WO2024158012A1 - 透明樹脂組成物 - Google Patents
透明樹脂組成物 Download PDFInfo
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- WO2024158012A1 WO2024158012A1 PCT/JP2024/002073 JP2024002073W WO2024158012A1 WO 2024158012 A1 WO2024158012 A1 WO 2024158012A1 JP 2024002073 W JP2024002073 W JP 2024002073W WO 2024158012 A1 WO2024158012 A1 WO 2024158012A1
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- 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
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/38—Layered products comprising a layer of synthetic resin comprising epoxy resins
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- C—CHEMISTRY; METALLURGY
- 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
- C08G59/20—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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- C—CHEMISTRY; METALLURGY
- 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
- C08G59/20—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
- C08G59/22—Di-epoxy compounds
- C08G59/24—Di-epoxy compounds carbocyclic
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- C—CHEMISTRY; METALLURGY
- 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
- C08G59/20—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
- C08G59/22—Di-epoxy compounds
- C08G59/30—Di-epoxy compounds containing atoms other than carbon, hydrogen, oxygen and nitrogen
- C08G59/306—Di-epoxy compounds containing atoms other than carbon, hydrogen, oxygen and nitrogen containing silicon
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- C—CHEMISTRY; METALLURGY
- 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
- C08G59/20—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
- C08G59/22—Di-epoxy compounds
- C08G59/30—Di-epoxy compounds containing atoms other than carbon, hydrogen, oxygen and nitrogen
- C08G59/308—Di-epoxy compounds containing atoms other than carbon, hydrogen, oxygen and nitrogen containing halogen atoms
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- C—CHEMISTRY; METALLURGY
- 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
- C08G59/20—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
- C08G59/32—Epoxy compounds containing three or more epoxy groups
- C08G59/3218—Carbocyclic compounds
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- C—CHEMISTRY; METALLURGY
- 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
- C08G59/20—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
- C08G59/32—Epoxy compounds containing three or more epoxy groups
- C08G59/3254—Epoxy compounds containing three or more epoxy groups containing atoms other than carbon, hydrogen, oxygen or nitrogen
- C08G59/3281—Epoxy compounds containing three or more epoxy groups containing atoms other than carbon, hydrogen, oxygen or nitrogen containing silicon
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- C—CHEMISTRY; METALLURGY
- 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
- C08G59/20—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
- C08G59/32—Epoxy compounds containing three or more epoxy groups
- C08G59/3254—Epoxy compounds containing three or more epoxy groups containing atoms other than carbon, hydrogen, oxygen or nitrogen
- C08G59/329—Epoxy compounds containing three or more epoxy groups containing atoms other than carbon, hydrogen, oxygen or nitrogen containing halogen atoms
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/04—Coating
Definitions
- the present invention relates to a transparent resin composition.
- Transparent resin compositions are used as sealing materials and adhesive materials for transparent parts of electronic devices, including light-emitting diode (LED) devices and transparent flexible printed circuit boards (FPCs).
- LED light-emitting diode
- FPCs transparent flexible printed circuit boards
- Patent Document 1 discloses an example of such a transparent resin composition, which contains a bisphenol AF type epoxy resin, a thermoplastic resin, and a curing accelerator.
- Thermosetting resin compositions such as that described in Patent Document 1 may warp due to shrinkage during curing. For this reason, there is a demand for resin compositions that can form cured products with excellent warping suppression. There is also a demand for transparent resin compositions that can form cured products with excellent yellowing resistance for use in transparent parts of electronic devices such as LED devices and transparent FPCs.
- Methods for preventing warping include using inorganic fillers or flexible resins, but the former significantly reduces the transparency of the cured product, while the latter significantly reduces the glass transition temperature of the cured product, impairing its heat resistance.
- the present invention was made in light of the above-mentioned circumstances, and its purpose is to provide a transparent resin composition capable of forming a cured product that has excellent warping suppression, yellowing resistance, and heat resistance.
- the present invention capable of achieving the above object is as follows.
- the transparent resin composition according to the above [1] further comprising a polymer compound.
- the present invention makes it possible to obtain a transparent resin composition that can form a cured product that has excellent warping suppression, yellowing resistance, and heat resistance.
- the present invention comprises the following components (A) to (C):
- the present invention provides a transparent resin composition comprising (A) an epoxy resin having a fluoroalkyl group and/or an alicyclic structure and no siloxane structure, (B) an epoxy resin having a siloxane structure, and (C) a curing accelerator.
- each component may be used alone or in combination of two or more. The following describes the component (A) in order.
- Epoxy resin having a fluoroalkyl group and/or an alicyclic structure and no siloxane structure an epoxy resin having a fluoroalkyl group and/or an alicyclic structure and not having a siloxane structure is used as component (A).
- component (A) a cured product having excellent yellowing resistance can be formed.
- epoxy resin means a thermosetting compound having epoxy groups and an epoxy equivalent of 5,000 g/mol or less.
- epoxy equivalent of an epoxy resin means the number of grams of an epoxy resin containing 1 mol of epoxy groups (unit: g/mol). The value of the epoxy equivalent can be calculated according to the method specified in JIS K 7236. Theoretically, the epoxy equivalent can be calculated by dividing the molar mass (g/mol) of an epoxy resin by the number of epoxy groups that the resin has.
- the fluoroalkyl group that the component (A) may have is preferably a C 1-6 fluoroalkyl group, more preferably a C 1-6 perfluoroalkyl group, and particularly preferably a trifluoromethyl group.
- C xy (x and y: integers) means that the number of carbon atoms is x to y.
- fluoroalkyl group means an alkyl group substituted with a fluorine atom
- perfluoroalkyl group means an alkyl group in which all hydrogen atoms are substituted with fluorine atoms.
- examples of the "C 1-6 fluoroalkyl group” include a fluoromethyl group, a difluoromethyl group, a perfluoromethyl group (i.e., a trifluoromethyl group), a 2-fluoroethyl group, a 2,2,2-trifluoroethyl group, a perfluoroethyl group, a 2,2-difluoropropyl group, a perfluoropropyl group, a perfluorobutyl group, a perfluoropentyl group, and a perfluorohexyl group.
- examples of the "C 1-6 perfluoroalkyl group” include those perfluoroalkyl groups among the above examples of the "C 1-6 fluoroalkyl group”.
- the alicyclic structure that the component (A) may have is preferably a C 3-12 alicyclic structure.
- the alicyclic structure may be any of a monocyclic structure, a bicyclic structure, a condensed polycyclic structure, and a condensed polycyclic structure containing a bicyclic ring.
- the component (A) may have one type of alicyclic structure, or may have two or more types of alicyclic structures.
- the alicyclic structure that the component (A) may have is more preferably a C 3-8 cycloalkane ring structure and/or a dicyclopentadiene ring structure.
- the component (A) is more preferably an epoxy resin that has at least one selected from the group consisting of a fluoroalkyl group, a C 3-8 cycloalkane ring structure, and a dicyclopentadiene ring structure, and does not have a siloxane structure.
- examples of the "C 3-8 cycloalkane ring” include a cyclopropane ring, a cyclobutane ring, a cyclopentane ring, a cyclohexane ring, a cycloheptane ring, and a cyclooctane ring.
- the alicyclic structure that the component (A) may have is more preferably a C 5-6 cycloalkane ring structure (that is, a cycloheptane ring structure, a cyclohexane ring structure).
- An example of an epoxy resin that has a fluoroalkyl group and does not have a siloxane structure is a bisphenol AF type epoxy resin that has a trifluoromethyl group.
- the fluorine-containing epoxy resin described in WO2011/089947 can also be used as an epoxy resin that has a fluoroalkyl group and does not have a siloxane structure.
- "X type epoxy resin” (an example of X: bisphenol AF) means an epoxy resin that has a structure derived from X, as is well known in the field of epoxy resins.
- epoxy resins that have an alicyclic structure and no siloxane structure examples include bisphenol TMC type epoxy resins that have a cyclohexane ring structure and bisphenol Z type epoxy resins that have a cyclohexane ring structure.
- epoxy resins that have a cyclohexane ring structure and no siloxane structure e.g., Daicel's "EHPE3150"
- component (A) can also be used as component (A).
