CN110373080B - Thermosetting composition, cured film and color filter - Google Patents

Thermosetting composition, cured film and color filter Download PDF

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CN110373080B
CN110373080B CN201910264727.3A CN201910264727A CN110373080B CN 110373080 B CN110373080 B CN 110373080B CN 201910264727 A CN201910264727 A CN 201910264727A CN 110373080 B CN110373080 B CN 110373080B
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thermosetting composition
compound
film
cured film
methyl
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CN110373080A (en
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木村佑希
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JNC Corp
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • 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
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
    • C08G59/42—Polycarboxylic acids; Anhydrides, halides or low molecular weight esters thereof
    • C08G59/4207—Polycarboxylic acids; Anhydrides, halides or low molecular weight esters thereof aliphatic
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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
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    • C08F232/00—Copolymers of cyclic compounds containing no unsaturated aliphatic radicals in a side chain, and having one or more carbon-to-carbon double bonds in a carbocyclic ring system
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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
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
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    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
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    • C08K5/10—Esters; Ether-esters
    • C08K5/11—Esters; Ether-esters of acyclic polycarboxylic acids
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • C08K5/04—Oxygen-containing compounds
    • C08K5/15—Heterocyclic compounds having oxygen in the ring
    • C08K5/151—Heterocyclic compounds having oxygen in the ring having one oxygen atom in the ring
    • C08K5/1515—Three-membered rings
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L35/00—Compositions of homopolymers or 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, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L45/00—Compositions of homopolymers or copolymers of compounds having no unsaturated aliphatic radicals in side chain, and having one or more carbon-to-carbon double bonds in a carbocyclic or in a heterocyclic ring system; Compositions of derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
    • C—CHEMISTRY; METALLURGY
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    • 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
    • C09D133/00—Coating compositions based on homopolymers or 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 only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
    • C09D133/04—Homopolymers or copolymers of esters
    • C09D133/14—Homopolymers or copolymers of esters of esters containing halogen, nitrogen, sulfur or oxygen atoms in addition to the carboxy oxygen
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
    • G02B1/10—Optical coatings produced by application to, or surface treatment of, optical elements
    • G02B1/14—Protective coatings, e.g. hard coatings
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/20—Filters
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/1335—Structural association of cells with optical devices, e.g. polarisers or reflectors
    • G02F1/133509—Filters, e.g. light shielding masks
    • G02F1/133514—Colour filters
    • G02F1/133519—Overcoatings

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  • Crystallography & Structural Chemistry (AREA)
  • Epoxy Resins (AREA)
  • Polymerisation Methods In General (AREA)
  • Optical Filters (AREA)

Abstract

The invention provides a thermosetting composition, a cured film and a color filter. A thermosetting composition comprising a copolymer (A) which is a reaction product derived from a monomer (a) represented by the following formula (1) and a monomer (B) other than the monomer (a), a compound (B) having three or more epoxy groups, a compound (C) having four or more (meth) acryloyl groups, and a solvent (D). The thermosetting composition of the present invention can form a cured film excellent in heat resistance, gas barrier properties, tack free properties, adhesion, flatness, and transparency. The hardened film can be suitably used in electronic parts. In the formula (1), R1And R2Independently hydrogen, alkyl group having 1 to 3 carbon atoms or phenyl group.

Description

Thermosetting composition, cured film and color filter
Technical Field
The present invention relates to a thermosetting composition which can be used for forming an insulating material in an electronic component, a passivation film, a buffer coating film, an interlayer insulating film, a planarization film in a semiconductor device, an interlayer insulating film in a liquid crystal display element, a protective film for a color filter (color filter), and the like, a transparent film formed from the thermosetting composition, and an electronic component having the film.
Background
The manufacturing process of a device such as a liquid crystal display device includes a step of forming an organic thin film having various functions. Examples of the step include a black matrix resist film formation/patterning/heat treatment step, a color filter protective film formation/patterning/heat treatment step, an Indium Tin Oxide (ITO) conductive film formation step, an ITO patterning photoresist film formation/patterning/wet etching/resist stripping step, an ITO annealing step, an alignment film formation/heat treatment/rubbing (polarized light exposure) step, and the like. In these various steps, the element is sometimes exposed to various chemicals such as an organic solvent, an acid, and an alkali solution, and when an electrode is formed by sputtering, the surface may be locally exposed to a high temperature. Therefore, a surface protective film may be provided for the purpose of preventing deterioration, damage, or alteration of the surface of each element. These protective films are required to have various properties that can withstand various treatments in the manufacturing steps as described above. Specifically, chemical resistance such as heat resistance, solvent resistance, acid resistance, alkali resistance, etc., water resistance, adhesion to a substrate such as glass, transparency, scratch resistance, coatability, flatness, light resistance, etc., are required. In particular, in recent years, in order to improve the display quality of a display, it has been required to expand the color gamut, and the required characteristics of a color filter have become strict, and accordingly, there has been a problem that a pigment/dye is eluted from the color filter, and it has been strongly required to improve the gas barrier property of a protective film.
Heretofore, in order to provide a protective film, it has been proposed to use a polyimide material as the protective film (patent document 1). In addition, protective films using silicone materials, which are characterized by high heat resistance and transparency, have also been proposed (patent documents 2 and 3). Alternatively, a protective film using an epoxy resin and a melamine resin, or a protective film using an acrylic resin or a polyester resin has been proposed (patent document 4, patent document 5, and patent document 6). In addition, thermosetting materials containing a multifunctional acrylate in a composition have also been proposed (patent documents 7, 8, and 9).
However, in order to prepare a polyimide or a polyimide precursor (polyamic acid) solution, a polyimide solvent having a strong dissolving power, such as N-methylpyrrolidone or γ -butyrolactone, is required for the protective film using a polyimide material, and there is a problem that an organic thin film of a substrate is dissolved. In particular, when used as a protective film for a color filter, the above problem becomes a serious problem and causes a decrease in gas barrier properties. In addition, polyimide also has a problem of coloration because the edge of the light absorption band extends into the visible light region due to Charge Transfer (CT) interaction. On the other hand, in the case of using a siloxane material (sol-gel material), although heat resistance and transparency are sufficient, since the temperature required for completion of the reaction of silanol groups is 300 ℃ or higher, there is also a problem that deterioration of the organic thin film of the substrate is caused, or cracks (fissures) are generated in the thin film by curing shrinkage. Furthermore, there is also the difficulty that the-Si-O-Si-bond of the siloxane material is easily hydrolyzed by alkali. In addition, in the case of using a material of an epoxy resin and a melamine resin, there is no problem in using a solvent or in the heat treatment temperature, but there is also a problem of yellowing. In the material using the acrylic resin, although the gas barrier property is improved, a problem is likely to occur in the coexistence with other characteristics. In addition, in the material containing a polyfunctional acrylate, although the gas barrier property can be improved, a film obtained by drying a solvent after application has a viscosity, and there is a problem that dust from the environment adheres to the surface to generate a film defect.
