WO2017064992A1 - 熱硬化性樹脂組成物 - Google Patents
熱硬化性樹脂組成物 Download PDFInfo
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- WO2017064992A1 WO2017064992A1 PCT/JP2016/078083 JP2016078083W WO2017064992A1 WO 2017064992 A1 WO2017064992 A1 WO 2017064992A1 JP 2016078083 W JP2016078083 W JP 2016078083W WO 2017064992 A1 WO2017064992 A1 WO 2017064992A1
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
- C08F290/08—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated side groups
- C08F290/14—Polymers provided for in subclass C08G
- C08F290/147—Polyurethanes; Polyureas
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F212/00—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 an aromatic carbocyclic ring
- C08F212/02—Monomers containing only one unsaturated aliphatic radical
- C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
- C08F212/06—Hydrocarbons
- C08F212/08—Styrene
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D3/00—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials
- B05D3/02—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by baking
- B05D3/0254—After-treatment
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- C08F120/00—Homopolymers 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
- C08F120/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F120/10—Esters
- C08F120/34—Esters containing nitrogen, e.g. N,N-dimethylaminoethyl (meth)acrylate
- C08F120/36—Esters containing nitrogen, e.g. N,N-dimethylaminoethyl (meth)acrylate containing oxygen in addition to the carboxy oxygen, e.g. 2-N-morpholinoethyl (meth)acrylate or 2-isocyanatoethyl (meth)acrylate
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- 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
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/14—Methyl esters, e.g. methyl (meth)acrylate
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- 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
- C08F220/10—Esters
- C08F220/34—Esters containing nitrogen, e.g. N,N-dimethylaminoethyl (meth)acrylate
- C08F220/36—Esters containing nitrogen, e.g. N,N-dimethylaminoethyl (meth)acrylate containing oxygen in addition to the carboxy oxygen, e.g. 2-N-morpholinoethyl (meth)acrylate or 2-isocyanatoethyl (meth)acrylate
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- 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
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- 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
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/01—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to unsaturated polyesters
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- 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
- C08F299/00—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers
- C08F299/02—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers from unsaturated polycondensates
- C08F299/04—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers from unsaturated polycondensates from polyesters
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- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/14—Polycondensates modified by chemical after-treatment
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/14—Polycondensates modified by chemical after-treatment
- C08G59/1433—Polycondensates modified by chemical after-treatment with organic low-molecular-weight compounds
- C08G59/1438—Polycondensates modified by chemical after-treatment with organic low-molecular-weight compounds containing oxygen
- C08G59/1455—Monocarboxylic acids, anhydrides, halides, or low-molecular-weight esters thereof
- C08G59/1461—Unsaturated monoacids
- C08G59/1466—Acrylic or methacrylic acids
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/68—Polyesters containing atoms other than carbon, hydrogen and oxygen
- C08G63/685—Polyesters containing atoms other than carbon, hydrogen and oxygen containing nitrogen
- C08G63/6854—Polyesters containing atoms other than carbon, hydrogen and oxygen containing nitrogen derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/6858—Polycarboxylic acids and polyhydroxy compounds in which at least one of the two components contains aliphatic unsaturation
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
- C08L67/06—Unsaturated polyesters
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- 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
- C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
- C09D163/10—Epoxy resins modified by unsaturated compounds
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- 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
- C09D167/00—Coating compositions based on polyesters obtained by reactions forming a carboxylic ester link in the main chain; Coating compositions based on derivatives of such polymers
- C09D167/06—Unsaturated polyesters having carbon-to-carbon unsaturation
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- 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
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2203/00—Applications
- C08L2203/16—Applications used for films
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2203/00—Applications
- C08L2203/20—Applications use in electrical or conductive gadgets
- C08L2203/206—Applications use in electrical or conductive gadgets use in coating or encapsulating of electronic parts
Definitions
- the present invention relates to a thermosetting resin composition, a thermosetting resin composition for a protective film, a thermosetting resin composition for a flattening film, and a cured film, a protective film or a flattening film using the resin composition.
- the present invention relates to a manufacturing method.
- Electronic devices such as liquid crystal displays and CCD / CMOS image sensors are exposed to high temperatures such as sputtering, dry etching, solder reflow, etc., in the manufacturing process, exposure to chemicals such as solvents or acid or alkali solutions. Processing is performed.
- a cured film having resistance to such treatment is formed on the element as a protective film.
- Such a protective film is required to have chemical resistance, high transparency, heat resistance, and the like.
- the electronic device has unevenness caused by, for example, a color filter, a circuit wiring portion, a light shielding film, or an inner lens.
- the cured film is also required to have level difference flatness from the viewpoint of ensuring a process margin when manufacturing an electronic device and ensuring uniformity of device characteristics (Patent Documents 1 to 4).
- the present invention has been made based on the above circumstances, and its purpose is to provide a thermosetting resin composition capable of forming a cured film having excellent chemical resistance, heat resistance, transparency and flatness. It is to be. Another object of the present invention is to provide a cured film, a protective film and a planarizing film having excellent chemical resistance, heat resistance and transparency.
- the present invention contains a polymer having a structural unit represented by the following formula (1), 0 to 30% by mass of a curing agent and a solvent with respect to the polymer, and when the curing agent is contained,
- the agent is a thermosetting resin composition that is at least one compound selected from the group consisting of a polyfunctional (meth) acrylate compound and a polyfunctional blocked isocyanate compound.
- a 1 represents an alkenyl group or alkynyl group having 2 or 3 carbon atoms
- a 2 represents an alkenylene group or alkynylene group having 2 carbon atoms.
- the 0 to 30% by mass of the curing agent is 30% with respect to 100% by mass of the polymer in which the thermosetting resin composition of the present invention contains no curing agent or has a structural unit represented by the above formula (1). It means that the curing agent is contained with the upper limit being mass%.
- thermosetting resin composition of the present invention contains a polyfunctional (meth) acrylate compound as a curing agent, that is, a polyfunctional acrylate compound or a polyfunctional methacrylate compound, the heat resistance of the cured film produced from the resin composition From the viewpoint, a polyfunctional acrylate compound is preferable.
- the present invention also provides a method for producing a cured film, a protective film, or a planarizing film by applying the thermosetting resin composition on a substrate and then baking the thermosetting resin composition using a heating unit. is there.
- the cured film produced from the thermosetting resin composition of the present invention has excellent chemical resistance, heat resistance and transparency. Thereby, the cured film produced from the thermosetting resin composition of the present invention is exposed to a solvent or a chemical solution such as an acid or alkali solution in the production process or the formation process of peripheral devices such as wiring.
- a solvent or a chemical solution such as an acid or alkali solution in the production process or the formation process of peripheral devices such as wiring.
- a process exposed to a high temperature such as sputtering, dry etching, or solder reflow is performed, the possibility that the element is deteriorated or damaged can be significantly reduced.
- thermosetting resin composition of the present invention is suitable as a material for forming a protective film or a planarizing film.
- FIG. 1 is a schematic view showing a cured film produced by applying and baking the thermosetting resin composition of the present invention on a stepped substrate.
