufficient sensitivity of the prior art resist composition in forming fine patterns.
Within the scope of the above object, there is provided a photosensitive resin composition comprising a resin component and an acid generator, the acid generator being any one of the imide sulfonate photoacid generators described above.
Within the scope of the above object, there is provided an application of the above photosensitive resin composition, including an application of the photosensitive resin composition in the preparation of a protective film, an interlayer insulating material, and a pattern transfer material of an electronic component. Illustratively, a patterning method includes mixing, film forming, and patterning a photosensitive resin composition.
As a preferred embodiment, when the photosensitive resin composition of the present invention is applied as a positive resist, the exposed portion is dissolved by an alkali developer treatment after exposure to realize patterning treatment, and a pattern having excellent sensitivity and good contrast can be formed due to the increase in sensitivity of the imide sulfonate photoacid generator, and a sufficiently high sensitivity can be obtained even when a fine pattern is formed. Particularly preferred wavelengths of the active energy rays used are 365nm (I line), 385nm and 405nm (H line) in order to further improve the resolution and sensitivity.
Detailed Description
The resist composition in the prior art is usually insufficient in sensitivity when forming a fine pattern, and in order to solve the problem, the present application provides an imide sulfonate photoacid generator, a photosensitive resin composition containing the photoacid generator, and applications thereof.
The imide sulfonate photoacid generator of the present invention has a structure represented by the following general formula (a1) or (a 2):
Figure BDA0002786528990000051
wherein R is1、R2、R3、R4And R4"is as defined above.
In order to further improve the structural stability and the application performance of the imide sulfonate photoacid generator, R is preferably in the structures represented by general formulae (A1) and (A2)1Selected from the following groups: c1-C8Linear or branched alkyl of (a); c1-C8Linear or branched perfluoroalkyl of (a); a perfluorophenyl group; at least one hydrogen atom being bound by C1-C6A linear or branched alkyl or fluoroalkyl group of (a), or an amino-substituted phenyl group; a camphor group; azidonaphthalenone groups.
Further preferably, R1Can be selected from methyl, propyl, octyl, perfluoromethyl, perfluoroethyl, perfluoropropyl, perfluorobutyl, perfluoropentyl, perfluorophenyl, camphoryl, azidonaphthalenone groups, p-methylphenyl, p-aminophenyl, m-isopropylphenyl, or perfluoromethylphenyl groups.
Preferably, in the structures represented by the general formulae (A1) and (A2), R is2、R3、R4And R4The "may be the same or different and each is independently selected from the group consisting of: hydrogen; a nitro group; an amine group; a cyano group; c1-C10Linear or branched alkyl of (2), C3-C10Optionally, -CH therein2-may be substituted by-O-, -S-; phenyl, optionally, in which at least one hydrogen atom may be replaced by C1-C4Alkyl or alkoxy of (a); c4-C18N, S or O containing heterocyclic group; c2-C6Straight or branched alkynyl 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-, -S-or-NH-; c2-C6Straight-chain or branched alkenyl of (a); with C3-C6Cycloalkyl or C6-C10Aryl of (A) is a sealTerminal C2-C6Alkenyl of (a); r1' -CO-, wherein R1' represents hydrogen, 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-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-C6An alkylene group of (a); c1-C6Optionally, hydrogen on the alkyl group may be substituted by fluorine; c6-C10Arylsulfonyloxy of (a); c1-C12Optionally, the hydrogen on the alkyl group may be substituted by fluorine. R2And R3May be linked to each other to form a five-membered ring or a six-membered ring. Provided that, in the general formula (A1), R2、R3And R4Not hydrogen at the same time; in the general formula (A2), R2、R3And R4"not simultaneously hydrogen.
Further preferably, R2、R3、R4And R4The "may be the same or different and each is independently selected from the group consisting of: hydrogen; a nitro group; an amine group; a cyano group; a phenyl group; a thienyl group; methyl, ethyl, propyl, butyl, hexyl, cyclohexyl, cyclohexylmethyl, 3-methylpentane, octyl and dodecyl, optionally, one or more of which-CH2-may be substituted by-O-, -S-; c7-C10Optionally, at least one hydrogen atom on the phenyl group may be substituted by a methyl group, and/or at least one-CH in the alkyl group2-may be substituted by-O-, -S-or-NH-; r1' -CO-, wherein R1' represents hydrogen, methyl, phenyl, alkoxyphenyl; r2’-CO-O-R3' -, wherein R2' represents a methyl group, R3' represents an ethynylene group; r4’-O-CO-R5' -, wherein R4' represents methyl, ethyl, propyl, butyl, pentyl or hexyl, R5' represents a methylene group or a void; ethynyl, propynyl, isopentynyl or pentynyl; propenyl, hexenyl, isobutenyl, ethenyl. R2And R3May be linked to each other to form a five-membered thiophene ring. Provided that, in the general formula (A1), R2、R3And R4Not hydrogen at the same time; in the general formula (A2), R2、R3And R4"not simultaneously hydrogen.
Illustratively, the photoacid generators of the present invention may be selected from the following structures:
Figure BDA0002786528990000081
Figure BDA0002786528990000091
Figure BDA0002786528990000101
Figure BDA0002786528990000111
the invention also relates to a preparation method of the imide sulfonate photoacid generator, which comprises the following steps:
reacting halogenated derivative of thiophene with pinacol diboron to form boron reagent, coupling with bromo-1, 8 naphthalic anhydride, hydroamination, and finally with sulfonic anhydride (R)1-SO2)2O or sulfonyl chloride R1-SO2Carrying out esterification reaction on the-Cl to obtain a target compound;
the process route is as follows:
Figure BDA0002786528990000121
wherein X represents a halogen such as fluorine, chlorine, bromine, iodine; r1、R2、R3、R4And R4"is as defined above.
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, esterification, etc. And specific preparation process conditions are easily determined by those skilled in the art after knowing the structure of the photoacid generator and the above preparation process concept.
As described above, the compounds of the general formulae (a1) and (a2) of the present invention are nonionic photoacid generators, have a photosensitive group and an acid-generating group, and a sulfonate group is directly linked to an imide structure, and can generate N — O bond cleavage under irradiation of active energy rays to generate sulfonic acid having strong acidity. The structure has high sensitivity and strong absorption to active energy rays with the wavelength of 300-450nm, particularly 365nm (I line), 385nm and 405nm (H line), and can generate acid quickly under lower exposure. At the same time, it has good solubility, thermal stability and storage stability. The photoacid generator of the present invention can be used for any known uses of photoacid generators, such as resist films, liquid resists, negative resists, positive resists, resists for MEMS, materials for stereolithography and micro-stereolithography, and the like. Among them, as a photoacid generator in a resist composition, a resist can be prepared together with a resin having an acid-dissociable group and applied to semiconductor lithography.