Under the circumstances, a material having all of the other properties, particularly, viscosity, flatness, adhesion to a substrate, transparency, and gas barrier properties, is demanded.
[ Prior art documents ]
[ patent document ]
[ patent document 1] Japanese patent laid-open No. Sho 62-163016
[ patent document 2] Japanese patent laid-open No. Sho 62-242918
[ patent document 3] Japanese patent laid-open No. Hei 7-331178
[ patent document 4] Japanese patent laid-open No. Sho 63-131103
[ patent document 5] Japanese patent laid-open No. Hei 8-50289
[ patent document 6] Japanese patent laid-open No. 2013-253263
[ patent document 7] Japanese patent laid-open No. 2009-203364
[ patent document 8] Japanese patent laid-open publication 2011-68779
[ patent document 9] Japanese patent laid-open No. 2012 and 41535
Disclosure of Invention
[ problems to be solved by the invention ]
The problem of the present invention is to provide a thermosetting composition that provides a cured film having excellent gas barrier properties, tack-free properties (tack-free properties), adhesion, flatness, and transparency, and a cured film formed from the thermosetting composition, and further to provide an electronic component having the cured film.
[ means for solving problems ]
The present inventors have made extensive studies to solve the above problems, and as a result, the present invention has been completed by using a thermosetting composition containing a copolymer obtained by copolymerizing a monomer having an acid anhydride group with another monomer, a compound having at least three or more epoxy groups, a compound having at least four or more (meth) acryloyl groups, and a solvent. The present invention includes the following configurations.
[1] A thermosetting composition comprising a copolymer (A) which is a reaction product derived from a monomer (a) represented by the following formula (1) and a monomer (B) other than the monomer (a), a compound (B) having three or more epoxy groups, a compound (C) having four or more (meth) acryloyl groups, and a solvent (D):
Figure BDA0002016418810000031
in the formula (1), R1And R2Independently hydrogen, alkyl group having 1 to 3 carbon atoms or phenyl group.
[2] The thermosetting composition according to item [1], wherein the monomer (b) is at least one selected from a compound represented by the following formula (2) and indene (indene):
Figure BDA0002016418810000032
in the formula (2), R1And R2Independently hydrogen, C1-C3 alkyl or phenyl, R3Is a monovalent organic group.
[3] The thermosetting composition according to [1], wherein the compound (B) having three or more epoxy groups is a compound having an aromatic ring.
[4] A cured film formed from the thermosetting composition according to any one of [1] to [3 ].
[5] A color filter having the cured film according to item [4] as a transparent protective film.
[ Effect of the invention ]
The thermosetting composition according to a preferred embodiment of the present invention is a material capable of forming a cured film having excellent gas barrier properties, non-tackiness, adhesion, flatness, and transparency, and particularly excellent gas barrier properties, and when used as a color filter protective film for a color liquid crystal display element, the thermosetting composition can improve display quality. In particular, the composition is useful as a protective film for a color filter produced by a dyeing method, a pigment dispersion method, an electrodeposition method, and a printing method. In addition, the film can be used as a protective film and a transparent insulating film for various optical materials.
Detailed Description
1. The thermosetting composition of the present invention
The thermosetting composition of the present invention is a thermosetting composition comprising a copolymer (a) containing a compound represented by formula (1), a compound (B) having three or more epoxy groups, a compound (C) having four or more (meth) acryloyl groups, and a solvent (D). In the thermosetting composition of the present invention, it is preferable that: the amount of the compound (B) having three or more epoxy groups is 10 to 500 parts by weight and the amount of the compound (C) having four or more (meth) acryloyl groups is 50 to 200 parts by weight based on 100 parts by weight of the copolymer (A).
1-1. copolymer (A)
The copolymer (a) is obtained by radical copolymerization of a raw material essentially comprising the compound represented by the above formula (1) as the monomer (a), and a compound selected from the group consisting of the compound represented by the formula (2) and indene as the monomer (b) other than the monomer (a), in the presence of a radical initiator. The other monomer (b) may contain compounds other than the above-mentioned compounds.
When the compound represented by the formula (2) and a compound other than indene are used in the other monomer (b), the amount of the compound added is preferably 0 to 40 wt%, more preferably 0 to 20 wt%, based on the whole monomers used in radical polymerization, from the viewpoint of heat resistance.
In addition, at least a solvent is required for the synthesis of the copolymer (A). The solvent may be left as it is to prepare a liquid or gel composition in consideration of handling properties, or the solvent may be removed to prepare a solid composition in consideration of handling properties.
Other compounds than those described above may be contained within a range not impairing the object of the present invention. Examples of the other raw materials include radical polymerizable monomers and chain transfer agents.
1-1-1. monomer (a) and monomer (b)
In the present invention, the material for obtaining the copolymer (a) contains a compound represented by formula (1) as the monomer (a). The other monomer (b) contains at least one compound selected from the group consisting of the compound represented by the formula (2) and indene. Specific examples of the compound of formula (1) include maleic anhydride, citraconic anhydride, 2, 3-dimethylmaleic anhydride, phenylmaleic anhydride and 2, 3-diphenylmaleic anhydride. Specific examples of the compound represented by the formula (2) include N-methylmaleimide, N-ethylmaleimide, N-propylmaleimide, N-cyclohexylmaleimide, N-phenylmaleimide and N-benzylmaleimide. The compound represented by the formula (2) and the monomer (b) other than indene may be contained within a range not impairing the characteristics of the present invention. Specific examples of such cases include: methacrylic acid, methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, glycidyl methacrylate, 2-hydroxyethyl methacrylate, benzyl methacrylate, 2-phenoxyethyl methacrylate, 2-phenylethyl methacrylate, isobornyl methacrylate, dicyclopentanyl methacrylate, 2,2, 2-trifluoroethyl methacrylate.