- the present invention is a thermosetting resin composition containing a specific polymer, 0 to 30% by mass of a curing agent and a solvent based on the polymer.
- the solid content obtained by removing the solvent from the thermosetting resin composition of the present invention is usually 0.01% by mass to 80% by mass.
- the polymer contained in the thermosetting resin composition of the present invention is a polymer having a structural unit represented by the formula (1).
- examples of the alkenyl group having 2 or 3 carbon atoms represented by A 1 include a vinyl group and an allyl group.
- examples of the alkynyl group having 2 or 3 carbon atoms include an ethynyl group ( -C ⁇ CH group) and propargyl group (-CH 2 -C ⁇ CH group).
- examples of the alkenylene group having 2 carbon atoms represented by A 2 include an ethene-1,2-diyl group (—CH ⁇ CH— group), and an alkynylene having 2 carbon atoms.
- examples of the group include an ethyne-1,2-diyl group (—C ⁇ C— group).
- polymer examples include a polymer having a structural unit represented by the following formula (1a).
- the polymer having the structural unit represented by the formula (1a) is a polyaddition of monoallyl diglycidyl isocyanurate and fumaric acid, maleic acid or maleic anhydride (fumaric acid is preferred because of easy polymer synthesis). It can be produced by a reaction or a polyaddition reaction of monoallyl isocyanuric acid with diglycidyl fumarate or diglycidyl maleate.
- the raw material monomers are benzene, toluene, xylene, ethyl lactate, butyl lactate, methyl pyruvate, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, 2-butanone, 2-heptanone, cyclopentanone, It is preferably carried out in a solution state dissolved in an organic solvent such as cyclohexanone, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate and N-methylpyrrolidone.
- triphenylphosphine, tributylphosphine, tris (4-methylphenyl) phosphine, tris (4-nonylphenyl) phosphine, tris (4-methoxyphenyl) phosphine, tris (2,6-dimethoxyphenyl) Phosphines such as phosphine, triphenylphosphine triphenylborane, tetraphenylphosphonium chloride, tetraphenylphosphonium bromide, benzyltriphenylphosphonium chloride, benzyltriphenylphosphonium bromide, ethyltriphenylphosphonium chloride, ethyltriphenylphosphonium bromide, tetraphenylphosphonium Tetraphenylborate, tetraphenylphosphonium tetra (4-methylphenyl) borate, tetraphenyl Quatern
- the reaction temperature and reaction time of the polyaddition reaction depend on the compound used, concentration, etc., but are appropriately selected from the range of reaction time of 0.1 hour to 100 hours and reaction temperature of 20 ° C. to 200 ° C. .
- the catalyst When the catalyst is used, it can be used in the range of 0.001% by mass to 30% by mass with respect to the total mass of the raw material monomers used for the polyaddition reaction.
- the polymer thus obtained is usually in a solution state dissolved in the organic solvent, and can be used in the thermosetting resin composition of the present invention without isolation in this state.
- the polymer solution obtained as described above is put into a poor solvent such as hexane, diethyl ether, toluene, methanol, water and the like which has been stirred to reprecipitate the polymer, and the generated precipitate is decanted.
- the polymer can be made into an oily product or powder by filtering and washing as necessary, followed by drying at normal temperature or reduced pressure at room temperature or heating. By such an operation, unreacted compounds coexisting with the polymer and the catalyst can be removed.
- the oily substance or powder of the polymer may be used as it is, or the oily substance or powder may be redissolved in a solvent described later and used as a solution.
- the ratio of monoallyl diglycidyl isocyanurate used in the polyaddition reaction to fumaric acid, maleic acid or maleic anhydride is preferably a molar ratio of 3: 2 to 2: 3, more preferably 5: 4 to 4: 5, or 1: 1.
- the ratio of monoallyl isocyanuric acid used in the polyaddition reaction to diglycidyl fumarate or diglycidyl maleate is preferably 3: 2 to 2: 3, more preferably 5: 4 to 4: 5 or 1: 1.
- the weight average molecular weight of the polymer is usually 500 to 200,000, preferably 1,000 to 100,000.
- the weight average molecular weight is a value obtained by using gel as a standard sample by gel permeation chromatography (GPC).
- the polymer having the structural unit represented by the formula (1) may be used alone or in combination of two or more.
- the content of the polymer in the thermosetting resin composition of the present invention is usually 30% by mass to 100% by mass, preferably 50% by mass, based on the content in the solid content of the resin composition. Thru
- thermosetting resin composition of this invention is not specifically limited, For example, the method which melt
- the solvent contained in the thermosetting resin composition of the present invention is not particularly limited as long as it dissolves the polymer contained in the resin composition.
- examples of such solvents 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 monomethyl ether acetate.
- propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl from the viewpoint of improving the leveling property of the coating film formed by applying the thermosetting resin composition of the present invention on the substrate.
- Ether, propylene glycol monopropyl ether, 2-heptanone, ethyl lactate, butyl lactate, methyl pyruvate, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, cyclopentanone, cyclohexanone and ⁇ -butyrolactone are preferred.
- thermosetting resin composition of this invention can form a cured film with the polymer contained in the said resin composition, it can contain a hardening
- the curing agent include a polyfunctional (meth) acrylate compound having two or more (meth) acryloyl groups in the molecule, or a polyfunctional block isocyanate compound having two or more blocked isocyanate groups in the molecule. be able to.
- the number of (meth) acryloyl groups or blocked isocyanate groups in the monomer molecule is, for example, 2 to 15.
- curing agents can be used alone or in combination of two or more.
- (meth) acryloyl group means methacryloyl group and acryloyl group
- (meth) acrylate means methacrylate and acrylate
- (meth) acrylic acid means methacrylic acid and acrylic acid.
- polyfunctional (meth) acrylate compound examples include ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, tetraethylene glycol di ( (Meth) acrylate, propylene glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, Neopentyl glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, tricyclodecane dimethanol di (meth) acrylate, dicyclo Tantanyl di (meth) acrylate, bisphenol A di (meth) acrylate, ethoxylated bisphenol A di (meth)
- polyfunctional (meth) acrylate compound examples include 2-hydroxyethyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, glycerin di (meth) acrylate, pentaerythritol tri (meth) acrylate, and dipentaerythritol penta.
- (Meth) acrylate having a hydroxy group such as (meth) acrylate, Or polyfunctional (meth) acrylate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 1,3-xylene diisocyanate, 1,4-xylene diisocyanate, xylylene diisocyanate, 1,5-naphthalene diisocyanate, m-phenylene diisocyanate, p-phenylene diisocyanate, diphenylmethane diisocyanate, 4,4′-diphenylmethane diisocyanate, 4,4′-dibenzyl diisocyanate, isophorone diisocyanate, 1,6-hexamethylene diisocyanate, dicyclohexylmethane diisocyanate, 2,2,4 Trimethylhexamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, 1,3-bis (isocyana
- polyfunctional (meth) acrylate compound examples include ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, glycerin diglycidyl ether, glycerin triglycidyl ether, and 1,6-hexanediol diglycidyl.
