WO2013008680A1 - 硬化性エポキシ樹脂組成物 - Google Patents
硬化性エポキシ樹脂組成物 Download PDFInfo
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- WO2013008680A1 WO2013008680A1 PCT/JP2012/066966 JP2012066966W WO2013008680A1 WO 2013008680 A1 WO2013008680 A1 WO 2013008680A1 JP 2012066966 W JP2012066966 W JP 2012066966W WO 2013008680 A1 WO2013008680 A1 WO 2013008680A1
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- resin composition
- epoxy resin
- compound
- alicyclic
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- KSEBMYQBYZTDHS-UHFFFAOYSA-N ferulic acid Natural products COC1=CC(C=CC(O)=O)=CC=C1O KSEBMYQBYZTDHS-UHFFFAOYSA-N 0.000 description 1
- 235000001785 ferulic acid Nutrition 0.000 description 1
- 229940114124 ferulic acid Drugs 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- IVJISJACKSSFGE-UHFFFAOYSA-N formaldehyde;1,3,5-triazine-2,4,6-triamine Chemical compound O=C.NC1=NC(N)=NC(N)=N1 IVJISJACKSSFGE-UHFFFAOYSA-N 0.000 description 1
- 150000004675 formic acid derivatives Chemical class 0.000 description 1
- 150000002240 furans Chemical class 0.000 description 1
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 1
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 description 1
- 238000010559 graft polymerization reaction Methods 0.000 description 1
- 229910052621 halloysite Inorganic materials 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 125000006341 heptafluoro n-propyl group Chemical group FC(F)(F)C(F)(F)C(F)(F)* 0.000 description 1
- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 1
- FDVKPDVESAUTEE-UHFFFAOYSA-N hexane-1,6-diol;2-methylpentane-2,4-diol Chemical compound CC(O)CC(C)(C)O.OCCCCCCO FDVKPDVESAUTEE-UHFFFAOYSA-N 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 description 1
- 150000002460 imidazoles Chemical class 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 239000001282 iso-butane Substances 0.000 description 1
- 229910052622 kaolinite Inorganic materials 0.000 description 1
- 238000007561 laser diffraction method Methods 0.000 description 1
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 1
- 239000001095 magnesium carbonate Substances 0.000 description 1
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 1
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
- 239000000347 magnesium hydroxide Substances 0.000 description 1
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 1
- 235000012254 magnesium hydroxide Nutrition 0.000 description 1
- HCWCAKKEBCNQJP-UHFFFAOYSA-N magnesium orthosilicate Chemical compound [Mg+2].[Mg+2].[O-][Si]([O-])([O-])[O-] HCWCAKKEBCNQJP-UHFFFAOYSA-N 0.000 description 1
- GVALZJMUIHGIMD-UHFFFAOYSA-H magnesium phosphate Chemical compound [Mg+2].[Mg+2].[Mg+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O GVALZJMUIHGIMD-UHFFFAOYSA-H 0.000 description 1
- 239000004137 magnesium phosphate Substances 0.000 description 1
- 229910000157 magnesium phosphate Inorganic materials 0.000 description 1
- 229960002261 magnesium phosphate Drugs 0.000 description 1
- 235000010994 magnesium phosphates Nutrition 0.000 description 1
- 239000000391 magnesium silicate Substances 0.000 description 1
- 229910052919 magnesium silicate Inorganic materials 0.000 description 1
- 235000019792 magnesium silicate Nutrition 0.000 description 1
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 1
- 235000019341 magnesium sulphate Nutrition 0.000 description 1
- 239000001630 malic acid Substances 0.000 description 1
- 235000011090 malic acid Nutrition 0.000 description 1
- IJFXRHURBJZNAO-UHFFFAOYSA-N meta--hydroxybenzoic acid Natural products OC(=O)C1=CC=CC(O)=C1 IJFXRHURBJZNAO-UHFFFAOYSA-N 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- 125000006178 methyl benzyl group Chemical group 0.000 description 1
- 239000010445 mica Substances 0.000 description 1
- 229910052618 mica group Inorganic materials 0.000 description 1
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 1
- YPHQUSNPXDGUHL-UHFFFAOYSA-N n-methylprop-2-enamide Chemical compound CNC(=O)C=C YPHQUSNPXDGUHL-UHFFFAOYSA-N 0.000 description 1
- 125000004923 naphthylmethyl group Chemical group C1(=CC=CC2=CC=CC=C12)C* 0.000 description 1
- 229930014626 natural product Natural products 0.000 description 1
- 229910000008 nickel(II) carbonate Inorganic materials 0.000 description 1
- ZULUUIKRFGGGTL-UHFFFAOYSA-L nickel(ii) carbonate Chemical compound [Ni+2].[O-]C([O-])=O ZULUUIKRFGGGTL-UHFFFAOYSA-L 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 125000006344 nonafluoro n-butyl group Chemical group FC(F)(F)C(F)(F)C(F)(F)C(F)(F)* 0.000 description 1
- ZCYXXKJEDCHMGH-UHFFFAOYSA-N nonane Chemical compound CCCC[CH]CCCC ZCYXXKJEDCHMGH-UHFFFAOYSA-N 0.000 description 1
- BKIMMITUMNQMOS-UHFFFAOYSA-N normal nonane Natural products CCCCCCCCC BKIMMITUMNQMOS-UHFFFAOYSA-N 0.000 description 1
- HMZGPNHSPWNGEP-UHFFFAOYSA-N octadecyl 2-methylprop-2-enoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)C(C)=C HMZGPNHSPWNGEP-UHFFFAOYSA-N 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 125000001820 oxy group Chemical group [*:1]O[*:2] 0.000 description 1
- 125000005702 oxyalkylene group Chemical group 0.000 description 1
- 125000006340 pentafluoro ethyl group Chemical group FC(F)(F)C(F)(F)* 0.000 description 1
- 125000004817 pentamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 1
- WCVRQHFDJLLWFE-UHFFFAOYSA-N pentane-1,2-diol Chemical compound CCCC(O)CO WCVRQHFDJLLWFE-UHFFFAOYSA-N 0.000 description 1
- ULDDEWDFUNBUCM-UHFFFAOYSA-N pentyl prop-2-enoate Chemical compound CCCCCOC(=O)C=C ULDDEWDFUNBUCM-UHFFFAOYSA-N 0.000 description 1
- 125000005804 perfluoroheptyl group Chemical group FC(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)* 0.000 description 1
- 125000005005 perfluorohexyl group Chemical group FC(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)* 0.000 description 1
- 125000005007 perfluorooctyl group Chemical group FC(C(C(C(C(C(C(C(F)(F)F)(F)F)(F)F)(F)F)(F)F)(F)F)(F)F)(F)* 0.000 description 1
- 125000005008 perfluoropentyl group Chemical group FC(C(C(C(C(F)(F)F)(F)F)(F)F)(F)F)(F)* 0.000 description 1
- 125000004344 phenylpropyl group Chemical group 0.000 description 1
- 150000003003 phosphines Chemical class 0.000 description 1
- 150000003014 phosphoric acid esters Chemical class 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920001983 poloxamer Polymers 0.000 description 1
- 229920001521 polyalkylene glycol ether Polymers 0.000 description 1
- 229920001748 polybutylene Polymers 0.000 description 1
- 239000003505 polymerization initiator Substances 0.000 description 1
- 229920006375 polyphtalamide Polymers 0.000 description 1
- 150000007519 polyprotic acids Polymers 0.000 description 1
- 229920000734 polysilsesquioxane polymer Polymers 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- XRVCFZPJAHWYTB-UHFFFAOYSA-N prenderol Chemical compound CCC(CC)(CO)CO XRVCFZPJAHWYTB-UHFFFAOYSA-N 0.000 description 1
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- QTECDUFMBMSHKR-UHFFFAOYSA-N prop-2-enyl prop-2-enoate Chemical compound C=CCOC(=O)C=C QTECDUFMBMSHKR-UHFFFAOYSA-N 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 125000002572 propoxy group Chemical group [*]OC([H])([H])C(C([H])([H])[H])([H])[H] 0.000 description 1
- NHARPDSAXCBDDR-UHFFFAOYSA-N propyl 2-methylprop-2-enoate Chemical compound CCCOC(=O)C(C)=C NHARPDSAXCBDDR-UHFFFAOYSA-N 0.000 description 1
- PNXMTCDJUBJHQJ-UHFFFAOYSA-N propyl prop-2-enoate Chemical compound CCCOC(=O)C=C PNXMTCDJUBJHQJ-UHFFFAOYSA-N 0.000 description 1
- YQUVCSBJEUQKSH-UHFFFAOYSA-N protochatechuic acid Natural products OC(=O)C1=CC=C(O)C(O)=C1 YQUVCSBJEUQKSH-UHFFFAOYSA-N 0.000 description 1
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- 238000000790 scattering method Methods 0.000 description 1
- 239000003566 sealing material Substances 0.000 description 1
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- SCPYDCQAZCOKTP-UHFFFAOYSA-N silanol Chemical compound [SiH3]O SCPYDCQAZCOKTP-UHFFFAOYSA-N 0.000 description 1
- 239000005368 silicate glass Substances 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Inorganic materials [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000011973 solid acid Substances 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 239000012756 surface treatment agent Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 239000011975 tartaric acid Substances 0.000 description 1
- 235000002906 tartaric acid Nutrition 0.000 description 1
- 238000011191 terminal modification Methods 0.000 description 1
- 229920006027 ternary co-polymer Polymers 0.000 description 1
- ISXSCDLOGDJUNJ-UHFFFAOYSA-N tert-butyl prop-2-enoate Chemical compound CC(C)(C)OC(=O)C=C ISXSCDLOGDJUNJ-UHFFFAOYSA-N 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- TZLPVFCPHOVVII-UHFFFAOYSA-N tetrakis(4-methylphenyl)phosphanium tetraphenylphosphanium Chemical class C1(=CC=C(C=C1)[P+](C1=CC=C(C=C1)C)(C1=CC=C(C=C1)C)C1=CC=C(C=C1)C)C.C1(=CC=CC=C1)[P+](C1=CC=CC=C1)(C1=CC=CC=C1)C1=CC=CC=C1 TZLPVFCPHOVVII-UHFFFAOYSA-N 0.000 description 1
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 1
- QURCVMIEKCOAJU-UHFFFAOYSA-N trans-isoferulic acid Natural products COC1=CC=C(C=CC(O)=O)C=C1O QURCVMIEKCOAJU-UHFFFAOYSA-N 0.000 description 1
- 238000005809 transesterification reaction Methods 0.000 description 1
- 238000001721 transfer moulding Methods 0.000 description 1
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 description 1
- SRPWOOOHEPICQU-UHFFFAOYSA-N trimellitic anhydride Chemical compound OC(=O)C1=CC=C2C(=O)OC(=O)C2=C1 SRPWOOOHEPICQU-UHFFFAOYSA-N 0.000 description 1
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 description 1
- 125000003258 trimethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])[*:1] 0.000 description 1
- NLSXASIDNWDYMI-UHFFFAOYSA-N triphenylsilanol Chemical compound C=1C=CC=CC=1[Si](C=1C=CC=CC=1)(O)C1=CC=CC=C1 NLSXASIDNWDYMI-UHFFFAOYSA-N 0.000 description 1
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 1
- 229920001567 vinyl ester resin Polymers 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 238000004383 yellowing Methods 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
- 229910052984 zinc sulfide Inorganic materials 0.000 description 1
- JBCJMTUHAXHILC-UHFFFAOYSA-N zinc;octanoic acid Chemical compound [Zn+2].CCCCCCCC(O)=O JBCJMTUHAXHILC-UHFFFAOYSA-N 0.000 description 1
- DRDVZXDWVBGGMH-UHFFFAOYSA-N zinc;sulfide Chemical compound [S-2].[Zn+2] DRDVZXDWVBGGMH-UHFFFAOYSA-N 0.000 description 1
Images
Classifications
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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
- C08G59/226—Mixtures of di-epoxy compounds
-
- 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
- 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
- C08G59/26—Di-epoxy compounds heterocyclic
-
- 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
- C08G59/40—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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L21/00—Compositions of unspecified rubbers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L53/00—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; 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
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; 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
- C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
- C08L83/04—Polysiloxanes
- C08L83/06—Polysiloxanes containing silicon bound to oxygen-containing groups
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/20—Filters
- G02B5/26—Reflecting filters
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
- C08K5/0025—Crosslinking or vulcanising agents; including accelerators
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/34—Heterocyclic compounds having nitrogen in the ring
- C08K5/3467—Heterocyclic compounds having nitrogen in the ring having more than two nitrogen atoms in the ring
- C08K5/3477—Six-membered rings
- C08K5/3492—Triazines
- C08K5/34924—Triazines containing cyanurate groups; Tautomers thereof
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
- H01L2224/01—Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
- H01L2224/42—Wire connectors; Manufacturing methods related thereto
- H01L2224/47—Structure, shape, material or disposition of the wire connectors after the connecting process
- H01L2224/48—Structure, shape, material or disposition of the wire connectors after the connecting process of an individual wire connector
- H01L2224/4805—Shape
- H01L2224/4809—Loop shape
- H01L2224/48091—Arched
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L33/00—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L33/48—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by the semiconductor body packages
- H01L33/58—Optical field-shaping elements
- H01L33/60—Reflective elements
Definitions
- the present invention relates to a curable epoxy resin composition, a cured product obtained by curing the curable epoxy resin composition, a curable resin composition for light reflection comprising the curable epoxy resin composition, and an optical semiconductor element.
- the present invention relates to an optical semiconductor device including at least a reflector made of the cured product.
- Such a light emitting device generally has an optical semiconductor element and a transparent resin that protects the periphery of the optical semiconductor element, and further improves the efficiency of extracting light emitted from the optical semiconductor element.
- a light emitting device having a reflector (reflecting material) for reflecting light is widely used.
- the reflector is required to have high light reflectivity and to continuously exhibit such high light reflectivity.
- a resin composition in which an inorganic filler or the like is dispersed in a polyamide resin (polyphthalamide resin) having a terephthalic acid unit as an essential constituent unit is known (Patent Literature). 1 to 3).
- thermosetting resin composition for light reflection containing a thermosetting resin containing an epoxy resin and an inorganic oxide having a refractive index of 1.6 to 3.0 in a specific ratio.
- thermosetting resin composition for light reflection containing a thermosetting resin containing an epoxy resin and an inorganic oxide having a refractive index of 1.6 to 3.0 in a specific ratio.
- thermosetting resin component contains a thermosetting resin component and one or more filler components, and the difference between the refractive index of the entire thermosetting resin component and the refractive index of each filler component, and the volume ratio of each filler component
- Patent Document 5 A light-reflective thermosetting resin composition in which the calculated parameters are controlled within a specific range is known (see Patent Document 5).
