WO2006068185A1 - エポキシ樹脂、エポキシ樹脂組成物及びその硬化物 - Google Patents
エポキシ樹脂、エポキシ樹脂組成物及びその硬化物 Download PDFInfo
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- WO2006068185A1 WO2006068185A1 PCT/JP2005/023505 JP2005023505W WO2006068185A1 WO 2006068185 A1 WO2006068185 A1 WO 2006068185A1 JP 2005023505 W JP2005023505 W JP 2005023505W WO 2006068185 A1 WO2006068185 A1 WO 2006068185A1
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- Prior art keywords
- epoxy resin
- resin composition
- formula
- parts
- epoxy
- Prior art date
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- 239000004416 thermosoftening plastic Substances 0.000 description 1
- AAAQKTZKLRYKHR-UHFFFAOYSA-N triphenylmethane Chemical compound C1=CC=CC=C1C(C=1C=CC=CC=1)C1=CC=CC=C1 AAAQKTZKLRYKHR-UHFFFAOYSA-N 0.000 description 1
- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical compound [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 0.000 description 1
Classifications
-
- 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
- C08G59/02—Polycondensates containing more than one epoxy group per molecule
- C08G59/04—Polycondensates containing more than one epoxy group per molecule of polyhydroxy compounds with epihalohydrins or precursors thereof
- C08G59/06—Polycondensates containing more than one epoxy group per molecule of polyhydroxy compounds with epihalohydrins or precursors thereof of polyhydric phenols
-
- 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
- C08G59/245—Di-epoxy compounds carbocyclic aromatic
-
- 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
-
- 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
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K1/00—Printed circuits
- H05K1/02—Details
- H05K1/03—Use of materials for the substrate
- H05K1/0313—Organic insulating material
- H05K1/032—Organic insulating material consisting of one material
- H05K1/0326—Organic insulating material consisting of one material containing O
Definitions
- the present invention relates to an epoxy resin having a high molecular orientation, an epoxy resin having an excellent property of toughness and thermal conductivity in the cured product, an epoxy resin composition, and a cured product thereof.
- Patent Document 1 describes that an epoxy resin having a mesogenic group in the molecule exhibits high thermal conductivity in the cured product.
- Patent Document 2 describes an epoxy resin having a mesogenic group. It has been reported that a cured product having excellent thermal conductivity can be obtained by applying a magnetic field to the resin and orienting it after orientation.
- Patent Document 3 describes that a polymer having liquid crystallinity can be processed at a temperature higher than the melting point to obtain a molded product having excellent mechanical strength.
- Patent Document 1 Japanese Patent Application Laid-Open No. 2003-268070
- Patent Document 2 Japanese Unexamined Patent Application Publication No. 2004-175926
- Patent Document 3 Japanese Patent No. 2664405
- epoxy resins having mesogenic groups described in the above documents generally have a drawback that their molecular structure is complicated and production is difficult.
- thermoplastic liquid crystal polymers have a melting point of 250 to 350 ° C. Therefore, the molding conditions are generally very strict as compared with thermosetting resins.
- the present invention is an epoxy resin that is easy to manufacture and can easily realize a state in which molecules are oriented, and the cured product exhibits optical anisotropy, and further has toughness, It is an object of the present invention to provide an epoxy resin that gives a cured product having excellent thermal conductivity.
- the present invention provides
- nf is an average straightness 0.:! To 20, preferably ⁇ to 0.2 to 15 and particularly preferably to ⁇ 0.5 to 5.
- a phenolic compound represented by the formula (1) is reacted in the presence of epihalohydrin and an alkali metal hydroxide to obtain a low molecular weight epoxy resin, and the epoxy resin and the following formula (3)
- the epoxy resin of the present invention is an epoxy resin having a very high molecular orientation and has excellent properties of toughness and thermal conductivity in its hardened material, such as composite materials, electrical and electronic materials, It is particularly useful for printed wiring boards, solder resists, semiconductor encapsulants, retardation films, molding materials, adhesives, and the like.
- the epoxy resin of the present invention has the following formula (2)
- the phenolic compound of the formula (2) is a crystal having a melting point of around 163 ° C., and a commercially available product can be purchased as, for example, p, p′_BPF (manufactured by Honshu Chemical Co., Ltd.).
- a method for producing the crystalline epoxy resin of the present invention a method in which the reaction product of the compound of formula (3) and epi-halohydrin is chain-extended with the compound of formula (2) can be adopted.