- Ether neopentyl glycol diglycidyl ether, bisphenol A diglycidyl ether, bisphenol E diglycidyl ether, bisphenol F diglycidyl ether, bisphenol S diglycidyl ether, hydrogenated bisphenol A diglycidyl ether, diglycidyl phthalate, diterephthalic acid diester Glycidyl ester, tris (2,3-epoxypropyl) isocyanurate, 3 ', 4'-epoxy (Meth) acrylic acid is added to a compound having two or more epoxy groups, such as cyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, butanetetracarboxylic acid tetra (3,4-epoxycyclohexylmethyl) modified ⁇ -caprolactone. Mention may also be made of polyfunctional epoxy (meth) acrylates synthesized by reaction.
- polyfunctional (meth) acrylate compound examples include (meth) acrylate monomers having an epoxy group such as glycidyl (meth) acrylate, glycidyloxybutyl (meth) acrylate, and 3,4-epoxycyclohexylmethyl (meth) acrylate.
- a polyfunctional epoxy (meth) acrylate synthesized by reacting (meth) acrylic acid with a homopolymer or copolymer obtained by radical polymerization of can also be mentioned.
- the copolymer means a polymer obtained by polymerizing two or more monomers.
- the copolymer may be a copolymer obtained by polymerizing two or more kinds of (meth) acrylates having an epoxy group, or may be obtained by polymerizing (meth) acrylates having an epoxy group and other (meth) acrylates. It may be a copolymer.
- the following product can be mentioned, for example.
- Aronix [registered trademark] M-208, M-210, M-211B, M-215, M-220, M-225, M-233, M-240, M-245, M-260, M-270, M-303, M-305, M-306, M-309, M-310, M-313, M-315, M-321, M-321 M-350, M-360, M-400, M-402, M-403, M-404, M-405, M-406, M-408, M-450, M-450 M-452, M-460, M-510, M-520, M-1100, M-1200, M-1210, M-1310, M-1600, M-1960, M-1960 M-6100, M-6200, M-6250, M-6500, M-7100, M 7300K, the M-8030, the M-8060, the M-8100, the M-8530, the M-8560, the M-9050 (registered trademark] M-208, M-210, M-211
- KAYARAD registered trademark
- NPGDA PEG400DA
- FM-400 R-167, HX-220, HX-620, R-526, R-551, R-712, R-604, R-684, GPO-303, TMPTA, HDDA, TPGDA, KS-HDDA, KS-TPGDA, MANDA, THE-330, TPA-320, TPA-330, PET- 30, T-1420, T-1420 (T), RP-1040, DPHA, DPEA-12, D-310, D-310, D-330, DPCA-20, DPCA-30, DPCA -60, DPCA-120, FM-700, DN-0075, DN-2475, TC-120S, R-115, R-130, R-38 EAM-2160, CCR-1291H, CCR-1235, ZAR-1035, ZAR-2000, ZFR-1401H, ZFA-1491H, ZCR-1569H, ZCR-1601H, ZCR-1797H ZCR-1798
- Purple light (registered trademark) UV-1400B, UV-1700B, UV-2000B, UV-2010B, UV-2750B, UV-3000B, UV-3200B, UV-3210EA, UV-3210EA, UV-3300B UV-3310B, UV-3500BA, UV-3520TL, UV-3610D80, UV-3630D80, UV-3640PE80, UV-3700B, UV-6100B, UV-6300B, UV-6640B, UV-6640B UV-7000, UV-7000B, UV-7461TE, UV-7510B, UV-7550B, UV-7600B, UV-7605B, UV-7610B, UV-7620EA, UV-7630B, UV-7630B, UV-7640B, UV-7650B, UV-N 001, the same UV-NS034, the UV-NS054, the UV-NS063, the UV-NS077 (manufactured by Nippon Synthetic Chemical Industry Co., Ltd.).
- Beamset [registered trademark] 243NS, 255, 261, 271, 502H, 504H, 505A-6, 550B, 575, 577, 700, 710, 730, 750, 750 AQ-17, EM-90, EM-92, 371, 381 (above Arakawa Chemical Industries, Ltd.).
- FANCLIL registered trademark
- polyfunctional (meth) acrylate compounds may be used alone or in combination of two or more.
- the polyfunctional blocked isocyanate compound has two or more isocyanate groups in which one or more isocyanate groups are blocked by an appropriate protecting group.
- the protecting group block portion
- the resulting isocyanate group causes a crosslinking reaction with the resin.
- Such a polyfunctional blocked isocyanate compound can be obtained, for example, by reacting an appropriate blocking agent with a polyfunctional isocyanate compound having two or more isocyanate groups in one molecule.
- polyfunctional isocyanate compound examples include 1,4-tetramethylene diisocyanate, 1,5-pentamethylene diisocyanate, 1,6-hexamethylene diisocyanate, 2,2,4-trimethyl-1,6-hexamethylene diisocyanate, 1,3,6-hexamethylene triisocyanate, lysine diisocyanate, isophorone diisocyanate, 4,4′-dicyclohexylmethane diisocyanate, 1,3-bis (isocyanatemethyl) cyclohexane, 1,4-cyclohexyl diisocyanate, 2,6 -Bis (isocyanatomethyl) tetrahydrodicyclopentadiene, bis (isocyanatemethyl) dicyclopentadiene, bis (isocyanatemethyl) adamantane, 2,5-diisocyanatomethyl Borene, norbornane diisocyanate, dicycloheptane triisocyanate
- the blocking agent examples include methanol, ethanol, isopropanol, n-butanol, heptanol, hexanol, 2-ethoxyhexanol, cyclohexanol, octanol, isononyl alcohol, stearyl alcohol, benzyl alcohol, 2-ethoxyethanol, methyl lactate, Ethyl lactate, amyl lactate, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether), tri Ethylene glycol monoethyl ether, N, -Alcohols such as dimethylaminoethanol, N, N-diethylaminoethanol, N, N-dibuty
- the following product can be mentioned, for example. Takenate (registered trademark) B-815N, B-830, B-842N, B-84N, B-870, B-870N, B-874, B-874N, B-882, B-882N, B-5010, B-7005, B-7030, B-7075 (Mitsui Chemicals, Inc.).
- Duranate (registered trademark) ME20-B80S, MF-B60B, MF-B60X, MF-B90B, MF-K60B, MF-K60X, SBN-70D, 17B-60P, 17B-60PX, TPA-B80E, TPA-B80X, E402-B80B, E402-B80T, K6000 (above, manufactured by Asahi Kasei Chemicals Corporation), Coronate (registered trademark) 2503, 2507, 2512, 2513, 2515, 2520, 2520, 2554, BI-301, AP-M, Millionate MS-50 (above, manufactured by Tosoh Corporation).
- Vernock [registered trademark] D-500, D-550, DB-980K (above, manufactured by DIC Corporation).
- Sumidur (registered trademark) BL-3175, BL-4165, BL-4265, BL-1100, BL-1265, Death module (registered trademark) TPLS-2957, TPLS-2062, TPLS-2078, TPLS-2117, BL-3475, Desmotherm (registered trademark) 2170, 2265 (manufactured by Sumika Bayer Urethane Co., Ltd.).