- the component (A) is (i)
- the epoxy resin has a fluoroalkyl group and does not have a siloxane structure and/or has an alicyclic structure and does not have a siloxane structure, (ii) More preferably, it is at least one selected from the group consisting of an epoxy resin having a C1-6 fluoroalkyl group and not having a siloxane structure, an epoxy resin having a C3-8 cycloalkane ring structure and not having a siloxane structure, and an epoxy resin having a dicyclopentadiene ring structure and not having a siloxane structure, (iii) More preferably, the epoxy resin is at least one selected from the group consisting of a bisphenol AF type epoxy resin, an epoxy resin having a cyclohexane ring structure and no siloxane structure, and an epoxy resin having a dicyclopentadiene ring structure and no siloxane structure, (iv)
- Component (A) may be a commercially available product, or may be produced by a known method (e.g., reaction of bisphenol AF, bisphenol TMC, or bisphenol Z with epichlorohydrin).
- Commercially available products of component (A) include, for example, Mitsubishi Chemical's "YX7760", “YX8000”, and “YX8034", Daicel's "EHPE3150”, “EHPE3150CE”, “Celloxide 2021P”, “Celloxide 2081P”, “Celloxide 2000”, and “Celloxide 8000", ADEKA's "EP-4088S”, and DIC's "HP- Examples include “7200”, “HP-7200L”, “HP-7200H”, "XD-1000” manufactured by Nippon Kayaku Co., Ltd., "Denacol EX-252" manufactured by Nagase ChemteX Corporation, “Shofree CDMDG” manufactured by Showa Denko K.K., "THI-DE", “DE-102”,
- the number of epoxy groups contained in the component (A) is preferably 2 to 10, and more preferably 2 to 4, from the viewpoints of adhesion strength and warping suppression of the cured product.
- the epoxy equivalent of the component (A) is preferably 50 to 5,000 g/mol, more preferably 80 to 2,000 g/mol, and even more preferably 100 to 1,500 g/mol.
- the content of component (A) is preferably 20 to 89 mass %, more preferably 25 to 80 mass %, and even more preferably 30 to 75 mass %, based on the non-volatile content of the transparent resin composition.
- the content refers to the total content of the multiple (A) components.
- the content of components other than component (A) when multiple components of that type are used, the content refers to the total content of those components.
- Epoxy resin having a siloxane structure an epoxy resin having a siloxane structure is used as the component (B).
- the stress of the transparent resin composition during heating can be alleviated, and a cured product having excellent warpage suppression can be formed.
- the component (B) is also effective in improving the yellowing resistance and heat resistance of the cured product.
- siloxane structure means a structure having a siloxane bond (Si-O-Si).
- the siloxane structure of component (B) may be linear, branched, or cyclic, preferably linear or cyclic, and more preferably linear.
- the linear siloxane structure that the component (B) may have is a linear polydi(C 1-6 alkyl)siloxane structure.
- the C 1-6 alkyl group (e.g., methyl group) in the siloxane structure may have a substituent.
- examples of the "C 1-6 alkyl group” include a methyl group, a dimethyl group, an ethyl group, a propyl group, a butyl group, a pentyl group and a hexyl group.
- the linear siloxane structure is preferably a polydimethylsiloxane structure.
- the methyl group in the polydimethylsiloxane structure may have a substituent.
- cyclic siloxane structure that component (B) can have include a hexa(C 1-6 alkyl)cyclotrisiloxane structure, an octa(C 1-6 alkyl)cyclotetrasiloxane structure, and a deca(C 1-6 alkyl)cyclopentasiloxane structure, with an octa(C 1-6 alkyl)cyclotetrasiloxane structure being preferred.
- the C 1-6 alkyl group e.g., a methyl group
- in the cyclic siloxane structure may have a substituent.
- the (B) component preferably has a glycidyl group.
- a (B) component having a glycidyl group has good compatibility with the (A) component, and by using a (B) component having a glycidyl group, a cured product with low haze and high transparency can be formed.
- the term "alicyclic epoxy group” refers to a condensed ring group consisting of an alicyclic group and an oxirane ring, in which two adjacent carbon atoms constituting the alicyclic group form an oxirane ring (epoxy group) with an oxygen atom.
- the component (B) is preferably a linear polydimethylsiloxane having an epoxy group and/or an octa(C 1-6 alkyl)cyclotetrasiloxane having an epoxy group, more preferably a linear polydimethylsiloxane having a glycidyl group and/or an octa(C 1-6 alkyl)cyclotetrasiloxane having a glycidyl group, and even more preferably a linear polydimethylsiloxane having a glycidyl group.
- the number of Si atoms in the siloxane structure of component (B) is preferably 2 to 12, and more preferably 2 to 8, from the standpoint of compatibility with component (A).
- the number of epoxy groups in one molecule of component (B) is preferably 2 to 10, and more preferably 2 to 4, from the viewpoints of adhesion strength and warping suppression of the cured product. From the viewpoint of adhesion strength of the cured product, the epoxy equivalent of the component (B) is preferably 100 to 350 g/mol, more preferably 120 to 330 g/mol, and even more preferably 150 to 300 g/mol.
- component (B) commercially available products may be used.
- Examples of commercially available products of component (B) include “X-22-163", “X-22-163A”, “X-22-163B”, “X-22-163C”, “X-22-169B”, “X-22-169AS”, "X-22-343", "X-22-2046", "X-22-2000", “X-40-2670", “X-40-2678", "X-40-2728", "KR-470", "KF-105", “KF-101", “KF-102", and “KF-1001” manufactured by Shin-Etsu Chemical Co., Ltd.
- the content of component (B) is preferably 0.1 to 20 mass %, more preferably 0.5 to 18 mass %, and even more preferably 1 to 15 mass %, based on the non-volatile content of the transparent resin composition.
- a curing accelerator is used as component (C).
- curing accelerator refers to an additive that accelerates the curing reaction between epoxy resins.
- curing agents particularly catalytic curing agents.
- curing accelerator (C) examples include phosphorus-based curing accelerators (e.g., phosphonium salts, phosphines), imidazole-based curing accelerators, amine-based curing accelerators, guanidine-based curing accelerators, and metal-based curing accelerators.
- phosphorus-based curing accelerators e.g., phosphonium salts, phosphines
- imidazole-based curing accelerators e.g., imidazole-based curing accelerators
- amine-based curing accelerators e.g., guanidine-based curing accelerators
- metal-based curing accelerators examples include metal-based curing accelerators.
- phosphonium salts include phosphonium borate compounds, tetraphenylphosphonium tetraphenylborate, n-butylphosphonium tetraphenylborate, tetrabutylphosphonium decanoate, (4-methylphenyl)triphenylphosphonium thiocyanate, tetraphenylphosphonium thiocyanate, and butyltriphenylphosphonium thiocyanate.
- Commercially available phosphonium salts can be used. An example of such a commercially available product is "TBP-DA" manufactured by Hokko Chemical Industry Co., Ltd.
- phosphines examples include triphenylphosphine, tricyclohexylphosphine, tributylphosphine, and methyldiphenylphosphine.
- Imidazole-based hardening accelerators include, for example, 2-methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-methylimidazole, 1-benzyl-2 -phenylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-undecylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-undecylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoeth
- Amine-based curing accelerators include, for example, trialkylamines such as triethylamine and tributylamine, 4-dimethylaminopyridine, benzyldimethylamine, 2,4,6-tris(dimethylaminomethyl)phenol, and 1,8-diazabicyclo(5,4,0)-undecene.
- guanidine-based curing accelerators include dicyandiamide, 1-methylguanidine, 1-ethylguanidine, 1-cyclohexylguanidine, 1-phenylguanidine, 1-(o-tolyl)guanidine, dimethylguanidine, diphenylguanidine, trimethylguanidine, tetramethylguanidine, pentamethylguanidine, 1,5,7-triazabicyclo[4.4.0]dec-5-ene, 7-methyl-1,5,7-triazabicyclo[4.4.0]dec-5-ene, 1-methylbiguanide, 1-ethylbiguanide, 1-n-butylbiguanide, 1-n-octadecylbiguanide, 1,1-dimethylbiguanide, 1,1-diethylbiguanide, 1-cyclohexylbiguanide, 1-allylbiguanide, 1-phenylbiguanide, and 1-(o-tolyl)biguan
- Metal-based curing accelerators include, for example, organometallic complexes or organometallic salts in which the metal is cobalt, copper, zinc, iron, nickel, manganese, or tin.