The imide sulfonate photoacid generator of the present invention is applied to a resist composition and is first dissolved in a solvent. The common solvent is an organic solvent, which can be selected from: esters such as gamma-butyrolactone (GBL), ethyl acetate, butyl acetate, ethyl lactate, methyl pyruvate, and the like; ketones such as acetone, butanone, cyclohexanone, methyl isoamyl ketone, 2-heptanone, and the like; ethers such as methyl ether, ethyl ether, propyl ether, butyl ether, anisole, ethylbenzyl ether, cresolmethyl ether, diphenyl ether, dibenzyl ether, butylphenyl ether and the like; polyhydric alcohols and derivatives such as ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, ethylene glycol monoacetate, diethylene glycol monoacetate, propylene glycol monoacetate, dipropylene glycol monoacetate, ethylene glycol monopropionate, diethylene glycol monopropionate, propylene glycol monopropionate, dipropylene glycol monopropionate, propylene glycol monomethyl ether, and Propylene Glycol Methyl Ether Acetate (PGMEA), etc.; aromatic organic solvents such as toluene, xylene, ethylbenzene, diethylbenzene, isopropylbenzene, cymene and mesitylene; nitrogen-containing polar solvents such as N, N' -tetramethylurea, N-methyl-2-pyrrolidone, N-dimethylformamide, N-dimethylacetamide, hexamethylphosphoramide, 1, 3-dimethyl-2-imidazolidinone, 2-trimethylpropionamide, and the like. These organic solvents may be used alone or as a mixed solvent of two or more.
The solvent dissolves the respective components in the resist composition to form a uniform solution for adjusting viscosity and coatability. The solvent is preferably one or a mixture of two or more of Propylene Glycol Methyl Ether Acetate (PGMEA), cyclohexanone, and γ -butyrolactone (GBL). In general, it is preferable to select the solvent amount so that the solid content concentration of the photosensitive composition is 5 to 30% (w/w).
The resist composition of the present invention can be classified into a positive type composition and a negative type composition according to the application. The positive type composition generally contains a resin component (B1) whose solubility in an alkali developing solution is increased by the action of an acid, in addition to the photoacid generator (a1) and/or (a 2). During patterning of the composition, the acid labile groups protected by protecting groups in the positive resin in the exposed areas are deprotected by the action of an acid generated from a photoacid generator to render them soluble in an alkali developer upon selective exposure. Thus, when the alkali development operation is performed, the unexposed region pattern remains to form a positive pattern. Unlike the positive type composition, the negative type composition uses a resin-crosslinking agent component (B2) that is crosslinked by an acid and is insoluble in an organic developer, in addition to the photoacid generator (a1) and/or (a 2). The exposed region is catalyzed by acid generated by a photoacid generator, the resin reacts with a crosslinking agent to form a polymer which is insoluble in an organic developer and remains, and the unexposed region is dissolved and removed by the organic developer to finally form a negative pattern.
In the positive/negative resist composition, imide sulfonate photoacid generators (A1) and (A2) can generate N-O bond fracture to generate sulfonic acid under the irradiation of active energy rays, and through a PEB process, the difference of the solubility of an exposed area and an unexposed area to a developing solution is realized. The imide sulfonic acid ester photoacid generator products (a1) and (a2) may be used singly or in combination. The imide sulfonate ester type photo-acid generator is preferably a compound of the above molecular formula 1 to 50. The content of the imide sulfonate photoacid generator (A1) and/or (A2) is 0.01 to 5%, preferably 0.1 to 3% (w/w), based on the mass of the solid content of the composition. When the amount is within this range, the sensitivity to active energy rays can be exhibited well, and the physical properties of the insoluble portion in an alkaline developer can be exhibited well.
In the positive resist composition of the present invention, the resin component (B1) may be obtained by vinyl polymerization of a vinyl monomer containing an alkali-soluble acidic group, in which a part or all of hydrogen atoms of the alkali-soluble acidic group is substituted with an acid-dissociable group as a protecting group, and optionally a hydrophobic group-containing vinyl monomer. The alkali-soluble acidic group may be a phenolic hydroxyl group, a carboxyl group or a sulfonic acid group, and the acid-dissociable group may be dissociated in the presence of a strong acid generated from the photoacid generator (a1) and/or (a 2).
For convenience of description, the unit structure formed by polymerization of the vinyl monomer containing the alkali-soluble acidic group is defined as an acid-based resin, and the acid-based resin and the unit structure formed by polymerization of the vinyl monomer containing the hydrophobic group constitute the resin component (B1). The acid-based resin itself is alkali-insoluble or poorly alkali-soluble.
The alkali-soluble acidic group in the resin component (B1) may be a phenolic hydroxyl group, a carboxyl group or a sulfonic acid group.
Wherein the phenolic hydroxyl group-containing resin (B1-1) is selected from the group consisting of novolak resins, polyhydroxystyrene-hydroxystyrene copolymers, hydroxystyrene-styrene- (meth) acrylic acid derivative copolymers, phenol-xylylene glycol condensation resins, cresol-xylylene glycol condensation resins, polyimides containing phenolic hydroxyl groups, polyamic acids containing phenolic hydroxyl groups, phenol-dicyclopentadiene condensation resins, and the like, preferred are novolak resins, polyhydroxystyrene-hydroxystyrene copolymers, hydroxystyrene-styrene- (meth) acrylic acid derivative copolymers, phenol-xylene glycol condensation resins, cresol-xylene glycol condensation resins. The phenolic hydroxyl group-containing resin may be used alone or in combination of two or more.
The novolak resin is 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 phenols are mainly alkyl phenols and aromatic phenols, and can be selected from phenol, o-cresol, m-cresol, p-cresol, o-ethyl phenol, m-ethyl phenol, p-ethyl phenol, o-butyl phenol, m-butyl phenol, p-butyl phenol, 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, catechol, phloroglucinol, hydroxydiphenyl, bisphenol A, gallic acid, alpha-naphthol, beta-naphthol, and the like. The aldehydes may be selected from formaldehyde, trioxymethylene, acetaldehyde, furfural, benzaldehyde, nitrobenzaldehyde, and the like. Specific examples of the novolak resin include phenol-formaldehyde condensation novolak resins, cresol-formaldehyde condensation novolak resins, phenol-naphthol-formaldehyde condensation novolak resins, and the like.
The molecular weight of the resin containing a phenolic hydroxyl group is preferably about 2000-20000. 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 phenolic hydroxyl group-containing resin as necessary.
The carboxyl groups may be derived from: unsaturated monocarboxylic acids such as (meth) acrylic acid, crotonic acid, cinnamic acid, and the like; unsaturated polycarboxylic acids such as maleic acid, itaconic acid, fumaric acid, citraconic acid, and the like; unsaturated polycarboxylic acid alkyl (C)1-C10) Esters, e.g. monoalkyl maleate, monoalkyl fumarateEsters and monoalkylcitraconates and the like; and salts thereof, such as alkali metal salts (sodium salts, potassium salts, etc.), alkaline earth metal salts (calcium salts, magnesium salts, etc.), amine salts, ammonium salts, and the like. The carboxyl groups are preferably derived from (meth) acrylic acid.
As a preferred example of the carboxyl group-containing resin, an acrylic resin is 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. The (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; 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 sulfonic acid group may be derived from: vinylsulfonic acid, (meth) allylsulfonic acid, styrenesulfonic acid, α -methylstyrene sulfonic acid, 2- (meth) acrylamido-2-methylpropanesulfonic acid, and salts thereof such as alkali metal salts (sodium, potassium, and the like), alkaline earth metal salts (calcium, magnesium, and the like), 1-3-stage amine salts, ammonium salts, quaternary ammonium salts, and the like.
The hydrophilic-lipophilic balance (HLB) value of the resin containing an alkali-soluble acidic group varies depending on the resin skeleton of the alkali-soluble resin, and is generally 4 to 19, preferably 6 to 17. The HLB value is more than or equal to 4, the developing property is better when the developing is carried out; if the HLB value is less than or equal to 19, the water resistance of the cured product is better.