- VESTANAT (registered trademark) B1358A, B1358 / 100, B1370, VESTAGON (registered trademark) B1065, B1400, B1530, BF1320, BF1540 (above, manufactured by Evonik Industries).
- the polyfunctional blocked isocyanate compound examples include a homopolymer or a copolymer obtained by radical polymerization of a (meth) acrylate having a blocked isocyanate group.
- the copolymer means a polymer obtained by polymerizing two or more monomers.
- the copolymer may be a copolymer obtained by polymerizing two or more kinds of (meth) acrylates having a blocked isocyanate group, or may be obtained by polymerizing (meth) acrylates having a blocked isocyanate group and other (meth) acrylates. The resulting copolymer may be used.
- Examples of such commercially available (meth) acrylates having a blocked isocyanate group include Karenz [registered trademark] MOI-BM, AOI-BM, MOI-BP, AOI-BP, manufactured by Showa Denko KK MOI-DEM, MOI-CP, MOI-MP, MOI-OEt, MOI-OBu, MOI-OiPr.
- These polyfunctional blocked isocyanate compounds may be used alone or in combination of two or more.
- the content in the thermosetting resin composition of the present invention is usually 1% by mass to 30% by mass based on the content in the solid content of the resin composition, preferably Is 1% by mass to 20% by mass, or 1% by mass to 10% by mass.
- thermosetting resin composition of this invention can also contain surfactant for the purpose of improving applicability
- the surfactant include polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene cetyl ether, polyoxyethylene alkyl ethers such as polyoxyethylene oleyl ether, polyoxyethylene octyl phenyl ether, polyoxyethylene Polyoxyethylene alkyl aryl ethers such as ethylene nonylphenyl ether, polyoxyethylene / polyoxypropylene block copolymers, sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, sorbitan monooleate, sorbitan trioleate, sorbitan Sorbitan fatty acid esters such as tristearate, polyoxyethylene sorbitan monolaurate, polyoxyethylene Nonionic surfactants such as polyoxyethylene sorbitan fatty acid esters such as rubit
- the content in the thermosetting resin composition of the present invention is usually 0.001% by mass to 3% by mass based on the content in the solid content of the resin composition. Yes, preferably 0.01% to 2% by weight, more preferably 0.03% to 1% by weight.
- thermosetting resin composition of the present invention is a radical polymerization initiator, an acid compound, a light stabilizer, a UV absorber, a sensitizer, a plasticizer, an oxidation, as necessary, as long as the effects of the present invention are not impaired.
- Additives such as inhibitors, adhesion assistants and antifoaming agents can be included.
- thermosetting resin composition of the present invention A method for producing a cured film, a protective film and a planarizing film using the thermosetting resin composition of the present invention will be described.
- the heat of the present invention is applied to a substrate (for example, a semiconductor substrate, a glass substrate, a quartz substrate, a silicon wafer, and a substrate on which various metal films or a color filter are formed) by an appropriate coating method such as a spinner or a coater.
- a heating means such as a hot plate or an oven to produce a cured film, a protective film, or a flattened film. Baking conditions are appropriately selected from a baking temperature of 80 ° C.
- the film thickness of the film produced from the thermosetting resin composition of the present invention is, for example, 0.001 ⁇ m to 1,000 ⁇ m, preferably 0.01 ⁇ m to 100 ⁇ m, more preferably 0.1 ⁇ m to 10 ⁇ m.
- thermosetting resin composition ⁇ Example 1> 20.0 g of the polymer solution obtained in Synthesis Example 1 and 0.01 g of DFX-18 (manufactured by Neos) as a surfactant were dissolved in 7.5 g of propylene glycol monomethyl ether and 5.9 g of ethyl lactate. It was set as the solution. Then, it filtered using the polyethylene micro filter with a hole diameter of 0.10 micrometer, and prepared the thermosetting resin composition. In this embodiment, no curing agent is added.
- Example 2 20.0 g of the polymer solution obtained in Synthesis Example 1, 0.6 g of KAYARAD (registered trademark) DPHA (manufactured by Nippon Kayaku Co., Ltd.) which is a polyfunctional acrylate compound as a curing agent, and DFX-18 (as a surfactant) 0.01 g (manufactured by Neos Co., Ltd.) was dissolved in 11.1 g of propylene glycol monomethyl ether and 6.8 g of ethyl lactate to prepare a solution. Then, it filtered using the polyethylene micro filter with a hole diameter of 0.10 micrometer, and prepared the thermosetting resin composition.
- KAYARAD registered trademark
- DPHA manufactured by Nippon Kayaku Co., Ltd.
- DFX-18 as a surfactant
- Example 3 20.0 g of the polymer solution obtained in Synthesis Example 1, 0.6 g of biscort # 802 (Osaka Organic Chemical Co., Ltd.) which is a polyfunctional acrylate compound as a curing agent, and DFX-18 ((Co., Ltd.) as a surfactant. ) Neos) 0.01 g was dissolved in 11.1 g of propylene glycol monomethyl ether and 6.8 g of ethyl lactate to give a solution. Then, it filtered using the polyethylene micro filter with a hole diameter of 0.10 micrometer, and prepared the thermosetting resin composition.
- Example 4 20.0 g of the polymer solution obtained in Synthesis Example 1, 0.6 g of polyfunctional urethane acrylate compound UA-510H (manufactured by Kyoeisha Chemical Co., Ltd.) as a curing agent, and DFX-18 (Co., Ltd.) as a surfactant. 0.01 g of Neos) was dissolved in 11.1 g of propylene glycol monomethyl ether and 6.8 g of ethyl lactate to prepare a solution. Then, it filtered using the polyethylene micro filter with a hole diameter of 0.10 micrometer, and prepared the thermosetting resin composition.
- Example 5 20.0 g of the polymer solution obtained in Synthesis Example 1 and TRIXENE BI-7982 which is a polyfunctional blocked isocyanate compound as a curing agent (propylene glycol monomethyl ether solution, solid content concentration 70 mass%) (manufactured by Vaxenden Chemicals) 0 0.8 g and 0.01 g of DFX-18 (manufactured by Neos Co., Ltd.) as a surfactant were dissolved in 10.8 g of propylene glycol monomethyl ether and 6.8 g of ethyl lactate to obtain a solution. Then, it filtered using the polyethylene micro filter with a hole diameter of 0.10 micrometer, and prepared the thermosetting resin composition.
- TRIXENE BI-7982 which is a polyfunctional blocked isocyanate compound as a curing agent
- 0 0.8 g and 0.01 g of DFX-18 manufactured by Neos Co., Ltd.
- Example 6 20.0 g of the polymer solution obtained in Synthesis Example 1 and Takenate (registered trademark) B-882N, which is a polyfunctional blocked isocyanate compound as a curing agent (butyl acetate and solvent naphtha solution, solid concentration 70% by mass) (Mitsui Chemicals) 0.8 g (manufactured by Co., Ltd.) and 0.01 g DFX-18 (manufactured by Neos Co., Ltd.) as a surfactant were dissolved in 10.8 g of propylene glycol monomethyl ether and 6.8 g of ethyl lactate to obtain a solution. Then, it filtered using the polyethylene micro filter with a hole diameter of 0.10 micrometer, and prepared the thermosetting resin composition.