- Organometallic complexes include, for example, organocobalt complexes such as cobalt(II) acetylacetonate and cobalt(III) acetylacetonate, organocopper complexes such as copper(II) acetylacetonate, organozinc complexes such as zinc(II) acetylacetonate, organoiron complexes such as iron(III) acetylacetonate, organonickel complexes such as nickel(II) acetylacetonate, and organomanganese complexes such as manganese(II) acetylacetonate.
- Organometallic salts include, for example, zinc octoate, tin octoate,
- the content of component (C) is preferably 0.1 to 5 mass %, more preferably 0.3 to 4 mass %, and even more preferably 0.5 to 3 mass %, based on the non-volatile content of the transparent resin composition.
- a phosphonium salt as a curing accelerator.
- the content of the phosphonium salt in the transparent resin composition of the present invention is preferably 90 to 100 mass %, more preferably 95 to 100 mass %, based on the entirety of component (C).
- component (C) is a phosphonium salt, that is, the entirety of component (C) is made of a phosphonium salt.
- the transparent resin composition of the present invention may contain components other than the components (A) to (C) (sometimes abbreviated as "other components” in this specification) within the scope of not impairing the effects of the present invention.
- the other components include polymer compounds, epoxy resins other than the components (A) and (B), organic solvents, light stabilizers, silane coupling agents, antioxidants, and ultraviolet absorbers.
- the other components may each be used alone or in combination of two or more. The other components will be described below in order.
- polymer compound In order to form a film of a transparent resin composition, it is preferable to use a polymer compound.
- the term "polymer compound” means a compound having a weight average molecular weight (hereinafter sometimes abbreviated as "Mw") of 1,000 or more. This Mw can be measured by gel permeation chromatography (GPC).
- polymer compounds include phenoxy resin, polyester polyol, polyether polyol, polycarbonate polyol, (meth)acrylic resin, etc.
- the preferred Mw of the phenoxy resin will be described later.
- the Mw of the polyester polyol is preferably 1,000 to 10,000.
- the Mw of the polyether polyol is 1,000 to 10,000.
- the Mw of the polycarbonate polyol is 1,000 to 10,000.
- the Mw of the (meth)acrylic resin is preferably 1,000 to 500,000.
- the polymer compound is preferably a phenoxy resin.
- phenoxy resin refers to a high molecular weight polyhydroxy polyether having a structure derived from bisphenols.
- phenoxy resins include those obtained by reacting bisphenols with epichlorohydrin and those obtained by reacting bisphenol-type epoxy resins.
- bisphenol-type epoxy resin refers to an epoxy resin having a structure derived from bisphenols (e.g., bisphenol AF).
- the phenoxy resin may have a structure other than that derived from bisphenols.
- the phenoxy resin may or may not have an epoxy group.
- "phenoxy resin having an epoxy group” and "epoxy resin” are distinguished by the epoxy equivalent. That is, in the present invention, those with an epoxy equivalent exceeding 5000 g/mol are classified as "phenoxy resin having an epoxy group", and those with an epoxy equivalent of 5000 g/mol or less are classified as "epoxy resin”.
- the epoxy equivalent of the phenoxy resin having an epoxy group is preferably more than 5,000 g/mol and not more than 40,000 g/mol, more preferably 7,000 to 35,000 g/mol, and even more preferably 8,000 to 30,000 g/mol.
- the weight average molecular weight of the phenoxy resin is preferably more than 10,000 and not more than 100,000, more preferably 20,000 to 80,000, and even more preferably 25,000 to 60,000, from the viewpoints of compatibility in the transparent resin composition and adhesion strength of the cured product.
- the phenoxy resin may be a commercially available product, or may be one produced by a known method (e.g., reaction of bisphenols with epichlorohydrin).
- Commercially available products include, for example, "YX7200B35”, “1256”, “4250”, “YX8100”, “YX6954BH30", “YX7553BH30", “YL7769BH30", “YX7876B40", “YL9008B40", “YL6794", "YL7213", “YL7891BH30", and “YL7482” manufactured by Mitsubishi Chemical Corporation, and "YP-50", “YP-70S", “FX-293", and "FX280S” manufactured by Nippon Steel Chemical & Material Co., Ltd.
- phenoxy resin is (i) Preferably, the phenoxy resin has a fluoroalkyl group and/or the phenoxy resin has an alicyclic structure, (ii) More preferably, it is a phenoxy resin having a C 1-6 fluoroalkyl group and/or a phenoxy resin having a C 3-8 cycloalkane ring structure, (iii) Even more preferably, it is a phenoxy resin having a C1-6 perfluoroalkyl group and/or a phenoxy resin having a C5-6 cycloalkane ring structure, (iv) More preferably, it is a phenoxy resin having a trifluoromethyl group and/or a phenoxy resin having a cyclohexane ring structure, (v) Particularly preferred are bisphenol AF type phenoxy resins and/or phenoxy resins having a cyclohexane ring structure. (vi) A phenoxy resin having a C 1-6
- its content is preferably 5 to 50% by mass, more preferably 7.5 to 45% by mass, and even more preferably 10 to 40% by mass, based on the non-volatile content of the transparent resin composition, from the viewpoints of film formation of the transparent resin composition and adhesion strength of the cured product.
- the content of the phenoxy resin is preferably 5 to 50 mass %, more preferably 7.5 to 45 mass %, and even more preferably 10 to 40 mass %, based on the non-volatile content of the transparent resin composition, from the viewpoints of film formation of the transparent resin composition and adhesion strength of the cured product.
- the transparent resin composition of the present invention may contain epoxy resins other than the component (A) and the component (B) (sometimes abbreviated as "other epoxy resins" in this specification) as long as the effects of the present invention (i.e., suppression of warping, resistance to yellowing, and heat resistance) are not impaired.
- the other epoxy resin is not particularly limited, and known epoxy resins can be used.
- the other epoxy resins include bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, biphenyl type epoxy resin, biphenyl alkyl type epoxy resin, naphthol type epoxy resin, and naphthalene type epoxy resin.
- a mixture of multiple types of epoxy resins may be used as the other epoxy resin.
- the epoxy equivalent of the other epoxy resin is preferably 50 to 5,000 g/mol, more preferably 80 to 2,000 g/mol, and even more preferably 100 to 1,500 g/mol, from the viewpoint of the adhesion strength of the cured product of the transparent resin composition.
- the content is preferably 1 to 40% by mass, more preferably 5 to 35% by mass, and even more preferably 10 to 30% by mass, based on the non-volatile content of the transparent resin composition, so as not to impede the effects of the present invention.
- the transparent resin composition of the present invention preferably does not contain other epoxy resins or contains other epoxy resins in a content of 50 mass% or less based on the total of component (A), component (B), and other epoxy resins (i.e., the content of other epoxy resins is limited to 50 mass% or less based on the total of component (A), component (B), and other epoxy resins).
- the content of other epoxy resins is more preferably 40 mass% or less, and even more preferably 35 mass% or less, based on the total of component (A), component (B), and other epoxy resins.
- the transparent resin composition of the present invention may contain an organic solvent. That is, the transparent resin composition of the present invention may be a varnish-like transparent resin composition containing an organic solvent.
- organic solvents examples include ketones such as acetone, methyl ethyl ketone (MEK), and cyclohexanone; acetate esters such as ethyl acetate, butyl acetate, cellosolve acetate, propylene glycol monomethyl ether acetate, and carbitol acetate; cellosolves such as cellosolve; carbitols such as butyl carbitol; aromatic hydrocarbons such as toluene and xylene; dimethylformamide, dimethylacetamide, and N-methylpyrrolidone.
- ketones such as acetone, methyl ethyl ketone (MEK), and cyclohexanone
- MEK methyl ethyl ketone
- acetate esters such as ethyl acetate, butyl acetate, cellosolve acetate, propylene glycol monomethyl ether acetate, and carbitol acetate
- an organic solvent When an organic solvent is used, its content is preferably 5 to 50 mass %, more preferably 10 to 45 mass %, and even more preferably 15 to 40 mass %, based on the total transparent resin composition.