The content of the acid-based resin in the resin component (B1) is 10 to 100% (w/w), preferably 25 to 85% (w/w). When within this range, better developability of the resist composition can be obtained.
The hydrophobic group-containing vinyl monomer may be selected from (meth) acrylate, aromatic olefin monomers, and the like.
The (meth) acrylate may be selected from: (meth) acrylic acid C1-C20Alkyl esters such as methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, n-hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, and the like; examples of the alicyclic group-containing (meth) acrylate include dicyclopentanyl (meth) acrylate, dicyclopentenyl (meth) acrylate, isobornyl (meth) acrylate, and the like.
The aromatic olefin monomer may be selected from alkanes and aromatics having a styrene skeleton, such as styrene, alpha-methylstyrene, vinyltoluene, 2, 4-dimethylstyrene, ethylstyrene, isopropylstyrene, butylstyrene, phenylstyrene, cyclohexylstyrene, benzylstyrene, vinylnaphthalene, and the like.
The content of the unit structure formed by polymerization of the hydrophobic group-containing vinyl monomer in the resin component (B1) is preferably 15 to 75% (w/w). When within this range, better developability of the resist composition can be obtained.
The acid-dissociable group as a protecting group may be selected from: substituted methyl, 1-substituted ethyl, 1-branched alkyl, silyl, germyl, alkoxycarbonyl, acyl, and cyclic acid-dissociable groups. The acid-dissociable group may be used alone or in combination of two or more.
The substituted methyl group may be selected from: methoxymethyl, methylthiomethyl, ethoxymethyl, ethylthiomethyl, methoxyethoxymethyl, benzyloxymethyl, benzylthiomethyl, phenacyl, bromobenzoylmethyl, methoxybenzoylmethyl, methylthiophenacyl, α -methylbenzoylmethyl, cyclopropylmethyl, benzyl, diphenylmethyl, triphenylmethyl, bromobenzyl, nitrobenzyl, methoxybenzyl, methylthiobenzyl, ethoxybenzyl, ethylthiobenzyl, piperonyl, methoxycarbonylmethyl, ethoxycarbonylmethyl, n-propoxycarbonylmethyl, isopropoxycarbonylmethyl, n-butoxycarbonylmethyl, t-butoxycarbonylmethyl and the like.
Said 1-substituted ethyl group may be selected from: 1-methoxyethyl group, 1-methylthioethyl group, 1-dimethoxyethyl group, 1-ethoxyethyl group, 1-ethylthioethyl group, 1-diethoxyethyl group, 1-ethoxypropyl group, 1-propoxyethyl group, 1-cyclohexyloxyethyl group, 1-phenoxyethyl group, 1-phenylthioethyl group, 1-diphenoxyethyl group, 1-benzyloxyethyl, 1-benzylthioethyl, 1-cyclopropylethyl, 1-phenylethyl, 1-diphenylethyl, 1-methoxycarbonylethyl, 1-ethoxycarbonylethyl, 1-n-propoxycarbonylethyl, 1-isopropoxycarbonylethyl, 1-n-butoxycarbonylethyl, 1-tert-butoxycarbonylethyl and the like.
The 1-branched alkyl group may be selected from: isopropyl, sec-butyl, tert-butyl, 1-dimethylpropyl, 1-methylbutyl, 1-dimethylbutyl, and the like.
Said silane groups, can be selected from: trimethylsilyl, ethyldimethylsilyl, methyldiethylsilyl, triethylsilyl, isopropyldimethylsilyl, methyldiisopropylsilyl, triisopropylsilyl, tert-butyldimethylsilyl, methyl di-tert-butylsilyl, tri-tert-butylsilyl, phenyldimethylsilyl, methyldiphenylsilyl, triphenylsilyl and the like.
The germyl group may be selected from: trimethylgermyl, ethyldimethylgermyl, methyldiethylgermyl, triethylgermyl, isopropyldimethylgermyl, methyldiisopropylgermyl, triisopropylgermyl, tert-butyldimethylgermyl, methyl di-tert-butylgermyl, tri-tert-butylgermyl, phenyldimethylgermyl, methyldiphenylgermyl, triphenylgermyl.
Said alkoxycarbonyl group may be selected from: methoxycarbonyl, ethoxycarbonyl, isopropoxycarbonyl, tert-butoxycarbonyl and the like.
Said acyl group, can be selected from: acetyl, propionyl, butyryl, heptanoyl, hexanoyl, pentanoyl, pivaloyl, isovaleryl, lauroyl, myristoyl, palmitoyl, stearoyl, oxalyl, malonyl, succinyl, glutaryl, adipyl, pimeloyl, suberoyl, azelaioyl, sebacoyl, acryloyl, propioloyl, methacryloyl, crotonyl, oleoyl, maleoyl, fumaroyl, mesoconyl, kacanoyl, benzoyl, phthaloyl, isophthaloyl, terephthaloyl, naphthoyl, toluoyl, atropic-oyl, cinnamoyl, furoyl, thenoyl, nicotinoyl, isonicotinoyl, p-toluenesulfonyl, methanesulfonyl, and the like.
The cyclic acid-dissociable group may be selected from: cyclopropyl, cyclopentyl, cyclohexyl, cyclohexenyl, 4-methoxycyclohexyl, tetrahydropyranyl, tetrahydrofuranyl, tetrahydrothiopyranyl, tetrahydrothiofuranyl, 3-bromotetrahydropyranyl, 4-methoxytetrahydropyranyl, 4-methoxytetrahydrothiopyranyl, 3-tetrahydrothiophene-1, 1-dioxide, and the like.
Among these acid-dissociable groups, preferred are tert-butyl, benzyl, 1-methoxyethyl, 1-ethoxyethyl, trimethylsilyl, tert-butoxycarbonyl, tert-butoxycarbonylmethyl, tetrahydropyranyl, tetrahydrofuranyl, tetrahydrothiopyranyl, tetrahydrothiofuranyl, and the like.
The introduction rate of the acid-dissociable group (the ratio of the number of acid-dissociable groups to the total of the unprotected acid groups and the acid-dissociable groups) in the acid-based resin is preferably 15 to 100%.
The acid-based resin has an average molecular weight of 1,000-150,000, preferably 3,000-100,000.
In the negative resist composition of the present invention, the resin-crosslinking agent component (B2) is mainly a phenolic hydroxyl group-containing resin (B2-1) and a crosslinking agent (B2-2).
The phenolic hydroxyl group-containing resin (B2-1) can be used in the same manner as described above for B1-1. The B2-1 accounts for 30-90% (w/w), preferably 40-80% (w/w) of the solid components of the composition.