1-1-2 solvent used in Synthesis of copolymer (A)
Specific examples of the solvent used for the synthesis to obtain the copolymer (a) include: ethyl acetate, butyl acetate, propyl acetate, butyl propionate, ethyl lactate, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, methyl 3-oxopropionate, ethyl 3-hydroxypropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl 2-hydroxypropionate, propyl 2-hydroxypropionate, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, methyl 2-hydroxy-2-methylpropionate, ethyl methoxyacetate, butyl propionate, ethyl lactate, methyl methoxyacetate, ethyl methoxyacetate, butyl propionate, butyl 2-ethoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 2-hydroxy-2-methylpropionate, ethyl ethoxypropionate, ethyl 2-ethoxypropionate, methyl 2-hydroxypropionate, ethyl 2, methyl propionate, ethyl propionate, and mixtures thereof, Methyl 2-methoxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutyrate, ethyl 2-oxobutyrate, 4-hydroxy-4-methyl-2-pentanone, 1, 4-butanediol, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, ethylene glycol monobutyl ether acetate, cyclohexanone, cyclopentanone, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, and diethylene glycol methyl ethyl ether. The solvent may be one of these solvents, or may be a mixture of two or more of these solvents.
1-1-3. radical initiator used in Synthesis of copolymer (A)
In the synthesis of the copolymer (A), a commercially available azo-based or peroxide-based radical initiator can be used as a radical initiator for initiating the polymerization reaction. Specific examples of the azo radical initiator include: 2,2 '-azobis (isobutyronitrile), 2' -azobis (2-methylbutyronitrile), 2 '-azobis (2, 4-dimethoxyvaleronitrile), 2' -azobis (4-dimethoxy-2, 4-dimethylvaleronitrile). Specific examples of the peroxide-based radical initiator include: benzoyl peroxide, dicumyl peroxide, tert-butyl peroxybenzoate and bis (4-tert-butylcyclohexyl) peroxydicarbonate. The radical initiator may be used alone or in combination of two or more.
1-1-4 molecular weight regulator used in Synthesis of copolymer (A)
The copolymer (a) may further contain a molecular weight modifier during synthesis to suppress increase in molecular weight and exhibit excellent storage stability. Examples of the molecular weight modifier include: thiols, xanthates, quinones, hydroquinones, and 2, 4-diphenyl-4-methyl-1-pentene.
Specific examples of the molecular weight modifier include: 2-hydroxy-1, 4-naphthoquinone, benzoquinone, 1, 4-naphthoquinone, 1, 4-dihydroxynaphthalene, 2, 5-di-tert-butylhydroquinone, hydroquinone, methylhydroquinone, tert-butylhydroquinone, methoquinone, p-benzoquinone, methyl-p-benzoquinone, tert-butyl-p-benzoquinone, anthraquinone, n-hexylmercaptan, n-octylmercaptan, n-dodecylmercaptan, tert-dodecylmercaptan, thioglycolic acid, dimethylxanthate sulfide, diisopropylxanthate disulfide, 2, 4-diphenyl-4-methyl-1-pentene.
The molecular weight regulators may be used alone or in combination of two or more.
1-1-5. Synthesis method of copolymer (A)
With respect to the copolymer (a) used in the present invention, the compound represented by the formula (1) and a monomer selected from the group consisting of the compound represented by the formula (2) and indene are polymerized in the solvent and in the presence of a thermal radical initiator.
In the synthesis of the copolymer (A), the polymerization heat (heat of polymerization) is large because the monomers of the formulae (1) and (2) are copolymerized. When polymerization control is difficult due to the heat of polymerization, the heat of polymerization can be reduced by using a chain transfer agent. The chain transfer agent is not particularly limited, and 2, 4-diphenyl-4-methyl-1-pentene may be suitably used.
It is preferable to use 80 parts by weight or more of the reaction solvent based on 100 parts by weight of the solute because the reaction proceeds smoothly. The reaction is carried out for 0.2 to 20 hours at the temperature of between 40 and 200 ℃.
The radical polymerization is preferably carried out at a reaction temperature of 40 to 120 ℃ and more preferably at a reaction temperature of 60 to 80 ℃.
The weight average molecular weight of the copolymer obtained is preferably 1,000 to 1,000,000, more preferably 3,000 to 500,000. When the content is in these ranges, the coating property and the flatness are good.
The weight average molecular weight herein is a value in terms of polystyrene determined by Gel Permeation Chromatography (GPC) (column temperature: 35 ℃ C., flow rate: 1 ml/min). The standard polystyrene is measured using polystyrene having a molecular weight of 645 to 132,900 (e.g., calibration kit (PL 2010-0102) from Agilent Technologies, Inc.), a column using PL gel mixing (PLgel MIXED) -D (Agilent Technologies, Inc.), and Tetrahydrofuran (THF) as a mobile phase. The weight average molecular weight of a commercially available product in the present specification is a value described in a catalog (catalog).
1-2. Compound (B) having three or more epoxy groups
The epoxy compound used in the present invention is a compound having three or more epoxy groups per molecule. The epoxy compound (B) may be one kind or two or more kinds.
1-2-1 examples of Compound (B) having three or more epoxy groups
Examples of the compound (B) having three or more epoxy groups include: teckomo (TECHMORE) VG3101L (trade name, PrINATAIC (Printec) Inc.); EHPE3150 (trade name, xylonite (Daicel) corporation); EPPN-501H, EPPN-502H (all trade names, Nippon chemical Co., Ltd.); jER 1032H60 (trade name, mitsubishi chemical corporation); danacol (Denacol) EX-313, danacol (Denacol) EX-314, danacol (Denacol) EX-321, danacol (Denacol) EX-411, danacol (Denacol) EX-421, danacol (Denacol) EX-512, danacol (Denacol) EX-521, danacol (Denacol) EX-612, danacol (Denacol) EX-614B, danacol (Denacol) DLC-302, danacol (Denacol) DLC-402 (trade name, long chemical into (Nagase cheex) stock limited); NC-3000, NC-3000-L, NC-3000-H, NC-3100 (trade name, Nippon chemical Co., Ltd.); EPPN-201 (trade name, Nippon chemical Co., Ltd.); jER 152, jER 154 (both trade names, Mitsubishi chemical Co., Ltd.); EOCN-102S, EOCN-103S, EOCN-104S, EOCN-1020 (all trade names, Nippon chemical Co., Ltd.); jER 157S65, jER 157S70 (both trade names, Mitsubishi chemical Co., Ltd.); 1, 3-bis [2- (3, 4-epoxycyclohexyl) ethyl ] tetramethyldisiloxane (trade name, Gelest Incorporated); TSL9906 (trade name, maiden Performance Materials, llc); cooteosil (COATOSIL) MP200 (trade name, Japan mai-shogaku (Momentive Performance Materials Japan) llc); empty-Per-Sichuan-base (Cone.g., Suppon-base No. SQ506 (Conona) SQ 506; ES-1023 (trade name, shin-Etsu chemical industries, Ltd.).