- the transparent resin composition of the present invention may contain a light stabilizer.
- light stabilizers include hindered amine light stabilizers.
- hindered amine light stabilizers include bis(2,2,6,6-tetramethyl-4-piperidyl)sebacate, bis(1,2,2,6,6-pentamethyl-4-piperidinyl)-2-butyl-2-(4-hydroxy-3,5-di-tert-butylbenzyl)propanedioate, butane-1,2,3,4-tetracarboxylate tetrakis(1,2,2,6,6-pentamethyl-4-piperidinyl, 1,2,3,4-butanediol, tetrakis(1,2,2,6,6-pentamethyl-4-piperidinyl), tetrakis(2,2,6,6-tetramethyl-4-piperidinyl) tetracarboxylate, mixed ester of 1,
- Light stabilizers can be used. Examples of such commercially available products include “Tinuvin 770 DF” and “Tinuvin PA 144” manufactured by BASF, and "ADK STAB LA-52", “ADK STAB LA-57”, “ADK STAB LA-63P”, “ADK STAB LA-68", “ADK STAB LA-72", “ADK STAB LA-81”, and “ADK STAB LA-87” manufactured by ADEKA.
- a light stabilizer When a light stabilizer is used, its content is preferably 0.1 to 10% by mass, more preferably 0.4 to 8% by mass, and even more preferably 0.8 to 5% by mass, based on the non-volatile content of the transparent resin composition, from the viewpoint of improving yellowing resistance.
- the transparent resin composition of the present invention may contain a silane coupling agent in order to improve the adhesive strength to glass of a cured product obtained from the composition.
- the silane coupling agent is preferably at least one selected from the group consisting of a (meth)acryloyl group-containing silane coupling agent, an epoxy group-containing silane coupling agent, and a vinyl group-containing silane coupling agent.
- the silane coupling agent is more preferably a (meth)acryloyl group-containing silane coupling agent, and even more preferably an acryloyl group-containing silane coupling agent.
- Examples of (meth)acryloyl group-containing silane coupling agents include 3-acryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane, and 8-methacryloxyoctyltrimethoxysilane.
- epoxy group-containing silane coupling agents include 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, and 8-glycidoxyoctyltrimethoxysilane.
- vinyl group-containing silane coupling agents examples include vinyltrimethoxysilane, vinyltriethoxysilane, and 7-octenyltrimethoxysilane.
- silane coupling agents can be used. Examples of such commercially available products include “KBM-5103”, “KBM-502”, “KBM-503”, “KBE-502”, “KBE-503”, “KBM-5803", “KBM-303", “KBM-402”, “KBM-403”, “KBE-402”, “KBE-403”, “KBM-4803", “KBM-1003", “KBE-1003", and “KBM-1083” manufactured by Shin-Etsu Chemical Co., Ltd.
- the silane coupling agent is preferably at least one selected from the group consisting of 3-acryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 8-methacryloxyoctyltrimethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 8-glycidoxyoctyltrimethoxysilane, vinyltrimethoxysilane, and 7-octenyltrimethoxysilane, and more preferably 3-acryloxypropyltrimethoxysilane and/or 3-glycidoxypropyltrimethoxysilane. From the viewpoint of suppressing warpage of the cured product, the silane coupling agent is preferably at least one selected from the
- silane coupling agent When a silane coupling agent is used, its content is preferably 0.1 to 20% by mass, more preferably 0.4 to 15% by mass, and even more preferably 0.8 to 10% by mass, based on the non-volatile content of the transparent resin composition, from the viewpoint of adhesion strength of the cured product.
- antioxidant examples include hindered phenol-based antioxidants, phosphorus-based antioxidants, and sulfur-based antioxidants.
- Specific examples of the antioxidant include dibutylhydroxytoluene (BHT), pentaerythritol tetrakis(3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate) (BASF Japan, Ltd., "IRGANOX 1010"), 2,2-thiodiethylenebis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate] (BASF Japan, Ltd., "IRGANOX 1035”), and 1,3,5-tris[[3,5-bis(1,1-dimethylethyl)-4-hydroxyphenyl]methyl]-1,3,5-triazine-2,4,6(1H,3H,5H)-trione (BASF Japan, Ltd., "IRGANOX 3114").
- UV absorber examples include a benzophenone-based ultraviolet absorbing agent, a benzotriazole-based ultraviolet absorbing agent, a salicylic acid-based ultraviolet absorbing agent, and a triazine-based ultraviolet absorbing agent.
- benzophenone-based UV absorbers include 2-hydroxy-4-octyloxybenzophenone, 2,4-dihydroxy-benzophenone, 2-hydroxy-4-methoxy-benzophenone, 2-hydroxy-4-methoxybenzophenone-5-sulfonic acid, 2-hydroxy-4-n-octyl-benzophenone, 2-hydroxy-4-n-dodecyloxy-benzophenone, bis(5-benzoyl-4-hydroxy-2-methoxyphenyl)methane, 2,2'-dihydroxy-4-methoxy-benzophenone, and 2,2'-dihydroxy-4,4'-dimethoxybenzophenone.
- Benzotriazole-based ultraviolet absorbers include, for example, 2-(2'-hydroxy-5'-methylphenyl)benzotriazole, 2-[2'-hydroxy-3',5'-bis( ⁇ , ⁇ -dimethylbenzyl)phenyl]-benzotriazole, 2-(2'-hydroxy-3',5-di-tert-butylphenyl)-benzotriazole, 2-(2'-hydroxy-3'-tert-butyl-5'-methylphenyl)-5-chlorobenzotriazole, Azole, 2-(2'-hydroxy-3',5'-di-tert-butylphenyl)-5-chlorobenzotriazole, 2-(2'-hydroxy-3',5'-di-tert-amyl)benzotriazole, 2-(2'-hydroxy-5'-tert-octylphenyl)benzotriazole, and 2,2-methylenebis[4-(1,1,3,3-tetramethylbutyl
- salicylic acid-based UV absorbers examples include phenyl salicylate, 4-tert-butylphenyl-2-hydroxybenzoate, phenyl-2-hydroxybenzoate, 2,4-di-tert-butylphenyl-3,5-di-tert-butyl-4-hydroxybenzoate, and hexadecyl-3,5-di-tert-butyl-4-hydroxybenzoate.
- triazine-based ultraviolet absorbers examples include 2-(4,6-diphenyl-1,3,5-triazin-2-yl)-5-hexyloxyphenol, 2-(4,6-diphenyl-1,3,5-triazin-2-yl)-5-[2-(2-ethylhexanoyloxy)ethoxy]phenol, 2-[4,6-bis(dimethylphenyl)-1,3,5-triazin-2-yl]-5-[3-[(2-ethylhexyl)oxy]-2-hydroxypropoxy]-phenol, and 2,4,6-tris(2-hydroxy-4-hexyloxy-3-methylphenyl)-1,3,5-triazine.
- Other ultraviolet absorbers include, for example, ethyl 2-cyano-3,3-diphenylacrylate.
- the ultraviolet absorbing agent may be a commercially available product.
- Commercially available products include “Chimassorb 81 FL”, “Tinuvin P”, “Tinuvin 213", “Tinuvin 234", “Tinuvin 326", “Tinuvin 360”, “Tinuvin 571", “Tinuvin 1577 ED", and “Tinuvin 120" manufactured by BASF Corporation, and “EV Examples include ERSORB 11, EVERSORB 12, EVERSORB 40, EVERSORB 71, EVERSORB 73, EVERSORB 78, EVERSORB 80, EVERSORB 109, Kusumoto Chemicals' 5405, and ADEKA's Adeka STAB LA-46 and Adeka STAB LA-F70.
- the transparent resin composition of the present invention may contain an inorganic filler to the extent that the transparency of the cured product is maintained. From the viewpoint of transparency, it is preferable that the transparent resin composition of the present invention does not contain an inorganic filler or contains an inorganic filler in an amount of 30 mass% or less based on the non-volatile content of the transparent resin composition (i.e., the content of the inorganic filler is limited to 30 mass% or less based on the non-volatile content of the transparent resin composition).
