WO2021057813A1 - Générateur de photo-acide de sulfimide, composition de résine photosensible, procédé de formation de motifs, utilisation de la composition de résine photosensible - Google Patents

Générateur de photo-acide de sulfimide, composition de résine photosensible, procédé de formation de motifs, utilisation de la composition de résine photosensible Download PDF

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Publication number
WO2021057813A1
WO2021057813A1 PCT/CN2020/117236 CN2020117236W WO2021057813A1 WO 2021057813 A1 WO2021057813 A1 WO 2021057813A1 CN 2020117236 W CN2020117236 W CN 2020117236W WO 2021057813 A1 WO2021057813 A1 WO 2021057813A1
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group
acid
resin composition
photosensitive resin
alkyl group
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PCT/CN2020/117236
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English (en)
Chinese (zh)
Inventor
钱晓春
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常州强力先端电子材料有限公司
常州强力电子新材料股份有限公司
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Priority claimed from CN201910908579.4A external-priority patent/CN112552280A/zh
Priority claimed from CN202010906176.9A external-priority patent/CN114114839A/zh
Application filed by 常州强力先端电子材料有限公司, 常州强力电子新材料股份有限公司 filed Critical 常州强力先端电子材料有限公司
Publication of WO2021057813A1 publication Critical patent/WO2021057813A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D401/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom
    • C07D401/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings
    • C07D401/04—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings directly linked by a ring-member-to-ring-member bond
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/02—Printing inks
    • C09D11/03—Printing inks characterised by features other than the chemical nature of the binder
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/30—Inkjet printing inks
    • C09D11/38—Inkjet printing inks characterised by non-macromolecular additives other than solvents, pigments or dyes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/60—Additives non-macromolecular
    • C09D7/63—Additives non-macromolecular organic
    • 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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/55—Design of synthesis routes, e.g. reducing the use of auxiliary or protecting groups

Definitions

  • the present invention relates to the technical field of photosensitive materials, in particular to a sulfonimide photoacid generator, a photosensitive resin composition, a patterning method and the application of the photosensitive resin composition.
  • Photolithography technology refers to making a resist film from a resist material, coating and molding it on a substrate, so that the resist film is selectively exposed to light or electron beam radiation through a mask with a predetermined pattern formed thereon Then, a developing process is performed to form a resist pattern having a predetermined shape on the resist film.
  • the resist material in which the exposed part is changed to dissolve in the developer is called a positive resist material
  • the resist material in which the exposed part is changed to be insoluble in the developer is called a negative resist material.
  • the refinement of pattern feature size is rapidly developing.
  • the wavelength of the exposure light source high-energy radiation
  • ultraviolet rays which have been represented by g-line and i-line, are gradually converted to KrF excimer lasers or ArF excimer lasers for mass production of semiconductor elements.
  • F2 excimer lasers electron beams, EUV (extreme ultraviolet) and X-rays that have shorter wavelengths than these excimer lasers.
  • the resist composition is required to improve the lithographic characteristics so as to have a high sensitivity to the exposure light source and a resolution capable of reproducing the formation of fine-sized patterns. Therefore, the resist material must have lithographic characteristics such as sensitivity to the above-mentioned exposure light source and the ability to reproduce the resolution with fine-sized patterns.
  • a resist material that satisfies such requirements chemically amplified resists containing alkaline resins can be used.
  • the alkali solubility of the alkaline resins can be changed by the action of an acid.
  • chemically amplified positive resists include The base resin of the acid agent increases the alkali solubility by the acid generated by the acid generator. When the resist pattern is formed, the acid is generated from the acid generator by exposure, and the exposed area becomes soluble in the alkaline developer.
  • this type of positive resist composition still needs further improvement for miniaturization technology to adjust the sensitivity, sensitivity, resolution, and contrast of the formed pattern in the formation of the resist pattern.
  • one of the typical examples is a resin composition containing a resin and a photoacid generator.
  • the resin may be, for example, t-butyl carboxylic acid or t-butyl ether of phenol, methyl Silyl ether and so on.
  • active energy rays such as ultraviolet rays
  • the photoacid generator decomposes to produce strong acid (optionally, further heating (PEB) after exposure), under the action of strong acid, carboxylic acid derivatives or phenol derivatives are deprotected to produce carboxylic acid Or phenol.
  • PEB further heating
  • Non-ionic photoacid generators used in chemically amplified resists, which can be divided into two types: non-ionic and ionic.
  • the ionic photoacid generator often has insufficient compatibility with the solvent, and is prone to phase separation in the resist material, so that it cannot fully function.
  • Non-ionic photoacid generators usually have problems such as insufficient sensitivity at long wavelengths and poor solubility in solvents.
  • R 1 represents a C 1 -C 20 linear or branched alkyl or fluoroalkyl group, a C 6 -C 18 substituted or unsubstituted aryl group, or a camphor group
  • R 2 -R 7 are each independently To represent the following groups: hydrogen; halogen; C 1 -C 20 linear or branched alkyl or haloalkyl, optionally in which -CH 2 -may be substituted by -O-; phenyl, any
  • at least one hydrogen atom may be substituted by a C 1 -C 8 alkyl group or alkoxy group
  • a C 7 -C 20 phenyl alkyl group optionally, at least one hydrogen atom on the phenyl group may be It is substituted with alkyl or alkoxy of C 1 -C 8, alkyl -CH 2 - may be substituted with -O- or -S-;
  • R 1 'CO- wherein R 1' represents a C
  • the compound of the general formula (A) of the present invention belongs to a non-ionic photoacid generator, has a light-absorbing group and an acid-generating group (acid generating unit), can realize long-wave absorption, and has a wavelength of 300-450nm, especially 365nm (I line ) And 405nm (H line) active energy rays have high sensitivity and strong absorption, and can produce acid quickly under short-time irradiation. At the same time, it also has good solubility.