The crosslinking agent (B2-2) is a compound obtained by crosslinking and polymerizing the phenolic hydroxyl group-containing resin (B2-1) under the catalysis of an acid generated by the photoacid generator (A), and may be selected from bisphenol A-based epoxy compounds, bisphenol F-based epoxy compounds, bisphenol S-based epoxy compounds, novolac-based epoxy compounds, phenol-novolac-based epoxy compounds, poly (hydroxystyrene) -based epoxy compounds, oxetane compounds, methylol-containing melamine compounds, methylol-containing benzoguanamine compounds, methylol-containing urea compounds, methylol-containing phenol compounds, alkoxyalkyl-containing melamine compounds, alkoxyalkyl-containing benzoguanamine compounds, alkoxyalkyl-containing urea compounds, alkoxyalkyl-containing phenol compounds, carboxymethyl-containing melamine resins, carboxymethyl-containing benzoguanamine resins, phenol-containing compounds, phenol compounds, and phenol compounds, A carboxymethyl group-containing urea resin, a carboxymethyl group-containing phenol resin, a carboxymethyl group-containing melamine compound, a carboxymethyl group-containing benzoguanamine compound, a carboxymethyl group-containing urea compound, a carboxymethyl group-containing phenol compound, and the like. Among these crosslinking agents, methoxymethyl group-containing melamine compounds (e.g., hexamethoxymethylmelamine, etc.), methoxymethyl group-containing glycoluril compounds, methoxymethyl group-containing urea compounds, and the like are preferable. Illustratively, methoxymethyl-containing melamine compounds are commercially available under trade names such as semel (CYMEL)300, CYMEL301, CYMEL303, and CYMEL305 (manufactured by mitsui cyanamide (stock)), methoxymethyl-containing glycoluril compounds are commercially available under trade names such as CYMEL1174 (manufactured by mitsui cyanamide (stock)), and methoxymethyl-containing urea compounds are commercially available under trade names such as MX290 (manufactured by mitsui and chemist (stock)).
In view of the reduction in the residual film rate and the problem of resolution, the content of the crosslinking agent (B2-2) is usually 10mol to 50 mol%, preferably 15mol to 40 mol%, relative to all the acidic functional groups in the phenolic hydroxyl group-containing resin (B2-1).
As an optional component, the above positive-or negative-type resist composition may further contain an aromatic carboxylic acid compound (C), i.e., at least one carboxylic acid group is bonded to an aromatic group. The aromatic carboxylic acid compound can promote deprotection reaction of the resin component in the composition after exposure.
The aromatic carboxylic acid compound (C) may be at least one selected from a low-molecular-weight aromatic carboxylic acid compound and a high-molecular-weight aromatic carboxylic acid compound.
In the aromatic carboxylic acid compound, in addition to the carboxylic acid group, 1 or more substituents may be present, and the substituents may be selected from: halogen, hydroxy, mercapto, sulfide, silyl, silanol, nitro, nitroso, sulfonate, sulfoxidePhosphono and phosphonate groups; alkyl, alkenyl, cycloalkyl, cycloalkenyl, aryl, and aralkyl groups; and a bond containing a hetero atom such as O, Si, N, etc., such as an ether bond, a thioether bond, a carbonyl bond, a thiocarbonyl bond, an ester bond, an amide bond, a urethane bond, an imino bond, a carbonate bond, a sulfonyl bond, a sulfinyl bond, an azo bond, etc. The above substituents may be linear, branched or cyclic. As the substituent on the aromatic carboxylic acid compound, C is preferred1-C12Alkyl, aryl, alkoxy and halogen.
The low molecular weight aromatic carboxylic acid compound may be a monocarboxylic acid compound or a polyvalent carboxylic acid compound. Illustratively, the low molecular weight aromatic carboxylic acid compound may be selected from: 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, meta-aminobenzoic acid and para-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; alkoxynaphthoic 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-4-naphthoic acid, 1-methoxy-5-naphthoic acid, 1-methoxy-6-naphthoic acid, 2-methoxy-7-naphthoic acid, 2-methoxy-8-naphthoic acid, 1-ethoxy-2-naphthoic acid, and, 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 an aromatic high molecular weight compound having an aromatic group to which a carboxylic acid group is bonded. Suitably, the monomers thereof have a carboxylic acid group and an unsaturated double bond bound to the aromatic group and do not include an acid labile group protected by a protecting group. The polymer compound may be a homopolymer or a copolymer. As preferable comonomers used together with the above monomers, the above monomers for producing the acrylic resin, such as (meth) acrylic acid, 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.
Optionally, conventional auxiliaries in this field may also be included in the resist composition, and are not described in detail herein.
The photosensitive resin composition of the present invention is particularly suitable for use as a resist. In application, a resin solution in which an organic solvent is dissolved or dispersed is first applied to a substrate by, for example, spin coating, the solvent is then evaporated by heating to form a resist film on the substrate, and then a wiring pattern is formed by performing light irradiation (i.e., exposure) in the shape of a wiring pattern, followed by heat treatment (PEB) after the exposure and then alkali development.
The drying conditions of the resin solution after coating vary depending on the solvent used, and are preferably carried out at 50 ℃ to 150 ℃ for 1 to 30 minutes, and the amount of the residual solvent (wt%) after drying is appropriately determined.
After a resist film is formed on a substrate, a wiring pattern shape is irradiated with light. The light irradiation may use a low-pressure mercury lamp, a medium-pressure mercury lamp, a high-pressure mercury lamp, an ultra-high-pressure mercury lamp, a xenon lamp, a metal halide lamp, an electron beam irradiation apparatus, an X-ray irradiation apparatus, a laser (e.g., an argon laser, a dye laser, a nitrogen laser, an LED, a helium cadmium laser), or the like, preferably a high-pressure mercury lamp and an LED lamp.
The temperature of the post-exposure heat treatment (PEB) is usually 40 ℃ to 200 ℃, preferably 60 ℃ to 150 ℃. If the temperature is less than 40 ℃, the deprotection reaction or the crosslinking reaction cannot be sufficiently performed, and thus the difference in solubility between the exposed portion and the unexposed portion is insufficient and a pattern cannot be formed; if the temperature is higher than 200 ℃, the productivity is deteriorated. The heating time is usually 0.5 to 30 minutes.
The development is carried out with an alkali developer, and the alkali developing method includes using an alkali developer. The alkaline developer may be selected from aqueous solutions of 0.1-10% (w/w) tetramethylammonium hydroxide, sodium hydroxide, potassium hydroxide, sodium bicarbonate, and may further comprise water-soluble organic solvents such as methanol, ethanol, isopropanol, tetrahydrofuran, N-methylpyrrolidone, etc. The developing method may be selected from a dipping method, a spraying method and a spraying method, and the spraying method is preferred. The temperature of the developer is preferably used at 25 to 40 c, and the developing time is appropriately determined according to the thickness of the resist film, finally to obtain a pattern corresponding to the mask.
The invention also aims to provide application of the photosensitive resin composition, which comprises application of the photosensitive resin composition in preparation of protective films, interlayer insulating materials and pattern transfer materials of electronic components.
Specifically, the above applications may include the use of the photosensitive resin composition for forming an interlayer insulating film, a TFT for a liquid crystal display device, a panel; can also be used as a protective film for color filters and spacing columns; can also be 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.
Detailed Description
The present invention is described in detail below with reference to examples, but it should not be construed as limiting the scope of the present invention.
Preparation examples
Example 1
Synthesis of photoacid generator 2
Figure BDA0002786528990000261
13.80g of 2-bromo-5-n-octylthiophene was charged into a four-necked flask, dissolved in 201.24g of toluene, and 20.02g of pinacol diboron, 0.04g of dibenzylideneacetone dipalladium, 0.48g of 2-dicyclohexylphosphorus-2, 4, 6-triisopropylbiphenyl (x-phos) and 20.71g of potassium acetate were added with stirring, and the mixture was heated to 120 ℃ under reflux, stirred for 4 hours, subjected to HPLC control, and then cooled to room temperature, whereby the solution was brownish. Water was added thereto, and stirring was carried out, insoluble matters were filtered off, liquid separation was carried out, the organic layer was washed with water 3 times, and then toluene was distilled off under reduced pressure at 60 ℃ to obtain 14.82g of a deep yellow oil.