- the reaction product of Epihaguchi hydrin is inferior in work efficiency compared with the above-mentioned method because of its high crystallinity.
- epichlorohydrin and epibromohydrin can be used as the epihalohydrin.
- the amount of epihalohydrin is usually 2 to 15 moles, preferably 3 to 12 moles per mole of the hydroxyl group of the compound of the formula (2).
- Examples of the alkali metal hydroxide include sodium hydroxide and potassium hydroxide.
- an aqueous solution that is solid or an aqueous solution that is acceptable may be used, the alkali metal hydroxide is continuously added to the reaction system and simultaneously reduced in pressure.
- a method may be employed in which sewage under normal pressure or atmospheric pressure and epihalohydrin are distilled and further separated, water is removed, and epihalohydrin is continuously returned to the reaction system.
- the amount of the alkali metal hydroxide to be used is usually 0.9 to: 1.2 monole, preferably 0.95 to 1.15 monole, per 1 equivalent of the hydroxyl group of the compound of formula (2).
- the reaction temperature is usually 20 to 110 ° C, preferably 25 to 100 ° C.
- the reaction time is usually 0.5 to 15 hours, preferably 1 to 10 hours.
- Addition of an alcohol such as methanol, ethanol, propanol or butanol, or an aprotic polar solvent such as dimethyl sulfoxide or dimethyl sulfone is preferable for promoting the reaction.
- the amount used is usually 3 to 30% by weight, preferably 5 to 20% by weight, based on the amount of epichlorohydrin.
- the amount used is usually 10 to 150% by weight, preferably 15 to 120% by weight, based on the amount of epihalohydrin.
- reaction of epihalohydrin with the compound of formula (2) is added to the mixture of both as a quaternary ammonium salt catalyst such as tetramethyl ammonium chloride, tetramethyl ammonium bromide, trimethylbenzyl ammonium chloride, etc. 30 to: Add a solid or aqueous solution of an alkali metal hydroxide to a halohydrin ether compound of the formula (2) obtained by reacting at 110 ° C. for 0.5 to 8 hours 20 to: 100 ° It may be a method of reacting with C for 1 to 10 hours and dehydrohalogenating (ring closure).
- a quaternary ammonium salt catalyst such as tetramethyl ammonium chloride, tetramethyl ammonium bromide, trimethylbenzyl ammonium chloride, etc. 30 to: Add a solid or aqueous solution of an alkali metal hydroxide to a halohydrin ether compound of the formula (2) obtained by reacting at 110 ° C.
- the reaction product of these epoxidation reactions is washed with water or without washing with water, excess epihalohydrin and solvent are removed under reduced pressure by heating.
- the recovered epoxy resin is dissolved in toluene, methyl isobutyl ketone, etc., and an aqueous solution of an alkali metal hydroxide such as sodium hydroxide or potassium hydroxide is added to perform ring closure.
- an alkali metal hydroxide such as sodium hydroxide or potassium hydroxide is added to perform ring closure.
- the amount of alkali metal hydroxide used is usually 0.01 to 0.3 mol, preferably 0.05 to 0.2 mol, per mol of the hydroxyl group of the compound of formula (2).
- the reaction temperature is usually 50 to 120 ° C, and the reaction time is usually 0.5 to 2 hours.
- the low-molecular weight epoxy resin (A) is obtained by removing the produced salt by filtration, washing with water, and removing the solvent under reduced pressure by heating.
- the epoxy equivalent of the epoxy resin (A) is usually 160 to 200 g / eq, and bis (4-oxyglycidylphenyl) methane is the main component.
- the charge ratio of epoxy resin (A) to 4, 4'-biphenol is The amount of the hydroxyl group of the compound of the formula (3) is usually from 0.05 to 0.95 monole, preferably from 0.1 to 0.9 monole per 1 mol of the epoxy group of the epoxy resin (A). .
- the non-reaction can be carried out without a catalyst, but it is preferable to use a catalyst in order to accelerate the reaction.
- Catalysts that can be used include triphenylphosphine, tetramethylammonium chloride, sodium hydroxide, potassium hydroxide, benzyltriphenylphosphonium chloride, butyltriphenylphosphonium, ethyltriphenylphosphonium. Examples thereof include dydo and etyltriphenyl phosphonium bromide.
