WO2013108716A1 - Composition de résine photosensible négative - Google Patents

Composition de résine photosensible négative Download PDF

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Publication number
WO2013108716A1
WO2013108716A1 PCT/JP2013/050428 JP2013050428W WO2013108716A1 WO 2013108716 A1 WO2013108716 A1 WO 2013108716A1 JP 2013050428 W JP2013050428 W JP 2013050428W WO 2013108716 A1 WO2013108716 A1 WO 2013108716A1
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WO
WIPO (PCT)
Prior art keywords
component
photosensitive resin
resin composition
negative photosensitive
monomer
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PCT/JP2013/050428
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English (en)
Japanese (ja)
Inventor
真 畑中
芽育 内山
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日産化学工業株式会社
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Application filed by 日産化学工業株式会社 filed Critical 日産化学工業株式会社
Priority to JP2013554281A priority Critical patent/JP6150072B2/ja
Priority to KR1020147022183A priority patent/KR102027756B1/ko
Priority to CN201380004941.6A priority patent/CN104040432B/zh
Publication of WO2013108716A1 publication Critical patent/WO2013108716A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/52—Amides or imides
    • C08F220/54—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide
    • C08F220/58—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide containing oxygen in addition to the carbonamido oxygen, e.g. N-methylolacrylamide, N-(meth)acryloylmorpholine
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
    • C08F222/36—Amides or imides
    • C08F222/40—Imides, e.g. cyclic imides
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/20—Filters
    • 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
    • G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
    • H05B33/00—Electroluminescent light sources
    • H05B33/02—Details
    • H05B33/04—Sealing arrangements, e.g. against humidity
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
    • H05B33/00—Electroluminescent light sources
    • H05B33/12—Light sources with substantially two-dimensional radiating surfaces
    • H05B33/22—Light sources with substantially two-dimensional radiating surfaces characterised by the chemical or physical composition or the arrangement of auxiliary dielectric or reflective layers
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
    • C08F222/36—Amides or imides
    • C08F222/38—Amides