- the reflectors made of the above-mentioned polyamide resins described in Patent Documents 1 to 3 are affected by light and heat emitted from the optical semiconductor element over time, particularly in a light emitting device using a high-power blue light semiconductor or white light semiconductor as a light source. There was a problem that it deteriorated due to yellowing or the like and sufficient light reflectivity could not be maintained. Further, with the adoption of lead-free solder, the heating temperature in the reflow process (solder reflow process) during the manufacture of the light emitting device tends to be higher. There was also a problem that the light reflectivity was deteriorated.
- the reflector is subjected to stress due to cutting or temperature change (for example, heating at a very high temperature such as a reflow process or a cooling cycle).
- it is required to be tough, such as being less prone to crack (cracking) (this characteristic is sometimes referred to as “crack resistance”). This is because if the reflector is cracked, the light reflectivity is lowered (that is, the light extraction efficiency is lowered), and it is difficult to ensure the reliability of the light emitting device.
- an object of the present invention is to provide a curable epoxy resin composition that has a high light reflectivity, is excellent in heat resistance and light resistance, is strong, and gives a cured product in which the light reflectivity is less likely to deteriorate over time. There is to do.
- Another object of the present invention is to cure the curable epoxy resin composition, have high light reflectivity, excellent heat resistance and light resistance, and toughness, and the light reflectivity over time. It is in providing the hardened
- Another object of the present invention is to provide a light-reflective curable resin composition capable of obtaining an optical semiconductor device in which a decrease in luminance of light over time is suppressed.
- Another object of the present invention is to provide a highly reliable optical semiconductor device in which the luminance of light is less likely to decrease over time.
- the present inventor includes an alicyclic epoxy compound, a monoallyl diglycidyl isocyanurate compound, and a white pigment as essential components, and further includes a curing agent and a curing accelerator, or curing. It has been found that a curable epoxy resin composition containing a catalyst has high light reflectivity, is excellent in heat resistance and light resistance, and is tough, and the light reflectivity hardly decreases over time. Furthermore, the inventor includes an alicyclic epoxy compound, a monoallyl diglycidyl isocyanurate compound, a siloxane derivative having two or more epoxy groups in the molecule, an alicyclic polyester resin, and a white pigment as essential components.
- the curable epoxy resin composition containing a curing agent and a curing accelerator or a curing catalyst has particularly high light reflectivity, excellent heat resistance and light resistance, and toughness, and light reflectivity over time. It has been found that a cured product that is difficult to decrease is given. The present invention has been completed based on these findings.
- the present invention relates to an alicyclic epoxy compound (A) and the following formula (1).
- a curable epoxy resin composition comprising a monoallyl diglycidyl isocyanurate compound (B) represented by the formula: a white pigment (C), a curing agent (D), and a curing accelerator (F). I will provide a.
- the present invention provides an alicyclic epoxy compound (A) and the following formula (1): [Wherein R 1 and R 2 represent a hydrogen atom or an alkyl group having 1 to 8 carbon atoms]
- the curable epoxy resin composition characterized by including the monoallyl diglycidyl isocyanurate compound (B) represented by these, a white pigment (C), and a curing catalyst (E) is provided.
- the curable epoxy resin composition is provided in which the alicyclic epoxy compound (A) is a compound having a cyclohexene oxide group.
- the alicyclic epoxy compound (A) is represented by the following formula (I-1)
- the said curable epoxy resin composition which is a compound represented by these is provided.
- the curable epoxy resin composition comprising the siloxane derivative (G) having two or more epoxy groups in the molecule is provided.
- the curable epoxy resin composition containing the alicyclic polyester resin (H) is provided.
- the said alicyclic polyester resin (H) provides the said curable epoxy resin composition which is an alicyclic polyester resin which has an alicyclic ring in a principal chain.
- the curable epoxy resin composition containing rubber particles is provided.
- the curable epoxy resin composition comprising at least one leveling agent selected from the group consisting of a silicone leveling agent and a fluorine leveling agent is provided.
- the curable epoxy resin composition containing a polyol compound is provided.
- the curable epoxy resin composition containing an acrylic block copolymer is provided.
- the present invention also provides a cured product obtained by curing the curable epoxy resin composition.
- the present invention also provides a curable resin composition for light reflection comprising the curable epoxy resin composition.
- the present invention also provides an optical semiconductor device comprising at least an optical semiconductor element and a reflector made of a cured product of the light reflecting curable resin composition.
- the curable epoxy resin composition of the present invention Since the curable epoxy resin composition of the present invention has the above-described configuration, the cured product obtained by curing the curable epoxy resin composition has high light reflectivity, and is excellent in heat resistance and light resistance. In addition, since it is tough and does not easily crack, the light reflectivity is unlikely to deteriorate with time. Therefore, the curable epoxy resin composition of the present invention can be preferably used as a curable resin composition for light reflection for various uses related to optical semiconductor devices, particularly for LED packages. Furthermore, a reflector (reflecting material) made of a cured product of the curable epoxy resin composition (curable resin composition for light reflection) of the present invention can continue to exhibit high light reflectivity for a long period of time. An optical semiconductor device (light emitting device) including at least an element and the reflector can exhibit high reliability as a long-life optical semiconductor device.
- the curable epoxy resin composition of the present invention comprises an alicyclic epoxy compound (A) and the following formula (1).
- the alicyclic epoxy compound (A) constituting the curable epoxy resin composition of the present invention is a compound having at least an alicyclic (aliphatic ring) structure and an epoxy group in the molecule (in one molecule). More specifically, the alicyclic epoxy compound (A) includes, for example, (i) an epoxy group composed of two adjacent carbon atoms and oxygen atoms constituting the alicyclic ring (“alicyclic epoxy group”). And (ii) a compound in which an epoxy group is directly bonded to the alicyclic ring by a single bond. However, the alicyclic epoxy compound (A) does not include a siloxane derivative (G) having two or more epoxy groups in the molecule described later.
- G siloxane derivative
- a compound having an epoxy group (alicyclic epoxy group) composed of two adjacent carbon atoms and oxygen atoms constituting an alicyclic ring is arbitrarily selected from known or commonly used compounds. be able to.
- the above compound has an epoxy group composed of two adjacent carbon atoms and oxygen atoms constituting the cyclohexane ring, that is, a compound having a cyclohexene oxide group (alicyclic epoxy compound). preferable.
- the alicyclic epoxy compound (alicyclic epoxy resin) represented by I) is preferable.
- X represents a single bond or a linking group (a divalent group having one or more atoms).
- the linking group include divalent hydrocarbon groups, carbonyl groups, ether groups (ether bonds), thioether groups (thioether bonds), ester groups (ester bonds), carbonate groups (carbonate bonds), amide groups (amides). Bond), and a group in which a plurality of these are linked.
- Examples of the alicyclic epoxy compound in which X in the formula (I) is a single bond include compounds represented by the following formula.
- an alicyclic epoxy compound for example, a commercial product such as a trade name “Celoxide 8000” (manufactured by Daicel Corporation) can be used.
- Examples of the divalent hydrocarbon group include a linear or branched alkylene group having 1 to 18 carbon atoms and a divalent alicyclic hydrocarbon group.
- Examples of the linear or branched alkylene group having 1 to 18 carbon atoms include a methylene group, a methylmethylene group, a dimethylmethylene group, an ethylene group, a propylene group, and a trimethylene group.
- Examples of the divalent alicyclic hydrocarbon group include 1,2-cyclopentylene group, 1,3-cyclopentylene group, cyclopentylidene group, 1,2-cyclohexylene group, 1,3-cyclohexene group.
- divalent cycloalkylene groups including cycloalkylidene groups
- the linking group X is preferably a linking group containing an oxygen atom, and specifically includes, for example, —CO— (carbonyl group), —O—CO—O— (carbonate group), —COO— ( Ester group), —O— (ether group), —CONH— (amide group), a group in which a plurality of these groups are linked, one or more of these groups and one or more of divalent hydrocarbon groups And a group in which and are linked.
- Examples of the divalent hydrocarbon group include those exemplified above.
- Representative examples of the alicyclic epoxy compound represented by the above formula (I) include compounds represented by the following formulas (I-1) to (I-10). As these compounds, for example, commercially available products such as trade names “Celoxide 2021P” and “Celoxide 2081” (manufactured by Daicel Corporation) can also be used. In the following formulas (I-5) and (I-7), l and m each represents an integer of 1 to 30.
- R in the following formula (I-5) is an alkylene group having 1 to 8 carbon atoms, and is a methylene group, ethylene group, propylene group, isopropylene group, butylene group, isobutylene group, s-butylene group, pentylene group, hexylene.
- linear or branched alkylene groups such as a group, heptylene group, and octylene group.
- a linear or branched alkylene group having 1 to 3 carbon atoms such as a methylene group, an ethylene group, a propylene group, and an isopropylene group is preferable.
- n1 to n6 each represents an integer of 1 to 30.
- Examples of the compound in which the epoxy group is directly bonded to the alicyclic ring with a single bond include compounds represented by the following formula (II).
- R ′ is a group obtained by removing p —OH from a p-valent alcohol, and p and n each represent a natural number.
- Examples of the p-valent alcohol [R ′-(OH) p ] include alcohols having 1 to 15 carbon atoms, and more specifically 2,2-bis (hydroxymethyl) -1-butanol and the like. And polyhydric alcohols.
- p is preferably 1 to 6
- n is preferably 1 to 30. When p is 2 or more, n in each () (in parentheses) may be the same or different.
- the alicyclic epoxy compound (A) can be used alone or in combination of two or more.
- the alicyclic epoxy compound (A) 3,4-epoxycyclohexylmethyl (3,4-epoxy) cyclohexanecarboxylate represented by the above formula (I-1), trade name “Celoxide 2021P” Is particularly preferred.
- the amount of use (content) of the alicyclic epoxy compound (A) is not particularly limited, but when the curable epoxy resin composition of the present invention contains the curing agent (D) as an essential component, a white pigment (C 10 to 90% by weight, more preferably 15 to 80% by weight, and still more preferably 18 to 70% by weight, based on the total amount (100% by weight) of the curable epoxy resin composition excluding).
- the amount (content) of the alicyclic epoxy compound (A) excludes the white pigment (C).
- the amount is preferably 25 to 95% by weight, more preferably 30 to 92% by weight, and still more preferably 35 to 90% by weight with respect to the total amount (100% by weight) of the curable epoxy resin composition.
- the curable epoxy resin composition of the present invention contains one or both of a siloxane derivative (G) having two or more epoxy groups in the molecule and an alicyclic polyester resin (H) (especially both)
- the amount (content) of the alicyclic epoxy compound (A) used is not particularly limited, but when the curable epoxy resin composition of the present invention contains the curing agent (D) as an essential component, The content is preferably 5 to 90% by weight, more preferably 8 to 80% by weight, still more preferably 10 to 75% by weight, based on the total amount (100% by weight) of the curable epoxy resin composition excluding the white pigment (C).
- the curing catalyst (E) is an essential component.
- the amount used (content) is 10 to 95% by weight based on the total amount (100% by weight) of the curable epoxy resin composition excluding the white pigment (C). It is preferably 15 to 85% by weight, more preferably 20 to 75% by weight.
- the usage-amount (content) of an alicyclic epoxy compound (A) with respect to the total amount (100 weight%) of an alicyclic epoxy compound (A) and a monoallyl diglycidyl isocyanurate compound (B) is especially limited. However, it is preferably 50 to 95% by weight, more preferably 50 to 90% by weight, still more preferably 60 to 90% by weight, and particularly preferably 70 to 90% by weight.
- the amount of the alicyclic epoxy compound (A) used is less than 50% by weight, the solubility of the monoallyl diglycidyl isocyanurate compound (B) is not sufficient, and it may be easily precipitated when placed at room temperature.
- the usage-amount of an alicyclic epoxy compound (A) exceeds 95 weight%, the toughness of hardened
- the monoallyl diglycidyl isocyanurate compound (B) constituting the curable epoxy resin composition of the present invention is represented by the following general formula (1).
- R 1 and R 2 are the same or different and each represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms.
- alkyl group having 1 to 8 carbon atoms examples include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, s-butyl, pentyl, hexyl, heptyl, octyl and the like. Examples thereof include a chain or branched alkyl group. Of these, a linear or branched alkyl group having 1 to 3 carbon atoms such as a methyl group, an ethyl group, a propyl group, and an isopropyl group is preferable.
- R 1 and R 2 in the above formula (1) are particularly preferably hydrogen atoms.
- monoallyl diglycidyl isocyanurate compound (B) examples include monoallyl diglycidyl isocyanurate, 1-allyl-3,5-bis (2-methylepoxypropyl) isocyanurate, 1- (2-methyl And propenyl) -3,5-diglycidyl isocyanurate, 1- (2-methylpropenyl) -3,5-bis (2-methylepoxypropyl) isocyanurate, and the like.
- a monoallyl diglycidyl isocyanurate compound (B) can be used individually or in combination of 2 or more types.
- the monoallyl diglycidyl isocyanurate compound (B) can be arbitrarily mixed as long as it dissolves in the alicyclic epoxy compound (A), and the alicyclic epoxy compound (A) and the monoallyl diglycidyl isocyanurate compound (B).
- the ratio of alicyclic epoxy compound (A): monoallyl diglycidyl isocyanurate compound (B) is preferably 50:50 to 95: 5 (weight ratio), more preferably 50: 50 to 90:10 (weight ratio). Outside this range, it becomes difficult to obtain the solubility of the monoallyl diglycidyl isocyanurate compound (B).
- the monoallyl diglycidyl isocyanurate compound (B) may be modified in advance by adding a compound that reacts with an epoxy group such as alcohol or acid anhydride.
- the white pigment (C) which is an essential component of the curable epoxy resin composition of the present invention, plays a role of exerting high light reflectivity on a cured product obtained by curing the curable epoxy resin composition.
- white pigment (C) known or commonly used white pigments can be used, and are not particularly limited.
- Inorganic white pigments such as clay, boehmite, pseudoboehmite, inorganic oxides, metal salts such as alkaline earth metal salts; styrene resins, benzoguanamine resins, urea-formalin resins, melamine-formalin resins, amide resins, etc.
- Organic white pigments such as resin pigments (plastic pigments); hollow particles having a hollow structure (balloon structure), and the like. These white pigments can be used alone or in combination of two or more.
- Examples of the inorganic oxide include aluminum oxide (alumina), magnesium oxide, antimony oxide, titanium oxide (rutile type titanium oxide, anatase type titanium oxide, brookite type titanium oxide), zirconium oxide, zinc oxide, silicon oxide (dioxide dioxide). Silicon).
- Examples of the alkaline earth metal salt include magnesium carbonate, calcium carbonate, barium carbonate, magnesium silicate, calcium silicate, magnesium hydroxide, magnesium phosphate, magnesium hydrogen phosphate, magnesium sulfate, calcium sulfate, and sulfuric acid. Examples include barium.
- Examples of the metal salt other than the alkaline earth metal salt include aluminum silicate, aluminum hydroxide, and zinc sulfide.