- the amount of the catalyst used is usually 0.01 to 10 parts by weight, preferably 0.05 to 5 parts by weight, based on 1 mol of the epoxy group of the epoxy resin (A).
- a solvent for controlling the reaction temperature examples include cyclopentanone, cyclohexanone, methylisobutylketone, methylethylketone, acetone, toluene, N-methylpyrrolidone, N, N-dimethylsulfoxide, N, N-dimethylformamide, and the like.
- the amount of the solvent used is usually 5 to 150% by weight, preferably 10 to 100% by weight, based on the total weight of the epoxy resin (A) and the compound of the formula (3).
- the reaction temperature is usually from 60 to 180 ° C, preferably from 70 to 160 ° C.
- the progress of the reaction can be traced by GPC (gel permeation chromatography) and so on until the compound of formula (3) is not completely detected.
- the reaction time is usually 0.5 to 15 hours, preferably 1 to 10 hours.
- the ability to obtain the epoxy resin (B) of the present invention by distilling off the solvent used as necessary from the reaction mixture thus obtained. Obtaining crystalline powder as follows depending on the use of the epoxy resin. Can do.
- crystals of the epoxy resin of the present invention are precipitated by adding a poor solvent and cooling.
- the poor solvent include methyl isobutyl ketone, methyl ethyl ketone, acetone, toluene, methanol, ethanol and water.
- the amount of the poor solvent to be added is usually 50 to 400% by weight, preferably 100 to 300% by weight, based on the total weight of the epoxy resin (A) and the compound of formula (3).
- the crystalline epoxy resin (B) of the present invention can be obtained by filtering and drying.
- the resinous epoxy resin (B) can be crystallized by heating it above its melting point and gradually cooling it. It is a matter of making it a lunar month lumps.
- the reaction is carried out without a solvent, after completion of the reaction, the product is dissolved in a good solvent such as N-methylpyrrolidone, dimethyl sulfoxide, N, N-dimethylformamide, and then methanol, ethanol
- a good solvent such as N-methylpyrrolidone, dimethyl sulfoxide, N, N-dimethylformamide, and then methanol, ethanol
- the epoxy resin of the present invention can be obtained in good yield by adding a water-soluble poor solvent such as isopropanol, acetone, methyl ethyl ketone, and further adding water.
- the amount of the good solvent used is usually 5 to 200% by weight, preferably 10 to 150% by weight, based on the total weight of the epoxy resin (A) and the compound of the formula (3).
- the amount of the water-soluble poor solvent used is usually 5 to 200% by weight, preferably 10 to 150% by weight, based on the theoretical yield of the epoxy resin.
- the amount of water used is usually 50 to 400% by weight, preferably 100 to 300% by weight, based on the total weight of the epoxy resin (A) and the compound of formula (3).
- the epoxy resin (B) thus obtained is a crystalline one, usually having a melting point of 70 to 180.
- the epoxy equivalent of the epoxy resin (B) of the present invention is usually 200 to 2000 g / eq, preferably 250 to 1500 g / eq, particularly preferably 250 to 1000 g / eq.
- DSC differential thermal analyzer
- endothermic peaks are often observed at two or more locations. This phenomenon indicates that the epoxy resin (B) has liquid crystallinity.
- the temperature range in which the epoxy resin (B) exhibits optical anisotropy is 100 to 200 ° C.
- n in the formula (1) of the obtained epoxy resin is usually a force representing an average value of 0.:! To 20, preferably 0.3 to 5, particularly preferably 0.5 to 2.
- the value of n can be estimated for the obtained resin by GPC, NMR measurements or calculations from epoxy equivalents.
- the obtained epoxy resin (B) can be used even in the crystalline state in the preparation of the epoxy resin composition. Can be used. In the resin state, the softening point is usually 45 to 100 ° C.
- the epoxy resin of the present invention is By combining with a curing agent, curing accelerator, cyanate resin, etc., it can be used as a curable resin composition.
- Specific examples of applications include printed wiring boards, sono-redder resists, semiconductor encapsulants, retardation films, molding materials, and adhesives.
- the epoxy resin composition of the present invention contains the epoxy resin of the present invention and a curing agent as essential components.
- the epoxy resin of the present invention can be used alone or in combination with other epoxy resins.
- the proportion of the epoxy resin of the present invention in the total epoxy resin is preferably 30% by weight or more, especially 40% by weight or more.