  • the present invention also provides an acid generation method, which irradiates the above-mentioned photoacid generator, that is, the compound of general formula (A) with active energy rays.
  • the molecule of the compound of general formula (A) contains a sulfonic acid ester group, which is directly connected to the imide structure.
  • the structure has the characteristics of photo-decomposition and can be photodegraded to produce strong sulfonic acid under the irradiation of active energy rays.
  • the active energy rays are active energy rays with a wavelength between 300-450 nm in the near-ultraviolet light region and visible light region, and active energy rays with wavelengths of 365 nm (I line) and 405 nm (H line) are particularly preferred.
  • the photoacid generator of the present invention can be used for any known application of the photoacid generator, such as paints, coating agents, inks, inkjet inks, resist films, liquid resists, negative resists, and positive resists. Etchants, resists for MEMS, negative photosensitive materials, materials for stereo lithography and micro stereo lithography, etc. It is most suitable as a photoacid generator in a resist, and a resist is prepared together with a resin having acid dissociation properties for use in semiconductor photolithography.
  • Another main purpose of the present invention is to provide a photosensitive resin composition, a patterning method and application of the photosensitive resin composition to solve the problem of the sensitivity of the positive resist composition in the prior art when forming fine patterns. The problem of insufficient.
  • a photosensitive resin composition comprising a resin component and an acid generator, the acid generator being any one of the above-mentioned sulfonimide photoacid generators.
  • a patterning method including mixing, forming a film and patterning a photosensitive resin composition, the photosensitive resin composition being any one of the above-mentioned photosensitive resin compositions .
  • an application of any of the above-mentioned photosensitive resin compositions includes applying the photosensitive composition to protective films, interlayer insulating materials, and pattern transfer materials for electronic components. In preparation.
  • a sulfonimide photoacid generator capable of producing high acid at the I line and H line is provided, which has the structure shown in the following general formula (A):
  • R 1 represents a C 1 -C 20 linear or branched alkyl or fluoroalkyl group, a C 6 -C 18 substituted or unsubstituted aryl group, or a camphor group
  • R 2 -R 7 are each independently To represent the following groups: hydrogen; halogen; C 1 -C 20 linear or branched alkyl or haloalkyl, optionally in which -CH 2 -may be substituted by -O-; phenyl, any
  • at least one hydrogen atom may be substituted by a C 1 -C 8 alkyl group or alkoxy group
  • a C 7 -C 20 phenyl alkyl group optionally, at least one hydrogen atom on the phenyl group may be It is substituted with alkyl or alkoxy of C 1 -C 8, alkyl -CH 2 - may be substituted with -O- or -S-;
  • R 1 'CO- wherein R 1' represents a C
  • the beneficial effect of the above-mentioned acid generator of the present invention is embodied in that the photoacid generator can achieve long-wave absorption, and has activity at wavelengths of 300-450nm, especially 365nm (I line) and 405nm (H line).
  • Energy ray has high sensitivity and strong absorption; photolysis can produce strong sulfonic acid; and has good solubility.
  • R 1 is a C 1 -C 6 linear or branched perfluoro An alkyl group, a perfluorophenyl group, a phenyl group in which at least one hydrogen atom is substituted with a C 1 -C 6 alkyl group or a fluoroalkyl group, or a camphor group.
  • R 1 may be selected from trifluoromethyl, perfluorobutyl, p-methylphenyl, pentafluorophenyl, camphor and the like.
  • R 1 is perfluoromethyl, perfluoroethyl, perfluoropropyl, perfluorobutyl, perfluoropentyl, perfluorophenyl, camphoryl, p-methylphenyl or all Fluoromethylphenyl.
  • R 2 -R 7 is selected from any one of methyl, ethyl, propyl, butyl, and pentyl, and the rest is H; or R 2 and R 4 -R 7 are hydrogen, R 3 is selected from any one of the following groups: halogen, halomethyl, and haloethyl; or R 2 , R 4 -R 7 are hydrogen, and R 3 is selected from any one of the following groups: Methyl, ethyl, propyl, butyl, pentyl, and one of -CH 2 -is replaced by -O-; or R 2 , R 4 -R 7 are hydrogen, and R 3 is selected from the following groups Any one of: C 7 -C 10 phenylalkyl group, optionally, one hydrogen atom on the phenyl group can be replaced by a methyl group, and/or one -CH 2 -in the alkyl group can be- O- or -S-
  • the photoacid generator having the structure represented by the general formula (A) of the present invention can be selected from the following structures:
  • the present invention also relates to a preparation method of the above-mentioned sulfonimide photoacid generator, which comprises the following steps:
  • steps (1)-(3) are all conventional reactions in the field of organic synthesis. Based on the knowledge of the synthetic route disclosed in the present invention, specific reaction conditions are easily determined by those skilled in the art.
  • the reaction of step (1) is carried out in an organic solvent.
  • the organic solvent used is not particularly limited, as long as it can dissolve the raw materials without adversely affecting the reaction, such as dioxane, dichloroethane, tert-butanol, toluene, xylene, DMF, and DMSO.
  • the hydroxylamination reaction in step (2) and the esterification reaction in step (3) are also carried out in an organic solvent.
  • the organic solvent used is not particularly limited, as long as it can dissolve the raw materials without adversely affecting the reaction, such as dichloromethane, dichloroethane, benzene, toluene, xylene and the like.