- the content of the inorganic filler is more preferably 20 mass% or less, even more preferably 10 mass% or less, and particularly preferably 5 mass% or less based on the non-volatile content of the transparent resin composition.
- the average total light transmittance of a 60 ⁇ m-thick transparent resin composition layer formed from the transparent resin composition of the present invention at a wavelength of 380 to 780 nm is preferably 80% or more, more preferably 85% or more, and even more preferably 90% or more. This average value can be measured by the method described in the Examples section below.
- the average total light transmittance of a 60 ⁇ m-thick cured layer formed from the transparent resin composition of the present invention at wavelengths of 380 to 780 nm is preferably 80% or more, more preferably 85% or more, and even more preferably 90% or more. This average value can be measured by the method described in the Examples section below.
- the present invention also provides a resin sheet having a laminated structure including a support and a transparent resin composition layer formed from the transparent resin composition of the present invention.
- a protective film may be used in the present invention. That is, the resin sheet of the present invention may have a laminated structure including a support, a transparent resin composition layer, and a protective film in this order.
- Another layer e.g., a release layer, an adhesive layer
- the thickness of the transparent resin composition layer is preferably 1 ⁇ m or more, more preferably 1.5 ⁇ m or more, even more preferably 2 ⁇ m or more, particularly preferably 5 ⁇ m or more, and is preferably 150 ⁇ m or less, preferably 120 ⁇ m or less, more preferably 100 ⁇ m or less, and even more preferably 80 ⁇ m or less.
- the support examples include plastic films such as polyethylene, polypropylene, polyvinyl chloride, cycloolefin polymer, polyethylene terephthalate (hereinafter sometimes abbreviated as "PET"), polyethylene naphthalate, polycarbonate, and polyimide, and metal foils such as aluminum foil, stainless steel foil, and copper foil. Among these, polyethylene terephthalate and polyethylene naphthalate are preferred, and inexpensive polyethylene terephthalate is particularly preferred.
- the support may have a release layer on the surface that is bonded to the transparent resin composition layer. Examples of the release agent that forms the release layer include silicone resin-based release agents, alkyd resin-based release agents, and fluororesin-based release agents.
- the support may be subjected to a matte treatment, corona treatment, or antistatic treatment on the surface that is bonded to the transparent resin composition layer.
- the thickness of the support is preferably 10 to 250 ⁇ m, and more preferably 20 to 200 ⁇ m.
- the overall thickness of the support with the release layer is within the above range.
- the resin sheet can be produced, for example, by (1) producing a varnish-like transparent resin composition, (2) applying this to a support using a die coater or the like to form a coating film, and (3) drying the resulting coating film to form a transparent resin composition layer.
- a varnish-like transparent resin composition There are no particular limitations on the method for producing the varnish-like transparent resin composition, and it can be produced by mixing an organic solvent and each component using a known device such as a rotary mixer.
- the coating can be dried by known methods such as heating and hot air blowing. There are no particular limitations on the drying conditions. It is preferable to dry until the content of the organic solvent in the transparent resin composition layer is 10 mass % or less. The content of the organic solvent in the transparent resin composition layer after drying is more preferably 5 mass % or less.
- the drying time and drying temperature vary depending on the content of the organic solvent in the varnish-like transparent resin composition and its boiling point, but the drying temperature is, for example, about 50 to 150°C, and the drying time is, for example, about 3 to 10 minutes.
- the resin sheet can be stored in a roll. If the resin sheet has a protective film, the resin sheet can be used by peeling off the protective film.
- the present invention also provides an electronic device comprising a cured layer formed from the transparent resin composition of the present invention.
- Examples of the electronic device include an LED device and an electronic device including a transparent FPC.
- the cured layer is preferably formed by heating the transparent resin composition layer.
- the transparent resin composition layer can be heated by known equipment (e.g., a hot air circulating oven, an infrared heater, a heat gun, a high-frequency induction heating device).
- the curing temperature is preferably 80°C or higher, more preferably 100°C or higher, from the viewpoint of promoting the curing reaction, and is preferably 210°C or lower, more preferably 180°C or lower, from the viewpoint of preventing coloration of the cured layer.
- the curing time is preferably 10 minutes or more, more preferably 20 minutes or more, and preferably 180 minutes or lower, more preferably 120 minutes or lower.
- ⁇ Phenoxy resin> "YX7200B35" manufactured by Mitsubishi Chemical Corporation, a solution of a phenoxy resin having a biphenyl structure and a structure derived from bisphenol TMC, organic solvent: methyl ethyl ketone, non-volatile content: 35%, weight average molecular weight: 30,000, epoxy equivalent: 9,000 g/mol
- LA-52 manufactured by ADEKA Corporation, 1,2,3,4-butanetetracarboxylic acid tetrakis(2,2,6,6-tetramethyl-4-piperidinyl), CAS number: 91788-83-9)
- Example 1 24 parts of the phenoxy resin solution "YX7200B35" (phenoxy resin: 8.4 parts), 12 parts of the (A) component "YX7760", 6 parts of another epoxy resin "ZX-1059", and 1 part of the (B) component "X-22-163" were mixed, and the resulting mixture was heated to dissolve the (A) and (B) components. 0.4 parts of the (C) component "TBP-DA” was mixed therein to prepare a varnish-like transparent resin composition.
- Example 2 A varnish-like transparent resin composition was prepared in the same manner as in Example 1, except that 12 parts of the component (A) "EHPE3150” was used instead of 12 parts of the component (A) "YX7760".
- Example 3 A varnish-like transparent resin composition was prepared in the same manner as in Example 1, except that 18 parts of the (A) component "EP-4088S” was used instead of 12 parts of the (A) component "YX7760" and 6 parts of the other epoxy resin "ZX-1059".
- Example 4 A varnish-like transparent resin composition was prepared in the same manner as in Example 1, except that the amount of component (B) “X-22-163” used was changed from 1 part to 3 parts.
- Example 5 A varnish-like transparent resin composition was prepared in the same manner as in Example 1, except that 1 part of the component (B) "X-40-2728" was used instead of 1 part of the component (B) "X-22-163".
- Example 6 A varnish-like transparent resin composition was prepared in the same manner as in Example 1, except that 1 part of the component (B) "KR-470" was used instead of 1 part of the component (B) "X-22-163".
- Example 7 A varnish-like transparent resin composition was prepared in the same manner as in Example 1, except that 0.26 parts of the light stabilizer "LA-52" was added.
- Example 8 A varnish-like transparent resin composition was prepared in the same manner as in Example 1, except that 0.26 parts of a silane coupling agent "KBM-403" was added.
- Example 9 A varnish-like transparent resin composition was prepared in the same manner as in Example 1, except that 0.26 parts of a silane coupling agent "KBM-5103" was added.
- Example 1 A varnish-like transparent resin composition was prepared in the same manner as in Example 1, except that 18 parts of another epoxy resin "ZX-1059” was used instead of 12 parts of the (A) component "YX7760” and 6 parts of the other epoxy resin "ZX-1059.”
- Example 2 A varnish-like transparent resin composition was prepared in the same manner as in Example 1, except that the component (B) “X-22-163” was not used.
- the obtained resin sheet was heated at 150°C for 90 minutes to thermally cure the transparent resin composition layer, and a sheet having a laminated structure of "PET film/cured layer” (hereinafter referred to as "cured sheet (1)") was obtained.
- cured sheet (1) a sheet having a laminated structure of "PET film/cured layer”
- ⁇ Haze measurement> The haze (%) was measured in accordance with JIS K 7136. Specifically, a portion of the cured product sheet (1) obtained in ⁇ Preparation of evaluation sample> where the cured product layer had a uniform thickness was cut into a 3 cm square, and the haze (%) was measured using a haze meter HZ-V3 (halogen lamp) manufactured by Suga Test Instruments Co., Ltd. under D65 light with air as a reference. The results are shown in Table 1 below. The smaller the haze value, the more transparent the cured product.