- Examples of the curing agent contained in the epoxy resin composition of the present invention include amine compounds, acid anhydride compounds, amide compounds, and phenol compounds.
- Specific examples of curing agents that can be used include polyamides synthesized from diaminodiphenylmethane, diethylenetriamine, triethylenetetramine, diaminodiphenylsulfone, isophorone diamine, dicyandiamide, linolenic acid dimer and ethylene diamine.
- Resin phthalic anhydride, anhydrous trimellitic acid, pyromellitic anhydride, maleic anhydride, tetrahydrophthalic anhydride, methyl tetrahydrophthalic anhydride, methyl nadic anhydride, hexahydrophthalic anhydride, methyl hexahydrophthalic anhydride, Examples include, but are not limited to, phenol novolacs, modified products thereof, imidazoles, BF-amine complexes, guanidine derivatives, and the like.
- the amount of the curing agent used in the epoxy resin composition of the present invention is preferably 0.7 to 1.2 equivalents relative to 1 equivalent of epoxy group of the epoxy resin. If it is less than 0.7 equivalent to 1 equivalent of epoxy group, or exceeds 1.2 equivalent, curing may be incomplete and good cured properties may not be obtained.
- a curing accelerator can also be used in the epoxy resin composition of the present invention.
- curing accelerators that can be used include imidazoles such as 2-methylimidazole, 2_ethylimidazole, 2_ethyl_4-methylimidazole, 2- (dimethylenoreaminomethyl) phenol, 1,8_diazabicyclo ( 5, 4, 0) tertiary amines such as undecene_7, phosphines such as triphenylphosphine, and metal compounds such as tin octylate.
- the curing accelerator is used in an amount of 0.:! To 5.0 parts by weight based on 100 parts by weight of the epoxy resin as necessary.
- the epoxy resin composition of the present invention may optionally contain an inorganic filler.
- the inorganic filler that can be used include silica, alumina, and talc.
- the inorganic filler is used in an amount of 0 to 90% by weight in the epoxy resin composition of the present invention.
- various compounding agents such as a silane coupling agent, a release agent such as stearic acid, palmitic acid, zinc stearate and calcium stearate, and a pigment can be added to the epoxy resin composition of the present invention.
- the epoxy resin composition of the present invention can be obtained by uniformly mixing the respective components.
- the epoxy resin composition of the present invention can be easily hardened by a method similar to a conventionally known method.
- the epoxy resin composition of the present invention, a curing agent and, if necessary, a curing accelerator, an inorganic filler, and a compounding agent are mixed thoroughly as required using an extruder, kneader, roll, etc.
- a cured product can be obtained by melting the epoxy resin composition after melting and molding it using a casting or transfer molding machine, and further heating at 80 to 200 ° C. for 2 to 10 hours.
- An organic solvent can be added to the epoxy resin composition of the present invention to form a varnish-like composition (hereinafter simply referred to as varnish).
- Solvents used include, for example, ⁇ -butyrate ratatones, ⁇ ⁇ ⁇ -methylpyrrolidone, ⁇ , ⁇ -dimethylformamide, ⁇ , ⁇ -dimethylacetamide, ⁇ , ⁇ -dimethylimidazolidinone, and other amide-based homozygous 1J , Selephones such as tetramethylene sulphone, diethylene glycol dimethyl ether, diethylene glycol jetyl etherol, propylene glycol nore, propylene glycol nole monomethino ethenore, propylene glycol nole mono methino ethenore monoacetate, propylene glycol nore mono butino rea Ether solvents such as tellurium, ketone solvents such as methyl ethyl ketone,
- the epoxy resin composition of the present invention is obtained by drying the above varnish on a planar support by various coating methods such as a gravure coating method, screen printing, metal mask method, and spin coating method known per se. It is possible to obtain a sheet by drying after coating so that the thickness becomes a predetermined thickness, for example, 5 to 100 ⁇ m. In this case, which coating method is used is appropriately selected depending on the type, shape, size, and thickness of the coating film.
- the base material examples include various polymers such as polyamide, polyamidoimide, polyarylate, polyethylene terephthalate, polybutylene terephthalate, polyether ether ketone, polyetheroleimide, polyetherenoketone, polyketone, polyethylene, and polypropylene, and / or It is a metal foil such as a finolome made of the copolymer or a copper foil, and particularly preferably a polyimide or a metal foil. Further, a sheet-like cured product can be obtained by further heating.