  • the raw materials used in the above preparation methods are all known compounds in the prior art, and they can be purchased commercially or conveniently prepared by known synthetic methods such as coupling and FuK.
  • the compound of the general formula (A) of the present invention belongs to a non-ionic photoacid generator, has a light-absorbing group and an acid-generating group (acid generating unit), can realize long-wave absorption, and has a wavelength of 300-450nm, especially 365nm (I line ) And 405nm (H line) active energy rays have high sensitivity and strong absorption, and can produce acid quickly under short-time irradiation. At the same time, it also has good solubility.
  • the molecule of the compound of general formula (A) contains a sulfonic acid ester group, which is directly connected to the imide structure.
  • the structure has the characteristics of photo-decomposition and can be photodegraded to produce strong sulfonic acid under the irradiation of active energy rays.
  • the active energy rays are active energy rays with a wavelength between 300-450 nm in the near-ultraviolet light region and visible light region, and active energy rays with wavelengths of 365 nm (I line) and 405 nm (H line) are particularly preferred.
  • a photosensitive resin composition in a typical embodiment of the present application, includes a resin component and an acid generator, and the acid generator is a sulfonimide photoacid generator .
  • the acid labile group includes at least one of a carboxyl group and a phenolic hydroxyl group, which can 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 accounts for 1 to 80% of the resin component content, preferably 3 to 70%, optionally 26%, 45%, within this range, the photosensitive composition can be obtained with Better developability.
  • the cross-linking group is a functional group that can be thermally cross-linked when the patterned film to be formed is post-baked.
  • Groups suitable for crosslinking can be selected from epoxy groups, oxetanyl groups, and groups containing unsaturated double bonds (for example, (meth)acryloyl groups.
  • the content of crosslinking groups is preferably It is 20 to 70% (w/w). Within this range, a film with excellent mechanical properties and chemical resistance can be formed by thermal crosslinking between crosslinking groups during PEB (heating after exposure).
  • (meth)acrylates having no epoxy group (meth)acrylates having an alicyclic skeleton are preferred, and in (meth)acrylates having an alicyclic skeleton, the alicyclic group may be Monocyclic or polycyclic, the monocyclic alicyclic group can be selected from cyclopentyl and cyclohexyl, and the polycyclic alicyclic group can be selected from norbornyl, isobornyl, tricyclononyl 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 Base-2,2-dimethylpropyl vinyl ether, 2-ethylbutyl vinyl ether, hydroxyethyl vinyl ether, diethylene glycol vinyl ether, dimethylaminoethyl vinyl ether, Diethylaminoethyl vinyl ether and benzyl vinyl ether, etc.
  • the aldehyde can be selected from formaldehyde, acetaldehyde, furfural, benzaldehyde, nitrobenzaldehyde and the like.
  • the acid catalyst can be selected from hydrochloric acid, sulfuric acid, formic acid, acetic acid, oxalic acid and the like.
  • the molecular weight of the novolak resin is preferably 1,000 to 50,000, and a resin in which at least a part of the hydroxyl groups of the novolak resin is protected by a protective group can be used as the resin component.
  • 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 to react.
  • the above-mentioned protective group includes at least one of the following groups:
  • Alkyl group, and any two of R 8 , R 9 , and R 10 are suitable for bonding to each other to form a ring;
  • R 11 , R 12 and R 13 each independently represent a C 1 -C 20 hydrocarbon group, and R 11 , R 12 , Any two of R 13 are suitable for bonding to each other to form a ring;
  • R 14 represents a C 1 -C 6 straight chain alkyl group, a C 1 -C 6 branched chain alkyl group, a C 1 -C 6 cyclic alkyl group Base, and n is 0 or 1.
  • R 8 , R 9 and R 10 are alkyl groups
  • exemplary can be selected from methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl Base, sec-butyl, tert-butyl, n-pentyl, isopentyl, tert-pentyl, n-hexyl, n-heptyl, n-octyl, 2-ethyl n-hexyl, n-nonyl, n-decyl, etc.;
  • any two groups of R 3 , R 4 and R 5 are bonded to each other to form a ring, it is preferably a C 5 -C 20 monocyclic or polycyclic aliphatic hydrocarbon, and exemplary can be selected from cyclopentane , Cyclohexane, cycloheptane, cyclooctane, adam
  • the ring structure can be selected from cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclononyl, cyclodecyl, cycloundecyl, cyclododecane Group, and a polycyclic group of the following molecular formula (formula b 1 -formula b 8 );
  • R 11 , R 12 and R 13 when R 11 , R 12 and R 13 are aromatic hydrocarbon groups, they can be selected from phenyl, naphthyl, anthracenyl, biphenyl, phenanthryl, and fluorenyl.
  • R 11 , R 12 and R 13 contain both aliphatic and aromatic groups, they can be selected from benzyl, phenethyl, 3-phenyl-n-propyl, 4-phenyl-n-butyl, ⁇ - Naphthylmethyl, ⁇ -naphthylmethyl, 2-( ⁇ -naphthyl)ethyl, 2-( ⁇ -naphthyl)ethyl and the like.
  • the aromatic ring may be substituted or partially substituted, and the substituents are selected from halogen atoms, hydroxyl groups, C 1 -C 10 alkyl groups or alkoxy groups, C 2 -C 10 alkanoyl groups and alkanoyloxy groups.