Definitions

  • the present invention relates to a negative photosensitive resin composition and a cured film obtained therefrom. More specifically, the present invention relates to a photosensitive resin composition suitable for use in display materials, a cured film thereof, and various materials using the cured film.
  • an epoxy cation polymerization UV curable resin containing an epoxy compound and a photoacid generator is highly transparent and can be made thick (for example, Patent Document 1).
  • Patent Document 1 Since the coating film has tack after application and before exposure, handling properties are poor.
  • development with an organic solvent is essential because development with an aqueous alkali solution is not possible.
  • Alkali development is considered possible by introducing a carboxyl group into the polymer.
  • the reaction between the epoxy group and the carboxyl group is likely to occur during the polymerization. It is difficult to control the synthesis of the polymer. Even if the reaction can be controlled to synthesize a polymer, the storage stability is low.
  • a radical polymerization negative material containing a polymer having an acryloyl group, a polyfunctional acrylic monomer, and a photo radical initiator is known (for example, Patent Document 2).
  • alkali development is possible by introducing a carboxyl group into the polymer, but in order to increase the film thickness, it is necessary to increase the viscosity and the handling property is poor.
  • polymerization is a radical system, it is easy to receive oxygen inhibition of the surface at the time of photocuring, and the film thickness reduction on the surface is a problem.
  • the positive type material has high resolution, but it is difficult to increase the film thickness and the transparency is low (for example, Patent Document 3).
  • the present invention has been made in view of the above circumstances, can be thickened, has no tack before exposure, can be patterned with high resolution by alkali development, and the resulting coating film has high transparency.
  • An object of the present invention is to provide a negative photosensitive resin composition having small shrinkage even after post-baking.
  • a negative photosensitive resin composition containing the following component (A), component (B) and solvent (C):
  • (C) component: solvent
  • the negative photosensitive resin composition according to the first aspect wherein (ii) the monomer having an alkali-soluble group of component (A) is maleimide
  • the negative photosensitive resin according to the first aspect or the second aspect further containing 0.1 to 10 parts by mass of a sensitizer as component (D) based on 100 parts by mass of the photosensitive resin composition.
  • the negative photosensitive resin composition As a 4th viewpoint, the negative photosensitive resin composition as described in a 1st viewpoint or a 2nd viewpoint containing the polymer which further has a hydroxyl group as (E) component, As a fifth aspect, the negative photosensitive resin composition according to the first aspect to the third aspect, wherein the component (A) is a copolymer obtained by copolymerizing a monomer mixture containing a monomer having a hydroxy group, As a sixth aspect, the negative photosensitive resin composition according to the first aspect to the fifth aspect, which further contains a crosslinking agent as the component (F), As a seventh aspect, a cured film obtained using the negative photosensitive resin composition according to any one of the first aspect to the sixth aspect, As an eighth aspect, an interlayer insulating film for a liquid crystal display comprising the cured film according to the seventh aspect, As a ninth aspect, an optical filter comprising the cured film according to the seventh aspect, It is about.
  • the photosensitive resin composition of the present invention has no tack before exposure, can be developed with alkali, and can form a coating film pattern with high transparency and resolution even with a thick film, and is therefore optimal for forming a structure as an optical member. .
  • the negative photosensitive resin composition of the present invention is a photosensitive resin composition containing the following component (A), component (B) and solvent (C).
  • component a copolymer obtained by copolymerizing at least (i) N-alkoxymethyl (meth) acrylamide and (ii) a monomer mixture containing a monomer having an alkali-soluble group
  • component a photoacid generator
  • Solvent Solvent
  • Component (A) is a copolymer obtained by copolymerizing a monomer mixture containing at least (i) N-alkoxymethyl (meth) acrylamide and (ii) a monomer having an alkali-soluble group.
  • the copolymer refers to a polymer obtained by copolymerization using a monomer having an unsaturated double bond, such as acrylic acid ester, methacrylic acid ester, acrylamide, methacrylamide, and styrene.