- metal oxides such as inorganic glass (for example, sodium silicate glass, aluminum silicate glass, sodium borosilicate glass, quartz, etc.), silica, alumina, calcium carbonate, barium carbonate, Inorganic hollow particles composed of inorganic substances such as nickel carbonate, calcium silicate and other metal salts (including natural products such as shirasu balloon); styrene resins, acrylic resins, silicone resins, acrylic-styrene resins, vinyl chloride -Based resins, vinylidene chloride-based resins, amide-based resins, urethane-based resins, phenol-based resins, styrene-conjugated diene-based resins, acrylic-conjugated diene-based resins, olefin-based polymers (including cross-linked products of these polymers), etc.
- inorganic glass for example, sodium silicate glass, aluminum silicate glass, sodium borosilicate glass, quartz, etc.
- silica
- the said hollow particle may be comprised from the single material, and may be comprised from 2 or more types of materials.
- the hollow portion of the hollow particles (the space inside the hollow particles) may be in a vacuum state or may be filled with a medium.
- the refractive index is low. Hollow particles filled with a medium (for example, an inert gas such as nitrogen or argon or air) are preferred.
- the white pigment (C) is subjected to known or conventional surface treatment (for example, surface treatment with a surface treatment agent such as a metal oxide, a silane coupling agent, a titanium coupling agent, an organic acid, a polyol, or silicone). It may be what was done. By performing such a surface treatment, the compatibility and dispersibility with other components of the white pigment (C) in the curable epoxy resin composition may be improved.
- a surface treatment agent such as a metal oxide, a silane coupling agent, a titanium coupling agent, an organic acid, a polyol, or silicone.
- the white pigment (C) is preferably an inorganic oxide or an inorganic hollow particle from the viewpoint of availability, heat resistance, and light resistance, and more preferably aluminum oxide, magnesium oxide, antimony oxide, titanium oxide, zirconium oxide, One or more white pigments selected from the group consisting of silicon oxide and inorganic hollow particles.
- the white pigment (C) is preferably titanium oxide because it has a higher refractive index.
- the shape of the white pigment (C) is not particularly limited, and examples thereof include a spherical shape, a crushed shape, a fiber shape, a needle shape, a scale shape, and a whisker shape. Among these, from the viewpoint of dispersibility of the white pigment (C), a spherical white pigment is preferable, and a true spherical white pigment (for example, a spherical white pigment having an aspect ratio of 1.2 or less) is particularly preferable.
- the center particle diameter of the white pigment (C) is not particularly limited, but is preferably 0.1 to 50 ⁇ m from the viewpoint of improving light reflectivity.
- the center particle diameter of the inorganic oxide is not particularly limited, but is preferably 0.1 to 50 ⁇ m, more preferably 0.1 to 30 ⁇ m, and still more preferably. It is 0.1 to 20 ⁇ m, particularly preferably 0.1 to 10 ⁇ m, and most preferably 0.1 to 5 ⁇ m.
- the center particle diameter of the hollow particles is not particularly limited, but is preferably 0.1 to 50 ⁇ m, more preferably 0.1 to 30 ⁇ m.
- the said center particle size means the particle size (median diameter) in the integrated value 50% in the particle size distribution measured by the laser diffraction / scattering method.
- the amount of white pigment (C) used (blending amount) in the curable epoxy resin composition of the present invention is not particularly limited, but is the total amount of compounds containing epoxy groups (total epoxy groups) contained in the curable epoxy resin composition.
- the content of compound is preferably 80 to 500 parts by weight, more preferably 90 to 400 parts by weight, and still more preferably 100 to 380 parts by weight with respect to 100 parts by weight. If the amount used is less than 80 parts by weight, the light reflectivity of the cured product tends to decrease. On the other hand, when the amount used exceeds 500 parts by weight, the toughness of the cured product tends to decrease.
- the white pigment (C) can be produced by a known or conventional production method.
- commercially available products can be used.
- curing agent (D) which comprises the curable epoxy resin composition of this invention bears the role which hardens the compound which has an epoxy group.
- curing agent (D) a well-known thru
- the curing agent (D) is preferably an acid anhydride which is liquid at 25 ° C. More specifically, for example, methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, dodecenyl succinic anhydride, methylendomethylene Examples include tetrahydrophthalic anhydride.
- solid acid anhydrides at room temperature such as phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, and methylcyclohexene dicarboxylic acid anhydride are also liquid at room temperature (about 25 ° C.). It can use preferably as a hardening
- anhydrides of saturated monocyclic hydrocarbon dicarboxylic acids are included. preferable.
- the curing agent (D) a product name “Ricacid MH-700” (manufactured by Shin Nippon Rika Co., Ltd.), a product name “HN-5500” (manufactured by Hitachi Chemical Co., Ltd.), etc. Commercial products can also be used.
- the amount of use (content) of the curing agent (D) is not particularly limited, but is 50 to 200 parts by weight with respect to the total amount (100 parts by weight) of the compound having an epoxy group contained in the curable epoxy resin composition. And more preferably 100 to 145 parts by weight. More specifically, it is preferably used at a ratio of 0.5 to 1.5 equivalents per 1 equivalent of epoxy groups in the compound having all epoxy groups contained in the curable epoxy resin composition of the present invention. .
- curing agent (D) is less than 50 weight part, hardening will become inadequate and there exists a tendency for the toughness of hardened
- curing agent (D) exceeds 200 weight part, hardened
- the curing accelerator (F) is a compound having a function of accelerating the curing rate when the compound having an epoxy group is cured by the curing agent (D).
- the curing accelerator (F) known or conventional curing accelerators can be used, and are not particularly limited.
- 1,8-diazabicyclo [5.4.0] undecene-7 DBU
- Salts thereof eg, phenol salts, octylates, p-toluenesulfonates, formates, tetraphenylborate salts
- 1,5-diazabicyclo [4.3.0] nonene-5 DBN
- salts thereof Eg, phenol salt, octylate, p-toluenesulfonate, formate, tetraphenylborate salt
- Imidazole compounds phosphoric acid esters, phosphines such as triphenylphosphine; tetraphenylphosphonium tetra (p- tolyl) phosphonium compounds such as borate, tin octylate, organic metal salts such as zinc octylate; metal chelate and the like.
- a hardening accelerator (F) can be used individually or in combination of 2 or more types.
- the amount of use (content) of the curing accelerator (F) is not particularly limited, but is 0.05 to 0.05 with respect to the total amount (100 parts by weight) of the compound having an epoxy group contained in the curable epoxy resin composition.
- the amount is preferably 5 parts by weight, more preferably 0.1 to 3 parts by weight, still more preferably 0.2 to 3 parts by weight, and particularly preferably 0.25 to 2.5 parts by weight.
- the usage-amount of a hardening accelerator (F) is less than 0.05 weight part, the hardening promotion effect may become inadequate.
- the curable epoxy resin composition of the present invention may contain a curing catalyst (E) instead of the above-mentioned curing agent (D).
- a curing catalyst (E) instead of the above-mentioned curing agent (D).
- the curing catalyst (E) by using the curing catalyst (E), the curing reaction of the compound having an epoxy group can be advanced to obtain a cured product.
- the curing catalyst (E) is not particularly limited.
- a cationic catalyst cationic polymerization initiator capable of generating a cationic species by starting ultraviolet irradiation or heat treatment to initiate polymerization can be used. .
- Examples of the cation catalyst that generates cation species by ultraviolet irradiation include hexafluoroantimonate salt, pentafluorohydroxyantimonate salt, hexafluorophosphate salt, and hexafluoroarsenate salt. These cationic catalysts can be used alone or in combination of two or more.
- cationic catalyst examples include trade names “UVACURE1590” (manufactured by Daicel Cytec Co., Ltd.), trade names “CD-1010”, “CD-1011”, “CD-1012” (above, manufactured by Sartomer, USA), Commercial products such as trade name “Irgacure 264” (manufactured by Ciba Japan Co., Ltd.) and trade name “CIT-1682” (manufactured by Nippon Soda Co., Ltd.) can also be preferably used.
- Examples of the cation catalyst that generates cation species by heat treatment include aryldiazonium salts, aryliodonium salts, arylsulfonium salts, and allene-ion complexes. These cationic catalysts can be used alone or in combination of two or more.
- Examples of the cationic catalyst include trade names “PP-33”, “CP-66”, “CP-77” (manufactured by ADEKA), trade names “FC-509” (manufactured by 3M), Name “UVE1014” (manufactured by GE), trade name “Sun-Aid SI-60L”, “Sun-Aid SI-80L”, “Sun-Aid SI-100L”, “Sun-Aid SI-110L”, “Sun-Aid SI-150L” (and above)
- Commercially available products such as Sanshin Chemical Co., Ltd.) and trade name “CG-24-61” (manufactured by Ciba Japan Co., Ltd.) can be preferably used.
- a compound of a chelate compound of a metal such as aluminum or titanium and acetoacetic acid or diketones and a silanol such as triphenylsilanol, or a metal such as aluminum or titanium and acetoacetic acid or diketones A compound of the above chelate compound and a phenol such as bisphenol S can also be used.
- the use amount (content) of the curing catalyst (E) is not particularly limited, but is 0.01 to 15 with respect to the total amount (100 parts by weight) of the compound having an epoxy group contained in the curable epoxy resin composition. Part by weight is preferable, more preferably 0.01 to 12 parts by weight, still more preferably 0.05 to 10 parts by weight, and particularly preferably 0.1 to 10 parts by weight.
- the curable epoxy resin composition of the present invention may contain a siloxane derivative (G) having two or more epoxy groups in the molecule and / or an alicyclic polyester resin (H).
- the curable epoxy resin composition of the present invention preferably contains a siloxane derivative (G) having two or more epoxy groups in the molecule and an alicyclic polyester resin (H). That is, the curable epoxy resin composition of the present invention comprises an alicyclic epoxy compound (A), a monoallyl diglycidyl isocyanurate compound (B) represented by the above formula (1), and two or more in the molecule.
- the curable epoxy resin composition of the present invention may contain a siloxane derivative (G) having two or more epoxy groups in the molecule (in one molecule).
- the siloxane derivative (G) having two or more epoxy groups in the molecule is a compound having a siloxane skeleton and having two or more epoxy groups in the molecule.
- the siloxane derivative (G) having two or more epoxy groups in the molecule plays a role of improving the heat resistance, light resistance, and crack resistance of the cured product and suppressing the decrease in luminous intensity of the optical semiconductor device.
- the siloxane skeleton in the siloxane derivative (G) having two or more epoxy groups in the molecule is not particularly limited.
- a cyclic siloxane skeleton; a linear silicone, a cage-type or ladder-type polysilsesquioxane And a polysiloxane skeleton are preferable from the viewpoint of improving the heat resistance and light resistance of the cured product and suppressing the decrease in luminous intensity.
- the siloxane derivative (G) having two or more epoxy groups in the molecule is preferably a cyclic siloxane having two or more epoxy groups in the molecule or a linear silicone having two or more epoxy groups in the molecule.
- numerator can be used individually or in combination of 2 or more types.
- the siloxane derivative (G) having two or more epoxy groups in the molecule is a cyclic siloxane having two or more epoxy groups
- the number of Si—O units forming the siloxane ring (the number of silicon atoms forming the siloxane ring)
- it is preferably 2 to 12 and more preferably 4 to 8 from the viewpoint of improving the heat resistance and light resistance of the cured product.
- the weight average molecular weight of the siloxane derivative (G) having two or more epoxy groups in the molecule is not particularly limited, but is preferably 100 to 3000, more preferably 180 from the viewpoint of improving the heat resistance and light resistance of the cured product. ⁇ 2000.
- the weight average molecular weight of the siloxane derivative (G) having two or more epoxy groups in the molecule can be measured as a value in terms of standard polystyrene by, for example, GPC (gel permeation chromatography) method.
- the number of epoxy groups (number of epoxy groups in one molecule) of the siloxane derivative (G) having two or more epoxy groups in the molecule is not particularly limited as long as it is two or more, but the heat resistance of the cured product, From the viewpoint of improving light resistance, 2 to 4 are preferable.
- the epoxy equivalent (based on JIS K7236) of the siloxane derivative (G) having two or more epoxy groups in the molecule is not particularly limited, but is preferably 180 to 400 from the viewpoint of improving the heat resistance and light resistance of the cured product. More preferably, it is 240 to 400, and more preferably 240 to 350.
- the epoxy group in the siloxane derivative (G) having two or more epoxy groups in the molecule is not particularly limited, but from the viewpoint of improving the heat resistance and light resistance of the cured product, adjacent two carbons constituting the aliphatic ring.
- An epoxy group composed of an atom and an oxygen atom (alicyclic epoxy group) is preferable, and among them, a cyclohexene oxide group is particularly preferable.
- siloxane derivative (G) having two or more epoxy groups in the molecule examples include 2,4-di [2- (3- ⁇ oxabicyclo [4.1.0] heptyl ⁇ ) ethyl. ] -2,4,6,6,8,8-hexamethyl-cyclotetrasiloxane, 4,8-di [2- (3- ⁇ oxabicyclo [4.1.0] heptyl ⁇ ) ethyl] -2,2 , 4,6,6,8-hexamethyl-cyclotetrasiloxane, 2,4-di [2- (3- ⁇ oxabicyclo [4.1.0] heptyl ⁇ ) ethyl] -6,8-dipropyl-2, 4,6,8-tetramethyl-cyclotetrasiloxane, 4,8-di [2- (3- ⁇ oxabicyclo [4.1.0] heptyl ⁇ ) ethyl] -2,6-dipropyl-2,4 6,8-tty
- siloxane derivative (G) having two or more epoxy groups in the molecule examples include alicyclic epoxy group-containing silicone resins described in JP-A-2008-248169, and JP-A-2008-19422.
- An organopolysilsesquioxane resin having at least two epoxy functional groups in one molecule can also be used.
- siloxane derivative (G) having two or more epoxy groups in the molecule examples include a trade name “X-40-2678” (Shin-Etsu Chemical Co., Ltd.), which is a cyclic siloxane having two or more epoxy groups in the molecule. )), Trade name “X-40-2670” (manufactured by Shin-Etsu Chemical Co., Ltd.), and trade name “X-40-2720” (manufactured by Shin-Etsu Chemical Co., Ltd.) can also be used. .
- the amount (content) of the siloxane derivative (G) having two or more epoxy groups in the molecule is not particularly limited, but is the total amount (100 weight) of the component (A), the component (B), and the component (G). %) Is preferably 5 to 80% by weight, more preferably 8 to 78% by weight, still more preferably 10 to 70% by weight, and particularly preferably 20 to 60% by weight.
- the amount of the siloxane derivative (G) having two or more epoxy groups in the molecule is less than 5% by weight, the heat resistance and light resistance of the cured product may be lowered.
- numerator exceeds 80 weight%, the crack resistance of hardened
- the total amount of the derivative (G) is not particularly limited, but is preferably 30% by weight or more (eg, 30 to 100% by weight), and particularly preferably 40% by weight or more from the viewpoint of improving heat resistance, light resistance, and crack resistance. preferable.