  • R 11 is preferably a hydrogen atom
  • R 12 is preferably a methyl group
  • R 13 is preferably an ethyl, isobutyl, cyclohexyl, 2-ethyl-n-hexyl or octadecyl group
  • R 12 and When R 13 is bonded to each other to form a ring a C 4 -C 6 heterocyclic ring containing O, S or N atoms is preferred
  • R 11 and R 12 are bonded to each other to form a ring, a C 3 -C 12- membered saturated aliphatic hydrocarbon is preferred ring.
  • the formula (b) may preferably be a group of the following molecular formula (formula b 9 -formula b 14 ):
  • the formula (c) can be selected from t-butoxycarbonyl and t-butoxycarbonylmethyl.
  • the amount of the above acid generator can refer to the amount of conventional acid generators in the prior art.
  • the weight content of the acid generator is 0.5 to 5% relative to the mass of the solid content of the photosensitive resin composition.
  • the resin component is selected from any one of (meth)acrylic resin, polyhydroxystyrene resin and phenolic resin polymer.
  • the above-mentioned resin composition further includes an aromatic carboxylic acid compound, that is, at least one carboxyl group is bonded to an aromatic group, and the aromatic group can be an aromatic hydrocarbon group and an aromatic heterocyclic group.
  • the aromatic carboxylic acid compound can promote the deprotection reaction of the acid labile group protected by the protecting group in the resin component of the composition after exposure.
  • the aromatic carboxylic acid compound is used in combination with the above-mentioned resin component and acid generator of the present application, the resolution of the pattern can be further improved. It is preferable that the weight content of the aromatic carboxylic acid compound is 3 to 35% with respect to the mass of the solid content of the photosensitive resin composition.
  • the above-mentioned aromatic carboxylic acid compound can be selected from at least one of a low-molecular-weight aromatic carboxylic acid compound or a high-molecular-weight aromatic carboxylic acid compound; wherein the low-molecular-weight aromatic carboxylic acid compound includes at least two carboxyl groups and/or monocarboxylates with substituents.
  • Acid compounds, polycarboxylic acid compounds; Macromolecular aromatic carboxylic acid compounds include macromolecular compounds containing carboxyl groups bonded to aromatic groups and unsaturated double bonds.
  • the aromatic carboxylic acid compound in addition to the carboxyl group, it can also have one or more substituents, which can be selected from halogens, hydroxyl groups, mercapto groups, sulfide groups, silyl groups, silanol groups, nitro groups, and nitroso groups.
  • substituents can be selected from halogens, hydroxyl groups, mercapto groups, sulfide groups, silyl groups, silanol groups, nitro groups, and nitroso groups.
  • Group, sulfonate group, phosphonyl group and phosphonate group when the substituent on the aromatic group is an organic group, it can be selected from alkyl, alkenyl, cycloalkyl, cycloalkenyl, aryl And aralkyl groups; the organic group may contain bonds or substituents other than hydrocarbyl groups, such as O, Si, N and other heteroatoms.
  • the heteroatom bonds may include ether bonds, thioether bonds, carbonyl bonds, and thiocarbonyl bonds , Ester bond, amide bond, urethane bond and imino bond, carbonate bond, sulfonyl bond, sulfinyl bond and azo bond, etc.
  • the organic group can be linear, branched or cyclic.
  • a C 1 -C 12 alkyl group, an aryl group, an alkoxy group and a halogen are preferable.
  • 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, as follows:
  • the low molecular weight aromatic carboxylic acid compound may be a monocarboxylic acid compound or a multivalent 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 the carboxyl group.
  • the low molecular weight aromatic carboxylic acid compound can be selected from the following carboxylic acids: benzoic acid; hydroxybenzoic acid such as salicylic acid, m-hydroxybenzoic acid and p-hydroxybenzoic acid, etc.; alkyl benzoic acid such as o-toluic acid, m-toluic acid, etc.
  • halogenated benzoic acid such as o-chlorobenzoic acid, m-chlorobenzoic acid, p-chlorobenzoic acid, o-bromobenzoic acid, m-bromobenzoic acid and p-bromobenzoic acid
  • alkoxy benzoic acid such as o Methoxy benzoic acid, m-methoxy benzoic acid, p-methoxy benzoic acid, o-ethoxy benzoic acid, m-ethoxy benzoic acid and p-ethoxy benzoic acid
  • amino benzoic acid such as anthoxy benzoic acid, M-aminobenzoic acid and p-aminobenzoic acid
  • acyloxy benzoic acid such as o-acetoxy benzoic acid, m-acetoxy benzoic acid and p-acetoxy benzoic acid
  • naphthoic acid such as 1-naphth
  • the high molecular weight aromatic carboxylic acid compound may be a polymer 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 polymer aromatic carboxylic acid compound.
  • As a preferred copolymerization component it is used together with a monomer having a carboxyl group bound to an aromatic group and an unsaturated double bond.
  • the above-mentioned (meth)acrylic acid as a monomer for preparing acrylic resins can be used, such as (meth) ) Unsaturated carboxylic acids other than acrylic acid, (meth)acrylates, (meth)acrylamides, allyl compounds, vinyl ethers, vinyl esters and styrene.
  • the above-mentioned resin composition further includes a cross-linking compound.
  • the weight content of the cross-linking compound is 10-50% relative to the mass of the solid content of the photosensitive resin composition.
  • the bridging compound contains at least one cross-linking group, which is thermally cross-linked in the case of PEB.
  • the above-mentioned crosslinking group includes an epoxy group, an oxetanyl group, and a group containing an unsaturated double bond (such as a vinyl group).
  • the bridging compounds include: bridging low molecular compounds and bridging high molecular compounds.
  • the bridging group low-molecular compound includes: at least one of a bifunctional or higher-functional polyfunctional epoxy compound, a polyoxetane compound, and a polymerizable monomer containing a vinyl group.