- cured product sheet (2) The part of the resin sheet before curing obtained in ⁇ Preparation of evaluation sample> where the thickness of the cured product layer was uniform was cut into an 8 cm square, and two adjacent sides of the four sides were taped to a flat substrate, and the transparent resin composition layer was thermally cured by heating in an oven at 150°C for 90 minutes to obtain a sheet having a laminated structure of "PET film/cured product layer" (hereinafter referred to as "cured product sheet (2)"). The cured product sheet (2) was removed from the oven and allowed to cool, and then the height to which the corner not in contact with the tape had warped (hereinafter referred to as "warping height”) was measured, and the warping suppression was evaluated according to the following criteria.
- the varnish-like transparent resin composition prepared in the examples or comparative examples was applied to a release-treated surface of a PET film ("NS80A” manufactured by Fujimori Kogyo Co., Ltd.) using a die coater so that the thickness of the transparent resin composition layer after drying would be 60 ⁇ m, and the coating was dried at 100° C. for 7 minutes to form a transparent resin composition layer, thereby obtaining a resin sheet having a laminated structure of "PET film/transparent resin composition layer".
- the obtained resin sheet was heated in an oven at 150 ° C. for 30 minutes, and then the transparent resin composition layer was peeled off from the PET film and laminated on a PET film ("E7004" manufactured by Toyobo Co., Ltd.) treated with a silicone-based release agent to form a laminate.
- This lamination was carried out by reducing the pressure for 20 seconds using a vacuum laminator (manufactured by Nikko Materials Co., Ltd., V-160) to a pressure of 5 hPa or less, and then pressing at 80 ° C. and a pressure of 0.1 MPa for 20 seconds. Thereafter, the obtained laminate was further heated in an oven at 150 ° C.
- the transparent resin composition of the present invention is useful, for example, as a sealing material or adhesive material for transparent parts of electronic devices, including LED devices and transparent FPCs.
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Abstract
Description
[1] 以下の(A)成分~(C)成分:
(A)フルオロアルキル基および/または脂環式構造を有し、且つシロキサン構造を有さないエポキシ樹脂、
(B)シロキサン構造を有するエポキシ樹脂、並びに
(C)硬化促進剤
を含む透明樹脂組成物。
[2] さらに高分子化合物を含む前記[1]に記載の透明樹脂組成物。
[3] (B)成分が、グリシジル基を有する前記[1]または[2]に記載の透明樹脂組成物。
[4] (B)成分の含有量が、透明樹脂組成物の不揮発分に対して、0.1~20質量%である前記[1]~[3]のいずれか一つに記載の透明樹脂組成物。
[5] (B)成分の1分子中のエポキシ基の数が2~10であり、且つ(B)成分のエポキシ当量が、150~350g/molである前記[1]~[4]のいずれか一つに記載の透明樹脂組成物。
[6] 支持体および前記[1]~[5]のいずれか一つに記載の透明樹脂組成物により形成された透明樹脂組成物層を含む積層構造を有する樹脂シート。
[7] 前記[1]~[5]のいずれか一つに記載の透明樹脂組成物により形成された硬化物層を含む電子デバイス。
(A)フルオロアルキル基および/または脂環式構造を有し、且つシロキサン構造を有さないエポキシ樹脂
(B)シロキサン構造を有するエポキシ樹脂、並びに
(C)硬化促進剤
を含む透明樹脂組成物を提供する。特段の記載がない限り、本発明では、各成分はいずれも1種のみを使用してもよく、2種以上を併用してもよい。以下、(A)成分等について順に説明する。
本発明では、(A)成分として、フルオロアルキル基および/または脂環式構造を有し、且つシロキサン構造を有さないエポキシ樹脂を使用する。(A)成分を使用することによって、耐黄変性に優れる硬化物を形成することができる。
本明細書中、「フルオロアルキル基」とは、フッ素原子で置換されたアルキル基を意味し、「パーフルオロアルキル基」とは、全ての水素原子がフッ素原子で置換されたアルキル基を意味する。
(i)好ましくはフルオロアルキル基を有し、且つシロキサン構造を有さないエポキシ樹脂および/または脂環式構造を有し、且つシロキサン構造を有さないエポキシ樹脂であり、
(ii)より好ましくはC1-6フルオロアルキル基を有し、且つシロキサン構造を有さないエポキシ樹脂、C3-8シクロアルカン環構造を有し、且つシロキサン構造を有さないエポキシ樹脂、およびジシクロペンタジエン環構造を有し、且つシロキサン構造を有さないエポキシ樹脂からなる群から選ばれる少なくとも一つであり、
(iii)さらに好ましくはビスフェノールAF型エポキシ樹脂、シクロヘキサン環構造を有し、且つシロキサン構造を有さないエポキシ樹脂、およびジシクロペンタジエン環構造を有し、且つシロキサン構造を有さないエポキシ樹脂からなる群から選ばれる少なくとも一つであり、
(iv)特に好ましくはビスフェノールAF型エポキシ樹脂、シクロヘキサン環構造を有し、且つシロキサン構造を有さないエポキシ樹脂、またはジシクロペンタジエン環構造を有し、且つシロキサン構造を有さないエポキシ樹脂であり、
(v)最も好ましくはビスフェノールAF型エポキシ樹脂である。
(A)成分のエポキシ当量は、硬化物の密着強度の観点から、好ましくは50~5,000g/mol、より好ましくは80~2,000g/mol、さらに好ましくは100~1,500g/molである。
本発明では、(B)成分として、シロキサン構造を有するエポキシ樹脂を使用する。(B)成分を使用することによって、透明樹脂組成物の加熱時の応力を緩和し、反り抑制に優れる硬化物を形成することができる。また、(B)成分は、硬化物の耐黄変性および耐熱性の向上にも効果がある。
本明細書中、「C1-6アルキル基」としては、例えば、メチル基、ジメチル基、エチル基、プロピル基、ブチル基、ペンチル基、ヘキシル基が挙げられる。
直鎖状シロキサン構造は、好ましくはポリジメチルシロキサン構造である。ポリジメチルシロキサン構造中のメチル基は、置換基を有していてもよい。
(B)成分の1分子中のエポキシ基の数は、硬化物の密着強度および反り抑制の観点から、好ましくは2~10、より好ましくは2~4である。
(B)成分のエポキシ当量は、硬化物の密着強度の観点から、好ましくは100~350g/mol、より好ましくは120~330g/mol、さらに好ましくは150~300g/molである。