14.80g of the obtained dark yellow oily substance was put into a four-necked flask, 301.24g of toluene was added thereto and dissolved, and 12.02g of 4-bromo-1, 8-naphthalic anhydride and 0.30g of Pd (PPh) were added thereto under stirring3)2Cl2And 18.51g of potassium carbonate, warmed to 90 ℃, stirred continuously for 5h, HPLC controlled, then cooled to room temperature and the solution was tan. Water was added thereto and stirred, insoluble matter was filtered off, liquid separation was carried out, the organic layer was washed with water 3 times, then toluene was distilled off under reduced pressure at 60 ℃ and subjected to column separation and recrystallization to obtain 11.35g of a solid.
11.35g of the obtained solid was dissolved in 200.2g of methanol, 2.79g of hydroxylamine hydrochloride and 3.60g of triethylamine were added, and the mixture was stirred at 25 ℃ for 0.5 hour, then heated to 70 ℃ for 12 hours, cooled, washed with water 3 times, methanol was distilled off, and toluene was added to crystallize, thereby obtaining 3.55g of a solid.
Adding 3.55g of the obtained solid into 60.00g of dichloromethane, adding 0.73g of pyridine and 2.55g of trifluoromethanesulfonic anhydride, reacting at 0-5 ℃ for 2h, heating to room temperature, adding 1.0g of activated carbon for decolorization, washing twice at room temperature, adjusting the pH to 2 with hydrochloric acid (35.0%), washing twice at room temperature, adjusting the pH to 8 with ammonia water, washing with water to 7, distilling at 60 ℃ under normal pressure until 10g of dichloromethane remains, cooling to below 40 ℃, adding 20.0g of methanol, cooling to 5-10 ℃, stirring for 0.5h, and performing suction filtration. And (3) drying in a vacuum drying oven at 40 ℃ to obtain 3.69g of light yellow solid, namely the compound shown in the formula 2.
By passing1H NMR on the product StructureThe results were characterized as follows:
1H NMR(400MHz,CDCl3)δ8.40(dd,J＝7.5,1.6Hz,2H),8.27-7.91(d,J＝7.5Hz,2H),7.61(t,J＝7.5Hz,1H),7.39-6.85(d,J＝7.5Hz,2H),2.80(t,J＝7.1Hz,2H),1.64(p,J＝7.0Hz,2H),1.40–1.32(m,2H),1.35–1.21(m,8H),0.94–0.84(m,3H)。
example 2
Synthesis of photoacid generator 4
Figure BDA0002786528990000281
The compound represented by formula 4 was synthesized in 56% yield following the same procedure as example 1.
By passing1The product structure was characterized by H NMR as follows:
1H NMR(400MHz,CDCl3):δ8.42–8.27(m,3H),7.83-7.61(t,J＝7.5Hz,2H),7.29-6.90(d,J＝7.5Hz,2H),2.75(t,J＝7.1Hz,2H),1.60(p,J＝7.1Hz,2H),1.37–1.27(m,2H),1.31–1.21(m,8H),0.94–0.84(m,3H)。
example 3
Synthesis of photoacid generator 9
Figure BDA0002786528990000282
The compound represented by formula 9 was synthesized in 56% yield following the same procedure as in example 1.
By passing1The product structure was characterized by H NMR as follows:
1H NMR(400MHz,CDCl3):δ8.42–8.27(m,3H),7.77(d,J＝1.5Hz,1H),7.71–7.62(m,2H),7.27(dd,J＝1.4,0.7Hz,1H),2.45(s,3H)。
example 4
Synthesis of photoacid generator 20
Figure BDA0002786528990000291
The compound represented by formula 20 was synthesized in 44% yield following the same procedure as in example 1.
By passing1The product structure was characterized by H NMR as follows:
1H NMR(400MHz,CDCl3):δ8.43-7.89(d,J＝7.5Hz,4H),7.67–7.58(m,2H),7.25(d,J＝7.5Hz,1H),3.51(s,1H)。
example 5
Synthesis of photoacid generator 27
Figure BDA0002786528990000292
The compound represented by formula 27 was synthesized in 58% yield following the same procedure as in example 1.
By passing1The product structure was characterized by H NMR as follows:
1H NMR(400MHz,CDCl3):δ8.43(dd,J＝7.5,1.5Hz,2H),8.29-7.89(d,J＝7.5Hz,2H),7.62-7.50(d,J＝7.5Hz,3H)。
example 6
Synthesis of photoacid generator 28
Figure BDA0002786528990000301
The compound represented by formula 28 was synthesized in 36% yield following the same procedure as in example 1.
By passing1The product structure was characterized by H NMR as follows:
1H NMR(400MHz,CDCl3):δ8.43(dd,J＝7.6,1.6Hz,2H),8.24–7.85(d,J＝7.5Hz,3H),7.66–7.58(m,2H)。
example 7
Synthesis of photoacid generator 35
Figure BDA0002786528990000302
The compound represented by formula 35 was synthesized in 40% yield following the same procedure as in example 1.
By passing1The product structure was characterized by H NMR as follows:
1H NMR(400MHz,CDCl3):δ8.46–8.42(dd,J＝7.5,1.6Hz,2H),8.27–7.68(d,J＝7.5Hz,4H),7.63(t,J＝7.5Hz,1H),2.51(s,3H)。
example 8
Synthesis of photoacid generator 38
Figure BDA0002786528990000311
The compound represented by formula 38 was synthesized in 36% yield following the same procedure as in example 1.
By passing1The product structure was characterized by H NMR as follows:
1H NMR(400MHz,CDCl3):δ8.47–8.39(dd,J＝7.5,1.6Hz,2H),8.24–7.72(d,J＝7.5Hz,6H),7.60(t,J＝7.5Hz,1H),7.07–7.01(m,2H),3.82(s,3H)。
example 9
Synthesis of photoacid generator 42
Figure BDA0002786528990000312
The compound represented by formula 42 was synthesized in 41% yield following the same procedure as example 1.
By passing1The product structure was characterized by H NMR as follows:
1H NMR(400MHz,CDCl3):δ8.42–8.22(dd,J＝7.5,1.6Hz,3H),7.88–7.46(d,J＝7.5Hz,3H),6.54(d,J＝7.5Hz,1H),3.84(s,3H)。
example 10
Synthesis of photoacid generator 47
Figure BDA0002786528990000321
The compound represented by formula 47 was synthesized in 41% yield following the same procedure as in example 1.
By passing1The product structure was characterized by H NMR as follows:
1H NMR(400MHz,CDCl3):δ8.43-8.24(m,3H),7.85-7.70(d,J＝7.5Hz,3H),7.63(t,J＝7.5Hz,1H),3.88(s,3H)。
example 11
Synthesis of photoacid generator 50
Figure BDA0002786528990000322
The compound represented by formula 50 was synthesized in 34% yield following the same procedure as in example 1.
By passing1The product structure was characterized by H NMR as follows:
1H NMR(400MHz,CDCl3):δ8.43-8.29(m,3H),7.91(d,J＝7.5Hz,1H),7.63–7.24(t,J＝7.5Hz,3H),0.42(s,9H)。
comparative example Compound
Comparative example 1
Nonionic photoacid generator (A1)
Figure BDA0002786528990000323
Comparative example 2
Nonionic photoacid generator (A. about.2)
Figure BDA0002786528990000331
Evaluation of Performance
The photoacid generator compounds synthesized in examples and the compounds of comparative examples were evaluated for their performance, respectively, and the evaluation indices included molar absorption coefficient, solubility, and resist hardening property.