  • the multifunctional epoxy compound can be selected from bifunctional epoxy resins, such as bisaldehyde A type epoxy resin and bisphenol S type epoxy resin; glycidyl ester type epoxy resin, such as dimer acid glycidol Esters and triglycidyl esters, etc.; glycidylamine epoxy resins, such as tetraglycidylaminodiphenylmethane and tetraglycidyl diaminomethylcyclohexane, etc.; heterocyclic epoxy resins, such as triglycidyl Isocyanurate, etc.; multifunctional epoxy resin, such as phloroglucinol triglycidyl ether, tetrahydroxyphenylethane tetraglycidyl ether, etc.
  • bifunctional epoxy resins such as bisaldehyde A type epoxy resin and bisphenol S type epoxy resin
  • glycidyl ester type epoxy resin such as dimer acid glycidol Esters
  • the alicyclic epoxy compound is also preferable as a polyfunctional epoxy compound, and it is easy to form a highly transparent film.
  • the polyfunctional oxetane compound can be selected from 3,3'-(oxybismethylene)bis(3-ethyloxetane), 4,4-bis[(3-ethyloxetane) 3-oxetanyl)methyl]biphenyl and 3,7-bis(3-oxetanyl)-5-oxanonane, etc.
  • the polymerizable monomer includes a monofunctional monomer and a multifunctional monomer.
  • Monofunctional monomers can be selected from (meth)acrylamide, methylol (meth)acrylamide, methoxymethyl (meth)acrylamide, ethoxymethyl (meth)acrylamide, propoxy Methyl(meth)acrylamide, N-methylol(meth)acrylamide, (meth)acrylic acid, maleic acid, crotonic acid, 2-acrylamide-2-methylpropanesulfonic acid, tert-butyl Acrylamide 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, these monofunctional monomers can be used alone or in combination of two or more.
  • the multifunctional monomer can be selected from 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, 2,2-bis(4-(meth)acryloyloxydiethoxyphenyl)propane , 2-Hydroxy-3-(meth)acryloxypropyl (meth)acrylate, ethylene glycol diglycidyl ether di(meth)acrylate, diethylene glycol diglycidyl ether two (meth) Base) acrylate, diglycidyl phthalate di(meth)acrylate, glycerol triacrylate, glycerol polyglycidyl ether poly(meth)acrylate,
  • the above-mentioned bridging group polymer compound includes at least one of epoxy group-containing resin and unsaturated double bond-containing resin.
  • Epoxy-containing resins can be formed by polymerization of epoxy-containing monomers or monomer mixtures, and can be selected from novolac epoxy resins, such as phenol novolac type epoxy resins, brominated phenol novolac type epoxy resins, etc. ; Alicyclic epoxy resins, such as epoxidized products of dicyclopentadiene-type phenolic resins; and aromatic epoxy resins, such as epoxidized products of naphthalene-type phenolic resins.
  • aliphatic (meth)acrylates having a chain aliphatic epoxy group and aliphatic (meth)acrylates having an alicyclic epoxy group are preferred, and an alicyclic group is particularly preferred.
  • Aliphatic (meth)acrylate of formula epoxy 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).
  • the epoxy-containing polymer is a copolymer of an epoxy-containing (meth)acrylate and another monomer
  • the other monomer has an unsaturated carboxylic acid, such as but not limited to maleic acid, Citraconic acid; or (meth)acrylates without epoxy groups, such as but not limited to methyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate; (meth)acrylamide, such as but not limited to 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 ether (such as but not limited to hexyl vinyl ether, chloroethyl vinyl ether), vinyl ester (such as but not limited to vinyl butyrate, vinyl chloroacetate), styrene (such as but not limited to benzene Ethylene, chloromethyl styrene) and so on
  • the copolymer of (meth)acrylate having an epoxy group and other monomers preferably does not contain derivative Units from unsaturated carboxylic acids.
  • the molecular weight of the epoxy group-containing resin is preferably 5,000 to 15,000.
  • 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 by reacting at least a part of the carboxyl group contained in the polymer containing the unit derived from the (meth)acrylate and/or the epoxyalkyl (meth)acrylate having the alicyclic epoxy group acquired. Resins (hereinafter collectively referred to as "resin containing a structural unit having an ethylenically unsaturated group") can be appropriately 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 2,000 to 30,000, and good heat resistance, film strength, and good developability can be obtained.
  • the above-mentioned photosensitive composition further includes a solvent to facilitate film formation.
  • the solvent is used in the photosensitive composition to adjust coating performance and viscosity.
  • the solvent preferably contains an aprotic organic solvent, and a photosensitive composition excellent in sensitivity and resolution can be obtained.
  • the photosensitive resin composition of the present application may also include the following auxiliary materials: dissolution control agents, dissolution inhibitors, basic compounds, surfactants, dyes, pigments, plasticizers, photosensitizers, light Any one or more of absorbents, anti-halation agents, storage stabilizers, defoamers, adhesion promoters, phosphors, and magnetic materials.