本発明では、(C)成分として、硬化促進剤を使用する。本明細書中、「硬化促進剤」とは、エポキシ樹脂同士の硬化反応を促進する添加剤を意味する。なお、エポキシ分野において、エポキシ樹脂同士の硬化反応を促進する添加剤は、硬化剤(特に、触媒型の硬化剤)と呼ばれることがある。
本発明の透明樹脂組成物は、本発明の効果を阻害しない範囲で、(A)成分~(C)成分以外の成分(本明細書中「他の成分」と略称することがある)を含んでいてもよい。他の成分としては、例えば、高分子化合物、(A)成分および(B)成分以外のエポキシ樹脂、有機溶剤、光安定剤、シランカップリング剤、酸化防止剤、紫外線吸収剤が挙げられる。他の成分は、いずれも、1種のみを使用してもよく、2種以上を併用してもよい。以下、他の成分について順に説明する。
透明樹脂組成物のフィルムを形成するために、高分子化合物を使用することが好ましい。本明細書中、「高分子化合物」とは、重量平均分子量(以下「Mw」と略称することがある)が1,000以上である化合物を意味する。このMwは、ゲル浸透クロマトグラフィー(GPC)によって測定することができる。
(i)好ましくはフルオロアルキル基を有するフェノキシ樹脂および/または脂環式構造を有するフェノキシ樹脂であり、
(ii)より好ましくはC1-6フルオロアルキル基を有するフェノキシ樹脂および/またはC3-8シクロアルカン環構造を有するフェノキシ樹脂であり、
(iii)より一層好ましくはC1-6パーフルオロアルキル基を有するフェノキシ樹脂および/またはC5-6シクロアルカン環構造を有するフェノキシ樹脂であり、
(iv)さらに好ましくはトリフルオロメチル基を有するフェノキシ樹脂および/またはシクロヘキサン環構造を有するフェノキシ樹脂であり、
(v)特に好ましくはビスフェノールAF型フェノキシ樹脂および/またはシクロヘキサン環構造を有するフェノキシ樹脂であり、
(vi)最も好ましくはシクロヘキサン環構造を有するフェノキシ樹脂である。
本発明の透明樹脂組成物は、本発明の効果(即ち、反り抑制、耐黄変性および耐熱性)を阻害しない範囲で、(A)成分および(B)成分以外のエポキシ樹脂(本明細書中「他のエポキシ樹脂」と略称することがある)を含んでいてもよい。
本発明の透明樹脂組成物は、有機溶剤を含んでいてもよい。即ち、本発明の透明樹脂組成物は、有機溶剤を含むワニス状の透明樹脂組成物であってもよい。
本発明の透明樹脂組成物は、該組成物から得られる硬化物のガラスに対する密着強度を向上させるために、シランカップリング剤を含んでいてもよい。
酸化防止剤としては、例えば、ヒンダードフェノール系酸化防止剤、リン系酸化防止剤、硫黄系酸化防止剤が挙げられる。酸化防止剤の具体例としては、ジブチルヒドロキシトルエン(BHT)、ペンタエリスリトールテトラキス(3-(3,5-ジ-tert-ブチル-4-ヒドロキシフェニル)プロピオネート)(BASFジャパン社製「IRGANOX 1010」)、2,2-チオジエチレンビス[3-(3,5-ジ-tert-ブチル-4-ヒドロキシフェニル)プロピオネート](BASFジャパン社製「IRGANOX 1035」)、1,3,5-トリス[[3,5-ビス(1,1-ジメチルエチル)-4-ヒドロキシフェニル]メチル]-1,3,5-トリアジン-2,4,6(1H,3H,5H)-トリオン(BASFジャパン社製「IRGANOX 3114」)が挙げられる。
紫外線吸収剤としては、例えば、ベンゾフェノン系紫外線吸収剤、ベンゾトリアゾール系紫外線吸収剤、サリチル酸系紫外線吸収剤、トリアジン系紫外線吸収剤が挙げられる。
その他の紫外線吸収剤としては、例えば、エチル 2-シアノ-3,3-ジフェニルアクリレートが挙げられる。
本発明の透明樹脂組成物は、硬化物の透明性が維持される範囲で、無機フィラーを含んでいてもよい。透明性の観点から、本発明の透明樹脂組成物は、無機フィラーを含まないか、または無機フィラーを、透明樹脂組成物の不揮発分に対して30質量%以下の量で含むこと(即ち、無機フィラーの含有量を、透明樹脂組成物の不揮発分に対して30質量%以下に制限すること)が好ましい。無機フィラーの含有量は、透明樹脂組成物の不揮発分に対して、より好ましくは20質量%以下、さらに好ましくは10量%以下、特に好ましくは5質量%以下である。
本発明の透明樹脂組成物から形成される厚さ60μmの透明樹脂組成物層の、波長380~780nmの全光線透過率の平均値は、好ましくは80%以上、より好ましくは85%以上、さらに好ましくは90%以上である。この平均値は、後述の実施例欄に記載する方法によって測定することができる。
本発明の透明樹脂組成物から形成される厚さ60μmの硬化物層の、波長380~780nmの全光線透過率の平均値は、好ましくは80%以上、より好ましくは85%以上、さらに好ましくは90%以上である。この平均値は、後述の実施例欄に記載する方法によって測定することができる。
本発明は、支持体および本発明の透明樹脂組成物から形成された透明樹脂組成物層を含む積層構造を有する樹脂シートも提供する。本発明では保護フィルムを使用してもよい。即ち、本発明の樹脂シートは、支持体、透明樹脂組成物層、および保護フィルムをこの順に含む積層構造を有していてもよい。支持体と透明樹脂組成物層との間、および透明樹脂組成物層と保護フィルムとの間に、他の層(例えば、離型層、接着層)が存在していてもよい。
本発明は、本発明の透明樹脂組成物により形成された硬化物層を含む電子デバイスも提供する。電子デバイスとしては、例えば、LEDデバイス、透明FPC等を含む電子デバイスが挙げられる。
<(A)成分>
「YX7760」(三菱ケミカル社製、ビスフェノールAF型エポキシ樹脂、常温で固体状、エポキシ当量:245g/mol)
「EHPE3150」(ダイセル社製、シクロヘキサン環構造を有するエポキシ樹脂、常温で固体状、エポキシ当量:180g/mol)
「EP-4088S」(ADEKA社製、ジシクロペンタジエン構造を有するエポキシ樹脂、常温で液状、エポキシ当量:170g/mol)
「X-22-163」(信越化学工業社製、両末端にグリシジル基を有する(即ち、分子内に2個のグリシジル基を有する)直鎖状ポリジメチルシロキサン、シロキサン構造中のSi原子の数:2、エポキシ当量:200g/mol)
「X-40-2728」(信越化学工業社製、分子内に2個のグリシジル基を有する環状シロキサン、シロキサン構造中のSi原子の数:4、エポキシ当量:280g/mol)
「KR-470」(信越化学工業社製、分子内に4個の脂環エポキシ基を有する環状シロキサン、シロキサン構造中のSi原子の数:4、エポキシ当量:200g/mol)
「ZX-1059」(新日鉄住金化学社製、ビスフェノールA型エポキシ樹脂(50%)およびビスフェノールF型エポキシ樹脂(50%)の混合物、常温で液状、エポキシ当量:165g/mol)
「TBP-DA」(北興化学工業社製、テトラブチルホスホニウムデカン酸塩)
「YX7200B35」(三菱ケミカル社製、ビフェニル構造およびビスフェノールTMCに由来する構造を有するフェノキシ樹脂の溶液、有機溶剤:メチルエチルケトン、不揮発分:35%、重量平均分子量:30,000、エポキシ当量:9,000g/mol)
「LA-52」(ADEKA社製、1,2,3,4-ブタンテトラカルボン酸テトラキス(2,2,6,6-テトラメチル-4-ピペリジニル)、CAS番号:91788-83-9)
「KBM-403」(信越化学工業社製、3-グリシドキシプロピルトリメトキシシラン)
「KBM-5103」(信越化学工業社製、3-アクリロキシプロピルトリメトキシシラン)
<実施例1>
フェノキシ樹脂の溶液「YX7200B35」24部(フェノキシ樹脂:8.4部)、(A)成分「YX7760」12部、他のエポキシ樹脂「ZX-1059」6部、および(B)成分「X-22-163」1部を混合し、得られた混合物を加熱して、(A)成分および(B)成分を溶解させた。そこへ、(C)成分「TBP-DA」0.4部を混合して、ワニス状の透明樹脂組成物を調製した。
(A)成分「YX7760」12部の代わりに、(A)成分「EHPE3150」12部を使用したこと以外は実施例1と同様にして、ワニス状の透明樹脂組成物を調製した。
(A)成分「YX7760」12部および他のエポキシ樹脂「ZX-1059」6部の代わりに、(A)成分「EP-4088S」18部を使用したこと以外は実施例1と同様にして、ワニス状の透明樹脂組成物を調製した。
(B)成分「X-22-163」の使用量を1部から3部に変更したこと以外は実施例1と同様にして、ワニス状の透明樹脂組成物を調製した。
(B)成分「X-22-163」1部の代わりに、(B)成分「X-40-2728」1部を使用したこと以外は実施例1と同様にして、ワニス状の透明樹脂組成物を調製した。
(B)成分「X-22-163」1部の代わりに、(B)成分「KR-470」1部を使用したこと以外は実施例1と同様にして、ワニス状の透明樹脂組成物を調製した。
光安定剤「LA―52」0.26部を添加したこと以外は実施例1と同様にして、ワニス状の透明樹脂組成物を調製した。
シランカップリング剤「KBM-403」0.26部を添加したこと以外は実施例1と同様にして、ワニス状の透明樹脂組成物を調製した。
シランカップリング剤「KBM-5103」0.26部を添加したこと以外は実施例1と同様にして、ワニス状の透明樹脂組成物を調製した。
(A)成分「YX7760」12部および他のエポキシ樹脂「ZX-1059」6部の代わりに、他のエポキシ樹脂「ZX-1059」18部を使用したこと以外は実施例1と同様にして、ワニス状の透明樹脂組成物を調製した。