(1) Molar absorptivity
The compound was diluted to 0.25mmol/L with acetonitrile, and the absorbance at a cell length of 1cm was measured in the range of 200-500nm using a UV-visible spectrophotometer (UpG-752, UpG). The molar absorption coefficient ε was calculated by the following equation at each wavelength.
ε(L·mol-1·cm-1)＝A/(0.00025mol/L*1cm)
In the formula, A represents absorbance at each wavelength.
The results are shown in table 1.
TABLE 1
Figure BDA0002786528990000332
Figure BDA0002786528990000341
(2) Solubility in water
The high solubility not only facilitates the purification of the photoacid generator compound, but also allows for an extended range of concentrations of the photoacid generator compound to be used in photoresists and different solvent systems. 1.0000g of the photoacid generator compound product was taken, and the solvent was gradually added at 25 ℃ until all the solids in each tube were dissolved, and the mass of the solvent used was recorded, and the solubility was represented by the following formula.
Figure BDA0002786528990000342
(3) Hardening of resist
A resin solution of 75 parts of P-hydroxystyrene resin (Maruka LINKER S-2P, Japan pill chemical), 25 parts of melamine curing agent (Benoke Biotech), 1 part of photoacid generator and 200 parts of Propylene Glycol Monomethyl Ether Acetate (PGMEA) was coated on a glass substrate (diameter 10cm) using a spin coater at 100 rpm/10S. Then, vacuum drying was carried out at 25 ℃ for 5min, and drying was carried out on a hot plate at 80 ℃ for 3min, thereby forming a resist film having a film thickness of about 3 μm. The resist film was exposed using an ultraviolet irradiation apparatus (IWATA UV-100D) fitted with a filter. Cumulative exposure measurements were made at 365nm, 385nm, or 405nm wavelengths. Subsequently, the substrate was exposed to heat (PEB) for 10min using a dryer at 120 ℃, and then was immersed in 0.5% potassium hydroxide for 30 seconds to develop the substrate, followed by washing with water and drying immediately. The resist film thickness was measured using a shape measuring microscope (Kinzhi VK-8500). The resist hardening was evaluated based on the minimum exposure amount at which the film thickness of the resist before and after development was changed to 10% or less, based on the following criteria.
As follows: the minimum exposure amount is 200mJ/cm2The following;
o: the lowest exposure is more than 200mJ/cm2And at 250mJ/cm2The following;
x: the lowest exposure is more than 250mJ/cm2。
The evaluation results are shown in Table 2.
TABLE 2
Figure BDA0002786528990000351
Figure BDA0002786528990000361
As shown in tables 1 and 2, the photoacid generators of the present invention have higher molar absorptions at 365nm, 385nm, 405nm, and even 436nm, respectively, and the absorption capacity is much higher than that of comparative example 1, and somewhat more superior to that of comparative example 2. Meanwhile, the photo-acid generator has good solubility, can meet the requirements of resist compositions with different proportions, and is applied to various fields; in terms of hardening of the resist, it is also possible to select the light source, which is advantageous over the comparative example.
Industrial applicability
The photoacid generators having the structures represented by the general formulae (a1) and (a2) according to the present invention have high sensitivity to I-line, 385nm, and H-line, and are useful for resist films, liquid resists, negative resists, positive resists, resists for MEMS, negative photosensitive materials, materials for stereolithography and micro stereolithography, and the like, in which the wavelength ranges from 300nm to 450 nm.
The following describes industrial applicability with reference to composition examples and comparative examples.
Examples of the photosensitive resin compositions
Each raw material was uniformly dissolved in 100% PGMEA (propylene glycol methyl ether acetate) to obtain a photosensitive resin composition having a solid content concentration of 20% (w/w). Wherein the component types and contents of the imide sulfonate photoacid generator (a), the resin component (B), and the aromatic carboxylic acid compound (C) are shown in table 3.
Composition example 1
Wherein the resin component (B) is B1A resin of the type represented by the formula B11And formula B12And formula B13The repeating unit shown is constituted, and the numerical value below the right of each repeating unit represents the content (mass%) of the repeating unit in the resin. B is1The weight average molecular weight of the resin was about 9820.
Formula B11：
Figure BDA0002786528990000371
Formula B12：
Figure BDA0002786528990000372
Formula B13：
Figure BDA0002786528990000373
The imide sulfonic acid ester photo-acid generator (A) is an imide sulfonic acid ester photo-acid generator shown in a formula 2, and the molecular formula structure of the imide sulfonic acid ester photo-acid generator is as follows:
formula 2:
Figure BDA0002786528990000374
the aromatic carboxylic acid compound (C) is C1A compound of type (la), prepared from (la) a molar ratio of 1: 1 with 2,3,3 ', 4' -biphenyltetracarboxylic dianhydride.
A formula C':
Figure BDA0002786528990000375
composition example 2
Composition example 2 differs from composition example 1 in that the imide sulfonic acid ester type photoacid generator (a) is an imide sulfonic acid ester type photoacid generator represented by formula 4, and its molecular formula structure is:
formula 4:
Figure BDA0002786528990000381
the remaining component types and contents are shown in table 3.
Composition example 3
Composition example 3 differs from composition example 1 in that the imide sulfonic acid ester type photoacid generator (a) is an imide sulfonic acid ester type photoacid generator represented by formula 20, and its molecular formula structure is:
formula 20:
Figure BDA0002786528990000382
the remaining component types and contents are shown in table 3.
Composition example 4
Composition example 4 differs from composition example 1 in that the imide sulfonic acid ester type photoacid generator (a) is an imide sulfonic acid ester type photoacid generator represented by formula 27, and its molecular formula structure is:
formula 27:
Figure BDA0002786528990000383
the remaining component types and contents are shown in table 3.
Composition example 5
Composition example 5 differs from composition example 1 in that the imide sulfonic acid ester type photoacid generator (a) is an imide sulfonic acid ester type photoacid generator represented by formula 35, and its molecular formula structure is:
formula 35:
Figure BDA0002786528990000391
the remaining component types and contents are shown in table 3.
Composition example 6
Composition example 6 differs from composition example 1 in that the imide sulfonic acid ester type photoacid generator (a) is an imide sulfonic acid ester type photoacid generator represented by formula 47, and its molecular formula structure is:
formula 47:
Figure BDA0002786528990000392
the remaining component types and contents are shown in table 3.
Composition example 7
Composition example 7 differs from composition example 1 in that the imide sulfonic acid ester type photoacid generator (a) is an imide sulfonic acid ester type photoacid generator represented by formula 50, and its molecular formula structure is:
formula 50:
Figure BDA0002786528990000393
the remaining component types and contents are shown in table 3.
Composition example 8
Composition example 8 differs from composition example 6 in that:
the resin component (B) is B2A resin of the type represented by the formula B21And formula B22And formula B23The repeating unit shown is constituted, and the numerical value below the right of each repeating unit represents the content (mass%) of the repeating unit in the resin. B2The weight average molecular weight of the resin was about 10000.
Formula B21：
Figure BDA0002786528990000401
Formula B22：
Figure BDA0002786528990000402
Formula B23：
Figure BDA0002786528990000403
The remaining component types and contents are shown in table 3.
Composition example 9
Composition example 9 differs from composition example 6 in that:
the resin component (B) is B3A resin of the type represented by the formula B31And formula B32The repeating unit shown is constituted, and the numerical value below the right of each repeating unit represents the content (mass%) of the repeating unit in the resin. B is3The weight average molecular weight of the resin was about 9580.