- the epoxy resin composition of the present invention is dissolved in a solvent such as toluene, xylene, acetone, methyl ethyl ketone, methyl isobutyl ketone, etc., and glass fiber, carbon fiber, polyester fiber, polyamide fiber, alumina fiber, paper, etc. It is also possible to obtain a cured product by hot press-molding a pre-preda obtained by impregnating the substrate with heat and drying.
- the solvent is used in an amount of 10 to 70% by weight, preferably 15 to 70% by weight in the mixture of the epoxy resin composition of the present invention and the solvent.
- the crystals were filtered and dried to obtain 103 parts of a white powdery epoxy resin (B1) of the present invention.
- the epoxy equivalent of this epoxy resin (B1) was 443 g / eq (n 1 ⁇ 09 of formula (1) (average value; calculated from epoxy equivalent)).
- DSC differential thermal analyzer
- the DSC measurement results showed two peak tops, 125 ° C and 160 ° C.
- the epoxy resin (B) was observed at a temperature rising rate of 1 ° C per minute using a polarizing microscope, it was confirmed that the epoxy resin exhibited optical anisotropy at 140 to 160 ° C. .
- Epoxy resin (B1) obtained in Example 1 as Example 2 8. 9 parts phenol alcohol resin XLC-3L (Mitsui Chemicals, softening point 71 ° C, hydroxyl equivalent) 174 g / eq) 3.5 parts, 2PHZ-PW (manufactured by Shikoku Kasei Co., Ltd.) as a curing accelerator, 0.1 part, and 5.4 parts of cyclopentanone as a solvent were mixed uniformly to prepare a varnish.
- phenol alcohol resin XLC-3L Mitsubishi Chemicals, softening point 71 ° C, hydroxyl equivalent
- 2PHZ-PW manufactured by Shikoku Kasei Co., Ltd.
- the epoxy resin (B2) of the present invention obtained in Example 3 as Example 4 and the high molecular weight bisphenol F-type epoxy resin as Comparative Example 1 (YDF-2001, Epoxy equivalent 471 g / eq. Manufactured by Tohto Kasei Co., Ltd.)
- phenol novolak Maywa Kasei Kogyo Co., Ltd., H_l, hydroxyl group equivalent 105gZeq.
- TPP triphenylphosphine
- Table 2 shows the results of measuring the physical properties of the cured product thus obtained.
- the physical property values were measured by the following methods.
- the epoxy resin of the present invention provides a cured product excellent in fracture toughness and thermal conductivity as compared with known bisphenol F-type epoxy resins.
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Epoxy Resins (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
Description
Claims
Priority Applications (3)
Application Number | Priority Date | Filing Date | Title |
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JP2006549030A JP5196625B2 (ja) | 2004-12-21 | 2005-12-21 | エポキシ樹脂、エポキシ樹脂組成物及びその硬化物 |
US11/722,415 US20080153976A1 (en) | 2004-12-21 | 2005-12-21 | Epoxy Resin, Epoxy Resin Composition, And Cured Material Thereof |
CN2005800440373A CN101084252B (zh) | 2004-12-21 | 2005-12-21 | 环氧树脂、环氧树脂组合物及其固化物 |
Applications Claiming Priority (2)
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JP2004369304 | 2004-12-21 | ||
JP2004-369304 | 2004-12-21 |
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WO2006068185A1 true WO2006068185A1 (ja) | 2006-06-29 |
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PCT/JP2005/023505 WO2006068185A1 (ja) | 2004-12-21 | 2005-12-21 | エポキシ樹脂、エポキシ樹脂組成物及びその硬化物 |
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US (1) | US20080153976A1 (ja) |
JP (1) | JP5196625B2 (ja) |
KR (1) | KR101217385B1 (ja) |
CN (1) | CN101084252B (ja) |
TW (1) | TWI397540B (ja) |
WO (1) | WO2006068185A1 (ja) |
Cited By (1)