(B)成分「X-22-163」を使用しなかったこと以外は実施例1と同様にして、ワニス状の透明樹脂組成物を調製した。
実施例または比較例で作製したワニス状の透明樹脂組成物を、PETフィルム(アズワン社製「ルミラーフィルム 188μm」)上に、乾燥後の透明樹脂組成物層の厚さが60μmとなるようにダイコーターにて塗布し、100℃で7分乾燥して、透明樹脂組成物層を形成し、「PETフィルム/透明樹脂組成物層」の積層構造を有する樹脂シートを得た。
<評価用サンプルの作製>で得られた樹脂シートの透明樹脂組成物層の厚さが均一である部分、および硬化物シートの硬化物層の厚さが均一である部分を、それぞれ3cm角にカットし、φ60mm積分球を装着したファイバ式分光光度計(大塚電子社製「MCPD-7700」)を用いて、積分球とサンプルの距離を30mmとした。これらの測定では、作製に使用したPETフィルムをリファレンスとして使用して、波長380~780nmにおける透明樹脂組成物層および硬化物層の全光線透過率の平均値を算出した。結果を下記表1に記載する。なお、透明樹脂組成物層および硬化物層の全光線透過率の平均値は同じであったため、下記表1では一つの値のみを記載した。
ヘーズ(%)は、JIS K 7136に準拠して測定した。詳しくは、<評価用サンプルの作製>で得られた硬化物シート(1)の、硬化物層の厚さが均一である部分を3cm角にカットし、スガ試験機社製ヘーズメーター HZ-V3(ハロゲンランプ)を用いて、空気をリファレンスとして、D65光にて、ヘーズ(%)を測定した。結果を下記表1に記載する。ヘーズ値が小さいほど、硬化物は透明である。
<評価用サンプルの作製>で得られた硬化物シート(1)の硬化物層の厚さが均一である部分を切り出し、φ60mm積分球を装着したファイバ式分光光度計(大塚電子社製「MCPD-7700」)を用いて、積分球とサンプルの距離を30mmとし、リファレンスは空気とし、視野角2度、光源D65にて色演算を実施し、L*a*b*表色系のb*を算出した。その後、硬化物シートを200℃のオーブンにて1時間静置させ、オーブンから取り出した後常温となるまで静置し、上記と同様にb*を測定した。オーブン加熱前後のb*の変化率(Δb*)を、下記式:
Δb*=オーブン加熱後のb*/オーブン加熱前のb*
から算出し、下記基準で耐黄変性を評価した。結果を下記表1に記載する。
(耐黄変性の評価基準)
良好(○):Δb*が2.0未満
可 (△):Δb*が2.0以上3.0未満
不良(×):Δb*が3.0以上
<評価用サンプルの作製>で得られた硬化前の樹脂シートの、硬化物層の厚さが均一である部分を8cm角にカットし、4辺のうち隣り合う2辺を平坦な基板上にテープで留め、オーブンにて150℃で90分加熱することにより透明樹脂組成物層を熱硬化して、「PETフィルム/硬化物層」の積層構造を有するシート(以下、「硬化物シート(2)」と記載する)を得た。硬化物シート(2)をオーブンから取り出し放冷したのちに、テープと接していない角が反りあがった高さ(以下「反りの高さ」と記載する)を測定し、下記基準で反り抑制を評価した。結果を下記表1に記載する。
(反り抑制の評価基準)
良好(○):反りの高さが20mm未満
可 (△):反りの高さが20mm以上30mm未満
不良(×):反りの高さが30mm以上
実施例または比較例で作製したワニス状の透明樹脂組成物を、PETフィルム(藤森工業社製「NS80A」)の離型処理面上に、乾燥後の透明樹脂組成物層の厚さが60μmとなるようにダイコーターにて塗布し、100℃で7分乾燥して、透明樹脂組成物層を形成し、「PETフィルム/透明樹脂組成物層」の積層構造を有する樹脂シートを得た。
(耐熱性の評価基準)
良好(○):ガラス転移温度が110℃以上
可 (△):ガラス転移温度が100℃以上110℃未満
不良(×):ガラス転移温度が100℃未満
他方、(A)成分を含まない比較例1の透明樹脂組成物から、耐黄変性が劣る硬化物が得られた。
また、(B)成分を含まない比較例2の透明樹脂組成物から、反り抑制および耐熱性に劣る硬化物が得られた。
Claims (7)
- 以下の(A)成分~(C)成分:
(A)フルオロアルキル基および/または脂環式構造を有し、且つシロキサン構造を有さないエポキシ樹脂、
(B)シロキサン構造を有するエポキシ樹脂、並びに
(C)硬化促進剤
を含む透明樹脂組成物。 - さらに高分子化合物を含む請求項1に記載の透明樹脂組成物。
- (B)成分が、グリシジル基を有する請求項1または2に記載の透明樹脂組成物。
- (B)成分の含有量が、透明樹脂組成物の不揮発分に対して、0.1~20質量%である請求項1または2に記載の透明樹脂組成物。
- (B)成分の1分子中のエポキシ基の数が2~10であり、且つ(B)成分のエポキシ当量が、150~350g/molである請求項1または2に記載の透明樹脂組成物。
- 支持体および請求項1または2に記載の透明樹脂組成物により形成された透明樹脂組成物層を含む積層構造を有する樹脂シート。
- 請求項1または2に記載の透明樹脂組成物により形成された硬化物層を含む電子デバイス。
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| CN113956791A (zh) * | 2021-10-06 | 2022-01-21 | 苏州世诺新材料科技有限公司 | 一种硬涂层形成用组合物、硬涂膜及其制备方法 |
| JP2022051490A (ja) * | 2021-02-22 | 2022-03-31 | サンアプロ株式会社 | 光硬化性組成物ならびにその硬化体 |
| JP2022135247A (ja) * | 2021-03-05 | 2022-09-15 | サンアプロ株式会社 | 硬化性組成物ならびにその硬化体 |
| CN116655681A (zh) * | 2023-05-16 | 2023-08-29 | 南方科技大学嘉兴研究院 | 含氟有机硅环氧单体及其制备方法、及其在制备压印胶的应用、压印胶及其制备方法、一种压印方法 |
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| JP6992635B2 (ja) | 2018-03-22 | 2022-01-13 | 味の素株式会社 | 樹脂組成物 |
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- 2024-01-24 CN CN202480008967.6A patent/CN120659823A/zh active Pending
- 2024-01-24 WO PCT/JP2024/002073 patent/WO2024158012A1/ja not_active Ceased
- 2024-01-24 KR KR1020257028269A patent/KR20250138257A/ko active Pending
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| JPH1053639A (ja) * | 1995-06-13 | 1998-02-24 | Canon Inc | 溶剤易溶性のフッ素含有エポキシ樹脂組成物およびそれを用いた表面処理方法 |
| JP2007322601A (ja) * | 2006-05-31 | 2007-12-13 | Bridgestone Corp | 導電性ローラ及びそれを用いた画像形成装置 |
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| JP2017115071A (ja) * | 2015-12-25 | 2017-06-29 | 株式会社ダイセル | 立体造形用硬化性組成物 |
| JP2017115072A (ja) * | 2015-12-25 | 2017-06-29 | 株式会社ダイセル | 立体造形用硬化性組成物 |
| JP2022051490A (ja) * | 2021-02-22 | 2022-03-31 | サンアプロ株式会社 | 光硬化性組成物ならびにその硬化体 |
| JP2022135247A (ja) * | 2021-03-05 | 2022-09-15 | サンアプロ株式会社 | 硬化性組成物ならびにその硬化体 |
| CN113956791A (zh) * | 2021-10-06 | 2022-01-21 | 苏州世诺新材料科技有限公司 | 一种硬涂层形成用组合物、硬涂膜及其制备方法 |
| CN116655681A (zh) * | 2023-05-16 | 2023-08-29 | 南方科技大学嘉兴研究院 | 含氟有机硅环氧单体及其制备方法、及其在制备压印胶的应用、压印胶及其制备方法、一种压印方法 |
Also Published As
| Publication number | Publication date |
|---|---|
| JPWO2024158012A1 (ja) | 2024-08-02 |
| KR20250138257A (ko) | 2025-09-19 |
| CN120659823A (zh) | 2025-09-16 |
| TW202436426A (zh) | 2024-09-16 |
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