Further, Techmoto (TECHMORE) VG3101L (trade name, Printtaceae (Printec) Inc.) is a mixture of 2- [4- (2, 3-epoxypropoxy) phenyl ] -2- [4- [1, 1-bis [4- (2, 3-epoxypropoxy) phenyl ] ethyl ] phenyl ] propane and 1, 3-bis [4- [1- [4- (2, 3-epoxypropoxy) phenyl ] -1-methylethyl ] phenyl ] ethyl ] phenoxy ] -2-propanol; EHPE3150 (trade name, Daicel, Inc.) is a1, 2-epoxy-4- (2-oxetanyl) cyclohexane adduct of 2, 2-bis (hydroxymethyl) -1-butanol, and Cottosil (COATASIL) MP200 (trade name, Momentive Performance Materials, Inc.) is a polymer using 3-glycidoxypropyltrimethoxysilane as a raw material component.
1-2-2 proportion of Compound (B) having three or more epoxy groups to copolymer (A)
The thermosetting composition of the present invention contains 10 to 500 parts by weight of the total amount of the compound (B) having three or more epoxy groups per 100 parts by weight of the copolymer (a). When the proportion of the total amount of the compound (B) having three or more epoxy groups is in the above range, the balance among flatness, heat resistance, chemical resistance and substrate adhesiveness is good. The total amount of the compound (B) having three or more epoxy groups is preferably in the range of 50 to 300 parts by weight, and is determined by adjusting the molar ratio to the copolymer and the epoxy curing agent.
1-3. Compound (C) having four or more (meth) acryloyl groups
The compound having a (meth) acryloyl group used in the present invention is a compound having four or more (meth) acryloyl groups per molecule. The compound (C) may be one or two or more.
1-3-1 examples of Compounds having four or more (meth) acryloyl groups
Specific examples of the compound (C) in the present invention include: pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, alkyl-modified dipentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, caprolactone-modified dipentaerythritol hexa (meth) acrylate, polyacid-modified (meth) acryloyl oligomer, polyester tetraacrylate, polyester pentaacrylate, polyester hexaacrylate, polyfunctional urethane acrylate oligomer, and the like.
These compounds may be used alone or in combination of two or more. In addition to these compounds, compounds having a (meth) acryloyl group having a trifunctional or lower functionality may be used within a range not impairing the characteristics of the present invention.
Among the compounds having four or more (meth) acryloyl groups, pentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, polyacid-modified (meth) acryloyl oligomer, or a mixture of these compounds is preferably used from the viewpoint of heat resistance and chemical resistance of the cured film.
As pentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, polyacid-modified (meth) acryloyl oligomer, or a mixture of these compounds, the following commercially available products can be used.
A specific example of pentaerythritol tetraacrylate is M-450 (trade name; Toyo Synthesis Co., Ltd., trimer < 10%). Specific examples of the mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate are arinex (Aronix) M-403 (pentamer 50-60 wt%), arinex (Aronix) M-400 (pentamer 40-50 wt%), arinex (Aronix) M-402 (pentamer 30-40 wt%), arinex (Aronix) M-404 (pentamer 30-40 wt%), arinex (Aronix) M-406 (pentamer 25-35 wt%), and arinex (Aronix) M-405 (pentamer 10-20 wt%) (both trade names; synthetic products of east asia, inc., numerical values are cited). Specific examples of the polyacid-modified (meth) acryloyl oligomer include Aronix M-510 and Aronix M-520 (trade names; Toyo Synthesis Co., Ltd.).
1-3-2. proportion of Compound (C) having four or more (meth) acryloyl groups to copolymer (A)
The proportion of the total amount of the compound (C) having four or more (meth) acryloyl groups in the thermosetting composition of the present invention is 50 to 300 parts by weight relative to 100 parts by weight of the copolymer (a). When the proportion of the total amount of the compound (C) having four or more (meth) acryloyl groups is in the above range, the balance among flatness, heat resistance, chemical resistance, and substrate adhesiveness is good. The total amount of the compound (C) having four or more (meth) acryloyl groups is preferably in the range of 50 to 200 parts by weight, and the total amount is determined by adjusting the molar ratio to the copolymer and the epoxy hardener.
1-4. solvent (D)
In the thermosetting composition of the present invention, a solvent may be added. The solvent (D) added to the composition of the present invention is preferably a solvent in which the copolymer (a), the compound (B) having three or more epoxy groups, and the compound (C) having four or more (meth) acryloyl groups are soluble. Specific examples of the solvent are ethyl acetate, butyl acetate, propyl acetate, butyl propionate, ethyl lactate, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, 3-methoxybutyl acetate, methyl 3-oxopropionate, ethyl 3-hydroxypropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl 2-hydroxypropionate, propyl 2-hydroxypropionate, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, methyl 2-hydroxy-2-methylpropionate, methyl lactate, methyl methoxyacetate, ethyl methoxyacetate, butyl propionate, butyl lactate, ethyl ethoxyacetate, ethyl 3-methoxypropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 2-hydroxypropionate, methyl 2-ethoxypropionate, methyl 2-hydroxypropionate, methyl acetate, ethyl lactate, ethyl ethoxypropionate, ethyl propionate, ethyl 2-ethoxypropionate, ethyl propionate, and the like, Ethyl 2-hydroxy-2-methylpropionate, methyl 2-methoxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutyrate, ethyl 2-oxobutyrate, 4-hydroxy-4-methyl-2-pentanone, 1, 4-butanediol, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, ethylene glycol monobutyl ether acetate, cyclohexanone, cyclopentanone, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, diethylene glycol methyl 2-ethoxy-2-methylpropionate, methyl pyruvate, ethyl 1, 4-hydroxy-4-methyl-2-pentanone, 1, 4-butanediol, propylene glycol monomethyl ether acetate, propylene glycol monoethyl acetate, ethylene glycol monobutyl ether acetate, and methyl ether acetate, Diethylene glycol dimethyl ether, diethylene glycol diethyl ether and diethylene glycol methyl ethyl ether. The solvent may be one of these solvents, or may be a mixture of two or more of these solvents.
The solvent (D) and the solvent used in the synthesis of the copolymer (a) described above may be a common compound. Therefore, the reaction solvent used in the synthesis of the copolymer (a) may be used as it is as the solvent (D), or after the synthesis, the reaction solvent may be distilled off under reduced pressure, and the residue may be dissolved in another solvent (D) and supplied to the thermosetting composition of the present invention.