- B-882N which is a polyfunctional blocked isocyanate compound as a curing agent (butyl acetate and solvent naphtha solution, solid concentration 70% by mass)
- Mitsubishi Chemicals 0.8 g
- DFX-18
- Example 7 20.0 g of the polymer solution obtained in Synthesis Example 1, 2.4 g of the polymer solution obtained in Synthesis Example 4 which is a polyfunctional blocked isocyanate compound as a curing agent, and DFX-18 (Neos Corporation) as a surfactant 0.01 g) was dissolved in 9.3 g of propylene glycol monomethyl ether and 6.8 g of ethyl lactate to prepare a solution. Then, it filtered using the polyethylene micro filter with a hole diameter of 0.10 micrometer, and prepared the thermosetting resin composition.
- the polymer used in this comparative example does not have the structural unit represented by the formula (1).
- the polymer used in this comparative example does not have the structural unit represented by the formula (1).
- thermosetting resin composition filtered using the polyethylene micro filter with a hole diameter of 0.10 micrometer, and prepared the thermosetting resin composition.
- the curing agent used in this comparative example does not correspond to either a polyfunctional (meth) acrylate compound or a polyfunctional blocked isocyanate compound.
- the polymer used in this comparative example does not have the structural unit represented by the formula (1).
- the curing agent used in this comparative example does not correspond to either a polyfunctional (meth) acrylate compound or a polyfunctional blocked isocyanate compound.
- thermosetting resin compositions prepared in Examples 1 to 7 and Comparative Examples 3 to 5 were used for each of the thermosetting resin compositions prepared in Comparative Examples 1 and 2 on a silicon wafer.
- the film was baked on a hot plate at 100 ° C. for 1 minute and further at 230 ° C. for 5 minutes to form a film having a thickness of 0.5 ⁇ m.
- thermosetting resin compositions prepared in Examples 1 to 7 and Comparative Examples 3 to 5 were applied on a quartz substrate using a spin coater, and then on a hot plate at 100 ° C. for 1 minute. Baking was performed at 230 ° C. for 5 minutes to form a film having a thickness of 0.5 ⁇ m.
- the transmittance of these films was measured using an ultraviolet-visible spectrophotometer UV-2550 (manufactured by Shimadzu Corporation) while changing the wavelength by 2 nm in the wavelength range of 400 nm to 800 nm. Further, this film was heated at 260 ° C.
- Table 1 shows the values of the minimum transmittance measured in the wavelength range of 400 nm to 800 nm before and after heating at 260 ° C. for 5 minutes.
- thermosetting resin compositions prepared in Examples 1 to 7 and Comparative Examples 3 to 5 were each formed on a stepped substrate (see FIG. 1) having a height of 0.5 ⁇ m, a line width of 10 ⁇ m, and a space between lines of 10 ⁇ m.
- the film was applied using a spin coater and baked on a hot plate at 100 ° C. for 1 minute and further at 230 ° C. for 5 minutes to form a film having a thickness of 0.5 ⁇ m.
- h1 step difference of the stepped substrate
- h2 step difference of the cured film, that is, the height difference between the height of the cured film on the line and the height of the cured film on the space
- the cured film prepared from the thermosetting resin composition of the present invention was highly solvent resistant and highly transparent in the wavelength range of 400 nm to 800 nm. Moreover, the cured film produced from the thermosetting resin composition of the present invention had a level difference flatness exceeding 50%.
- the cured films prepared from the thermosetting resin compositions prepared in Examples 1 to 4 have high step flatness with a flattening rate of 75% or more.