- the alicyclic polyester resin (H) is a polyester resin having at least an alicyclic structure (aliphatic ring structure).
- the alicyclic polyester resin (H) plays a role of improving the heat resistance, light resistance, and crack resistance of the cured product and suppressing the decrease in luminous intensity of the optical semiconductor device.
- the alicyclic polyester resin (H) is preferably an alicyclic polyester having an alicyclic ring (alicyclic structure) in the main chain. .
- the alicyclic polyester resin (H) is preferably a polyester resin in which a polymer main chain is constituted by part or all of carbon atoms constituting the alicyclic ring.
- an alicyclic polyester resin (H) can be used individually or in combination of 2 or more types.
- the alicyclic structure in the alicyclic polyester resin (H) is not particularly limited, and examples thereof include a monocyclic hydrocarbon structure and a bridged ring hydrocarbon structure (for example, a bicyclic hydrocarbon). Saturated monocyclic hydrocarbon structures and saturated bridged ring hydrocarbon structures in which all of the alicyclic rings (carbon-carbon bonds constituting the alicyclic rings) are carbon-carbon single bonds are preferred. Moreover, the alicyclic structure in the alicyclic polyester resin (H) may be introduced into either one of the structural unit derived from dicarboxylic acid or the structural unit derived from diol, or both may be introduced. Well, not particularly limited.
- the alicyclic polyester resin (H) has a structural unit derived from a monomer component having an alicyclic structure.
- the monomer having an alicyclic structure include diols and dicarboxylic acids having a known or commonly used alicyclic structure, and are not particularly limited.
- the alicyclic polyester resin (H) may have a structural unit derived from a monomer component having no alicyclic structure.
- the monomer component having no alicyclic structure is not particularly limited.
- aromatic dicarboxylic acids such as terephthalic acid, isophthalic acid, phthalic acid, and naphthalenedicarboxylic acid (including derivatives such as acid anhydrides); adipic acid Aliphatic dicarboxylic acids such as sebacic acid, azelaic acid, succinic acid, fumaric acid, maleic acid (including derivatives such as acid anhydrides); ethylene glycol, propylene glycol, 1,2-propanediol, 1,3-propane Diol, 1,3-butanediol, 1,4-butanediol, neopentyl glycol, 1,5-pentanediol, 1,6-hexanediol, 3-methylpentanediol, diethylene glyco
- a monomer component having no alicyclic structure also includes those obtained by bonding an appropriate substituent (for example, an alkyl group, an alkoxy group, a halogen atom, etc.) to the dicarboxylic acid or diol having no alicyclic structure.
- an appropriate substituent for example, an alkyl group, an alkoxy group, a halogen atom, etc.
- the ratio of the monomer unit having an alicyclic ring to the total monomer units (total monomer components) (100 mol%) constituting the alicyclic polyester resin (H) is not particularly limited, but is 10 mol% or more (for example, 10 to 80). Mol%) is preferable, more preferably 25 to 70 mol%, still more preferably 40 to 60 mol%. When the ratio of the monomer unit having an alicyclic ring is less than 10 mol%, the heat resistance, light resistance, and crack resistance of the cured product may be lowered.
- the alicyclic polyester resin (H) is particularly preferably an alicyclic polyester resin containing at least one structural unit represented by the following formulas (2) to (4).
- R 3 represents a linear, branched, or cyclic alkylene group having 2 to 15 carbon atoms.
- R 4 to R 7 are each independently a hydrogen atom, a linear or branched chain group. And an alkyl group having 1 to 4 carbon atoms of R 4 to R 7 may combine to form a ring.
- R 3 represents a linear, branched, or cyclic alkylene group having 2 to 15 carbon atoms.
- R 4 to R 7 are each independently a hydrogen atom, a linear or branched chain group. And a ring in which two members selected from R 4 to R 7 are bonded may be formed.
- R 3 represents a linear, branched, or cyclic alkylene group having 2 to 15 carbon atoms.
- R 4 to R 7 are each independently a hydrogen atom, a linear or branched chain group. And a ring in which two members selected from R 4 to R 7 are bonded may be formed.
- Preferred specific examples of the structural units represented by the above formulas (2) to (4) include, for example, a structure derived from 4-methyl-1,2-cyclohexanedicarboxylic acid and ethylene glycol represented by the following formula (5) Units are listed.
- the alicyclic polyester resin (H) having the structural unit can be obtained, for example, by polycondensation of methylhexahydrophthalic anhydride and ethylene glycol.
- the structural units represented by the above formulas (2) to (4) include, for example, those derived from 1,4-cyclohexanedicarboxylic acid and neopentyl glycol represented by the following formula (6):
- a structural unit is mentioned.
- the alicyclic polyester resin (H) having the structural unit can be obtained, for example, by polycondensation of 1,4-cyclohexanedicarboxylic acid and neopentyl glycol.
- the terminal structure of the alicyclic polyester resin (H) is not particularly limited, and may be a hydroxyl group or a carboxyl group, or a structure in which these hydroxyl group or carboxyl group is appropriately modified (for example, the terminal hydroxyl group is a mono group). It may be a structure esterified with a carboxylic acid or an acid anhydride, or a structure in which a terminal carboxyl group is esterified with an alcohol.
- the total content of the structural units (total content; all monomers constituting the structural unit)
- the unit is not particularly limited, but 20 mol% or more (for example, with respect to the total structural unit of the alicyclic polyester resin (H) (100 mol%; all monomer units constituting the alicyclic polyester resin (H)) (for example, 20 to 100 mol%), more preferably 50 to 100 mol%, still more preferably 80 to 100 mol%. If the content of the structural units represented by the above formulas (2) to (4) is less than 20 mol%, the heat resistance, light resistance and crack resistance of the cured product may be lowered.
- the number average molecular weight of the alicyclic polyester resin (H) is not particularly limited, but is preferably 300 to 100,000, more preferably 300 to 30,000. If the number average molecular weight of the alicyclic polyester resin (H) is less than 300, the toughness of the cured product may not be sufficient, and crack resistance may be reduced. On the other hand, when the number average molecular weight of the alicyclic polyester resin (H) exceeds 100,000, compatibility with other components (for example, the curing agent (D)) is lowered, and the mechanical properties of the cured product are adversely affected. Crack resistance may be reduced. In addition, the number average molecular weight of alicyclic polyester resin (H) can be measured as a value of standard polystyrene conversion by GPC (gel permeation chromatography) method, for example.
- an alicyclic polyester resin (H) can be used individually by 1 type or in combination of 2 or more types.
- the alicyclic polyester resin (H) is not particularly limited and can be produced by a known or conventional method. More specifically, for example, the alicyclic polyester resin (H) may be obtained by polycondensing the above-mentioned dicarboxylic acid and diol by a conventional method, or the above-mentioned dicarboxylic acid derivative (an acid anhydride, ester). , Acid halides, and the like) and diols may be obtained by polycondensation by a conventional method.
- the blending amount (content) of the alicyclic polyester resin (H) is not particularly limited, but when the curing agent (D) is an essential component, the alicyclic polyester resin.
- the amount is preferably 1 to 60% by weight, more preferably 5 to 30% by weight, based on the total amount (100% by weight) of (H) and the curing agent (D). If the blending amount of the alicyclic polyester resin (H) is less than 1% by weight, the crack resistance of the cured product may be lowered. On the other hand, when the compounding quantity of alicyclic polyester resin (H) exceeds 60 weight%, the heat resistance of hardened
- the amount (content) of the alicyclic polyester resin (H) is not particularly limited, but the alicyclic polyester The content is preferably 50 to 99% by weight, more preferably 65 to 99% by weight, based on the total amount (100% by weight) of the resin (H) and the curing catalyst (E).
- cured material may fall that the compounding quantity of alicyclic polyester resin (H) is less than 50 weight%.
- the blending amount of the alicyclic polyester resin (H) exceeds 99% by weight, the heat resistance of the cured product may be lowered.
- the curable epoxy resin composition of the present invention further includes at least one leveling agent selected from the group consisting of a silicone leveling agent (polysiloxane leveling agent) and a fluorine leveling agent.
- the curable epoxy resin composition of the present invention can form a cured product having higher heat resistance, light resistance, and crack resistance by including the leveling agent, and an optical semiconductor produced using the cured product. The apparatus is more unlikely to lose light intensity over time.
- the silicone leveling agent is a leveling agent containing a compound having a polysiloxane skeleton.
- known or conventional silicone leveling agents can be used and are not particularly limited. For example, trade names “BYK-300”, “BYK-301 / 302”, “BYK-306”, “ BYK-307, BYK-310, BYK-315, BYK-313, BYK-320, BYK-322, BYK-323, BYK-325, BYK- 330 ”,“ BYK-331 ”,“ BYK-333 ”,“ BYK-337 ”,“ BYK-341 ”,“ BYK-344 ”,“ BYK-345 / 346 ”,“ BYK-347 ”,“ BYK- ” 348 ”,“ BYK-349 ”,“ BYK-370 ”,“ BYK-375 ”,“ BYK-377 ”,“ BYK
- the compound having a polysiloxane skeleton is particularly preferably a silicone polymer (except for the component (C)) having at least a structural unit (repeating structural unit) represented by the following formula (7).
- the silicone leveling agent is preferably a leveling agent containing at least the silicone polymer.
- R 8 in the above formula (7) represents a linear or branched alkyl group which may have a substituent.
- the linear or branched alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group (n-butyl group), an isobutyl group, a s-butyl group, a t-butyl group, and pentyl.
- the substituent that the linear or branched alkyl group may have is not particularly limited, but for example, a hydroxyl group that may be protected with a protecting group [for example, a hydroxyl group, A substituted oxy group (for example, an alkoxy group having 1 to 4 carbon atoms such as a methoxy group, an ethoxy group, or a propoxy group)], a carboxyl group optionally protected by a protecting group [for example, a —COOR a group, etc .:
- R a represents a hydrogen atom or an alkyl group, and examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a s-butyl group, a t-butyl group, and a hexyl group.
- acryloyl group methacryloyl group, acryloyloxy group, methacryloyloxy group, vinyl , Propenyl group, an epoxy group, such as glycidyl groups.
- R 9 in the above formula (7) is a linear or branched alkyl group which may have a substituent, an aralkyl group which may have a substituent, an organic group containing a polyether chain, Or the organic group containing a polyester chain
- strand is shown.
- the linear or branched alkyl group for R 9 is not particularly limited, and examples thereof include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group (n-butyl group), an isobutyl group, and an s-butyl group.
- straight-chain or branched alkyl groups having 1 to 30 carbon atoms such as a group, t-butyl group and pentyl group.
- the aralkyl group is not particularly limited, and examples thereof include a benzyl group, a methylbenzyl group, a phenethyl group, a methylphenethyl group, a phenylpropyl group, and a naphthylmethyl group.
- the substituent that the linear or branched alkyl group may have and the substituent that the aralkyl group may have are not particularly limited.
- the substituent that the linear or branched alkyl group may have and the substituent that the aralkyl group may have are not particularly limited.
- examples thereof include the exemplified substituents.
- the organic group containing a polyether chain in R 9 is a monovalent organic group containing at least a polyether structure.
- the polyether structure in the organic group containing a polyether chain is not particularly limited as long as it has a structure having a plurality of ether bonds.
- polyethylene glycol structure polyethylene oxide structure
- polypropylene glycol structure polypropylene oxide structure
- polyoxyalkylene structures such as polybutylene glycol (polytetramethylene glycol) structures and polyether structures derived from multiple types of alkylene glycol (or alkylene oxide) (for example, poly (propylene glycol / ethylene glycol) structures). It is done.
- each alkylene glycol in the polyether structure derived from a plurality of types of alkylene glycols may be a block type (block copolymer type) or a random type (random copolymer type). Also good.
- the organic group containing the polyether chain may be an organic group consisting only of the polyether structure, or one or two or more of the polyether structure and one or two or more linking groups (one or more atoms may be bonded). It may be an organic group having a structure in which a divalent group) is linked.
- Examples of the linking group in the organic group containing a polyether chain include, for example, a divalent hydrocarbon group (particularly, a linear or branched alkylene group), a thioether group (—S—), an ester group (—COO—). ), An amide group (—CONH—), a carbonyl group (—CO—), a carbonate group (—OCOO—), a group in which two or more of these are bonded, and the like.
- the organic group containing the polyether chain is the substituent exemplified in the above R 8 (for example, hydroxyl group, carboxyl group, acryloyl group, methacryloyl group, acryloyloxy group, methacryloyloxy group, vinyl group, propenyl group, etc.
- examples of the organic group containing such a polyether structure include an organic group having the above substituent at the terminal (end on the opposite side to the silicon atom in Formula (7)). It is done.
- the organic group containing a polyester chain in R 9 is a monovalent organic group containing at least a polyester structure.
- the polyester structure in the organic group containing a polyester chain is not particularly limited as long as it has a structure having a plurality of ester bonds.
- aliphatic polyester structure, alicyclic polyester structure, aromatic polyester structure, aliphatic / Aromatic polyester structures, aliphatic / alicyclic polyester structures, alicyclic / aromatic polyester structures and the like can be mentioned.
- examples of the polyester structure include a polyester structure formed by polymerization of polycarboxylic acid (particularly dicarboxylic acid) and polyol (particularly diol).
- the polycarboxylic acid is not particularly limited, and examples thereof include aromatic dicarboxylic acids such as terephthalic acid, isophthalic acid, phthalic acid and naphthalenedicarboxylic acid (including derivatives such as acid anhydrides and esters); adipic acid and sebacic acid Aliphatic dicarboxylic acids such as azelaic acid, succinic acid, fumaric acid and maleic acid (including derivatives such as acid anhydrides and esters); 1,2-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, 1,4 -Cyclohexanedicarboxylic acid, 4-methyl-1,2-cyclohexanedicarboxylic acid, highmic acid, 1,4-decahydronaphthalenedicarboxylic acid,
- the polyol is not particularly limited.
- polyester structure examples include a polyester structure formed by polymerization of hydroxycarboxylic acid and a polyester structure formed by polymerization of lactone which is a cyclic ester of the hydroxycarboxylic acid (ring-opening polymerization).
- the hydroxycarboxylic acid is not particularly limited.
- p-hydroxybenzoic acid p-hydroxybenzoic acid, m-hydroxybenzoic acid, o-hydroxybenzoic acid (salicylic acid), 3-methoxy-4-hydroxybenzoic acid (vanillic acid), 4 -Methoxy-3-hydroxybenzoic acid (isovanillic acid), 3,5-dimethoxy-4-hydroxybenzoic acid (syringic acid), 2,6-dimethoxy-4-hydroxybenzoic acid, 3-methyl-4-hydroxybenzoic acid 4-methyl-3-hydroxybenzoic acid, 3-phenyl-4-hydroxybenzoic acid, 4-phenyl-3-hydroxybenzoic acid, 2-phenyl-4-hydroxybenzoic acid, 6-hydroxy-2-naphthoic acid, 3,4-dihydroxycinnamic acid (caffeic acid), (E) -3- (4-hydroxy-3-methoxy-phenyl) Nyl) propane-2-enolic acid (ferulic acid), 3- (4-hydroxyphenyl) -2-propenonic acid (coumaric
- the lactone is not particularly limited, and examples thereof include ⁇ -butyrolactone, ⁇ -valerolactone, ⁇ -caprolactone, ⁇ -enanthlactone, and ⁇ -caprolactone.