  • the copolymer of component (A) may be any copolymer having such a structure, and is not particularly limited with respect to the main chain skeleton and side chain type of the polymer constituting the copolymer.
  • the number average molecular weight of the copolymer of component (A) is excessively greater than 100,000, the developability of the unexposed area is lowered, while the number average molecular weight is less than 2,000 and excessively low. If it is, the components may be eluted during development because the exposed area is not sufficiently cured. Therefore, the number average molecular weight is in the range of 2,000 to 100,000.
  • N-alkoxymethyl (meth) acrylamide used for component (A) is represented by the structure of formula (1): (Wherein R 1 represents a hydrogen atom, a halogen atom or an alkyl group having 1 to 6 carbon atoms. In the formula, R 2 represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms.)
  • these monomers include N- (methoxymethyl) acrylamide, N- (methoxymethyl) methacrylamide, N- (n-butoxymethyl) acrylamide, N- (n-butoxymethyl) methacrylamide, N- ( And isobutoxymethyl) acrylamide, N- (isobutoxymethyl) methacrylamide and the like.
  • Monomers having an alkali-soluble group used for the component (A) include monomers having a carboxyl group, a phenolic hydroxyl group, an acid anhydride group, and a maleimide group.
  • the monomer having a carboxyl group include acrylic acid, methacrylic acid, crotonic acid, mono- (2- (acryloyloxy) ethyl) phthalate, mono- (2- (methacryloyloxy) ethyl) phthalate, and N- (carboxyphenyl).
  • Examples of the monomer having a phenolic hydroxyl group include hydroxystyrene, N- (hydroxyphenyl) acrylamide, N- (hydroxyphenyl) methacrylamide, N- (hydroxyphenyl) maleimide and the like.
  • Examples of the monomer having an acid anhydride group include maleic anhydride and itaconic anhydride.
  • Examples of the monomer having a maleimide group include maleimide.
  • the monomer which can be copolymerized with the monomer which has a specific functional group can be used together.
  • Specific examples of such monomers include acrylic ester compounds, methacrylic ester compounds, N-substituted maleimide compounds, acrylonitrile, acrylamide compounds, methacrylamide compounds, styrene compounds and vinyl compounds.
  • acrylic ester compounds methacrylic ester compounds, N-substituted maleimide compounds, acrylonitrile, acrylamide compounds, methacrylamide compounds, styrene compounds and vinyl compounds.
  • acrylic ester compound examples include methyl acrylate, ethyl acrylate, isopropyl acrylate, benzyl acrylate, naphthyl acrylate, anthryl acrylate, anthryl methyl acrylate, phenyl acrylate, 2,2,2-trifluoroethyl acrylate, tert- Butyl acrylate, cyclohexyl acrylate, isobornyl acrylate, 2-methoxyethyl acrylate, methoxytriethylene glycol acrylate, 2-ethoxyethyl acrylate, tetrahydrofurfuryl acrylate, 3-methoxybutyl acrylate, 2-methyl-2-adamantyl acrylate, 2 -Propyl-2-adamantyl acrylate, 8-methyl-8-tricyclodecyl acrylate 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 4-hydroxybutyl acrylate, 2,3
  • methacrylic acid ester compound examples include methyl methacrylate, ethyl methacrylate, isopropyl methacrylate, benzyl methacrylate, naphthyl methacrylate, anthryl methacrylate, anthryl methyl methacrylate, phenyl methacrylate, 2,2,2-trifluoroethyl methacrylate, tert- Butyl methacrylate, cyclohexyl methacrylate, isobornyl methacrylate, 2-methoxyethyl methacrylate, methoxytriethylene glycol methacrylate, 2-ethoxyethyl methacrylate, tetrahydrofurfuryl methacrylate, 3-methoxybutyl methacrylate, 2-methyl-2-adamantyl methacrylate, ⁇ -Butyrolactone methacrylate, 2-propyl- -Adamantyl methacrylate, 8-methyl-8-tricyclodec
  • N-substituted maleimide compound examples include N-methylmaleimide, N-phenylmaleimide, N-cyclohexylmaleimide, and the like.
  • styrene compound examples include styrene, methyl styrene, chlorostyrene, and bromostyrene.
  • vinyl compound examples include methyl vinyl ether, benzyl vinyl ether, vinyl naphthalene, vinyl anthracene, vinyl biphenyl, vinyl carbazole, 2-hydroxyethyl vinyl ether, phenyl vinyl ether, and propyl vinyl ether.
  • the method for obtaining a copolymer having a specific functional group used in the present invention is not particularly limited.
  • a monomer having a specific functional group, another monomer having a non-reactive functional group capable of copolymerization, and initiation of polymerization can be obtained by carrying out a polymerization reaction at a temperature of 50 to 110 ° C. in a solvent in which an agent or the like is present.
  • the solvent used will not be specifically limited if it dissolves the monomer which comprises the acrylic copolymer which has a specific functional group, and the acrylic copolymer which has a specific functional group.
  • the solvent described in the (C) solvent mentioned later is mentioned.
  • the acrylic copolymer having a specific functional group thus obtained is usually in a solution state dissolved in a solvent.