- the resin film produced from the resin composition prepared in Comparative Example 1 and Comparative Example 2 did not satisfy the solvent resistance.
- the cured films prepared from the thermosetting resin compositions prepared in Comparative Examples 3 to 5 have high solvent resistance and high transparency in the wavelength range of 400 nm to 800 nm. It was found to be less than 50% and poor in step flatness.
- Stepped substrate 2 Cured film 3: Line width 4: Line space h1: Stepped substrate step h2: Cured film step
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Abstract
Description
(式中、A1は炭素原子数2又は3のアルケニル基又はアルキニル基を表し、A2は炭素原子数2のアルケニレン基又はアルキニレン基を表す。)
本発明の熱硬化性樹脂組成物に含まれるポリマーは、前記式(1)で表される構造単位を有するポリマーである。前記式(1)において、A1で表される、炭素原子数2又は3のアルケニル基として、例えばビニル基及びアリル基が挙げられ、炭素原子数2又は3のアルキニル基として、例えばエチニル基(-C≡CH基)及びプロパルギル基(-CH2-C≡CH基)が挙げられる。さらに前記式(1)において、A2で表される、炭素原子数2のアルケニレン基として、エテン-1,2-ジイル基(-CH=CH-基)が挙げられ、炭素原子数2のアルキニレン基として、エチン-1,2-ジイル基(-C≡C-基)が挙げられる。
本発明の熱硬化性樹脂組成物に含まれる溶剤としては、当該樹脂組成物に含まれるポリマーを溶解するものであれば特に限定されない。そのような溶剤としては、例えば、エチレングリコールモノメチルエーテル、エチレングリコールモノエチルエーテル、メチルセロソルブアセテート、エチルセロソルブアセテート、ジエチレングリコールモノメチルエーテル、ジエチレングリコールモノエチルエーテル、プロピレングリコール、プロピレングリコールモノメチルエーテル、プロピレングリコールモノメチルエーテルアセテート、プロピレングリコールモノエチルエーテル、プロピレングリコールモノエチルエーテルアセテート、プロピレングリコールプロピルエーテルアセテート、プロピレングリコールモノブチルエーテル、プロピレングリコールモノブチルエーテルアセテート、トルエン、キシレン、メチルエチルケトン、シクロペンタノン、シクロヘキサノン、2-ヒドロキシプロピオン酸エチル、2-ヒドロキシ-2-メチルプロピオン酸エチル、エトキシ酢酸エチル、ヒドロキシ酢酸エチル、2-ヒドロキシ-3-メチルブタン酸メチル、3-メトキシプロピオン酸メチル、3-メトキシプロピオン酸エチル、3-エトキシプロピオン酸エチル、3-エトキシプロピオン酸メチル、ピルビン酸メチル、酢酸エチル、酢酸ブチル、乳酸エチル、乳酸ブチル、2-ヘプタノン、γ-ブチロラクトン、N-メチルピロリドン、及びN-エチルピロリドンを挙げることができる。これらの溶剤は、単独で使用しても、2種以上を組み合わせて使用してもよい。
また、本発明の熱硬化性樹脂組成物は、当該樹脂組成物に含まれるポリマーによって硬化膜の形成が可能であるが、硬化性を向上させる目的でさらに硬化剤を含有することもできる。当該硬化剤としては、例えば、分子内に2個以上の(メタ)アクリロイル基を有する多官能(メタ)アクリレート化合物、又は分子内に2個以上のブロックイソシアネート基を有する多官能ブロックイソシアネート化合物を挙げることができる。硬化剤としてモノマー化合物が用いられる場合、当該モノマー分子内の(メタ)アクリロイル基又はブロックイソシアネート基の数は、例えば2個乃至15個である。これらの硬化剤は、単独で又は2種以上を組み合わせて用いることができる。なお、本明細書において、(メタ)アクリロイル基はメタクリロイル基及びアクリロイル基を意味し、(メタ)アクリレートはメタクリレート及びアクリレートを意味し、(メタ)アクリル酸はメタクリル酸及びアクリル酸を意味する。
又は多官能(メタ)アクリレートに、2,4-トリレンジイソシアネート、2,6-トリレンジイソシアネート、1,3-キシレンジイソシアネート、1,4-キシレンジイソシアネート、キシリレンジイソシアネート、1,5-ナフタレンジイソシアネート、m-フェニレンジイソシアネート、p-フェニレンジイソシアネート、ジフェニルメタンジイソシアネート、4,4’-ジフェニルメタンジイソシアネート、4,4’-ジベンジルジイソシアネート、イソホロンジイソシアネート、1,6-ヘキサメチレンジイソシアネート、ジシクロヘキシルメタンジイソシアネート、2,2,4-トリメチルヘキサメチレンジイソシアネート、2,4,4-トリメチルヘキサメチレンジイソシアネート、1,3-ビス(イソシアナトメチル)ベンゼン、1,3-ビス(イソシアナトメチル)シクロヘキサン等のジイソシアネート化合物を反応させて合成した多官能ウレタン(メタ)アクリレートも挙げることができる。
アロニックス〔登録商標〕M-208、同M-210、同M-211B、同M-215、同M-220、同M-225、同M-233、同M-240、同M-245、同M-260、同M-270、同M-303、同M-305、同M-306、同M-309、同M-310、同M-313、同M-315、同M-321、同M-350、同M-360、同M-400、同M-402、同M-403、同M-404、同M-405、同M-406、同M-408、同M-450、同M-452、同M-460、同M-510、同M-520、同M-1100、同M-1200、同M-1210、同M-1310、同M-1600、同M-1960、同M-6100、同M-6200、同M-6250、同M-6500、同M-7100、同M-7300K、同M-8030、同M-8060、同M-8100、同M-8530、同M-8560、同M-9050(以上、東亜合成(株)製)。
タケネート〔登録商標〕B-815N、同B-830、同B-842N、同B-846N、同B-870、同B-870N、同B-874、同B-874N、同B-882、同B-882N、同B-5010、同B-7005、同B-7030、同B-7075(以上、三井化学(株)製)。
コロネート〔登録商標〕2503、同2507、同2512、同2513、同2515、同2520、同2554、同BI-301、同AP-M、ミリオネート MS-50(以上、東ソー(株)製)。
また、本発明の熱硬化性樹脂組成物は、塗布性を向上させる目的で、界面活性剤を含有することもできる。当該界面活性剤としては、例えば、ポリオキシエチレンラウリルエーテル、ポリオキシエチレンステアリルエーテル、ポリオキシエチレンセチルエーテル、ポリオキシエチレンオレイルエーテル等のポリオキシエチレンアルキルエーテル類、ポリオキシエチレンオクチルフェニルエーテル、ポリオキシエチレンノニルフェニルエーテル等のポリオキシエチレンアルキルアリールエーテル類、ポリオキシエチレン・ポリオキシプロピレンブロックコポリマー類、ソルビタンモノラウレート、ソルビタンモノパルミテート、ソルビタンモノステアレート、ソルビタンモノオレエート、ソルビタントリオレエート、ソルビタントリステアレート等のソルビタン脂肪酸エステル類、ポリオキシエチレンソルビタンモノラウレート、ポリオキシエチレンソルビタンモノパルミテート、ポリオキシエチレンソルビタンモノステアレート、ポリオキシエチレンソルビタントリオレエート、ポリオキシエチレンソルビタントリステアレート等のポリオキシエチレンソルビタン脂肪酸エステル類等のノニオン系界面活性剤、エフトップ〔登録商標〕EF301、同EF303、同EF352(以上、三菱マテリアル電子化成(株)製)、メガファック〔登録商標〕F-171、同F-173、同R-30、同R-40、同R-40-LM(以上、DIC(株)製)、フロラードFC430、同FC431(以上、住友スリーエム(株)製)、アサヒガード〔登録商標〕AG710、サーフロン〔登録商標〕S-382、同SC101、同SC102、同SC103、同SC104、同SC105、同SC106(旭硝子(株)製)、FTX-206D、FTX-212D、FTX-218、FTX-220D、FTX-230D、FTX-240D、FTX-212P、FTX-220P、FTX-228P、FTX-240G、DFX-18等のフタージェントシリーズ((株)ネオス製)等のフッ素系界面活性剤、及びオルガノシロキサンポリマーKP341(信越化学工業(株)製)を挙げることができる。これらの界面活性剤は、単独で使用しても、2種以上を組み合わせて使用してもよい。