- the polyester structure may be formed from a single hydroxycarboxylic acid or lactone, or may be formed from two or more hydroxycarboxylic acids or lactones.
- the polyester structure is not limited to the structure exemplified above.
- the polyester structure formed by polymerization of the above polycarboxylic acid and polyol the polyester structure formed by polymerization of hydroxycarboxylic acid, and the polymerization of lactone.
- a structure in which two or more of the formed polyester structures are combined may be used.
- the organic group containing the polyester chain may be an organic group consisting only of the polyester structure, or an organic group having a structure in which one or two or more of the polyester structures and one or two or more connecting groups are connected. It may be.
- Examples of the linking group in the organic group containing a polyester chain include a divalent hydrocarbon group (particularly, a linear or branched alkylene group), a thioether group (—S—), an ester group (—COO—). Amide group (—CONH—), carbonyl group (—CO—), carbonate group (—OCOO—), a group in which two or more of these are bonded, and the like.
- the organic group containing the polyester chain is the substituent exemplified in the above R 8 (for example, hydroxyl group, carboxyl group, acryloyl group, methacryloyl group, acryloyloxy group, methacryloyloxy group, vinyl group, propenyl group, etc.)
- examples of the organic group containing such a polyester structure include an organic group having the above substituent at the terminal (end on the opposite side to the silicon atom in Formula (7)).
- the silicone polymer may be a polymer having only a structural unit represented by the formula (7) as a repeating structural unit, or may have a structural unit other than the structural unit represented by the formula (7). It may be a polymer.
- the structural unit other than the structural unit represented by the formula (7) in the silicone polymer is not particularly limited, and examples thereof include a structural unit having a hydrosilyl group (Si—H).
- the silicone polymer may be a polymer having only one type of structural unit represented by formula (7), or a polymer having two or more types of structural units represented by formula (7). It may be. Moreover, the polymer which has 2 or more types of structural units other than the structural unit represented by Formula (7) may be sufficient.
- silicone polymer examples include polymers (polydimethylsiloxane or modified polydimethylsiloxane) represented by the following formulas (7a) to (7e).
- the silicone polymer represented by the above formula (7a) is polydimethylsiloxane.
- the x1 (the number of repeating dimethylsilyloxy structural units [—Si (CH 3 ) 2 —O—]) in the formula (7a) is not particularly limited, but is preferably 2 to 3000, more preferably 3 to 1500.
- the silicone-based polymer represented by the above formula (7b) is a polyether-modified product of polydimethylsiloxane in which a polyether structure is introduced into the side chain of polydimethylsiloxane.
- R 10 in formula (7b) represents a hydrogen atom or a methyl group.
- R 11 represents a hydrogen atom or a linear or branched alkyl group which may have a substituent.
- M1 (the number of repeating methylene structural units) in the formula (7b) is not particularly limited, but can be appropriately selected from a range of 1 to 30, for example.
- n1 (the number of repeating oxyethylene structural units or oxypropylene structural units) is not particularly limited, but can be appropriately selected from a range of 2 to 3000, for example.
- y1 (the number of repeating structural units including a polyether structure (polyether side chain)) in the formula (7b) is not particularly limited, but is preferably 1 to 3000, and more preferably 3 to 1500.
- x2 (the number of repeating dimethylsilyloxy structural units) is not particularly limited, but is preferably 2 to 3000, and more preferably 3 to 1500.
- the addition form of the structural unit having a polyether structure and the dimethylsilyloxy structural unit in the silicone polymer represented by the formula (7b) may be a block type or a random type. Moreover, when y1 is an integer greater than or equal to 2, the structural unit which has the polyether structure enclosed by the parenthesis to which y1 was attached
- the silicone polymer represented by the above formula (7c) is a polydimethylsiloxane long-chain alkyl-modified product (polymethylalkylsiloxane) in which a side chain of polydimethylsiloxane has an alkyl group that is longer than a methyl group. It is.
- R 12 in the formula (7c) represents a linear or branched alkyl group having 2 or more carbon atoms.
- y2 (the number of repeating methylalkylsilyloxy structural units) is not particularly limited, but is preferably 2 to 3000, more preferably 3 to 1500.
- x3 (the number of repeating dimethylsilyloxy structural units) is not particularly limited, but is preferably 0 to 3000, and more preferably 2 to 1500.
- the addition form of the methylalkylsilyloxy structural unit and the dimethylsilyloxy structural unit in the silicone polymer represented by the formula (7c) may be a block type or a random type.
- the methylalkylsilyloxy structural units surrounded by parentheses with y2 may be the same or different.
- the silicone polymer represented by the above formula (7d) is an aralkyl modified product of polydimethylsiloxane in which an aralkyl group is introduced into the side chain of polydimethylsiloxane.
- M2 the number of repeating methylene structural units in the formula (7d) is not particularly limited, but can be appropriately selected from a range of 1 to 30, for example.
- y3 the number of repeating methylaralkylsilyloxy structural units
- x4 (the number of repeating dimethylsilyloxy structural units) is not particularly limited, but is preferably 0 to 3000, and more preferably 2 to 1500.
- the addition form of the methylaralkylsilyloxy structural unit and the dimethylsilyloxy structural unit in the silicone polymer represented by the formula (7d) may be a block type or a random type.
- the methylaralkylsilyloxy structural units enclosed in parentheses with y3 may be the same or different.
- the silicone-based polymer represented by the above formula (7e) is a polyester-modified polydimethylsiloxane in which a polyester structure is introduced into the side chain of polydimethylsiloxane.
- R 13 and R 14 in formula (7e) are the same or different and each represents a divalent organic group (for example, a divalent hydrocarbon group).
- R 15 represents a hydrogen atom or a linear or branched alkyl group which may have a substituent.
- R 15 include the substituents exemplified in R 8 above.
- M3 (the number of repeating methylene structural units) in the formula (7e) is not particularly limited, but can be appropriately selected from a range of 1 to 30, for example.
- n2 (the number of repetitions of the condensation structure of polyol and polycarboxylic acid) is not particularly limited, but can be appropriately selected from the range of 2 to 3000, for example.
- y4 (the number of repeating structural units including a polyester structure (polyester side chain)) in the formula (7e) is not particularly limited, but is preferably 1 to 3000, and more preferably 3 to 1500.
- x5 (the number of repeating dimethylsilyloxy structural units) is not particularly limited, but is preferably 2 to 3000, and more preferably 3 to 1500.
- the addition form of the structural unit having a polyester structure and the dimethylsilyloxy structural unit in the silicone-based polymer represented by the formula (7e) may be a block type or a random type.
- y4 is an integer greater than or equal to 2
- subjected may be the same respectively, and may differ.
- the silicone polymer can be obtained by a known or conventional production method, and the production method is not particularly limited.
- a monomer having a structure corresponding to the structural unit represented by the formula (7) is polymerized.
- a compound having a predetermined structure with respect to the reactive group of the silicone polymer having a reactive group in the side chain (polydimethylsiloxane having a reactive group in the side chain, etc.) (for example, a polyether structure)
- a compound having a polyester structure can be produced by a method of reacting and bonding them.
- a commercial item can also be used as said silicone type polymer.
- the fluorine-based leveling agent is a leveling agent containing a compound having a fluorinated alkyl group in which some or all of the hydrogen atoms of the alkyl group are substituted with fluorine atoms.
- the fluorine leveling agent may be a known or conventional fluorine leveling agent, and is not particularly limited.
- the fluorine leveling agent is preferably a leveling agent containing at least the fluorine-containing acrylic polymer or a leveling agent containing at least the fluorine-containing polyether polymer.
- R 16 in the above formula (8) is a hydrogen atom, a fluorine atom, or a linear or branched alkyl having 1 to 4 carbon atoms in which part or all of the hydrogen atoms may be substituted with a fluorine atom. Indicates a group. Examples of the linear or branched alkyl group having 1 to 4 carbon atoms include methyl group, ethyl group, propyl group, isopropyl group, butyl group, s-butyl group, and t-butyl group.
- R 17 in the above formula (8) represents a fluorinated alkyl group (an alkyl group in which some or all of the hydrogen atoms are substituted with fluorine atoms).
- the fluorinated alkyl group is not particularly limited, and examples thereof include a difluoromethyl group, a 2,2-difluoroethyl group, a 2,2,2-trifluoroethyl group, and a 2,2,3,3-tetrafluoropropyl group.
- the fluorine-containing acrylic polymer may be a polymer having only the structural unit represented by the formula (8) as the repeating structural unit, or other than the structural unit represented by the formula (8). It may be a polymer having a structural unit.
- the fluorine-containing acrylic polymer may be a polymer having only one type of structural unit represented by formula (8), or may have two or more types of structural units represented by formula (8). It may be a polymer.
- the polymer which has 2 or more types of structural units other than the structural unit represented by Formula (8) may be sufficient.
- the structural unit other than the structural unit represented by the formula (8), which the fluorine-containing acrylic polymer may have, is not particularly limited and is a monomer component (monomer component) of the acrylic polymer. And structural units derived from known or commonly used monomers.
- the monomer examples include acrylic acid esters such as methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, and pentyl acrylate (including those having a functional group such as a hydroxyl group or a carboxyl group); methacrylic acid Methacrylic esters such as methyl, ethyl methacrylate, propyl methacrylate and butyl methacrylate (including those having functional groups such as hydroxyl and carboxyl groups); acrylamides such as acrylamide and N-methylacrylamide; methacrylamide and the like Examples include methacrylamides; allyl compounds; vinyl compounds such as aromatic vinyl compounds, vinyl ethers, and vinyl esters. Further, an ester of polyalkylene glycol ether and acrylic acid or methacrylic acid can also be used as the monomer.
- fluorine-containing acrylic polymer examples include a fluorine-containing acrylic polymer represented by the following formula (8a).
- R 18 in formula (8a) represents a hydrogen atom or a methyl group.
- R 19 represents a linear or branched alkyl group.
- the linear or branched alkyl group is not particularly limited. For example, methyl group, ethyl group, propyl group, isopropyl group, butyl group (n-butyl group), isobutyl group, s-butyl group, t -Linear or branched alkyl groups having 1 to 30 carbon atoms such as butyl group and pentyl group.
- R 20 in formula (8a) represents a hydrogen atom or a methyl group.
- R 21 represents a perfluoroalkyl group. Examples of the perfluoroalkyl group is not particularly limited, for example, perfluoroalkyl groups such as exemplified as R 17 in the formula (8) below.
- R 22 in the formula (8a) represents a hydrogen atom or a methyl group.
- R 23 represents an organic group containing a polyether chain.
- the organic group comprising the polyether chain is not particularly limited, for example, such as those exemplified as R 9 in the formula (7) below.
- r, s, and t each represent an integer of 1 to 3000.
- the fluorine-containing acrylic polymer can be obtained by a known or conventional production method, and the production method is not particularly limited.
- a monomer that gives a structural unit represented by the formula (8) by polymerization For example, it can be produced by a method of polymerizing perfluoroalkyl acrylate or perfluoroalkyl methacrylate.
- a commercial item can also be used as said fluorine-containing acrylic polymer.
- R 24 in the above formula (9) represents a trivalent linear or branched hydrocarbon group.
- the trivalent linear or branched hydrocarbon group include methane, ethane, propane, n-butane, isobutane, n-pentane, n-hexane, 2-methylpentane, 3-methylpentane, and heptane.
- groups in which three hydrogen atoms are removed from a linear or branched alkane such as 2-methylheptane, 3-methylheptane, octane, nonane, decane, etc. (alkane-triyl group).
- alkane-triyl group groups in which 3 hydrogen atoms are removed from a linear or branched alkane having 1 to 10 carbon atoms is preferable.
- R 25 in the above formula (9) represents a fluorinated alkyl group.
- the fluorinated alkyl group may be any alkyl group in which some or all of the hydrogen atoms are substituted with fluorine atoms, and is not particularly limited. Examples thereof include those exemplified as R 17 in the above formula (8). Can be mentioned.
- R 25 an alkyl group in which a part of hydrogen atoms is substituted with a fluorine atom is preferable.
- z (the number of repeating methylene structural units) represents an integer of 1 to 30. Among these, an integer of 1 to 10 is preferable.
- the fluorine-containing polyether polymer may be a polymer having only the structural unit represented by the formula (9) as a repeating structural unit, or other than the structural unit represented by the formula (9).
- the polymer which has the following structural unit may be sufficient.
- the fluorine-containing polyether polymer may be a polymer having only one type of structural unit represented by the formula (9), or two or more types of structural units represented by the formula (9). It may be a polymer.
- the polymer which has 2 or more types of structural units other than the structural unit represented by Formula (9) may be sufficient.
- the structural unit other than the structural unit represented by the formula (9) that the fluorine-containing polyether polymer may have is not particularly limited, and for example, an oxyethylene unit [—OCH 2 CH 2 — ], An oxyalkylene structural unit such as an oxypropylene unit [—OCH (CH 3 ) CH 2 —] and the like.
- R 26 in the following formula represents a hydrogen atom or a linear or branched alkyl group having 1 to 4 carbon atoms (for example, methyl group, ethyl group, propyl group, n-butyl group, etc.).
- R 25 and z in the following formula are the same as described above.
- fluorine-containing polyether polymer examples include a fluorine-containing polyether polymer represented by the following formula (9a).
- U, v, and w in the formula (9a) each represent an integer of 1 to 50.
- the sum of u and w is preferably an integer of 2 to 80, more preferably an integer of 4 to 30, and still more preferably an integer of 6 to 14.
- v is preferably an integer of 2 to 50, more preferably an integer of 5 to 20.
- the fluorine-containing polyether polymer can be obtained by a known or conventional production method, and the production method is not particularly limited.
- a monomer that gives a structural unit represented by the formula (9) by polymerization For example, it can be produced by a method of polymerizing (for example, ring-opening polymerization) of a cyclic ether compound such as an epoxy compound or an oxetane compound.
- a commercial item can also be used as the said fluorine-containing polyether type polymer.
- the non-volatile content (blending amount) of the leveling agent in the curable epoxy resin composition of the present invention is not particularly limited, but the total amount of the compound having an epoxy group contained in the curable epoxy resin composition (100 parts by weight) ) Is preferably 0.1 to 10 parts by weight, more preferably 0.1 to 5 parts by weight, still more preferably 0.1 to 4 parts by weight. If the leveling agent content (non-volatile content) is less than 0.1 parts by weight, the crack resistance of the cured product may decrease. On the other hand, if the leveling agent content (non-volatile content) exceeds 10 parts by weight, the heat resistance of the cured product may be reduced.