  • Anthracene ring-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-propyl) Carbonyloxy)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-naphthyloxy)anthracene, 2-methyl Base-9,10-bis(acetoxy)anthracene, 2-methyl-9,10-bis(propionyloxy)anthracene, 2-methyl-9,10-bis(n-prop
  • Compounds that contain naphthacene rings and are suitable for use as photosensitizers include, but are not limited to: alkylcarbonyloxy substituted naphthacene compounds, such as 2-methyl-5,11-dioxo-6,12-bis( Acetoxy) naphthacene, 2-ethyl-5,11-dioxo-6,12-bis(n-hexylcarbonyloxy)naphthalene, etc.; aryloxy substituted naphthacene compounds, such as 2-methyl -5,11-Dioxy-6,12-bis(benzoyloxy)naphthacene, 2-methyl-5,11-diox-6,12-bis(o-toluyloxy)naphthacene Benzene, etc.; aryloxycarbonyloxy substituted tetranaphthalene compounds, such as 2-methyl-5,11-dioxo-6,12-bis(phenoxycarbonyloxy)t
  • auxiliary agents those skilled in the art can choose from commonly used substances in the photosensitive resin composition, which will not be repeated here.
  • a patterning method including mixing, filming and patterning a photosensitive resin composition, the photosensitive resin composition being any of the above Photosensitive resin composition.
  • the above-mentioned patterning method may specifically include: coating the photosensitive composition on the carrier, 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 operations are as follows:
  • the photosensitive composition is mixed and coated on a substrate (silicon substrate, metal substrate, glass substrate, inorganic and/or organic film), preferably using a spinner to coat; the formed coating film is at 80 to 120°C as required Perform pre-bake for 40 to 120 seconds.
  • Actinic rays include low-pressure mercury lamps, medium-pressure mercury lamps, high-pressure mercury lamps, ultra-high-pressure mercury lamps, xenon lamps, metal halide lamps, electron beam irradiation devices, X-ray irradiation devices, lasers (argon laser, dye laser, nitrogen) Laser, LED, helium cadmium laser), preferably high-pressure mercury lamp and LED lamp.
  • the development is performed with an alkaline developer, and the alkaline development method includes the use of an alkaline developer to dissolve and remove the wiring pattern shape.
  • the alkaline developer may be selected from 0.1-10% (w/w) aqueous solutions of tetramethylammonium hydroxide, sodium hydroxide, potassium hydroxide, and sodium bicarbonate.
  • These alkaline developers may contain water-soluble organic solvents, Such as methanol, ethanol, isopropanol, tetrahydrofuran, N-methylpyrrolidone and so on.
  • the development method can be selected from the dipping method, spray method and spray method, preferably the spray method; the temperature of the developer is preferably used at 25-40 °C, the development time is appropriately determined according to the thickness of the resist, and finally the mask is faithful to the mask Patterned resist pattern.
  • the wavelength used for exposure can be selected from g, h, i lines, ArF excimer laser (wavelength 193nm), KrF excimer laser (wavelength 248nm), F2 excimer laser, EUV (extreme ultraviolet), VUV (vacuum ultraviolet) ), EB (electron beam), X-ray, soft X-ray etc. can be used for exposure.
  • g, h, i lines, ArF excimer laser, KrF excimer laser, EUV and EB are preferred.
  • an application of any one of the above-mentioned photosensitive resin compositions is provided.
  • the application includes applying the photosensitive composition to the protective film, interlayer insulating material, and image of electronic components.
  • Type transfer material is provided.
  • the above-mentioned applications can specifically include forming the photosensitive composition into an interlayer insulating film for use in TFTs and panels of liquid crystal display devices; it can also be used as a protective film for color filters and spacers, as well as PS photoresist and BCS photolithography. Glue is used for pattern transfer.
  • the above-mentioned electronic components include, but are not limited to, liquid crystal display devices, organic EL display devices, electronic components such as Micro-LED, Mini-LED, and quantum dot LED display devices.
  • steps (1)-(3) are all conventional reactions in the field of organic synthesis. Based on the knowledge of the synthetic route disclosed in the present invention, specific reaction conditions are easily determined by those skilled in the art.
  • the reaction of step (1) is carried out in an organic solvent.
  • the organic solvent used is not particularly limited, as long as it can dissolve the raw materials without adversely affecting the reaction, such as dioxane, dichloroethane, tert-butanol, toluene, xylene, DMF, and DMSO.
  • the hydroxylamination reaction in step (2) and the esterification reaction in step (3) are also carried out in an organic solvent.
  • the organic solvent used is not particularly limited, as long as it can dissolve the raw materials without adversely affecting the reaction, such as dichloromethane, dichloroethane, benzene, toluene, xylene and the like.
  • the raw materials used in the above preparation methods are all known compounds in the prior art, and they can be purchased commercially or conveniently prepared by known synthetic methods such as coupling and FuK.
  • the obtained light yellow solid 8.35 was dissolved in 200.52g methanol, and 3.51g hydroxylamine hydrochloride and 2.85g diethylamine were added dropwise. After the addition, the temperature was kept at 35°C and stirred for 1h, then the temperature was raised to 80°C, after 10h, cooled After washing 3 times with water, distilling out methanol, adding toluene to crystallize to obtain 6.04 g of solid.
  • the obtained solid 9.39 was dissolved in 201.56g methanol, and 3.50g hydroxylamine hydrochloride and 4.06g triethylamine were added dropwise. After the addition, the temperature was kept at 35°C and stirred for 1h, and then the temperature was raised to 80°C. After 10h, it was cooled and washed with water 3. Next, the methanol was distilled off, and toluene was added to crystallize to obtain 6.24g of solid.
  • the obtained solid 7.32 was dissolved in 201.53g methanol, and 2.45g hydroxylamine hydrochloride and 3.23g triethylamine were added dropwise. After the addition, the mixture was stirred at 25°C for 1h, and then heated to 70°C. After 6h, it was cooled and washed 3 times with water. , Distill off methanol, add toluene to crystallize, obtain 5.17g solid.