本発明の熱硬化性樹脂組成物を用いた硬化膜、保護膜及び平坦化膜の作製方法について説明する。基板(例えば、半導体基板、ガラス基板、石英基板、シリコンウエハー及びこれらの表面に各種金属膜又はカラーフィルター等が形成された基板)上に、スピナー、コーター等の適当な塗布方法により本発明の熱硬化性樹脂組成物を塗布後、ホットプレート、オーブン等の加熱手段を用いてベークして硬化させて、硬化膜、保護膜、又は平坦化膜を作製する。ベーク条件は、ベーク温度80℃乃至300℃、ベーク時間0.5分乃至60分間の中から適宜選択される。異なるベーク温度で2ステップ以上ベーク処理してもよい。また、本発明の熱硬化性樹脂組成物から作製される膜の膜厚としては、例えば0.001μm乃至1,000μmであり、好ましくは0.01μm乃至100μmであり、より好ましくは0.1μm乃至10μmである。
〔下記合成例で得られた共重合体の重量平均分子量の測定〕
装置:日本分光(株)製GPCシステム
カラム:Shodex〔登録商標〕KF-804L及び803L
カラムオーブン:40℃
流量:1mL/分
溶離液:テトラヒドロフラン
<合成例1>
モノアリルジグリシジルイソシアヌレート(MA-DGIC(四国化成工業(株)製))22.0g、フマル酸9.5g及びベンジルトリエチルアンモニウムクロリド0.9gをプロピレングリコールモノメチルエーテル129.7gに溶解させた後、この溶液を加熱還流しながら6時間反応させて、ポリマーの溶液(固形分濃度20質量%)を得た。得られたポリマーの重量平均分子量Mwは7,500であった。
モノアリルジグリシジルイソシアヌレート(MA-DGIC(四国化成工業(株)製))20.0g、コハク酸9.7g及びベンジルトリエチルアンモニウムクロリド0.9gをプロピレングリコールモノメチルエーテル130.4gに溶解させた後、この溶液を加熱還流しながら6時間反応させて、ポリマーの溶液(固形分濃度20質量%)を得た。得られたポリマーの重量平均分子量Mwは2,500であった。
テレフタル酸ジグリシジル(デナコール〔登録商標〕EX-711(ナガセケムテックス(株)製))22.0g、フマル酸9.6g及びベンジルトリエチルアンモニウムクロリド0.9gをプロピレングリコールモノメチルエーテル130.1gに溶解させた後、この溶液を加熱還流しながら6時間反応させて、ポリマーの溶液(固形分濃度20質量%)を得た。得られたポリマーの重量平均分子量Mwは5,100であった。
2-[(3,5-ジメチルピラゾリル)カルボニルアミノ]エチルメタクリレート(カレンズ〔登録商標〕MOI-BP(昭和電工(株)製))40.0g及び2,2’-アゾビスイソブチロニトリル2.6gをプロピレングリコールモノメチルエーテル79.1gに溶解させた後、この溶液を、プロピレングリコールモノメチルエーテル48.7gを80℃に保持したフラスコ中に3時間かけて滴下した。滴下終了後、さらに18時間反応させて、ポリマーの溶液(固形分濃度25質量%)を得た。得られたポリマーの重量平均分子量Mwは14,500であった。
メチルメタクリレート40.0g、2-ヒドロキシエチルメタクリレート4.7g、メタクリル酸2.4g及び2,2’-アゾビスイソブチロニトリル3.1gをプロピレングリコールモノメチルエーテルアセテート55.7gに溶解させた後、この溶液を、プロピレングリコールモノメチルエーテルアセテート55.7gを70℃に保持したフラスコ中に4時間かけて滴下した。滴下終了後、さらに18時間反応させて、ポリマーの溶液(固形分濃度30質量%)を得た。得られたポリマーの重量平均分子量Mwは9,300であった。
スチレン22.0g、2-ヒドロキシエチルメタクリレート13.7g、2-[(3,5-ジメチルピラゾリル)カルボニルアミノ]エチルメタクリレート(カレンズ〔登録商標〕MOI-BP(昭和電工(株)製))26.5g及び2,2’-アゾビスイソブチロニトリル2.8gをプロピレングリコールモノメチルエーテル65.1gに溶解させた後、この溶液を、プロピレングリコールモノメチルエーテル32.5gを70℃に保持したフラスコ中に4時間かけて滴下した。滴下終了後、さらに18時間反応させて、ポリマーの溶液(固形分濃度40質量%)を得た。得られたポリマーの重量平均分子量Mwは25,000であった。
<実施例1>
合成例1で得られたポリマーの溶液20.0g及び界面活性剤としてDFX-18((株)ネオス製)0.01gを、プロピレングリコールモノメチルエーテル7.5g及び乳酸エチル5.9gに溶解させて溶液とした。その後、孔径0.10μmのポリエチレン製ミクロフィルターを用いてろ過して、熱硬化性樹脂組成物を調製した。本実施例では硬化剤を添加しない。
合成例1で得られたポリマーの溶液20.0g、硬化剤として多官能アクリレート化合物であるKAYARAD〔登録商標〕DPHA(日本化薬(株)製)0.6g及び界面活性剤としてDFX-18((株)ネオス製)0.01gを、プロピレングリコールモノメチルエーテル11.1g及び乳酸エチル6.8gに溶解させて溶液とした。その後、孔径0.10μmのポリエチレン製ミクロフィルターを用いてろ過して、熱硬化性樹脂組成物を調製した。
合成例1で得られたポリマーの溶液20.0g、硬化剤として多官能アクリレート化合物であるビスコート#802(大阪有機化学工業(株)製)0.6g及び界面活性剤としてDFX-18((株)ネオス製)0.01gを、プロピレングリコールモノメチルエーテル11.1g及び乳酸エチル6.8gに溶解させて溶液とした。その後、孔径0.10μmのポリエチレン製ミクロフィルターを用いてろ過して、熱硬化性樹脂組成物を調製した。
合成例1で得られたポリマーの溶液20.0g、硬化剤として多官能ウレタンアクリレート化合物であるUA-510H(共栄社化学(株)製)0.6g及び界面活性剤としてDFX-18((株)ネオス製)0.01gを、プロピレングリコールモノメチルエーテル11.1g及び乳酸エチル6.8gに溶解させて溶液とした。その後、孔径0.10μmのポリエチレン製ミクロフィルターを用いてろ過して、熱硬化性樹脂組成物を調製した。
合成例1で得られたポリマーの溶液20.0g、硬化剤として多官能ブロックイソシアネート化合物であるTRIXENE BI-7982(プロピレングリコールモノメチルエーテル溶液、固形分濃度70質量%)(バクセンデンケミカルズ社製)0.8g及び界面活性剤としてDFX-18((株)ネオス製)0.01gを、プロピレングリコールモノメチルエーテル10.8g及び乳酸エチル6.8gに溶解させて溶液とした。その後、孔径0.10μmのポリエチレン製ミクロフィルターを用いてろ過して、熱硬化性樹脂組成物を調製した。
合成例1で得られたポリマーの溶液20.0g、硬化剤として多官能ブロックイソシアネート化合物であるタケネート〔登録商標〕B-882N(酢酸ブチル及びソルベントナフサ溶液、固形分濃度70質量%)(三井化学(株)製)0.8g及び界面活性剤としてDFX-18((株)ネオス製)0.01gを、プロピレングリコールモノメチルエーテル10.8g及び乳酸エチル6.8gに溶解させて溶液とした。その後、孔径0.10μmのポリエチレン製ミクロフィルターを用いてろ過して、熱硬化性樹脂組成物を調製した。
合成例1で得られたポリマーの溶液20.0g、硬化剤として多官能ブロックイソシアネート化合物である合成例4で得られたポリマーの溶液2.4g及び界面活性剤としてDFX-18((株)ネオス製)0.01gを、プロピレングリコールモノメチルエーテル9.3g及び乳酸エチル6.8gに溶解させて溶液とした。その後、孔径0.10μmのポリエチレン製ミクロフィルターを用いてろ過して、熱硬化性樹脂組成物を調製した。