  • the copolymer solution obtained as described above is re-precipitated by stirring with stirring such as diethyl ether or water, and the produced precipitate is filtered and washed, and then under normal pressure or reduced pressure.
  • the copolymer powder can be obtained by drying at room temperature or by heating. By such an operation, the polymerization initiator and unreacted monomer coexisting with the copolymer can be removed, and as a result, a purified copolymer powder can be obtained. If sufficient purification cannot be achieved by a single operation, the obtained powder may be redissolved in a solvent and the above operation may be repeated.
  • the polymerization solution of the acrylic copolymer may be used as it is, or the powder thereof may be redissolved in a solvent (C) described later and used as a solution.
  • the copolymer of component (A) may be a mixture of a plurality of types of specific copolymers.
  • N-alkoxymethyl (meth) acrylamide / alkali-soluble monomer / others 10 to 60/10 to 40/0 to 80 parts by weight.
  • the component (B) is a photoacid generator.
  • the kind of acid used for the thermosetting resin composition of the present invention is not particularly limited. Specific examples of such a photoacid generator include the following.
  • the content of the component (B) in the negative photosensitive resin composition of the present invention is preferably 0.5 to 20 parts by mass, more preferably 1 to 15 parts by mass with respect to 100 parts by mass of the component (A). More preferably, it is 2 to 10 parts by mass.
  • this ratio is less than 0.5 mass part, photoreactivity may fall and a sensitivity may fall.
  • permeability of the formed coating film may fall or the storage stability of a solution may fall.
  • Examples of such a solvent (C) include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, propylene glycol, propylene glycol monomethyl ether, propylene glycol.
  • solvents can be used alone or in combination of two or more.
  • solvents propylene glycol monomethyl ether, diethylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, ethyl lactate, butyl lactate and the like are preferable from the viewpoint of good coating properties and high safety.
  • These solvents are generally used as solvents for photoresist materials.
  • (D) component is a sensitizer.
  • the reaction rate of the photoacid generator as the component (B) is small with respect to the wavelength at which the coating film made of the negative photosensitive resin composition of the present invention is exposed, the reaction rate is improved by adding a sensitizer. be able to.
  • Such a sensitizer include 9,10-dibutoxyanthracene, 9-hydroxymethylanthracene, thioxanthone, 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2-chlorothioxanthone, 2,4-diethylthioxanthone, Anthraquinone, 1,2-dihydroxyanthraquinone, 2-ethylanthraquinone, 1,4-diethoxynaphthalene and the like can be mentioned.
  • one or more of the sensitizers can be used in combination.
  • the addition amount of these sensitizers is usually preferably 0.1 to 10 parts by mass, more preferably 0.1 to 8 parts by mass with respect to 100 parts by mass of the component (A). If the amount of the sensitizer is larger than the above, the transparency of the coating film may be lowered.
  • the component (E) is a polymer having a hydroxy group.
  • the polymer having a hydroxy group include a polymer obtained by polymerizing a monomer having a hydroxy group, cellulose, hydroxypropyl cellulose, a polymer obtained by copolymerizing diepoxy and dicarboxylic acid, and obtained by copolymerizing diepoxy and diphenol.
  • examples thereof include polymers, polyester polyols, polyether polyols, polycaprolactone polyols, and the like, and a polymer obtained by polymerizing a monomer having a hydroxy group, or hydroxypropyl cellulose is preferable.
  • polymer obtained by polymerizing the above-mentioned monomer having a hydroxy group a polymer obtained by copolymerizing a monomer having a hydroxy group alone or a copolymerizable monomer among the copolymerizable monomers mentioned in the component (A) described above. Can be mentioned.
  • monomers having a hydroxy group include 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 4-hydroxybutyl acrylate, 2,3-dihydroxypropyl acrylate, and 5- Acryloyloxy-6-hydroxynorbornene-2-carboxyl-6-lactone, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, 4-hydroxybutyl methacrylate, 2,3-dihydroxypropyl methacrylate and 5-methacryloyloxy-6- Hydroxynorbornene-2-carboxyl-6-lactone and the like.
  • Examples of the copolymerizable monomer include the copolymerizable monomers listed in the component (A).
  • These polymers having a hydroxy group can be used alone or in combination of two or more.
  • the content of the polymer having a hydroxy group as the component (E) is preferably 5 to 150 parts by mass based on 100 parts by mass of the copolymer as the component (A). More preferably, it is 10 to 120 parts by mass. If this ratio is less than the above, the sensitivity of the negative photosensitive resin composition may be reduced. On the other hand, if it is more than the above, the developability of the unexposed area will be reduced and the remaining amount will be reduced. May cause film and residue.