1-5. other ingredients
Various additives may be added to the thermosetting composition of the present invention to improve coating uniformity, adhesion, transparency, flatness and chemical resistance. The additives can be mainly listed as follows: a solvent; an anionic, cationic, nonionic, fluorine-based or silicon-based leveling agent/surfactant; adhesion improving agents such as silane coupling agents; antioxidants such as hindered phenol compounds, hindered amine compounds, phosphorus compounds and sulfur compounds; a molecular weight regulator; an epoxy hardener.
1-5-1. surfactant
In the thermosetting composition of the present invention, a surfactant may be added to improve coating uniformity. Specific examples of the surfactant include: polyflow No.75, Polyflow No.90, Polyflow No.95, Disperbyk 161, Disperbyk 162, Disperbyk 163, Disperbyk 164, Disperbyk 166, Disperbyk 170, Disperbyk 180, Disperbyk 181, Disperbyk 300, BYK-306, BYK-310, BYK-320, BYK-330, BYK-346, BYK-182, BYK-361N, BYK, UV-3578, and UV-3500, Japan K-342, BYK-361, BYK-341, BYK-N, BYK, Japan K-8970, Japan K-K, KP-368, KF-96-50CS, KF-50-100CS (all trade names, shin-Etsu Chemical industries, Ltd.), Sanflon (Surflon) -S611 (trade names, AGC Seimi Chemical industries, Ltd.), Forget (Ftergent)222F, Forget (Ftergent)208G, Forget (Ftergent)251, Forget (Ftergent)710FL, Forget (Ftergent)710FM, Forget (Ftergent)710FS, Forget (Ftergent)601AD, Forget (Ftergent)602A, Forget (Ftergent)650A, FTX-218 (all trade names, Nioos (Neos) Ltd.), Meijiafa (Megafac) F-410, Meijiafa) F-430, Meijiafa (Megaac) 477, Megac-F-475, Megac F-475, Megafac (Megafac) F-552, Megafac (Megafac) F-553, Megafac (Megafac) F-554, Megafac (Megafac) F-555, Megafac (Megafac) F-556, Megafac (Megafac) F-558, Megafac (Megafac) F-559, Megafac (Megafac) R-94, Megafac (Megafac) RS-75, Megafac (Megafac) RS-72-K, Megafac (Megafac) RS-76-NS, Megafac (Megafac) DS-21 (both trade names, Teson (Teflonic) (Takayasu Co., Ltd.), Digo Gatwin 4000, EvGatwain (Teflondin) 4100, Fedo (Teddy) Flow), Teddy (Teddy) 440, Tandy (Teddy) Tandy (Tanke) 450, Japanese Tandy (Tandy) Rad., Fluoroalkyl benzenesulfonate, fluoroalkyl carboxylate, fluoroalkyl polyoxyethylene ether, fluoroalkyl ammonium iodide, fluoroalkyl betaine, fluoroalkyl sulfonate, diglyceryl tetrakis (fluoroalkyl polyoxyethylene ether), fluoroalkyl trimethylammonium salt, fluoroalkyl sulfamate, polyoxyethylene nonylphenyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene alkyl ether, polyoxyethylene lauryl ether, polyoxyethylene oleyl ether, polyoxyethylene tridecyl ether, polyoxyethylene cetyl ether, polyoxyethylene stearyl ether, polyoxyethylene laurate, polyoxyethylene oleate, polyoxyethylene stearate, polyoxyethylene laurylamine, sorbitan laurate, sorbitan palmitate, sorbitan stearate, sorbitan oleate, sorbitan fatty acid ester, polyoxyethylene sorbitan laurate, polyoxyethylene sorbitan palmitate, fluoroalkyl iodide, fluoroalkyl betaine, and fluoroalkyl betaine, Polyoxyethylene sorbitan stearate, polyoxyethylene sorbitan oleate, polyoxyethylene naphthyl ether, alkylbenzene sulfonate and alkyl diphenyl ether disulfonate. It is preferable to use at least one selected from these surfactants.
Among these surfactants, when at least one selected from BYK-306, BYK-342, BYK-346, KP-341, KP-368, sandofan (Surflon) -S611, Forgelite (Ftergent)710FL, Forgelite (Ftergent)710FM, Forgelite (Ftergent)710FS, Forgelite (Ftergent)601AD, Forgelite (Ftergent)650A, Megafac (Megafac) F-477, Megafac (Megafac) F-556, Megafac (Megafac) F-559, Megafac (Megafac) RS-72-K, Megafac) DS-21, Digatun (TEGO) 4000, fluoroalkyl benzenesulfonate, fluoroalkyl carboxylate, fluoroalkyl polyoxyethylene ether, fluoroalkyl sulfonate, fluoroalkyl trimethylammonium salt, and fluoroalkyl sulfamate is used, the uniformity of the thermosetting composition is preferably high.
The content of the surfactant in the thermosetting composition of the present invention is preferably 0.01 to 10 parts by weight based on the total amount of the thermosetting composition.
1-5-2. coupling agent
The thermosetting composition of the present invention may further contain a coupling agent from the viewpoint of further improving the adhesion between the formed cured film and the substrate.
As such a coupling agent, for example, a silane-based, aluminum-based, or titanate-based coupling agent can be used. Specifically, there may be mentioned: 3-glycidoxypropyldimethylethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltrimethoxysilane (for example, trade name; Salai-Ace S510, Jieynzi (JNC) Co., Ltd.), silane-based coupling agents such as 2- (3, 4-epoxycyclohexyl) ethyltrimethoxysilane (for example, trade name; sala (Sila-Ace) S530, Jienwis (JNC) gmbh), 3-mercaptopropyltrimethoxysilane (for example, trade name; sala (Sila-Ace) S810, Jienwis (JNC) gmbh), a copolymer of 3-glycidoxypropyltrimethoxysilane (for example, trade name; cowasto (coat) MP200, Japan maiden material Japan) and the like); aluminum-based coupling agents such as aluminum acetyl alkoxy diisopropoxide; and titanate coupling agents such as tetraisopropylbis (dioctyl phosphite) titanate.
Among these coupling agents, 3-glycidoxypropyltrimethoxysilane is preferable because it has a large effect of improving adhesion.
In order to improve the adhesion between the formed cured film and the substrate, the content of the coupling agent is preferably 0.01 parts by weight or more and 10 parts by weight or less based on the total amount of the thermosetting composition.
1-5-3 antioxidant
The thermosetting composition of the present invention may further contain an antioxidant from the viewpoint of improving transparency and preventing yellowing of the cured film when exposed to high temperatures.