合成例2で得られたポリマーの溶液20.0g及び界面活性剤としてDFX-18((株)ネオス製)0.01gを、プロピレングリコールモノメチルエーテル7.5g及び乳酸エチル5.9gに溶解させて溶液とした。その後、孔径0.10μmのポリエチレン製ミクロフィルターを用いてろ過して、樹脂組成物を調製した。本比較例で用いたポリマーは、前記式(1)で表される構造単位を有さない。
合成例3で得られたポリマーの溶液20.0g及び界面活性剤としてDFX-18((株)ネオス製)0.01gを、プロピレングリコールモノメチルエーテル7.5g及び乳酸エチル5.9gに溶解させて溶液とした。その後、孔径0.10μmのポリエチレン製ミクロフィルターを用いてろ過して、樹脂組成物を調製した。本比較例で用いたポリマーは、前記式(1)で表される構造単位を有さない。
合成例1で得られたポリマーの溶液20.0g、硬化剤としてメチル化メラミン樹脂(ニカラック〔登録商標〕MW-390((株)三和ケミカル製))0.6g、硬化触媒としてp-トルエンスルホン酸一水和物0.06g及び界面活性剤としてDFX-18((株)ネオス製)0.01gを、プロピレングリコールモノメチルエーテル11.4g及び乳酸エチル6.9gに溶解させて溶液とした。その後、孔径0.10μmのポリエチレン製ミクロフィルターを用いてろ過して、熱硬化性樹脂組成物を調製した。本比較例で用いた硬化剤は、多官能(メタ)アクリレート化合物及び多官能ブロックイソシアネート化合物のいずれにも該当しない。
合成例5で得られたポリマーの溶液10.0g及び硬化剤としてメチル化メラミン樹脂(ニカラック〔登録商標〕MX-706(2-プロパノール溶液、固形分濃度70質量%)((株)三和ケミカル製))0.9g及び界面活性剤としてDFX-18((株)ネオス製)0.01gを、プロピレングリコールモノメチルエーテル13.0g及びプロピレングリコールモノメチルエーテルアセテート6.2gに溶解させて溶液とした。その後、孔径0.10μmのポリエチレン製ミクロフィルターを用いてろ過して、熱硬化性樹脂組成物を調製した。本比較例で用いたポリマーは、前記式(1)で表される構造単位を有さない。さらに本比較例で用いた硬化剤は、多官能(メタ)アクリレート化合物及び多官能ブロックイソシアネート化合物のいずれにも該当しない。
合成例6で得られたポリマーの溶液10.0gを、プロピレングリコールモノメチルエーテル17.5g及び乳酸エチル5.9gに溶解させて溶液とした。その後、孔径0.10μmのポリエチレン製ミクロフィルターを用いてろ過して、熱硬化性樹脂組成物を調製した。本比較例で用いたポリマーは、前記式(1)で表される構造単位を有さない。
実施例1乃至実施例7及び比較例3乃至比較例5で調製した熱硬化性樹脂組成物、並びに比較例1及び比較例2で調製した樹脂組成物をそれぞれ、シリコンウエハー上にスピンコーターを用いて塗布し、ホットプレート上において100℃で1分間、さらに230℃で5分間ベークを行い、膜厚0.5μmの膜を形成した。これらの膜に対して、プロピレングリコールモノメチルエーテル、プロピレングリコールモノメチルエーテルアセテート、酢酸ブチル、乳酸エチル、3-メトキシプロピオン酸メチル、3-エトキシプロピオン酸エチル、アセトン、メチルエチルケトン、シクロヘキサノン、γ-ブチロラクトン、N-メチルピロリドン、2-プロパノール及び2.38質量%濃度の水酸化テトラメチルアンモニウム水溶液に、それぞれ23℃の温度条件下、5分間浸漬した後、100℃で1分間乾燥ベークを行った。浸漬前及び乾燥ベーク後の膜厚測定を行い、膜厚変化を算出した。前記浸漬溶剤のうち1つでも、浸漬前の膜厚に対して10%以上の膜厚増減があった場合は“×”、全ての溶剤について膜厚増減が10%未満であった場合は“○”として耐溶剤性を評価した。評価結果を表1に示す。
実施例1乃至実施例7及び比較例3乃至比較例5で調製した熱硬化性樹脂組成物をそれぞれ、石英基板上にスピンコーターを用いて塗布し、ホットプレート上において100℃で1分間、さらに230℃で5分間ベークを行い、膜厚0.5μmの膜を形成した。これらの膜に対して、紫外線可視分光光度計UV-2550((株)島津製作所製)を用いて、波長400nm~800nmの範囲で波長を2nmずつ変化させて透過率を測定した。さらにこの膜を260℃で5分間加熱した後、再び波長400nm~800nmの範囲で波長を2nmずつ変化させて透過率を測定した。260℃で5分間加熱する前及び後での、波長400nm~800nmの範囲で測定された最低透過率の値を表1に示す。
実施例1乃至実施例7及び比較例3乃至比較例5で調製した熱硬化性樹脂組成物を、それぞれ高さ0.5μm、ライン幅10μm、ライン間スペース10μmの段差基板(図1参照)上にスピンコーターを用いて塗布し、ホットプレート上において100℃で1分間、さらに230℃で5分間ベークを行い、膜厚0.5μmの膜を形成した。図1の段差基板1に示すh1(段差基板の段差)とh2(硬化膜の段差、即ちライン上の硬化膜の高さとスペース上の硬化膜の高さとの高低差)の値から、“式:(1-(h2/h1))×100”を用いて平坦化率を求めた。評価結果を表1に示す。
2:硬化膜
3:ライン幅
4:ライン間スペース
h1:段差基板の段差
h2:硬化膜の段差
Claims (7)
- 前記硬化剤は多官能アクリレート化合物である請求項1又は請求項2に記載の熱硬化性樹脂組成物。
- さらに界面活性剤を含有する請求項1乃至請求項3のいずれか一項に記載の熱硬化性樹脂組成物。
- 平坦化膜用組成物である請求項1乃至請求項4のいずれか一項に記載の熱硬化性樹脂組成物。
- 保護膜用組成物である請求項1乃至請求項4のいずれか一項に記載の熱硬化性樹脂組成物。
- 請求項1乃至請求項6のいずれか一項に記載の熱硬化性樹脂組成物を基板上に塗布した後、加熱手段を用いて前記熱硬化性樹脂組成物をベークすることによる、硬化膜、保護膜又は平坦化膜の作製方法。
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JP2019172846A (ja) * | 2018-03-28 | 2019-10-10 | 日産化学株式会社 | 重合体及びそれを含む樹脂組成物 |
US20210311396A1 (en) * | 2018-07-31 | 2021-10-07 | Nissan Chemical Corporation | Resist underlayer film-forming composition |
WO2023181960A1 (ja) * | 2022-03-24 | 2023-09-28 | 日産化学株式会社 | 保護膜形成用組成物 |
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JP6904454B1 (ja) * | 2020-03-27 | 2021-07-14 | 横浜ゴム株式会社 | 2液硬化型接着剤組成物 |
KR102465032B1 (ko) * | 2022-06-24 | 2022-11-10 | 로움하이텍 주식회사 | 신규한 폴리이소시아누레이트, 이를 포함하는 반사 방지막 조성물 및 이를 채용하는 반사 방지막의 제조방법 |
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WO2023181960A1 (ja) * | 2022-03-24 | 2023-09-28 | 日産化学株式会社 | 保護膜形成用組成物 |
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US10774237B2 (en) | 2020-09-15 |
KR20180067516A (ko) | 2018-06-20 |
CN108137788A (zh) | 2018-06-08 |
TWI667282B (zh) | 2019-08-01 |
TW201728667A (zh) | 2017-08-16 |
KR102353991B1 (ko) | 2022-01-21 |
JPWO2017064992A1 (ja) | 2018-06-28 |
JP6421964B2 (ja) | 2018-11-14 |
US20180305578A1 (en) | 2018-10-25 |
CN108137788B (zh) | 2020-05-29 |
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