  • Non-ionic photoacid generator (B-1) Non-ionic photoacid generator
  • the performance evaluation of the photoacid generator compound synthesized in the preparation example and the compound of the comparative example was performed respectively, and the evaluation indicators included molar absorption coefficient, acid production, solubility, and resist curability.
  • a 365 represents the absorbance at 365 nm.
  • the high solubility not only makes the purification of the photoacid generator compound easy, but also enables the photoacid generator compound to expand the concentration range used in photoresist and different solvent systems. Take 1.0000g of the light acid generator compound product, and gradually add solvents (PGMEA, butyl acetate and cyclohexanone) at 25°C until the solids in each test tube are completely dissolved. Record the quality of the solvent used.
  • the solubility is expressed by the following formula .
  • a spin coater to mix 75 parts of p-hydroxystyrene resin (Maruka LINKER S-2P), 25 parts of melamine curing agent (Benok Biotech), 1 part of photoacid generator and 1 part of photoacid generator at 100rpm/10s.
  • a resin solution of 200 parts of propylene glycol monomethyl ether acetate (PGMEA) was coated on a glass substrate (diameter 10 cm). Next, vacuum drying was performed at 25° C. for 5 minutes, and then drying was performed on a hot plate at 80° C. for 3 minutes, thereby forming a resist film with a thickness of about 3 ⁇ m.
  • the resist film was exposed using an ultraviolet irradiation device (IWATA UV-100D) equipped with a filter.
  • IWATA UV-100D ultraviolet irradiation device
  • the cumulative exposure is measured at a wavelength of 365nm.
  • post-exposure heating PEB
  • PEB post-exposure heating
  • the film thickness of the resist was measured using a shape measuring microscope (Keyence VK-8500).
  • the resist curability was evaluated based on the following criteria based on the minimum exposure amount in which the film thickness change of the resist before and after development was within 10%.
  • the minimum exposure is less than 200mJ/cm 2 ;
  • the minimum exposure is greater than 200mJ/cm 2 and less than 250mJ/cm 2;
  • ⁇ The minimum exposure is greater than 250mJ/cm 2 .
  • the test results in Table 1 and Table 2 show that, compared with the compound of the comparative example, the photoacid generator of the present invention has a significantly higher molar absorption coefficient at both the I line and the H line, and the light absorption capacity is much higher than that of the comparative example. .
  • the photoacid generator compound of the present invention is excellent in acid production, and also has obvious advantages in solubility and resist hardenability.
  • the difference between the acid generator compounds shown in Preparation Examples 1-6 is only the difference in the positions of the substituents on the indole group, which are the 2-position, 3-position, 4-position, 5-position, 6-position and 7-position respectively. .
  • the test results in Table 1 and Table 2 show that, compared to other sites, the compound of Preparation Example 2 (that is, the indole group contains a 3-position substituent) has significantly higher molar absorption at both the I line and the H line. Coefficient, and the solubility and resist hardenability are more excellent.
  • the photoacid generator with the structure represented by the general formula (A) of the present invention has high sensitivity to I line and H line, and can be used for coatings, coating agents, inks, and inkjet inks in the wavelength range of 300nm-450nm , Resist films, liquid resists, negative resists, positive resists, resists for MEMS, negative photosensitive materials, materials for stereo lithography and micro stereo lithography, etc.
  • the resin component (A) adopts A 1 type resin, and the structural formula of each component is shown in formula A 11 -formula A 15.
  • the value at the bottom right of each repeating unit represents the content of the repeating unit in the resin (mass %).
  • composition example 2 The difference between composition example 2 and composition example 1 is that:
  • a 3 type resin is represented by formula A 31 -formula A 32 , and the value at the lower right of each structural unit represents the content (mass %) of the repeating unit in the resin.
  • the resin component (A) adopts A 1 type resin, and the structural formula of each component is shown in formula A 11 -formula A 15.
  • the value at the bottom right of each repeating unit represents the content of the repeating unit in the resin (mass %).
  • the aromatic carboxylic acid compound (B 1 ) is obtained by reacting an aromatic diol (B′) with a molar ratio of 1:1 with 2,3,3′,4′-biphenyltetracarboxylic dianhydride.
  • the sulfonimide photoacid generator (C) adopts the sulfonimide photoacid generator of type C 11 (that is, A1-9 above), and its molecular formula structure is:
  • composition example 4 The difference between composition example 4 and composition example 3 is that:
  • Resin component (A) adopts A 2 type resin, and the structural formula of each component is as shown in formula A 21 -formula A 24.
  • the value at the bottom right of each repeating unit represents the content of the repeating unit in the resin (mass %).
  • Resin component (A) adopts A 3 type resin, and the structural formula of each component is shown in formula A 31 -formula A 32 respectively.
  • the value at the bottom right of each structural unit represents the content of the repeating unit in the resin (mass %).
  • composition example 6 The difference between composition example 6 and composition example 3 is that:
  • Sulfonimide photoacid generator (C) adopts C 12 (that is, A2-4 above) type sulfonimide photoacid generator, and its molecular formula structure is:
  • composition example 7 The difference between composition example 7 and composition example 3 is that:
  • Sulfonimide photoacid generator (C) adopts C 13 (ie A3-2 above) type sulfonimide photoacid generator, and its molecular formula structure is:
  • composition example 8 The difference between composition example 8 and composition example 3 is that:
  • Sulfonimide photoacid generator (C) adopts C 14 (that is, A5-4 above) type sulfonimide photoacid generator, and its molecular formula structure is:
  • composition example 9 The difference between composition example 9 and composition example 3 is that:
  • Sulfonimide photoacid generator (C) adopts C 15 (that is, A9-2 above) type sulfonimide photoacid generator, and its molecular formula structure is:
  • composition example 10 The difference between composition example 10 and composition example 3 is that:
  • composition example 11 The difference between composition example 11 and composition example 3 is that:
  • composition example 12 The difference between composition example 12 and composition example 3 is that:
  • composition example 13 The difference between composition example 13 and composition example 3 is that:
  • C 11 type sulfonimide photoacid generator The content of C 11 type sulfonimide photoacid generator is different.