  • the crosslinking agent that is the component (F) of the present invention may be any crosslinking agent that can react with the component (A) by the acid generated in the component (B).
  • Examples of such a crosslinking agent include compounds such as an epoxy compound and a methylol compound, and a methylol compound is preferred.
  • methylol compound described above examples include compounds such as alkoxymethylated glycoluril, alkoxymethylated benzoguanamine, and alkoxymethylated melamine.
  • alkoxymethylated glycoluril examples include, for example, 1,3,4,6-tetrakis (methoxymethyl) glycoluril, 1,3,4,6-tetrakis (butoxymethyl) glycoluril, 1,3,4 , 6-tetrakis (hydroxymethyl) glycoluril, 1,3-bis (hydroxymethyl) urea, 1,1,3,3-tetrakis (butoxymethyl) urea, 1,1,3,3-tetrakis (methoxymethyl) Examples include urea, 1,3-bis (hydroxymethyl) -4,5-dihydroxy-2-imidazolinone, and 1,3-bis (methoxymethyl) -4,5-dimethoxy-2-imidazolinone.
  • glycoluril compounds (trade names: Cymel (registered trademark) 1170, Powderlink (registered trademark) 1174) manufactured by Mitsui Cytec Co., Ltd., methylated urea resins (trade name: UFR (registered trademark) 65) ), Butylated urea resin (trade names: UFR (registered trademark) 300, U-VAN10S60, U-VAN10R, U-VAN11HV), urea / formaldehyde resin (high condensation type, commercial product) manufactured by Dainippon Ink & Chemicals, Inc. Name: Beccamine (registered trademark) J-300S, P-955, N) and the like.
  • alkoxymethylated benzoguanamine examples include tetramethoxymethylbenzoguanamine.
  • Commercially available products manufactured by Mitsui Cytec Co., Ltd. (trade name: Cymel (registered trademark) 1123), manufactured by Sanwa Chemical Co., Ltd. (trade names: Nicalac (registered trademark) BX-4000, BX-37, BL- 60, BX-55H) and the like.
  • alkoxymethylated melamine examples include, for example, hexamethoxymethylmelamine.
  • methoxymethyl type melamine compounds (trade names: Cymel (registered trademark) 300, 301, 303, 350) manufactured by Mitsui Cytec Co., Ltd., butoxymethyl type melamine compounds (trade name: My Coat (registered trademark)) 506, 508), Sanwa Chemical's methoxymethyl-type melamine compound (trade names: Nicalak (registered trademark) MW-30, MW-22, MW-11, MS-001, MX-002, MX-730, MX-750, MX-035), butoxymethyl type melamine compounds (trade names: Nicalac (registered trademark) MX-45, MX-410, MX-302) and the like.
  • a compound obtained by condensing a melamine compound, urea compound, glycoluril compound and benzoguanamine compound in which the hydrogen atom of the amino group is substituted with a methylol group or an alkoxymethyl group may be used.
  • the high molecular weight compound manufactured from the melamine compound and the benzoguanamine compound which are described in US Patent 6,323,310 is mentioned.
  • Examples of commercially available products of the melamine compound include trade name: Cymel (registered trademark) 303 (manufactured by Mitsui Cytec Co., Ltd.).
  • Examples of commercially available products of the benzoguanamine compound include product name: Cymel (registered trademark) 1123 ( Mitsui Cytec Co., Ltd.).
  • cross-linking agents can be used alone or in combination of two or more.
  • the content of the crosslinking agent of the component (F) in the negative photosensitive resin composition of the present invention is preferably 5 to 100 parts by mass, more preferably based on 100 parts by mass of the copolymer of the component (A). Is 10 to 80 parts by mass. If this ratio is less than the above, the photo-curing property of the negative photosensitive resin composition may be reduced. On the other hand, if it is more than the above, the developability of the unexposed portion is reduced. This may cause residual film and residue.
  • the negative photosensitive resin composition of the present invention can be used as necessary as a quencher, a surfactant, a rheology modifier, a pigment, a dye, a storage stabilizer, an antifoaming agent, as long as the effects of the present invention are not impaired.
  • a dissolution accelerator such as a polyhydric phenol or polyvalent carboxylic acid.
  • the negative photosensitive resin composition of the present invention is obtained by dissolving the polymer of component (A) and the photoacid generator of component (B) in solvent (C), and each component (D) as desired.
  • the preferable example of the negative photosensitive resin composition of this invention is as follows. [1]: A negative photosensitive resin composition containing 0.5 to 20 parts by mass of the component (B) based on 100 parts by mass of the component (A) and dissolving these components in the solvent (C). [2]: The negative photosensitive resin composition further comprising 0.1 to 10 parts by mass of component (D) based on 100 parts by mass of component (A) in the composition of [1] above. [3] A negative photosensitive resin composition containing 5 to 150 parts by mass of the component (E) based on 100 parts by mass of the component (A) in the composition of the above [1] or [2]. [4] A negative photosensitive resin composition containing 5 to 100 parts by mass of the component (F) based on 100 parts by mass of the component (A) in the compositions [1] to [3].