The thermosetting composition of the present invention may contain an antioxidant such as a hindered phenol compound, a hindered amine compound, a phosphorus compound or a sulfur compound. Among them, from the viewpoint of weather resistance, hindered phenol type is preferable. Specific examples thereof include: xylol-jiano (Irganox)1010, xylol-jiano (Irganox)1010FF, xylol-jiano (Irganox)1035FF, xylol-jiano (Irganox)1076FD, xylol-jiano (Irganox)1098, xylol-jiano (Irganox)1135, xylol-jiano (Irganox)1330, xylol-jiano (Irganox)1726, xylol-jiano (Irganox)1425WL, xylol-jiano (Irganox)1520L, xylol-jiano (Irganox)245, xylol-jiano (Irganox) FF 245, xylol-jiano (Irganox) 311259, xylol-jiano (Irganox)3114, irgao-yako (irgao) 565, bas (irgao f) and/or bas); addicotabo (ADK STAB) AO-20, Addicotabo (ADK STAB) AO-30, Addicotabo (ADK STAB) AO-50, Addicotabo (ADK STAB) AO-60, Addicotabo (ADK STAB) AO-80 (all trade names, Addick (ADEKA) GmbH). Among them, more preferred are Irganox 1010 and Addicusta wave (ADK STAB) AO-60.
0.1 to 10 parts by weight of an antioxidant is added to the total amount of the thermosetting composition.
1-5-4 epoxy hardener
The composition of the present invention may further contain an epoxy hardener for the purpose of improving flatness and chemical resistance. Examples of the epoxy hardener include acid anhydride hardeners, amine hardeners, phenol hardeners, imidazole hardeners, DBU salt hardeners, pyrazole hardeners, triazole hardeners, and heat-sensitive acid generators such as sulfonium salts (sulfonium salts), benzothiazolium salts, ammonium salts, and phosphonium salts, and from the viewpoint of preventing coloration of a cured film and reliability of a cured film, acid anhydride hardeners, imidazole hardeners, or a combination of an acid anhydride hardener and an imidazole hardener are preferable.
Specific examples of the acid anhydride-based curing agent include aliphatic dicarboxylic acid anhydrides such as maleic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, and hexahydrotrimellitic anhydride; aromatic polycarboxylic acid anhydrides such as phthalic anhydride and trimellitic anhydride; and styrene-maleic anhydride copolymers. Among these acid anhydride-based curing agents, trimellitic anhydride and hexahydrotrimellitic anhydride, which have a good balance between heat resistance and solubility in solvents, are preferable.
Specific examples of the imidazole-based hardener include 2-undecylimidazole, 2-heptadecylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 2, 3-dihydro-1H-pyrrolo [1,2-a ] benzimidazole, 1-cyanoethyl-2-undecylimidazolium trimellitate, 1-benzyl-2-methylimidazole and 1-benzyl-2-phenylimidazole. Among these imidazole-based curing agents, 2-undecylimidazole, 2-phenyl-4-methylimidazole and 1-benzyl-2-phenylimidazole, which have a good balance between curing properties and solubility in solvents, are preferable.
In the case of using the epoxy hardener, the ratio of the epoxy hardener to 100 parts by weight of the compound (B) having three or more epoxy groups is 0.1 to 60 parts by weight. The amount of the epoxy hardener added when it is an acid anhydride hardener is preferably 0.1 to 1.5 equivalents of carboxylic acid anhydride groups or carboxyl groups in the epoxy hardener to epoxy groups. In this case, the carboxylic anhydride group is calculated as divalent. It is more preferable to add the carboxylic anhydride group or the carboxyl group so as to have an equivalent amount of 0.15 to 0.8 times, because the chemical resistance is further improved.
1-5-5 ultraviolet absorbent
The thermosetting composition of the present invention may contain an ultraviolet absorber from the viewpoint of further improving the deterioration suppressing ability of the formed transparent film.
Specific examples of the ultraviolet absorber include Bin P, Bin (TINUVIN)120, Bin (TINUVIN)144, Bin (TINUVIN)213, Bin (TINUVIN)234, Bin (TINUVIN)326, Bin (TINUVIN)571, and Bin (TINUVIN)765 (both trade names, BASF corporation, Japan).
0.01 to 10 parts by weight of an ultraviolet absorber is added to the total amount of the thermosetting composition.
1-5-6. anti-coagulating agent
The composition of the present invention may contain an anti-agglomerating agent from the viewpoint of preventing agglomeration without fusing the solid component with the solvent.
Specific examples of the anti-agglomerating agent are Dipper (Disperbyk) -145, Dipper (Disperbyk) -161, Dipper (Disperbyk) -162, Dipper (Disperbyk) -163, Dipper (Disperbyk) -164, Dipper (Disperbyk) -182, Dipper (Disperbyk) -184, Dipper (Disperbyk) -185, Dipper (Disperbyk) -2163, Dipper (Disperbyk) -2164, BYK-220S, Dipper (Disperbyk) -2015191, Dipper (Disperbyk) -199, all of which are tradenames; Nippon chemical company, Chemie Japan, Japan); FTX-218, Forget (Ftergent)710FM, Forget (Ftergent)710FS (all trade names, Nioos (Neos) Inc.); floron G-600 and Floron G-700 (trade names, Kyoto chemical Co., Ltd.).
0.01 to 10 parts by weight of an anti-coagulating agent is added to the total amount of the thermosetting composition.
1-5-7. thermal cross-linking agent
The composition of the present invention may contain a thermal crosslinking agent from the viewpoint of further improving heat resistance, chemical resistance, uniformity within the film surface, flexibility and elasticity.
Specific examples of thermal crosslinkers are nicardlac (Nikalac) MW-30HM, nicardlac (Nikalac) MW-100LM, nicardlac (Nikalac) MX-270, nicardlac (Nikalac) MX-280, nicardlac (Nikalac) MX-290, nicardlac (Nikalac) MW-390, and nicardlac (Nikalac) MW-750LM (all trade names, three and chemical (strand)).
0.1 to 10 parts by weight of a thermal crosslinking agent is added to the total amount of the composition.
1-6 preservation of thermosetting composition
The thermosetting composition of the present invention has good stability with time when stored at-30 to 25 ℃. When the storage temperature is from-20 ℃ to 10 ℃, precipitates are not present and are more preferred.
2. Cured film of thermosetting composition
The thermosetting composition of the present invention is prepared by mixing the copolymer (a), the compound (B) having three or more epoxy groups, the compound (C) having four or more (meth) acryloyl groups, and the solvent (D), and if necessary, an epoxy curing agent, a surfactant, an adhesion improver, an antioxidant, and other additives may be further added according to the desired characteristics.