  • Example 1 of the embodiment wherein the composition, imide photoacid class (C) C 2 using the sulfonimide type photoacid class, the structure having the formula:
  • composition comparative example 2 The difference between composition comparative example 2 and composition example 2 is that:
  • Sulfonimide photoacid generator (C) adopts C 2 type sulfonimide photoacid generator, and its molecular structure is:
  • Sulfonimide photoacid generator (C) adopts C 2 type sulfonimide photoacid generator, and its molecular structure is:
  • the photosensitive composition of each of the examples and the comparative example was coated with a film thickness of 3 ⁇ m that can form a pattern to form a coating film.
  • the formed coating film was prebaked at 90°C for 100 seconds.
  • the coating film was exposed through a mask for forming a hole pattern with a diameter of 10 ⁇ m, and then developed at 25° C. with a 2.0% tetramethylammonium hydroxide aqueous solution for 30 seconds.
  • the minimum exposure required to form a hole pattern with a diameter of 10 ⁇ m is determined by the above method. From the obtained minimum exposure value, the sensitivity is evaluated according to the following criteria. ( ⁇ -50mJ/cm 2 or less, X-300mJ/cm 2 or more)
  • the resin component (A) having an acid group protected by a protective group, an aromatic carboxylic acid compound (B) having a carboxyl group bonded to an aryl group, and a naphthalimide sulfonate having a predetermined structure (C) Mixing and forming a photosensitive composition containing a derivative can form a pattern excellent in sensitivity and resolution. If there is no resin protected by a protecting group, patterns cannot be formed.
  • the photosensitive composition of the present invention can be used as a positive photosensitive composition.
  • the difference between the width of the opening of the pattern mask and the width of the pattern is small, and it can form a fine pattern and suppress the pattern generation after development. Undercut, and excellent sensitivity.
  • It can be used as a photosensitive composition in protective films or interlayer insulating materials or pattern transfer materials for electronic components such as liquid crystal display devices, organic EL display devices, Micro-LED, Mini-LED, and quantum dot LED display devices.

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Abstract

Sont divulgués un générateur de photo-acide de sulfimide, une composition de résine photosensible, un procédé de formation de motifs et une utilisation de la composition de résine photosensible. La composition de résine photosensible comprend un composant de résine et un générateur d'acide, le générateur d'acide étant un générateur de photoacide de sulfimide, qui a une structure telle que représentée par la formule générale (A), qui est la suivante. Les molécules du générateur de photo-acide de sulfimide de formule générale (A) contiennent un groupe sulfonate, qui est directement lié à une structure imide. La structure présente des caractéristiques de craquage photosensibles et peut être photolysée sous l'effet de l'irradiation d'un rayonnement d'énergie active pour produire de l'acide sulfonique plus fort. Lorsque la composition de résine photosensible est appliquée à une solution de développement alcalin pour dissoudre une composition photosensible de type positif exposé, un motif ayant une excellente sensibilité et un bon rapport de contraste peut être formé en raison de l'augmentation de la photosensibilité du générateur de photo-acide de sulfimide ; même si un motif fin est formé, il peut également avoir une sensibilité suffisamment élevée.
PCT/CN2020/117236 2019-09-25 2020-09-23 Générateur de photo-acide de sulfimide, composition de résine photosensible, procédé de formation de motifs, utilisation de la composition de résine photosensible WO2021057813A1 (fr)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
CN201910908579.4A CN112552280A (zh) 2019-09-25 2019-09-25 一种高产酸的磺酰亚胺类光产酸剂
CN201910908579.4 2019-09-25
CN202010906176.9 2020-09-01
CN202010906176.9A CN114114839A (zh) 2020-09-01 2020-09-01 感光性树脂组合物、图形化方法及感光性树脂组合物的应用

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103995437A (zh) * 2013-02-20 2014-08-20 Az电子材料（卢森堡）有限公司 负型感光性硅氧烷组合物
CN104797560A (zh) * 2012-11-12 2015-07-22 Az电子材料（卢森堡）有限公司 芳香族酰亚胺化合物及其制造方法
EP3182203A1 (fr) * 2015-12-18 2017-06-21 Heraeus Precious Metals North America Daychem LLC Combinaison de dérivés de nit avec sensibilisateurs
CN107810179A (zh) * 2015-08-21 2018-03-16 贺利氏贵金属北美代顿有限责任公司 在阻剂应用中作为光酸产生剂的磺酸衍生物化合物

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104797560A (zh) * 2012-11-12 2015-07-22 Az电子材料（卢森堡）有限公司 芳香族酰亚胺化合物及其制造方法
CN103995437A (zh) * 2013-02-20 2014-08-20 Az电子材料（卢森堡）有限公司 负型感光性硅氧烷组合物
CN107810179A (zh) * 2015-08-21 2018-03-16 贺利氏贵金属北美代顿有限责任公司 在阻剂应用中作为光酸产生剂的磺酸衍生物化合物
EP3182203A1 (fr) * 2015-12-18 2017-06-21 Heraeus Precious Metals North America Daychem LLC Combinaison de dérivés de nit avec sensibilisateurs

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