- the content (blending amount) of the silicone polymer, the fluorinated acrylic polymer, and the fluorinated polyether polymer is not particularly limited.
- the amount is preferably 0.1 to 10 parts by weight, more preferably 0.1 to 5 parts by weight, still more preferably based on the total amount (100 parts by weight) of the epoxy group-containing compound contained in the curable epoxy resin composition. 0.1 to 4 parts by weight. If the content of the silicone polymer, the fluorinated acrylic polymer, and the fluorinated polyether polymer is less than 0.1 parts by weight, the crack resistance of the cured product may be lowered. On the other hand, when content exceeds 10 weight part, the heat resistance of hardened
- the “content (blending amount) of the silicone polymer, the fluorine-containing acrylic polymer, and the fluorine-containing polyether polymer” refers to the silicone polymer and the fluorine-containing acrylic polymer. And when 2 or more types are included among the said fluorine-containing polyether type
- the reflector made of the cured product of the resin composition can exhibit higher levels of heat resistance and crack resistance.
- a decrease in luminous intensity with time of the optical semiconductor device provided with the reflector (especially, a decrease in luminous intensity of the optical semiconductor device that emits high-luminance light) is suppressed.
- Such an effect is obtained by improving the adhesion of the curable epoxy resin composition of the present invention (or its cured product) to the sealing material (encapsulating resin for optical semiconductor elements), etc., by blending the leveling agent. It is estimated that
- the curable epoxy resin composition of the present invention preferably further contains a polyol compound.
- the curable epoxy resin composition of the present invention can form a cured product having higher heat resistance and crack resistance by containing the polyol compound, and an optical semiconductor device produced using the cured product is It is even less likely to cause a decrease in light intensity.
- the polyol compound is a polymer (oligomer or polymer) having a number average molecular weight of 200 or more having two or more hydroxyl groups in the molecule (in one molecule), such as polyether polyol, polyester polyol, polycarbonate polyol, etc. Is included.
- the said polyol compound can be used individually or in combination of 2 or more types.
- the hydroxyl group (two or more hydroxyl groups) of the polyol compound may be an alcoholic hydroxyl group or a phenolic hydroxyl group. Further, the number of hydroxyl groups (number of hydroxyl groups in one molecule) of the polyol compound is not particularly limited as long as it is 2 or more.
- the position of the hydroxyl group (two or more hydroxyl groups) of the polyol compound is not particularly limited, but may be present at least at the end of the polyol (end of the polymer main chain) from the viewpoint of reactivity with the curing agent. It is particularly preferable that it is present at least at both ends of the polyol.
- the polyol compound may be a solid or liquid as long as it can form a liquid curable epoxy resin composition after blending with other components.
- the number average molecular weight of the polyol compound may be 200 or more and is not particularly limited, but is preferably 200 to 100,000, more preferably 300 to 50,000, and still more preferably 400 to 40,000. When the number average molecular weight is less than 200, the cured product may be peeled off or cracks may be generated in the cured product after the solder reflow process. On the other hand, when the number average molecular weight exceeds 100,000, the liquid curable epoxy resin composition may not be precipitated or dissolved.
- the number average molecular weight of the said polyol compound means the number average molecular weight of standard polystyrene conversion measured by gel permeation chromatography (GPC).
- polystyrene resin examples include a polyester polyol (including a polyester polyol oligomer) having an ester skeleton (polyester skeleton) in the molecule, and a polyether polyol (polyether polyol oligomer) having an ether skeleton (polyether skeleton) in the molecule. And a polycarbonate polyol (including a polycarbonate polyol oligomer) having a carbonate skeleton (polycarbonate skeleton) in the molecule.
- polyol compound include a phenoxy resin and an epoxy equivalent of 1000 g / eq. Also included are bisphenol-type polymer epoxy resins exceeding the above, polybutadienes having a hydroxyl group, acrylic polyols, and the like.
- polyester polyol examples include polyester polyols obtained by condensation polymerization (for example, transesterification) of polyols, polycarboxylic acids (polybasic acids), and hydroxycarboxylic acids, and polyester polyols obtained by ring-opening polymerization of lactones. Etc.
- polyol examples include ethylene glycol, diethylene glycol, 1,2-propanediol, 2-methyl-1,3-propanediol, 1,3-propanediol, 1,4- Butanediol, 1,3-butanediol, 2,3-butanediol, 1,5-pentanediol, 2-methyl-1,5-pentanediol, 3-methyl-1,5-pentanediol, 2,3, 5-trimethyl-1,5-pentanediol, 1,6-hexanediol, 2-ethyl-1,6-hexanediol, 2,2,4-trimethyl-1,6-hexanediol, 2,6-hexanediol 1,8-octanediol, 1,4-cyclohexanedimethanol, 1,2-dimethylol Rhohexane
- Examples of the polycarboxylic acid as a monomer component constituting the polyester polyol include oxalic acid, adipic acid, sebacic acid, fumaric acid, malonic acid, succinic acid, glutaric acid, azelaic acid, citric acid, and 2,6-naphthalene.
- Examples include merit acid and trimellitic anhydride.
- Examples of the hydroxycarboxylic acid include lactic acid, malic acid, glycolic acid, dimethylolpropionic acid, and dimethylolbutanoic acid.
- Examples of the lactones include ⁇ -caprolactone, ⁇ -valerolactone, ⁇ -butyrolactone, and the like.
- the polyester polyol can be produced by a known or conventional production method, and is not particularly limited.
- condensation polymerization (polycondensation) of the polyol and polycarboxylic acid condensation polymerization of the hydroxycarboxylic acid, lactones, and the like.
- the conditions for the polymerization are not particularly limited, and can be appropriately selected from known or common reaction conditions.
- the polyol, polycarboxylic acid, and hydroxycarboxylic acid are known or commonly used derivatives (for example, a hydroxyl group is protected with an acyl group, an alkoxycarbonyl group, an organic silyl group, an alkoxyalkyl group, an oxacycloalkyl group, etc.
- Derivatives and derivatives in which the carboxyl group is derived from an alkyl ester, an acid anhydride, an oxide halide, or the like can also be used.
- polyester polyol examples include, for example, trade names "Placcel 205", “Placcel 205H”, “Placcel 205U”, “Placcel 205BA”, “Placcel 208", "Placcel 210", “Placcel 210CP”, “Placcel 210BA”, “Placcel 212”, “Plaxel 212CP”, “Plaxel 220”, “Plaxel 220CPB”, “Plaxel 220NP1”, “Plaxel 220BA”, “Plaxel 220ED”, “Plaxel 220EB”, “Plaxel 220EC”, “Plaxel 230”, “Plaxel 230CP”, “Plaxel 240”, “Plaxel 240CP”, “Plaxel 210N”, “Plaxel 220N”, “Plaxel L205AL”, “Plaxel L208” L, Plaxel L212AL, Plaxel L220AL, Plaxel L230AL, Plaxel 305, Plaxe
- polyether polyol examples include polyether polyols obtained by addition reaction of cyclic ether compounds to polyols, polyether polyols obtained by ring-opening polymerization of alkylene oxide, and the like.
- examples of the polyether polyol include ethylene glycol, diethylene glycol, 1,2-propanediol (propylene glycol), 2-methyl-1,3-propanediol, 1,3-propanediol, , 4-butanediol (tetramethylene glycol), 1,3-butanediol, 2,3-butanediol, 1,5-pentanediol, 2-methyl-1,5-pentanediol, 3-methyl-1,5 -Pentanediol, 2,3,5-trimethyl-1,5-pentanediol, 1,6-hexanediol, 2-ethyl-1,6-hexanediol, 2,2,4-trimethyl-1,6-hexane Diol, 2,6-hexanediol, 1,8-octanediol, 1,4-cyclohexanedimethano 1,2-diol
- the polyether polyol can be produced by a known or conventional production method, and is not particularly limited. For example, addition reaction of a cyclic ether compound to a polyol (ring-opening addition polymerization), ring-opening polymerization of an alkylene oxide ( (Homopolymerization or copolymerization).
- the conditions for the polymerization are not particularly limited, and can be appropriately selected from known or common reaction conditions.
- polyether polyol examples include trade name “PEP-101” (manufactured by Freund Sangyo Co., Ltd.), trade names “Adeka Pluronic L”, “Adeka Pluronic P”, “Adeka Pluronic F”, “Adeka Pluronic R”.
- the above polycarbonate polyol is a polycarbonate having two or more hydroxyl groups in the molecule.
- the polycarbonate polyol is preferably a polycarbonate diol having two terminal hydroxyl groups in the molecule.
- the polycarbonate polyol is prepared by a phosgene method or a carbonate exchange reaction using a dialkyl carbonate such as dimethyl carbonate or diethyl carbonate or diphenyl carbonate (Japanese Patent Laid-Open No. 62-187725, Japanese Patent Laid-Open No. No. 2-175721, JP-A-2-49025, JP-A-3-220233, JP-A-3-252420 and the like. Since the carbonate bond in the polycarbonate polyol is difficult to be thermally decomposed, the cured resin containing the polycarbonate polyol exhibits excellent stability even under high temperature and high humidity.
- Examples of the polyol used in the carbonate exchange reaction together with the dialkyl carbonate or diphenyl carbonate include 1,6-hexanediol, ethylene glycol, diethylene glycol, 1,3-propanediol, 1,4-butanediol, and 1,3-butane.
- polycarbonate polyol examples include, for example, trade names “Placcel CD205PL”, “Plaxel CD205HL”, “Plaxel CD210PL”, “Plaxel CD210HL”, “Plaxel CD220PL”, “Plaxel CD220HL” (manufactured by Daicel Corporation) Names “UH-CARB50”, “UH-CARB100”, “UH-CARB300”, “UH-CARB90 (1/3)”, “UH-CARB90 (1/1)”, “UC-CARB100” (and above, Ube) Products manufactured by Kosan Co., Ltd.), trade names such as “PCDL T4671”, “PCDL T4672”, “PCDL T5650J”, “PCDL T5651”, “PCDL T5652” (above, manufactured by Asahi Kasei Chemicals) be able to
- polyol compound other than the polyether polyol, polyester polyol, and polycarbonate polyol examples include, for example, trade names “YP-50”, “YP-50S”, “YP-55U”, “YP-70”, “ZX-1356-”.
- the amount (content) of the polyol compound used is not particularly limited, but is preferably 1 to 50 parts by weight, more preferably based on the total amount (100 parts by weight) of the component (A) and the component (B).
- the amount is 1.5 to 40 parts by weight, more preferably 5 to 30 parts by weight.
- the content of the polyol compound exceeds 50 parts by weight, the Tg of the cured product is excessively lowered, the volume change due to heating is increased, and problems such as non-lighting of the optical semiconductor device may occur. If the content of the polyol compound is less than 1 part by weight, the light reflectivity may be likely to decrease with time.
- the amount (content) of the polyol compound is not particularly limited, but the component (A ), Component (B), and component (G) in total amount (100 parts by weight), preferably 1 to 50 parts by weight, more preferably 1.5 to 40 parts by weight, still more preferably 5 to 30 parts by weight. Part.
- the content of the polyol compound exceeds 50 parts by weight, the Tg of the cured product is excessively lowered, the volume change due to heating is increased, and problems such as non-lighting of the optical semiconductor device may occur. If the content of the polyol compound is less than 1 part by weight, the light reflectivity may be likely to decrease with time.
- the curable epoxy resin composition of the present invention preferably further contains an acrylic block copolymer. More specifically, when the curable epoxy resin composition of the present invention includes an acrylic block copolymer, an optical semiconductor device manufactured using the curable epoxy resin composition is particularly high in luminance and high output. Even if it exists, it exists in the tendency for a light intensity to fall easily. That is, by using the acrylic block copolymer, a cured product obtained by curing the curable epoxy resin composition of the present invention can exhibit higher levels of heat resistance, light resistance, and crack resistance.
- the acrylic block copolymer is a block copolymer containing an acrylic monomer as an essential monomer component.
- acrylic monomer examples include methyl acrylate, ethyl acrylate, n-butyl acrylate, t-butyl acrylate, 2-ethylhexyl acrylate, methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, methacrylic acid.
- (Meth) acrylic acid alkyl esters such as t-butyl acid, 2-ethylhexyl methacrylate, lauryl methacrylate and stearyl methacrylate; (meth) acrylic acid esters having an alicyclic structure such as cyclohexyl acrylate and cyclohexyl methacrylate; methacryl (Meth) acrylic acid ester having an aromatic ring such as benzyl acid; (fluoro) alkyl ester of (meth) acrylic acid such as 2-trifluoroethyl methacrylate; acrylic acid, methacrylic acid, maleic acid, maleic anhydride, etc.
- a monomer other than the acrylic monomer may be used as a monomer component.
- the monomer other than the acrylic monomer include aromatic vinyl compounds such as styrene and ⁇ -methylstyrene, conjugated dienes such as butadiene and isoprene, and olefins such as ethylene, propylene and isobutene.
- acrylic block copolymer for example, the diblock copolymer which consists of two polymer blocks, the triblock copolymer which consists of three polymer blocks, four or more polymer blocks And a multi-block copolymer composed of these.
- the acrylic block copolymer includes a polymer block [S] (soft block) having a low glass transition temperature (Tg) and a polymer block [from the viewpoint of improving heat resistance, light resistance, and crack resistance.
- a block copolymer in which polymer blocks [H] (hard blocks) having a Tg higher than S] are alternately arranged is preferable, more preferably a polymer block [S] is provided in the middle, and a polymer is provided at both ends thereof.
- a triblock copolymer having an HSH structure having a block [H] is preferred.
- Tg of the polymer which comprises polymer block [S] of the said acrylic block copolymer is not specifically limited, Less than 30 degreeC is preferable.
- the Tg of the polymer constituting the polymer block [H] is not particularly limited, but is preferably 30 ° C. or higher.
- the acrylic block copolymer has a plurality of polymer blocks [H]
- the polymer blocks [H] may have the same composition or may be different.
- each polymer block [S] may have the same composition and may differ.
- the monomer component constituting the polymer block [H] in the acrylic block copolymer is not particularly limited.
- the Tg of the homopolymer is examples thereof include monomers having a temperature of 30 ° C. or higher, and more specifically, methyl methacrylate, styrene, acrylamide, acrylonitrile and the like.
- the monomer component constituting the polymer block [S] in the acrylic block copolymer is not particularly limited, and examples thereof include monomers having a Tg of the homopolymer of less than 30 ° C., and more specifically, Acrylic acid C 2-10 alkyl ester such as butyl acrylate and 2-ethylhexyl acrylate, butadiene (1,4-butadiene) and the like.
- the acrylic block copolymer in the curable epoxy resin composition of the present invention include, for example, a polymer in which the polymer block [S] is composed of butyl acrylate (BA) as a main monomer, Polymethyl methacrylate-block-polybutyl acrylate-block-polymethyl methacrylate terpolymer (PMMA-b-PBA-b-), wherein the polymer block [H] is a polymer composed mainly of methyl methacrylate (MMA). PMMA) and the like.