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WO2019208242A1 (ja) * | 2018-04-27 | 2019-10-31 | 東レ株式会社 | プリプレグおよび炭素繊維強化複合材料 |
Families Citing this family (6)
Publication number | Priority date | Publication date | Assignee | Title |
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JP4433368B2 (ja) | 2003-04-08 | 2010-03-17 | ジャパンエポキシレジン株式会社 | エポキシ樹脂粒状化物及びその製造方法 |
US20120244351A1 (en) * | 2009-09-29 | 2012-09-27 | Hideyuki Katagi | Multilayer resin sheet and method for producing the same, method for producing cured multilayer resin sheet, and highly thermally conductive resin sheet laminate and method for producing the same |
UA118255C2 (uk) * | 2012-12-07 | 2018-12-26 | Санофі | Композиція, яка містить антитіло до cd38 і леналідомід |
CN104356355B (zh) * | 2014-11-14 | 2017-11-03 | 宏昌电子材料股份有限公司 | 一种高韧性环氧树脂及其制备方法和应用 |
JP7119583B2 (ja) * | 2018-05-29 | 2022-08-17 | Tdk株式会社 | プリント配線板およびその製造方法 |
KR20230095527A (ko) * | 2021-12-22 | 2023-06-29 | 주식회사 포스코 | 전기강판 절연 피막 조성물, 전기강판, 및 이의 제조 방법 |
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JPH08109242A (ja) * | 1994-10-07 | 1996-04-30 | Yuka Shell Epoxy Kk | 半導体封止用エポキシ樹脂組成物 |
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JP2001261790A (ja) * | 2000-03-21 | 2001-09-26 | Sumitomo Bakelite Co Ltd | エポキシ樹脂組成物及び半導体装置 |
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US5310854A (en) * | 1989-08-23 | 1994-05-10 | The Dow Chemical Company | Epoxy resin composition and process therefor |
US4981926A (en) * | 1990-02-06 | 1991-01-01 | The Dow Chemical Company | Composition of epoxy resin, amino group-containing phosphonium catalyst and curing agent |
US5147905A (en) * | 1991-05-01 | 1992-09-15 | The Dow Chemical Company | Advanced and unadvanced compositions, nucleophilic derivatives thereof and curable and coating compositions thereof |
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JP2002212268A (ja) * | 2001-01-19 | 2002-07-31 | Japan Epoxy Resin Kk | 半導体封止用エポキシ樹脂組成物 |
JP3876709B2 (ja) * | 2001-12-25 | 2007-02-07 | 三菱電機株式会社 | 液状熱硬化性樹脂組成物、並びに液状熱硬化性樹脂組成物の製造方法と絶縁コイルの製造方法 |
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2005
- 2005-12-21 WO PCT/JP2005/023505 patent/WO2006068185A1/ja active Application Filing
- 2005-12-21 US US11/722,415 patent/US20080153976A1/en not_active Abandoned
- 2005-12-21 JP JP2006549030A patent/JP5196625B2/ja not_active Expired - Fee Related
- 2005-12-21 KR KR1020077014137A patent/KR101217385B1/ko active Active
- 2005-12-21 TW TW094145468A patent/TWI397540B/zh not_active IP Right Cessation
- 2005-12-21 CN CN2005800440373A patent/CN101084252B/zh not_active Expired - Fee Related
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JPH08109242A (ja) * | 1994-10-07 | 1996-04-30 | Yuka Shell Epoxy Kk | 半導体封止用エポキシ樹脂組成物 |
JPH09227653A (ja) * | 1996-02-23 | 1997-09-02 | Asahi Chiba Kk | 新規エポキシ樹脂およびエポキシ樹脂組成物 |
JP2001261790A (ja) * | 2000-03-21 | 2001-09-26 | Sumitomo Bakelite Co Ltd | エポキシ樹脂組成物及び半導体装置 |
Cited By (3)
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WO2019208242A1 (ja) * | 2018-04-27 | 2019-10-31 | 東レ株式会社 | プリプレグおよび炭素繊維強化複合材料 |
JPWO2019208242A1 (ja) * | 2018-04-27 | 2021-03-25 | 東レ株式会社 | プリプレグおよび炭素繊維強化複合材料 |
JP7264050B2 (ja) | 2018-04-27 | 2023-04-25 | 東レ株式会社 | プリプレグおよび炭素繊維強化複合材料 |
Also Published As
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TW200640975A (en) | 2006-12-01 |
KR101217385B1 (ko) | 2012-12-31 |
KR20070098814A (ko) | 2007-10-05 |
TWI397540B (zh) | 2013-06-01 |
CN101084252A (zh) | 2007-12-05 |
JPWO2006068185A1 (ja) | 2008-06-12 |
CN101084252B (zh) | 2012-06-13 |
JP5196625B2 (ja) | 2013-05-15 |
US20080153976A1 (en) | 2008-06-26 |
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