  • the ratio of the solid content in the negative photosensitive resin composition of the present invention is not particularly limited as long as each component is uniformly dissolved in the solvent, but is, for example, 1 to 80% by mass, It is 5 to 60% by mass, or 10 to 50% by mass.
  • solid content means what remove
  • the preparation method of the negative photosensitive resin composition of this invention is not specifically limited, As the preparation method, for example, (A) component (copolymer) is melt
  • A) component (copolymer) is melt
  • B) Component (photoacid generator) is mixed at a predetermined ratio to make a uniform solution, or at an appropriate stage of this preparation method, component (D) (sensitizer), ( E) Component (polymer having a hydroxy group), (F) component (crosslinking agent) and other additives may be further added and mixed.
  • the solution of the specific copolymer obtained by the polymerization reaction in the solvent (C) can be used as it is, and in this case, the solution of the component (A)
  • a solvent may be further added for the purpose of adjusting the concentration.
  • the (C) solvent used in the process of forming the specific copolymer and the (C) solvent used for concentration adjustment at the time of preparing the negative photosensitive resin composition may be the same, May be different.
  • the prepared negative photosensitive resin composition solution is preferably used after being filtered using a filter having a pore size of about 0.2 ⁇ m.
  • the negative photosensitive resin composition of the present invention is applied to a semiconductor substrate (for example, a silicon / silicon dioxide-coated substrate, a silicon nitride substrate, a substrate coated with a metal such as aluminum, molybdenum, or chromium, a glass substrate, a quartz substrate, or an ITO substrate. Etc.) by spin coating, flow coating, roll coating, slit coating, spin coating following slit, ink jet coating, etc., and then pre-dried in a hot plate or oven to form a coating film can do. Then, a negative photosensitive resin film is formed by heat-treating this coating film.
  • a semiconductor substrate for example, a silicon / silicon dioxide-coated substrate, a silicon nitride substrate, a substrate coated with a metal such as aluminum, molybdenum, or chromium, a glass substrate, a quartz substrate, or an ITO substrate. Etc.
  • a heating temperature and a heating time appropriately selected from the range of a temperature of 70 ° C. to 160 ° C. and a time of 0.3 to 60 minutes are adopted.
  • the heating temperature and heating time are preferably 80 to 140 ° C. and 0.5 to 10 minutes.
  • the film thickness of the negative photosensitive resin film formed from the negative photosensitive resin composition is, for example, 0.1 to 30 ⁇ m, for example, 0.5 to 20 ⁇ m, and further, for example, 1 to 15 ⁇ m.
  • the negative photosensitive resin film formed from the negative photosensitive resin composition of the present invention is exposed to light such as ultraviolet rays, ArF, KrF, and F 2 laser light using a mask having a predetermined pattern, Due to the action of the acid generated from the photoacid generator (PAG) of the component (B) contained in the negative photosensitive resin film, the exposed portion of the film becomes insoluble in the alkaline developer.
  • light such as ultraviolet rays, ArF, KrF, and F 2 laser light using a mask having a predetermined pattern
  • PEB post-exposure heating
  • alkaline developer examples include aqueous solutions of alkali metal hydroxides such as potassium hydroxide and sodium hydroxide, and aqueous solutions of quaternary ammonium hydroxides such as tetramethylammonium hydroxide, tetraethylammonium hydroxide, and choline.
  • Alkaline aqueous solutions such as amine aqueous solutions such as ethanolamine, propylamine, and ethylenediamine.
  • a surfactant or the like can be added to these developers.
  • a tetraethylammonium hydroxide 0.1 to 2.38 mass% aqueous solution is generally used as a photoresist developer, and the alkaline developer is also used in the photosensitive resin composition of the present invention. It can be developed satisfactorily without causing problems such as swelling.
  • any of a liquid piling method, a dipping method, a rocking dipping method and the like can be used as a developing method.
  • the development time at that time is usually 15 to 180 seconds.
  • the negative photosensitive resin film is washed with running water, for example, for 20 to 90 seconds, and then air-dried with compressed air or compressed nitrogen or by spinning to remove moisture on the substrate, and A patterned film is obtained.