Formula B31：
Figure BDA0002786528990000404
Formula B32：
Figure BDA0002786528990000405
The remaining component types and contents are shown in table 3.
Composition example 10
Composition example 10 differs from composition example 6 in that: the imide sulfonic acid ester photoacid generators represented by formula 47 have different contents.
The remaining component types and contents are shown in table 3.
Composition example 11
Composition example 11 differs from composition example 6 in that: the imide sulfonic acid ester photoacid generators represented by formula 47 have different contents.
The remaining component types and contents are shown in table 3.
Comparative composition example 1
Composition comparative example 1 differs from composition example 6 in that: does not contain the aromatic carboxylic acid compound (C).
The component types and contents are shown in table 3.
Comparative composition example 2
Composition comparative example 2 differs from composition example 1 in that: the imide sulfonic acid ester photoacid generator (a) is an imide sulfonic acid ester photoacid generator represented by a 1.
The component types and contents are shown in table 3.
Comparative composition example 3
Composition comparative example 3 differs from composition example 6 in that,
(1) using aromatic diol (C)′) With tetrahydrophthalic anhydride in a ratio of 1: 1 molar ratio of aromatic carboxylic acid compound C2。
(2) The remaining component types and contents are shown in table 3.
Comparative composition example 4
Composition comparative example 4 differs from composition example 6 in that,
(1) using a non-aromatic carboxylic acid compound polymethacrylic acid (C)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 3.
The photosensitive compositions prepared in composition examples 1 to 11 and composition comparative examples 1 to 4 were evaluated for sensitivity and resolution by the following methods, and the results are reported in Table 3.
(1) Sensitivity evaluation method
The photosensitive resin 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：○-50mJ/cm2X-300mJ/cm2The above.
(2) Evaluation of resolution
A mask for forming a hole pattern having a diameter of 5 μm was used except at 100mJ/cm2The coating formation, the coating exposure and the development were carried out in the same manner as in the sensitivity evaluation except that the exposure amount of (b) was used for the exposure. The coating film after development was observed, and the resolution was evaluated according to the following criteria: o-can form a pattern with a diameter of 5 μm, and X-cannot form a pattern with a diameter of 5 μm.
TABLE 3
Figure BDA0002786528990000421
Figure BDA0002786528990000431
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 (21)

1. An imide sulfonate photoacid generator having a structure represented by the following general formula (A1) or (A2):
Figure FDA0002786528980000011
wherein the content of the first and second substances,
R1is represented by C1-C20Linear or branched alkyl of (2), C3-C20Cyclic alkyl of (2), C1-C20Linear or branched fluoroalkyl, C3-C20Fluorinated cyclic alkyl group of6-C18Substituted or unsubstituted aryl, camphoryl, or mesitylA nitronaphthalenone group;
R2、R3、R4and R4The "may be the same or different and each is independently selected from the group consisting of: hydrogen; nitro, nitro-containing alkyl or nitro-containing aryl, wherein the hydrogen on the hydrocarbon group can be partially or completely replaced by fluorine; the amino, the alkyl containing the amino or the aromatic containing the amino, wherein the hydrogen on the hydrocarbon group can be partially or completely replaced by fluorine; cyano, cyano-containing alkyl, or cyano-containing aryl, wherein the hydrogen on the hydrocarbon group may be partially or fully substituted by fluorine; straight or branched alkyl, or cycloalkyl, optionally, -CH therein2-may be substituted by-O-, -S-, the hydrogen on the hydrocarbon group may be partially or fully substituted by fluorine; aryl, wherein the hydrogen on the aryl ring can be replaced by alkyl, alkoxy or fluorine, and the hydrogen on other positions can be partially or completely replaced by fluorine; 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-, -S-or-NH-; r1' -CO-, wherein R1' represents hydrogen, C1-C10Alkyl of (C)3-C10And optionally, at least one hydrogen atom in the phenyl group may be replaced by C1-C8Alkyl or alkoxy of (a); r2’-CO-O-R3' -, wherein R2' represents C1-C10Alkyl, phenyl, R3' represents null, C1-C8Alkylene oxide of, or C3-C8Optionally, at least one hydrogen atom in the phenyl group may be replaced by C1-C8Alkyl of (a); r is4’-O-CO-R5' -, wherein R4' represents C1-C10Alkyl of R5' represents C1-C10An alkylene group of (a); linear or branched alkenyl, cycloalkyl or aryl containing alkenyl, optionally wherein the hydrogens on the hydrocarbon group may be partially or fully substituted with fluorine; straight-chain or branched alkynyl containing cycloalkanesAlkynyl of aryl or aryl, wherein the hydrogen on the hydrocarbyl group may be partially or fully substituted with fluorine; alkylsulfonyloxy, cycloalkyl-or aryl-containing sulfonyloxy, optionally the hydrogen on the alkyl group may be partially or fully substituted by fluorine; alkylsilyl, cycloalkyl-containing silyl, optionally the hydrogen on the alkyl can be partially or fully substituted with fluorine; a heterocyclic group containing N, S or O;
R2and R3May be linked to each other to form a five-membered ring or a six-membered ring;
provided that R in the formula (A1)2、R3And R4Not simultaneously hydrogen, R in the general formula (A2)2、R3And R4"not simultaneously hydrogen.
2. The imide sulfonic acid ester photoacid generator according to claim 1, wherein R is1Selected from the following groups: c1-C8Linear or branched alkyl of (a); c1-C8Linear or branched perfluoroalkyl of (a); a perfluorophenyl group; at least one hydrogen atom being bound by C1-C6A linear or branched alkyl or fluoroalkyl group of (a), or an amino-substituted phenyl group; a camphor group; an azidonaphthalenone group.
3. The imide sulfonic acid ester photoacid generator according to claim 1, wherein: r1Selected from methyl, propyl, octyl, perfluoromethyl, perfluoroethyl, perfluoropropyl, perfluorobutyl, perfluoropentyl, perfluorophenyl, camphoryl, azidonaphthalenone groups, p-methylphenyl, p-aminophenyl, m-isopropylphenyl, or perfluoromethylphenyl groups.
4. The imide sulfonic acid ester photoacid generator according to claim 1, wherein R is2、R3、R4And R4The "may be the same or different and each is independently selected from the group consisting of: hydrogen; a nitro group; an amine group; a cyano group; c1-C10Linear or branched alkyl of (2), C3-C10Cycloalkyl of (4), optionallyIn which is-CH2-may be substituted by-O-, -S-; phenyl, optionally, in which at least one hydrogen atom may be replaced by C1-C4Alkyl or alkoxy of (a); c4-C18N, S or O containing heterocyclic group; c2-C6Straight or branched alkynyl of (a); c7-C10Optionally, at least one hydrogen atom on the phenyl group may be replaced by C1-C4Substituted by alkyl or alkoxy groups of which-CH is2-may be substituted by-O-, -S-or-NH-; c2-C6Linear or branched alkenyl of (a); with C3-C6Cycloalkyl or C6-C10Aryl of (A) is end-capped C2-C6Alkenyl of (a); r is1' -CO-, wherein R1' represents hydrogen, 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-C4Optionally, at least one hydrogen atom in the phenyl group may be replaced by C1-C4Is substituted with an alkyl group of (a); r4’-O-CO-R5' -, wherein R4' represents C1-C6Alkyl of R5' represents C1-C6An alkylene group of (a); c1-C6Optionally, hydrogen on the alkyl group may be substituted by fluorine; c6-C10Arylsulfonyloxy of (a); c1-C12Optionally, the hydrogen on the alkyl group may be substituted by fluorine;
R2and R3May be linked to each other to form a five-membered ring or a six-membered ring;
provided that, in the general formula (A1), R2、R3And R4Not hydrogen at the same time; in the general formula (A2), R2、R3And R4"not simultaneously hydrogen.