- the PMMA-b-PBA-b-PMMA is preferable from the viewpoint of improving heat resistance, light resistance, and crack resistance.
- the PMMA-b-PBA-b-PMMA is a hydrophilic group (for example, a hydroxyl group, a carboxyl group, an amino group, etc.) for the purpose of improving compatibility with the component (A) and the component (B), if necessary.
- a monomer having a group for example, hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, (meth) acrylic acid, or the like, copolymerized with a PMMA block and / or a PBA block. Good.
- the number average molecular weight of the acrylic block copolymer is not particularly limited, but is preferably 3000 to 500000, more preferably 30000 to 400000. If the number average molecular weight is less than 3000, the toughness of the cured product is not sufficient, and crack resistance may be reduced. On the other hand, when the number average molecular weight exceeds 500,000, the compatibility with the alicyclic epoxy compound (A) is lowered, and the mechanical properties of the cured product may be adversely affected and the crack resistance may be lowered.
- the acrylic block copolymer can be produced by a known or commonly used block copolymer production method.
- the method for producing the acrylic block copolymer in particular, living polymerization (living radical polymerization, living anion polymerization, living room polymerization, etc., from the viewpoint of easy control of the molecular weight, molecular weight distribution, terminal structure, etc. of the acrylic block copolymer. Cationic polymerization etc.) are preferred.
- the living polymerization can be carried out by a known or conventional method.
- acrylic block copolymer examples include, for example, trade names “Nano Strength M52N”, “Nano Strength M22N”, “Nano Strength M51”, “Nano Strength M52”, “Nano Strength M53” (manufactured by Arkema, PMMA- Commercial products such as “b-PBA-b-PMMA”, trade names “Nanostrength E21”, “Nanostrength E41” (manufactured by Arkema, PSt (polystyrene) -b-PBA-b-PMMA) can also be used.
- the amount (content) of the acrylic block copolymer used is not particularly limited, but is preferably 1 to 30 parts by weight with respect to the total amount (100 parts by weight) of the component (A) and the component (B). More preferably, it is 3 to 15 parts by weight, still more preferably 5 to 10 parts by weight.
- the usage-amount of an acrylic block copolymer is less than 1 weight part, the toughness of hardened
- the usage-amount of an acrylic block copolymer exceeds 30 weight part, compatibility with an alicyclic epoxy compound (A) may fall, and the crack resistance of hardened
- the amount of the acrylic block copolymer used (content) is not particularly limited, The amount is preferably 1 to 30 parts by weight, more preferably 3 to 15 parts by weight, still more preferably 5 to 5 parts by weight based on the total amount (100 parts by weight) of the component (A), the component (B) and the component (G). 10 parts by weight.
- the usage-amount of an acrylic block copolymer is less than 1 weight part, the toughness of hardened
- the usage-amount of an acrylic block copolymer exceeds 30 weight part compatibility with an alicyclic epoxy compound (A) may fall, and the crack resistance of hardened
- the curable epoxy resin composition of the present invention may further contain rubber particles.
- the rubber particles include rubber particles such as particulate NBR (acrylonitrile-butadiene rubber), reactive terminal carboxyl group NBR (CTBN), metal-free NBR, and particulate SBR (styrene-butadiene rubber).
- the rubber particles are preferably rubber particles having a multilayer structure (core-shell structure) composed of a core portion having rubber elasticity and at least one shell layer covering the core portion.
- the rubber particles are particularly composed of a polymer (polymer) having (meth) acrylic acid ester as an essential monomer component, and react with a compound having an epoxy group such as an alicyclic epoxy compound (A) on the surface.
- Rubber particles having a hydroxyl group and / or a carboxyl group (either one or both of a hydroxyl group and a carboxyl group) as the functional group to be obtained are preferred. If there are no hydroxyl groups and / or carboxyl groups on the surface of the rubber particles, the cured product may easily crack.
- the polymer constituting the core portion having rubber elasticity in the rubber particles is not particularly limited, but (meth) acrylic acid esters such as methyl (meth) acrylate, ethyl (meth) acrylate, and butyl (meth) acrylate are used.
- the essential monomer component is preferred.
- Examples of the polymer constituting the core portion having rubber elasticity include, for example, aromatic vinyls (aromatic vinyl compounds) such as styrene and ⁇ -methylstyrene, nitriles such as acrylonitrile and methacrylonitrile, and conjugates such as butadiene and isoprene. Diene, ethylene, propylene, isobutene and the like may be contained as a monomer component.
- the polymer which comprises the said core part which has the rubber elasticity contains 1 type, or 2 or more types selected from the group which consists of aromatic vinyl, a nitrile, and a conjugated diene with a (meth) acrylic acid ester as a monomer component. It is preferable to include it in combination. That is, as the polymer constituting the core part, for example, (meth) acrylic acid ester / aromatic vinyl, (meth) acrylic acid ester / conjugated diene and other binary copolymers; (meth) acrylic acid ester / aromatic And terpolymers such as group vinyl / conjugated dienes.
- the polymer constituting the core part may contain silicone such as polydimethylsiloxane and polyphenylmethylsiloxane, polyurethane, and the like.
- the polymer constituting the core part includes, as other monomer components, divinylbenzene, allyl (meth) acrylate, ethylene glycol di (meth) acrylate, diallyl maleate, triallyl cyanurate, diallyl phthalate, butylene glycol diacrylate, etc.
- One monomer (one molecule) may contain a reactive crosslinking monomer having two or more reactive functional groups.
- the core part of the rubber particles is, in particular, a core part composed of a (meth) acrylate ester / aromatic vinyl binary copolymer (particularly butyl acrylate / styrene) from the viewpoint of heat resistance. Is preferred.
- the core portion of the rubber particles can be manufactured by a commonly used method, for example, by a method of polymerizing the monomer by an emulsion polymerization method.
- the whole amount of the monomer may be charged at once and may be polymerized, or after polymerizing a part of the monomer, the remainder may be added continuously or intermittently to polymerize,
- a polymerization method using seed particles may be used.
- the polymer constituting the shell layer of the rubber particles is preferably a polymer different from the polymer constituting the core portion.
- the shell layer preferably has a hydroxyl group and / or a carboxyl group as a functional group capable of reacting with a compound having an epoxy group such as the alicyclic epoxy compound (A).
- the polymer constituting the shell layer preferably contains a (meth) acrylate ester such as methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate as an essential monomer component.
- a (meth) acrylate ester such as methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate as an essential monomer component.
- a (meth) acrylate ester such as methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate as an essential monomer component.
- a (meth) acrylate ester such as methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate
- an essential monomer component for example, when butyl acrylate is used as the (meth) acrylic acid ester in the core
- Examples of the monomer component that may be contained in addition to the (meth) acrylic acid ester include aromatic vinyl such as styrene and ⁇ -methylstyrene, and nitrile such as acrylonitrile and methacrylonitrile.
- aromatic vinyl such as styrene and ⁇ -methylstyrene
- nitrile such as acrylonitrile and methacrylonitrile.
- the monomer component constituting the shell layer it is preferable to contain the monomer alone or in combination of two or more together with (meth) acrylic acid ester, in particular, at least from the viewpoint of heat resistance. It is preferable that aromatic vinyl is included.
- the polymer constituting the shell layer forms a hydroxyl group and / or a carboxyl group as a functional group capable of reacting with a compound having an epoxy group such as an alicyclic epoxy compound (A) as a monomer component.
- a compound having an epoxy group such as an alicyclic epoxy compound (A) as a monomer component.
- Hydroxyalkyl (meth) acrylates such as 2-hydroxyethyl (meth) acrylate, ⁇ , ⁇ -unsaturated acids such as (meth) acrylic acid, ⁇ , ⁇ -unsaturated acid anhydrides such as maleic anhydride, etc. It is preferable to contain the monomer.
- the polymer constituting the shell layer in the rubber particles preferably contains one or more selected from the above monomers in combination with (meth) acrylic acid ester as a monomer component. That is, the shell layer is composed of, for example, a ternary copolymer such as (meth) acrylic acid ester / aromatic vinyl / hydroxyalkyl (meth) acrylate, (meth) acrylic acid ester / aromatic vinyl / ⁇ , ⁇ -unsaturated acid.
- a shell layer composed of a polymer or the like is preferable.
- the polymer constituting the shell layer includes, as the other monomer components, divinylbenzene, allyl (meth) acrylate, ethylene glycol di (meth) acrylate, diallyl maleate, trimethyl, as well as the above-described monomer.
- a reactive crosslinking monomer having two or more reactive functional groups may be contained in one monomer (one molecule) such as allyl cyanurate, diallyl phthalate, or butylene glycol diacrylate.
- the rubber particles can be obtained by covering the core portion with a shell layer.
- the method of coating the core part with a shell layer include a method of coating the surface of the core part having rubber elasticity obtained by the above method by applying a copolymer constituting the shell layer, and the above method Examples thereof include a graft polymerization method in which the core portion having rubber elasticity obtained by the above is used as a trunk component, and each component constituting the shell layer is used as a branch component.
- the average particle diameter of the rubber particles is not particularly limited, but is preferably 10 to 500 nm, more preferably 20 to 400 nm.
- the maximum particle size of the rubber particles is not particularly limited, but is preferably 50 to 1000 nm, more preferably 100 to 800 nm. If the average particle diameter exceeds 500 nm or the maximum particle diameter exceeds 1000 nm, the dispersibility of the rubber particles in the cured product may be reduced, and crack resistance may be reduced. On the other hand, if the average particle size is less than 10 nm or the maximum particle size is less than 50 nm, the effect of improving the crack resistance of the cured product may be difficult to obtain.
- the content (blending amount) of the rubber particles in the curable epoxy resin composition of the present invention is not particularly limited, but the total amount (100 parts by weight) of the compound having an epoxy group contained in the curable epoxy resin composition.
- the amount is preferably 0.5 to 30 parts by weight, more preferably 1 to 20 parts by weight.
- the content of the rubber particles is less than 0.5 parts by weight, the crack resistance of the cured product tends to decrease.
- the content of the rubber particles exceeds 30 parts by weight, the heat resistance of the cured product tends to decrease.
- the curable epoxy resin composition of the present invention can use various additives within a range that does not impair the effects of the present invention.
- a compound having a hydroxyl group such as ethylene glycol, diethylene glycol, propylene glycol, and glycerin
- the reaction can be allowed to proceed slowly.
- silane coupling agents such as ⁇ -glycidoxypropyltrimethoxysilane, surfactants, inorganic fillers such as silica and alumina, flame retardants, coloring, and the like within a range that does not adversely affect the effects of the present invention.
- Conventional additives such as an agent, an antioxidant, an ultraviolet absorber, an ion adsorbent, a pigment, a phosphor, and a release agent can be used.
- ⁇ Method for preparing curable epoxy resin composition It does not specifically limit as a manufacturing method of the curable epoxy resin composition of this invention, A well-known thru
- various mixers such as a dissolver and
- the curable epoxy resin composition of the present invention includes, for example, an alicyclic epoxy compound (A), a monoallyl diglycidyl isocyanurate compound (B), and a siloxane having two or more epoxy groups in the molecule.
- the ⁇ agent and the ⁇ agent can be prepared by stirring and mixing at a predetermined ratio, and degassing under vacuum as necessary.
- the alicyclic polyester resin (H) may be preliminarily mixed (blended) as a component of the ⁇ agent and / or the ⁇ agent, or the ⁇ agent, You may mix
- the white pigment (C) may be preliminarily mixed (blended) as a component of the ⁇ agent and / or ⁇ agent, or when the ⁇ agent and ⁇ agent are mixed, the ⁇ agent, ⁇ You may mix
- the temperature at the time of stirring and mixing when preparing the ⁇ agent is not particularly limited, but is preferably 30 to 150 ° C, more preferably 35 to 130 ° C. Further, the temperature at the time of stirring and mixing when preparing the ⁇ agent (when composed of two or more components) is not particularly limited, but is preferably 30 to 100 ° C., more preferably 35 to 80 ° C. .
- known apparatuses such as various mixers such as a dissolver and a homogenizer, a kneader, a roll, a bead mill, a self-revolving stirrer and the like can be used. Further, after stirring and mixing, defoaming may be performed under reduced pressure or under vacuum.
- the alicyclic polyester resin (H) and the curing agent (D) are mixed in advance to obtain a mixture thereof (a mixture of alicyclic polyester resin (H) and curing agent (D)), and then the curing accelerator (F) and other additives are blended into the mixture. It is preferable to prepare by preparing an agent and subsequently mixing the ⁇ agent and the ⁇ agent.
- the temperature at which the alicyclic polyester resin (H) and the curing agent (D) are mixed is not particularly limited, but is preferably 60 to 130 ° C, more preferably 90 to 120 ° C.
- the mixing time is not particularly limited, but is preferably 30 to 100 minutes, and more preferably 45 to 80 minutes. Although mixing is not specifically limited, It is preferable to carry out in nitrogen atmosphere. Moreover, the above-mentioned well-known apparatus can be used for mixing.
- alicyclic polyester resin (H) for example, alicyclic polyester resin (H). Or a hydroxyl group thereof).
- the curable epoxy resin composition of the present invention can be made into a cured product by heating and / or curing by irradiating light such as ultraviolet rays. Although it does not specifically limit as heating temperature (curing temperature) and heating time (curing time) in the case of hardening, For example, the conditions at the time of the below-mentioned reflector formation are employable.
- the reflectance of the cured product of the curable epoxy resin composition of the present invention is not particularly limited.
- the reflectance of light having a wavelength of 450 nm is preferably 90% or more, more preferably 90.5% or more. It is.
- the reflectance of light at 450 to 800 nm is preferably 90% or more, more preferably 90.5% or more.
- the reflectance is measured by using, for example, a cured product (thickness: 3 mm) of the curable epoxy resin composition of the present invention as a test piece and a spectrophotometer (trade name “spectrophotometer UV-2450”, Shimadzu Corporation). (Manufactured by Seisakusho).
- the cured product obtained by curing the curable epoxy resin composition of the present invention has high light reflectivity, excellent heat resistance and light resistance, and is tough. For this reason, since the said hardened
- curable resin composition for LED packages especially curable resin composition for reflectors (reflecting material) in an optical semiconductor device.
- the curable epoxy resin composition for light reflection of the present invention comprises the curable epoxy resin composition of the present invention.
- the “curable resin composition for light reflection” means a curable resin composition capable of forming a cured product having high light reflectivity by curing, specifically, For example, it means a curable resin composition capable of forming a cured product having a reflectance of 80% or more with respect to light having a wavelength of 450 nm.
- the curable resin composition for light reflection of the present invention for example, light provided with a reflector formed of a cured product having excellent physical properties such as light reflectivity, heat resistance, light resistance, and crack resistance. A semiconductor device can be obtained.
- the optical semiconductor device including the reflector Since the above-described reflector is less likely to cause a decrease in reflectance over time, the optical semiconductor device including the reflector has a light intensity that decreases over time even when the optical semiconductor device includes an optical semiconductor element with high output and high brightness. It is difficult and can demonstrate high reliability.