  • the pattern forming film is subjected to post-baking for thermosetting, specifically by heating using a hot plate, an oven, etc., thereby providing heat resistance, transparency, and flatness.
  • a film having a good relief pattern with excellent water absorption and chemical resistance can be obtained.
  • the post-bake is generally processed at a heating temperature selected from the range of 140 ° C. to 250 ° C. for 5 to 30 minutes when on a hot plate and 30 to 90 minutes when in an oven. The method is taken.
  • a desired cured film having a good pattern shape can be obtained by such post-baking.
  • the film thickness of the exposed area is sufficient at the time of development, with sufficiently high sensitivity even at a film thickness of about 10 ⁇ m. Reduction is very small, and a coating film having a fine pattern can be formed. Furthermore, this cured film is excellent in transparency, heat resistance and solvent resistance. Therefore, it can be suitably used for various films in liquid crystal displays, organic EL displays, touch panel elements, etc., for example, interlayer insulating films, protective films, insulating films, optical films and the like.
  • Examples 1 to 7 and Comparative Examples 1 and 2 According to the composition shown in the following Table 1, the component (A) is mixed with the component (B), the solvent (C), the component (D), and the component (E) and the component (F) at a predetermined ratio.
  • the negative photosensitive resin composition of each Example and each Comparative Example was prepared by stirring at room temperature for 3 hours to obtain a uniform solution.
  • the negative photosensitive resin composition was applied onto a silicon wafer using a spin coater, and then pre-baked on a hot plate at a temperature of 110 ° C. for 120 seconds to form a coating film.
  • the film thickness of this coating film was measured using F20 manufactured by FILMETRICS.
  • the negative photosensitive resin composition was applied onto a quartz substrate using a spin coater, and then pre-baked on a hot plate at a temperature of 110 ° C. for 120 seconds to form a coating film.
  • This coating film was irradiated with UV light having a light intensity at 365 nm of 5.5 mW / cm 2 for 36 seconds using a Canon UV irradiation device PLA-600FA.
  • This film was heated after exposure on a hot plate at a temperature of 95 ° C. for 120 seconds and then post-baked in an oven at a temperature of 150 ° C. for 15 minutes to form a cured film.
  • the cured film was measured for transmittance at a wavelength of 400 nm using a UV-visible spectrophotometer (SIMADSU UV-2550 model number, manufactured by Shimadzu Corporation).
  • the negative photosensitive resin composition was applied onto alkali-free glass using a spin coater, and then pre-baked on a hot plate at a temperature of 110 ° C. for 120 seconds to form a coating film.
  • the coating light intensity at 365nm by UV irradiation apparatus PLA-600FA manufactured by Canon Inc. in was 190 mJ / cm 2 irradiation through a mask of the UV line and space pattern of 5.5 mW / cm 2. Thereafter, post-exposure heating was performed on a hot plate at a temperature of 110 ° C. for 120 seconds.
  • TMAH tetramethylammonium hydroxide
  • the negative photosensitive resin composition was applied onto alkali-free glass using a spin coater, and then pre-baked on a hot plate at a temperature of 110 ° C. for 120 seconds to form a coating film.
  • This coating film was irradiated with ultraviolet rays having a light intensity of 365 m at 5.5 mW / cm 2 at a rate of 50 mJ / cm 2 through a 20 ⁇ m line & space pattern mask by an ultraviolet irradiation device PLA-600FA manufactured by Canon Inc. Thereafter, post-exposure heating was performed on a hot plate at a temperature of 110 ° C. for 120 seconds.
  • sensitivity The minimum exposure amount at which a 20 ⁇ m pattern was formed was defined as sensitivity.
  • each of the negative photosensitive resin compositions of Examples 1 to 7 can be applied with a thick film of 10 ⁇ m or more, and high transmittance and alkali development are possible even with a thick film. And maintained high resolution and sensitivity.
  • the film thickness could not be increased, and the remaining film ratio after post-baking was as low as 90% or less.
  • the tack entered after pre-baking, and development with an alkaline developer was not possible.
  • the negative photosensitive resin composition according to the present invention is a material for forming a cured film such as a protective film, a planarizing film, and an insulating film in various displays such as a thin film transistor (TFT) type liquid crystal display element, an organic EL element, and a touch panel element.
  • TFT thin film transistor
  • a protective film of a color filter e.g., a protective film of a color filter
  • an array flattening film e.g., an interlayer insulating film of a capacitive touch panel
  • an insulating film of an organic EL element e.g., a display surface antireflection layer