The thermosetting composition prepared as described above is applied to the surface of a substrate, and the solvent is removed by heating or the like, for example, to form a coating film. The thermosetting composition can be applied to the surface of the substrate by forming a coating film by a conventionally known method such as a spin coating method, a roll coating method, a dipping method, or a slit coating method. Then, the coating film is temporarily calcined by a hot plate, an oven, or the like. The temporary calcination conditions vary depending on the kind and blending ratio of each component, and are usually 70 to 150 ℃,5 to 15 minutes if an oven is used, and 1 to 5 minutes if a hot plate is used. Thereafter, main firing is performed to harden the coating film. The conditions for the main calcination vary depending on the kind and the blending ratio of each component, and the hardened film can be obtained by performing a heat treatment at 180 to 250 ℃, preferably 200 to 250 ℃, for 30 to 90 minutes if an oven is used, or for 5 to 30 minutes if a hot plate is used.
The cured film obtained in the above manner is very tough and excellent in transparency, heat resistance, chemical resistance, flatness, and adhesion because the copolymer (a) thermally reacts with the compound (B) having three or more epoxy groups and the compound (C) having four or more (meth) acryloyl groups to form a three-dimensional network when heated. For the same reason, excellent light resistance, sputtering resistance, scratch resistance, and coatability are also expected. Therefore, the cured film of the present invention is effective as a protective film for a color filter, and a liquid crystal display element or a solid-state imaging element can be manufactured using the color filter. In addition to the protective Film for a color filter, the cured Film of the present invention is also effective as a transparent insulating Film formed between a Thin Film Transistor (TFT) and a transparent electrode or between a transparent electrode and an alignment Film. Further, the cured film of the present invention is effective as a protective film for a Light Emitting Diode (LED) Light emitter.
[ examples ]
The present invention will be specifically described with reference to synthesis examples, examples and comparative examples, but the present invention is not limited to these examples.
For each component, compounds used in synthesis examples, and comparative examples are described.
Synthesis example 1 Synthesis of copolymer (A1) solution
Methyl 3-methoxypropionate (MMP), N-cyclohexylmaleimide, maleic anhydride, a radical initiator V-65 (manufactured by Wako pure chemical industries, Ltd.), and an α -methylstyrene dimer were charged in the following weight amounts in a four-necked flask with a stirrer, and heated and stirred at 80 ℃ for 2 hours under a dry nitrogen gas flow to obtain a radical copolymer.
Figure BDA0002016418810000161
The polymerization solution was cooled to room temperature, thereby obtaining a 30% by weight solution of a pale yellow transparent copolymer (A1). A portion of the solution was sampled and the weight average molecular weight was determined by GPC analysis (polystyrene standards). As a result, the weight-average molecular weight Mw of the obtained copolymer (A1) was 13,000.
Synthesis examples 2 to 5 Synthesis of solutions of copolymers (A2) to (A5)
According to the method of synthesis example 1, the components were reacted at the temperatures, times and proportions (unit: g) described in table 1 to obtain solutions of copolymers (a2) to (a 5).
Comparative Synthesis example 1 Synthesis of polymethacrylate (R1) solution
A (R1) solution was obtained by reacting a general epoxy group-containing polymethacrylate having no specific structure included in the claims at the temperature, time and ratio shown in table 1. Wherein the reaction temperature was 80 ℃ and was carried out for 2 hours.
TABLE 1
Figure BDA0002016418810000171
Unit of charged amount: keke (Chinese character of 'Keke')
The compounds used in synthesis examples and comparative synthesis examples, which are described in table 1 in short, are as follows.
MMP: 3-Methoxypropionic acid methyl ester
CHMI: n-cyclohexyl maleimide
NPM: n-phenylmaleimide
IN: indene
MAH: maleic anhydride
V-65: 2,2' -azobis (2, 4-dimethylvaleronitrile); heguang pure chemical industry (stock) manufacturing
α -MSD: alpha-methylstyrene dimer
GMA: glycidyl methacrylate
MMA: methacrylic acid methyl ester
[ example 1]
A 30 wt% solution of the copolymer (a1) obtained in synthesis example 1, VG3101L as a trifunctional epoxy compound, trimellitic anhydride (TMA) as a curing agent, S510 as a silane coupling agent, F-556 as a surfactant, and Propylene Glycol Monomethyl Ether Acetate (PGMEA) as a diluent solvent were mixed and dissolved in the proportions (parts by weight) described in table 2, and filtered through a membrane filter (pore size 0.2 μm) to obtain a thermosetting composition.
Examples 2 to 7 and comparative example 1
The components were mixed and dissolved in the proportions (parts by weight) shown in table 2 by the method of example 1 to obtain a thermosetting composition. The gas barrier property, viscosity, planarization rate, substrate adhesion property, and heat resistance were measured by the method of example 1, and the evaluation results are shown in table 3.
TABLE 2
Figure BDA0002016418810000181
Unit: parts by weight (excluding surfactants)
The obtained thermosetting compositions were used to evaluate heat resistance, planarization rate, and substrate adhesion by the following methods. The evaluation results of the cured films of examples 1 to 7 are summarized in table 3. In comparative example 1, the heat resistance, flattening rate, and substrate adhesion of a cured film formed using a general thermosetting composition containing a linear polyester having an unbranched structure were evaluated. The evaluation results are also shown in table 3.
[ method for evaluating gas Barrier Property ]
A thermosetting composition was spin-coated on a substrate having a color filter of RGB pixels under an ultraviolet-visible near-infrared spectrophotometer (trade name: V-670, manufactured by Nippon Denshoku Co., Ltd.) at 600rpm for 10 seconds, and pre-baked on a heating plate at 90 ℃ for 2 minutes. Then, post-baking was performed at 230 ℃ for 30 minutes in an oven, thereby obtaining a color filter substrate with a cured film having an average film thickness of a protective film of 1.5 μm.
Then, a predetermined amount of 1-methyl-2-pyrrolidone was dropped on the color filter with a cured film, and a cover glass covering 60% of the area of the color filter substrate with a cured film was set on the color filter substrate with a cured film, and heated at 160 ℃ for 5 minutes using a hot plate. After heating, the cover glass is removed, the cover glass and the color filter substrate with the hardened film are cleaned by a certain amount of 1-methyl-2-pyrrolidone, and the cleaning solution is set as a dissolution solution of the color filter substrate with the hardened film.
Then, the transmittance of the dissolution liquid was measured by the ultraviolet-visible near-infrared spectrophotometer using 1-methyl-2-pyrrolidone as a reference sample. From the measurement results, the case where the 560nm transmittance was 90% or more was regarded as "o", and the case where the transmittance was less than 90% was regarded as "x".