5. The imide sulfonic acid ester photoacid generator according to claim 1, wherein R is2、R3、R4And R4The "may be the same or different and each is independently selected from the group consisting of: hydrogen; a nitro group; an amine group; a cyano group; a phenyl group; a thienyl group; methyl, ethyl, propyl, butyl, hexyl, cyclohexyl, cyclohexylmethyl, 3-methylpentane, octyl and dodecyl, optionally, one or more of which-CH2-may be substituted by-O-, -S-; c7-C10Optionally, at least one hydrogen atom on the phenyl group may be substituted by a methyl group, and/or at least one-CH in the alkyl group2-may be substituted by-O-, -S-or-NH-; r1' -CO-, wherein R1' represents hydrogen, methyl, phenyl, alkoxyphenyl; r2’-CO-O-R3' -, wherein R2' represents a methyl group, R3' represents an ethynylene group; r4’-O-CO-R5' -, wherein R4' represents methyl, ethyl, propyl, butyl, pentyl or hexyl, R5' represents a methylene group or a void; ethynyl, propynyl, isopentynyl, or pentynyl; propenyl, hexenyl, isobutenyl, ethenyl;
R2and R3May be linked to each other to form a five-membered thiophene ring;
provided that, in the general formula (A1), R2、R3And R4Not hydrogen at the same time; in the general formula (A2), R2、R3And R4"not simultaneously hydrogen.
6. The method for producing an imide sulfonic acid ester type photoacid generator according to any one of claims 1 to 5, comprising the steps of:
reacting halogenated derivatives of thiophene with pinacol diboron to form boron reagents, coupling with bromo-1, 8 naphthalic anhydride, hydroamination, and finally with sulfonic anhydride (R)1-SO2)2O or sulfonyl chloride R1-SO2Carrying out esterification reaction on the-Cl to obtain a target compound;
the process route is as follows:
Figure FDA0002786528980000051
wherein X represents a halogen.
7. An acid production method comprising irradiating the imide sulfonic acid ester type photoacid generator according to any one of claims 1 to 5 with active energy rays.
8. The acid generation process of claim 7, wherein: the active energy ray is an active energy ray having a wavelength in the near ultraviolet region and the visible light region of 300-450nm, and particularly preferably active energy rays having wavelengths of 365nm (I line), 385nm and 405nm (H line).
9. Use of the imide sulfonic acid ester type photoacid generator according to any one of claims 1 to 5 for a material for resist films, liquid resists, negative resists, positive resists, resists for MEMS, stereolithography, and micro stereolithography.
10. A photosensitive resin composition comprising the imide sulfonate photoacid generator according to any one of claims 1 to 5.
11. The photosensitive resin composition according to claim 10, wherein: the composition is a positive resist composition, and further contains a resin component (B1) which has increased solubility in an alkali developing solution by the action of an acid.
12. The photosensitive resin composition according to claim 11, wherein: the resin component (B1) is obtained by vinyl polymerization of a vinyl monomer containing an alkali-soluble acidic group, in which a part or all of the hydrogen atoms of the alkali-soluble acidic group is substituted with an acid-dissociable group as a protecting group, and optionally a hydrophobic group-containing vinyl monomer.
13. The photosensitive resin composition according to claim 12, wherein: the alkali-soluble acidic group is a phenolic hydroxyl group, a carboxyl group or a sulfonic acid group.
14. The photosensitive resin composition according to claim 12, wherein: the acid-dissociable group is selected from the group consisting of a substituted methyl group, a 1-substituted ethyl group, a 1-branched alkyl group, a silyl group, a germyl group, an alkoxycarbonyl group, an acyl group, and a cyclic acid-dissociable group.
15. The photosensitive resin composition according to claim 14, wherein: the acid dissociable group is selected from the group consisting of a tert-butyl group, a benzyl group, a 1-methoxyethyl group, a 1-ethoxyethyl group, a trimethylsilyl group, a tert-butoxycarbonyl group, a tert-butoxycarbonylmethyl group, a tetrahydropyranyl group, a tetrahydrofuranyl group, a tetrahydrothiopyranyl group and a tetrahydrothiofuranyl group.
16. The photosensitive resin composition according to claim 12, wherein: the hydrophobic group-containing vinyl monomer is selected from (meth) acrylate, aromatic olefin monomer, and the like.
17. The photosensitive resin composition according to claim 10, wherein: the composition is a negative resist composition, and further contains a resin-crosslinking agent component (B2) which is crosslinked by the action of an acid and is insoluble in an organic developer.
18. The photosensitive resin composition according to claim 17, wherein: the resin-crosslinking agent component (B2) contains a phenolic hydroxyl group-containing resin (B2-1) and a crosslinking agent (B2-2).
19. The photosensitive resin composition according to claim 18, wherein: the crosslinking agent (B2-2) is selected from the group consisting of bisphenol A epoxy compounds, bisphenol F epoxy compounds, bisphenol S epoxy compounds, novolak resin epoxy compounds, poly (hydroxystyrene) epoxy compounds, oxetane compounds, methylol-containing melamine compounds, methylol-containing benzoguanamine compounds, methylol-containing urea compounds, methylol-containing phenol compounds, alkoxyalkyl-containing melamine compounds, alkoxyalkyl-containing benzoguanamine compounds, alkoxyalkyl-containing urea compounds, alkoxyalkyl-containing phenol compounds, carboxymethyl-containing melamine resins, carboxymethyl-containing benzoguanamine resins, carboxymethyl-containing urea resins, carboxymethyl-containing phenol resins, carboxymethyl-containing melamine compounds, carboxymethyl-containing benzoguanamine compounds, bisphenol S epoxy compounds, novolak resin, and the like, Urea compounds containing a carboxymethyl group and phenol compounds containing a carboxymethyl group.
20. The photosensitive resin composition according to any one of claims 10 to 19, wherein: the composition further comprises an aromatic carboxylic acid compound (C), i.e. at least one carboxylic acid group is bonded to an aromatic group.
21. Use of the photosensitive resin composition according to any one of claims 10 to 20 for the production of a protective film for electronic parts, an interlayer insulating material, a pattern transfer material.
CN202011299973.1A 2020-11-19 2020-11-19 Imide sulfonate photo-acid generator with high acid yield, composition and application Pending CN114516863A (en)

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CN103995437A (en) * 2013-02-20 2014-08-20 Az电子材料（卢森堡）有限公司 Negative type photosensitive
CN104797560A (en) * 2012-11-12 2015-07-22 Az电子材料（卢森堡）有限公司 Aromatic imide compound and method for producing same

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CN104797560A (en) * 2012-11-12 2015-07-22 Az电子材料（卢森堡）有限公司 Aromatic imide compound and method for producing same
CN103995437A (en) * 2013-02-20 2014-08-20 Az电子材料（卢森堡）有限公司 Negative type photosensitive

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115894438A (en) * 2021-09-30 2023-04-04 华为技术有限公司 Photosensitive molecules and uses thereof
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