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  • Physics & Mathematics (AREA)
  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • General Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Materials For Photolithography (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Optical Filters (AREA)
  • Polarising Elements (AREA)

Abstract

L'invention porte sur une composition de résine photosensible négative qui peut être mise sous forme d'un film épais, la composition étant exempte de caractère collant même avant exposition, ce qui permet de former un motif à une résolution élevée par développement alcalin et ce qui produit un film ayant une transparence élevée qui présente un retrait minimal après post-cuisson. La composition de résine photosensible négative selon l'invention contient les composants (A), (B) et (C). Le composant (A) est un copolymère obtenu par copolymérisation d'un mélange de monomères contenant au moins (i) un N-alcoxyméthyl(méth)acrylamide et (ii) un monomère ayant un groupe soluble dans les alcalis ; le composant (B) est un générateur de photoacide ; et le composant (C) est un solvant.
PCT/JP2013/050428 2012-01-19 2013-01-11 Composition de résine photosensible négative WO2013108716A1 (fr)

Priority Applications (3)

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JP2013554281A JP6150072B2 (ja) 2012-01-19 2013-01-11 ネガ型感光性樹脂組成物
KR1020147022183A KR102027756B1 (ko) 2012-01-19 2013-01-11 네가티브형 감광성 수지 조성물
CN201380004941.6A CN104040432B (zh) 2012-01-19 2013-01-11 负型感光性树脂组合物

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JP2012-008689 2012-01-19
JP2012008689 2012-01-19

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JP2017525785A (ja) * 2014-06-03 2017-09-07 ザ ケマーズ カンパニー エフシー リミテッド ライアビリティ カンパニー 光架橋フルオロポリマーを含む保護層
US9977329B2 (en) 2014-01-24 2018-05-22 Toray Industries, Inc. Negative photosensitive resin composition, cured film obtained by curing same, method for producing cured film, optical device provided with cured film, and backside-illuminated CMOS image sensor
JPWO2018155581A1 (ja) * 2017-02-22 2019-12-12 日産化学株式会社 硬化膜形成組成物、配向材および位相差材
WO2024101411A1 (fr) * 2022-11-10 2024-05-16 Jsr株式会社 Composition durcissable pour éléments électroluminescents organiques, produit durci pour éléments électroluminescents organiques et son procédé de production, élément électroluminescent organique et polymère

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JP6624379B2 (ja) * 2013-10-21 2019-12-25 日産化学株式会社 ネガ型感光性樹脂組成物
US11561470B2 (en) 2017-03-29 2023-01-24 Toray Industries, Inc. Negative photosensitive resin composition, cured film, element provided with cured film, organic EL display provided with cured film, and method for producing same
CN110412829A (zh) * 2018-04-26 2019-11-05 东友精细化工有限公司 负型感光性树脂组合物、光固化图案及图像显示装置
KR102170935B1 (ko) * 2019-08-28 2020-10-29 주식회사 삼양사 경화형 수지 조성물 및 그로부터 형성된 경화층을 포함하는 전자 장치
JP7393229B2 (ja) 2020-01-31 2023-12-06 Ntn株式会社 電力需給調整システムおよび電力需給調整方法
CN115160495B (zh) * 2022-08-15 2024-05-14 四川华造宏材科技有限公司 含马来酰亚胺结构的光刻胶成膜树脂及其制备方法

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JPH10142788A (ja) * 1996-11-14 1998-05-29 Toppan Printing Co Ltd 感光性着色組成物及びこれを用いたカラーフィルタ
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US9977329B2 (en) 2014-01-24 2018-05-22 Toray Industries, Inc. Negative photosensitive resin composition, cured film obtained by curing same, method for producing cured film, optical device provided with cured film, and backside-illuminated CMOS image sensor
JP2017525785A (ja) * 2014-06-03 2017-09-07 ザ ケマーズ カンパニー エフシー リミテッド ライアビリティ カンパニー 光架橋フルオロポリマーを含む保護層
JPWO2018155581A1 (ja) * 2017-02-22 2019-12-12 日産化学株式会社 硬化膜形成組成物、配向材および位相差材
WO2024101411A1 (fr) * 2022-11-10 2024-05-16 Jsr株式会社 Composition durcissable pour éléments électroluminescents organiques, produit durci pour éléments électroluminescents organiques et son procédé de production, élément électroluminescent organique et polymère

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KR20140117512A (ko) 2014-10-07
TWI569100B (zh) 2017-02-01
TW201348876A (zh) 2013-12-01
KR102027756B1 (ko) 2019-10-02
JPWO2013108716A1 (ja) 2015-05-11
CN104040432A (zh) 2014-09-10
CN104040432B (zh) 2018-09-14

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