[ evaluation method of tackiness ]
The thermosetting composition was spin-coated on a glass substrate at 600rpm for 10 seconds, and pre-baked on a heating plate at 90 ℃ for 2 minutes. When the surface of the coating film was touched with a finger, the case where no trace of the finger remained on the surface was indicated by "o", and the case where the surface was liquid and the trace of the finger remained was indicated by "x".
[ method for evaluating flatness ]
The obtained thermosetting composition was spin-coated on an uneven substrate (pattern substrate having a line of 100 μm, a space of 50 μm and a film thickness of 1 μm) having a resist pattern whose surface level difference was measured in advance using a level difference/surface roughness/fine shape measuring apparatus (trade name; P-17, KLA Tencor, Ltd.) for 10 seconds at 650rpm, and pre-baked on a hot plate at 80 ℃ for 2 minutes. Then, post-baking was performed at 230 ℃ for 30 minutes in an oven, thereby obtaining a color filter substrate with a cured film having an average film thickness of a protective film of 1.5 μm. Thereafter, the obtained color filter substrate with the cured film was measured for surface level differences. The planarization ratio was calculated from the maximum value of the surface level difference (hereinafter, abbreviated as "maximum level difference") of the color filter substrate without a cured film and the color filter substrate with a cured film by using the following calculation formula, and the results are shown in table 3. As for the flatness results, 100% to 80% were evaluated as ∈, 79% to 60% were evaluated as ∈, and less than 60% were evaluated as ×.
The planarization ratio (%) ((maximum step of uneven substrate-maximum step of uneven substrate with cured film)/maximum step of uneven substrate) × 100
[ method of evaluating adhesion ]
The obtained thermosetting composition was spin-coated on an uneven substrate (line: 100 μm, space: 50 μm, film thickness: 1.0 μm) at 650rpm for 10 seconds, and pre-baked on a hot plate at 80 ℃ for 2 minutes. Subsequently, the substrate was post-baked in an oven at 230 ℃ for 30 minutes, thereby obtaining a concave-convex substrate with a cured film. The obtained uneven substrate with a cured film and the glass substrate with a cured film produced in the same manner were subjected to a cross-cut test (Japanese Industrial Standards (JIS) K5400, peeling tape: manufactured by 3M No.361) according to the following classifications 0 to 5, and evaluated, with classification 0 to 1 being O, classification 2 to 3 being Delta, and classification 4 to 5 being X. The adhesion evaluation of the uneven substrate with the cured film was designated as "adhesion 1", and the adhesion evaluation of the glass substrate with the cured film was designated as "adhesion 2".
The cut edges are completely smooth and there is no peeling in the grid of any grid.
< classification 1 >. Small peeling of the coating film at the intersection of the cuts. In the cross-cut portion, the affected portion does not definitely exceed 5%.
< classification 2 >. the coating film peels off along the cut edges and/or at the intersections. In the cross-cut section, the affected part clearly exceeded 5% but not 15%.
The coating film is peeled off locally or entirely along the cut edge, and/or a plurality of portions of the mesh are peeled off locally or entirely. In the cross-cut section, the affected part clearly exceeds 15% but not 35%.
The coating film is peeled off locally or entirely along the cut edge, and/or the mesh at a plurality of positions is peeled off locally or entirely. In the cross-cut portion, the affected portion does not definitely exceed 35%.
< category 5 >. any degree of exfoliation that cannot be classified even for category 4.
[ method for evaluating Heat resistance ]
The thermosetting composition was spin-coated on a glass substrate at 600rpm for 10 seconds, and pre-baked on a heating plate at 90 ℃ for 2 minutes. Then, the glass substrate was post-baked in an oven at 230 ℃ for 30 minutes, thereby obtaining a hardened film-attached glass substrate (the post-PB film thickness). The obtained glass substrate with a cured film was measured for film thickness using a level difference/surface roughness/fine shape measuring apparatus (trade name; P-17, KLA TENCOR corporation) and set as an initial film thickness. Thereafter, the glass substrate with the cured film was baked in an oven at 230 ℃ for 60 minutes, and the film thickness was measured in the same manner (this was referred to as the post-EB film thickness). The residual film ratio was calculated by using the following formula, and the value with a residual film ratio between PB-EB of 98% or more was rated as "O", and the value with a residual film ratio less than 98% was rated as "X".
Residual film ratio (%) - (film thickness after EB/film thickness after PB) × 100
[ method for evaluating transparency ]
The obtained thermosetting composition was spin-coated on a glass substrate at 650rpm for 10 seconds and pre-baked on a hot plate at 80 ℃ for 2 minutes. Then, the glass substrate with the hardened film was heat-treated in an oven at 230 ℃ for 30 minutes to obtain a glass substrate with a film thickness of 1.5 μm. The light transmittance at 400nm of the cured film was measured with respect to the obtained glass substrate with a cured film by means of an ultraviolet-visible near-infrared spectrophotometer (trade name; V-670, manufactured by Nippon Denshoku Co., Ltd.). In this case, only the glass substrate was used as a reference, and the light transmittance of the cured film alone was calculated (in this case, interference due to multiple reflections was not considered). The case where the light transmittance was 98% or more was evaluated as "transparency", the case where the transmittance was less than 95% was evaluated as "transparency", and the interval therebetween was evaluated as "Δ".
From the results shown in table 3 it is clear that: the thermosetting compositions of examples 1 to 7 satisfy heat resistance, flatness, and adhesion. On the other hand, in comparative example 1, all the characteristics could not be satisfied.
TABLE 3
Figure BDA0002016418810000221
[ industrial applicability ]
The cured film obtained from the thermosetting composition of the present invention is excellent in heat resistance, flatness, and substrate adhesion, and is useful as a protective film for various optical materials such as color filters, LED light-emitting elements, and light-receiving elements, and an insulating film formed between TFTs and transparent electrodes, and between transparent electrodes and an alignment film.

Claims (4)

1. A thermosetting composition comprising a copolymer (A) which is a reaction product of a monomer (a) and a monomer (B) other than the monomer (a), wherein the monomer (a) is maleic anhydride, the monomer (B) is at least one selected from the group consisting of a compound represented by the following formula (2) and indene:
Figure FDA0003373611780000011
in the formula (2), R1And R2Independently hydrogen, C1-3 alkyl or phenyl, R3Is a monovalent organic group.
2. The thermosetting composition according to claim 1, wherein the compound (B) having three or more epoxy groups is a compound having an aromatic ring.
3. A cured film formed from the thermosetting composition according to claim 1 or claim 2.
4. A color filter having the cured film according to claim 3 as a transparent protective film.
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