- the optical semiconductor device of the present invention is an optical semiconductor device comprising at least an optical semiconductor element as a light source and a reflector made of a cured product of the curable epoxy resin composition (curable resin composition for light reflection) of the present invention.
- the reflector is a member that reflects light emitted from the optical semiconductor element in the optical semiconductor device, increases the directivity and luminance of the light, and improves the light extraction efficiency.
- FIG. 1 is a schematic view showing an example of an optical semiconductor device (optical semiconductor device of the present invention) having a reflector formed from a cured product of the curable epoxy resin composition (curable resin composition for light reflection) of the present invention.
- (A) is a perspective view and (b) is a sectional view.
- 1 is a reflector
- 2 is a metal wiring
- 3 is an optical semiconductor element (LED element)
- 4 is a bonding wire
- 5 is a sealing resin
- 6 is a package resin.
- the reflector 1 has a shape that surrounds the sealing resin 5 in a ring shape and is inclined so that the diameter of the ring increases upward.
- the light emitted from the optical semiconductor element 3 can be extracted with high efficiency by reflecting the light emitted from the optical semiconductor element 3 on the surface (reflection surface) of the reflector 1.
- a known or conventional molding method can be used, and is not particularly limited. For example, transfer molding, compression molding, injection molding, LIM molding (injection molding), dam molding by dispensing, etc. The method is mentioned.
- the reflector can be formed by injecting the curable epoxy resin composition of the present invention (a curable resin composition for light reflection) into a predetermined mold and curing by heating.
- the heating temperature is 80 to 200 ° C. (preferably 80 to 190 ° C., more preferably 80 to 180 ° C.)
- the heating time is 30 to 600 minutes (preferably 45 to 540 minutes, More preferably, it can be suitably adjusted within a range of 60 to 480 minutes.
- the heating temperature is increased, the heating time is shortened, and when the heating temperature is decreased, the heating time is preferably lengthened.
- the resin component may be decomposed.
- the heat curing treatment may be performed in one step, or may be performed in stages by performing heat treatment in multiple stages.
- the curing agent (D) when used, the first stage is heated at a temperature of 80 to 150 ° C. (preferably 100 to 140 ° C.) for 30 to 300 minutes (preferably 45 to 270 minutes). In the second stage, it is preferable to cure by heating at a temperature of 100 to 200 ° C. (preferably 110 to 180 ° C.) for 30 to 600 minutes (preferably 45 to 540 minutes). In addition, for example, when the curing catalyst (E) is used, as the first stage, it is heated at a temperature of 30 to 150 ° C.
- the optical semiconductor device of the present invention has at least a reflector made of a cured product of the curable epoxy resin composition (curable resin composition for light reflection) of the present invention, even when high-luminance light is output. Can emit light stably for a long time. Furthermore, since the reflector made of a cured product of the curable epoxy resin composition (curable resin composition for light reflection) of the present invention has excellent adhesion to the sealing resin (especially epoxy resin) of the optical semiconductor element, more Problems such as a decrease in light intensity over time are unlikely to occur. For this reason, the optical semiconductor device of this invention can exhibit high reliability as a long-life optical semiconductor device.
- the present invention will be described in more detail based on examples, but the present invention is not limited to these examples.
- the amount of silicone leveling agent (“BYK-300”, “AC FS 180”) and fluorine leveling agent (“BYK-340”, “AC 110a”) is the amount as a product. Indicates the quantity of the product itself. In Tables 1 to 4, “-” indicates that the corresponding component was not blended.
- Production Example 1 (Production of white pigment-containing epoxy resin: Examples 1 to 9) Monoallyl diglycidyl isocyanurate (manufactured by Shikoku Kasei Kogyo Co., Ltd., trade name “MA-DGIC”), alicyclic epoxy compound (manufactured by Daicel Co., Ltd., trade name “Celoxide 2021P”) shown in Table 1 The mixture was mixed according to the prescription (blending ratio) (unit: parts by weight) and stirred at 80 ° C. for 1 hour to dissolve monoallyl diglycidyl isocyanurate to obtain an epoxy resin (mixture).
- MA-DGIC alicyclic epoxy compound
- Production Example 3 (Production of curing agent composition containing at least a curing agent (hereinafter referred to as “K agent”): Examples 1 to 6 and Comparative Examples 1 to 4)
- Curing agent (acid anhydride) (manufactured by Shin Nippon Rika Co., Ltd., trade name “Licacid MH-700”), curing accelerator (manufactured by San Apro Co., Ltd., trade name “U-CAT 18X”), additive (Japanese)
- the formulation (mixing ratio) shown in Table 1 the product name “Ethylene Glycol” manufactured by Kojun Pharmaceutical Co., Ltd. is used as a self-revolving stirrer (manufactured by Shinky Corp. 250 ”) and mixed uniformly and degassed to obtain K agent.
- Examples 1-9, Comparative Examples 1-8 Manufacture of curable epoxy resin composition
- the white pigment-containing epoxy resin obtained in Production Example 1, the white pigment-containing epoxy resin obtained in Production Example 2, and the production example 3 were obtained so that the formulation (unit: parts by weight) shown in Table 1 was obtained.
- K agent, curing catalyst (manufactured by Sanshin Chemical Industry Co., Ltd., trade name “Sun-Aid SI-100L”), self-revolving stirrer (manufactured by Shinky Co., Ltd., trade name “Awatori Nerita AR-250”) Were mixed uniformly (2000 rpm, 5 minutes) and defoamed to obtain a curable epoxy resin composition.
- the curable epoxy resin composition was poured into a mold, placed in an oven (trade name “GPHH-201”, manufactured by ESPEC Corporation), and heated at 120 ° C. for 5 hours to obtain a cured product. .
- the curable epoxy resin composition obtained above was put in an oven (trade name “GPHH-201”, manufactured by ESPEC Corporation) and heated at 120 ° C. for 5 hours to obtain a cured product.
- Production Example 6 Manufacture of rubber particles
- 500 g of ion-exchanged water and 0.68 g of sodium dioctylsulfosuccinate were charged, and the temperature was raised to 80 ° C. while stirring under a nitrogen stream.
- a monomer mixture consisting of 9.5 g of butyl acrylate, 2.57 g of styrene, and 0.39 g of divinylbenzene corresponding to about 5% by weight of the amount required to form the core portion is added here.
- the obtained latex was frozen at minus 30 ° C., dehydrated and washed with a suction filter, and then blown and dried at 60 ° C. overnight to obtain rubber particles.
- the resulting rubber particles had an average particle size of 254 nm and a maximum particle size of 486 nm.
- the average particle size and the maximum particle size of the rubber particles are determined based on a nanotrac TM particle size distribution measuring device (trade name “UPA-EX150”, manufactured by Nikkiso Co., Ltd.) using the dynamic light scattering method as a measurement principle. ) Is used to measure the following sample, and in the obtained particle size distribution curve, the average particle size, which is the particle size when the cumulative curve becomes 50%, is the average particle size, and the frequency (%) of the particle size distribution measurement result is The maximum particle size at the time when it exceeded 0.00% was defined as the maximum particle size.
- a sample obtained by dispersing 1 part by weight of the rubber particle-dispersed epoxy compound obtained in Production Example 7 in 20 parts by weight of tetrahydrofuran was used as a sample.
- Production Example 7 Manufacture of rubber particle-dispersed epoxy compounds
- a dissolver 1000 rpm, 60 minutes
- Celoxide 2021P 3,4-epoxycyclohexylmethyl (3 , 4-epoxy) cyclohexanecarboxylate
- the viscosity was measured using a viscometer (trade name “DVU-EII type”, manufactured by Tokimec Co., Ltd.).
- Production Example 8 (Production of white pigment-containing epoxy resin: Examples 22 to 41) Monoallyl diglycidyl isocyanurate (trade name “MA-DGIC”, manufactured by Shikoku Kasei Kogyo Co., Ltd.), alicyclic epoxy compound (trade name “Celoxide 2021P”, manufactured by Daicel Corp.), 2 in the molecule Siloxane derivatives having an epoxy group (trade name “X-40-2678”, manufactured by Shin-Etsu Chemical Co., Ltd.), siloxane derivatives having three epoxy groups in the molecule (trade name “X-40-2720”, Shin-etsu) Manufactured by Chemical Industry Co., Ltd.), siloxane derivatives having 4 epoxy groups in the molecule (trade name “X-40-2670”, manufactured by Shin-Etsu Chemical Co., Ltd.), silicone leveling agent (trade name “BYK-”) 300 ”, manufactured by BYK Japan, Inc .; trade name“ AC FS 180 ”, manufactured by Algin Chemie), flu
- Production Example 9 (Production of K agent: Examples 22 to 41) Mixture of curing agent (acid anhydride) and alicyclic polyester resin (trade name “HN-7200”, manufactured by Hitachi Chemical Co., Ltd.), curing accelerator (trade name “U-CAT 18X”, San Apro Co., Ltd.) ), Additives (trade name “ethylene glycol”, manufactured by Wako Pure Chemical Industries, Ltd.) according to the formulation (mixing ratio) (unit: parts by weight) shown in Table 3 Using “Awatori Nerita AR-250” (manufactured by Shinky Co., Ltd.), the mixture was uniformly mixed and defoamed to obtain a K agent.
- Examples 22-41 Manufacture of curable epoxy resin composition
- the white pigment-containing epoxy resin obtained in Production Example 8 and the K agent obtained in Production Example 9 were mixed with a self-revolving stirrer (trade name “trade name“ Awatori Nerita AR-250 "(manufactured by Shinky Co., Ltd.) was mixed uniformly (2000 rpm, 5 minutes) and defoamed to obtain a curable epoxy resin composition.
- a self-revolving stirrer trade name “trade name“ Awatori Nerita AR-250 "(manufactured by Shinky Co., Ltd.
- the curable epoxy resin composition obtained above was put in an oven (trade name “GPHH-201”, manufactured by ESPEC Corporation) and heated at 120 ° C. for 5 hours to obtain a cured product.
- Examples 42 to 60, Comparative Examples 14 to 17 Manufacture of curable epoxy resin composition
- the white pigment-containing epoxy resin obtained in Production Example 10 and the alicyclic polyester resin obtained in Production Example 11 and a curing catalyst (trade name “Sun Aid” so as to have the formulation (unit: parts by weight) shown in Table 4 SI-100L ”(manufactured by Sanshin Chemical Industry Co., Ltd.) was mixed evenly using a self-revolving stirrer (trade name“ Awatori Nerita AR-250 ”, manufactured by Shinky Co., Ltd.) (2000 rpm For 5 minutes) and defoamed to obtain a curable epoxy resin composition.
- the curable epoxy resin composition obtained above was put in an oven (trade name “GPHH-201”, manufactured by ESPEC Corporation) and heated at 120 ° C. for 5 hours to obtain a cured product.
- Test pieces having a width of 5 mm, a length of 5 mm, and a thickness of 3 mm were prepared by cutting the cured products obtained in the examples and comparative examples.
- a micro cutting machine (trade name “BS-300CL”, manufactured by Meiwa Forsys Co., Ltd.) was used, and whether or not cracks occurred in the cured product during the cutting process. This was observed and confirmed using a digital microscope (trade name “VHX-900”, manufactured by Keyence Corporation).
- Tables 1 to 4 show the number of test pieces (number of cracks) (number of cracks) in which cracks were confirmed among 10 test pieces per sample as evaluation results.
- “n / 10” indicates the case where the number of test pieces in which cracks were confirmed (number of cracks) was n. Indicated.
- the initial reflectivity is 90% or more
- the reflectivity retention rate is 90% or more in the heat resistance test (heat aging 500 hours)
- the reflectivity retention rate is 90% or more in the light resistance test
- cracks during cutting processing In the presence / absence evaluation (toughness evaluation) and the crack presence / absence evaluation during reflow (toughness evaluation), the case where the number of cracks was 0 was determined as a comprehensive judgment (good). On the other hand, the thing other than this was made into comprehensive judgment x (defective). The results are shown in the column “Comprehensive judgment” in Tables 1 to 4.
- Example and the comparative example is as follows.
- MA-DGIC monoallyl diglycidyl isocyanurate, manufactured by Shikoku Kasei Kogyo Co., Ltd.
- EHPE3150 2 1,2-epoxy-4- (2-oxiranyl) cyclohexane adduct of 2-bis (hydroxymethyl) -1-butanol, manufactured by Daicel Corporation
- TEPIC-PAS B26 Trisglycidyl isocyanurate
- X-40-2678 siloxane derivative having two epoxy groups in the molecule, Shin-Etsu Chemical Co., Ltd.
- X-40-2720 siloxane derivative having three epoxy groups in the molecule, Shin-Etsu Chemical Co., Ltd.
- X-40-2670 manufactured by Co., Ltd .: Molecule A siloxane derivative having four epoxy groups, BYK-300 manufactured by Shin-Etsu Chemical Co., Ltd .: silicone leveling agent (leveling agent including a silicone polymer), AC FS 180 manufactured by Big Chemie Japan Co., Ltd .: silicone type Leveling agent (leveling agent including silicone polymer), BYK-340 manufactured by Algin Chemie: Fluorine leveling agent (leveling agent including fluorinated acrylic polymer), AC 110a manufactured by Big Chemie Japan Ltd .: Fluorine leveling Agent (leveling agent containing fluorine-containing polyether polymer), Algin Chemie CD220PL (Placcel CD220PL): Polycarbonatediol, Daicel Corporation PTMG2000: Polytetramethylene ether glycol, Mitsubishi Plaxel 308: Polycaprolactone polyol, manufactured by Gaku Co., Ltd.
- YP-70 Phenoxy resin, manufactured by Daicel Chemical Industries, Ltd.
- Epototo YD-6020 Long chain epoxy resin containing hydroxyl group, Nippon Steel Chemical Co., Ltd.
- M52N Nanostrength M52N
- Acrylic block copolymer manufactured by Arkema [White pigment] Titanium oxide, trade name “TCR-52”, manufactured by Sakai Chemical Industry Co., Ltd.
- HN-7200 4-methylhexahydrophthalic anhydride and alicyclic ring Mixture of polyester resin, manufactured by Hitachi Chemical Co., Ltd.
- Ethylene glycol manufactured by Wako Pure Chemical Industries, Ltd.
- Sun-Aid SI-100L Arylsulfonium salt, manufactured by Sanshin Chemical Industry Co., Ltd.
- the cured products (Examples) of the curable epoxy resin composition of the present invention have excellent light reflectivity, and without causing cracks during cutting and reflowing, It was tough. Furthermore, even after heat aging and ultraviolet aging, high light reflectivity was maintained, and heat resistance and light resistance were excellent.
- the alicyclic polyester resin or alicyclic polyester resin and a siloxane derivative having two or more epoxy groups in the molecule is also included ( In Examples 10 to 60), even after heating for a longer time (500 hours), the light reflectivity was hardly lowered, and extremely excellent heat resistance was exhibited.
- a cured product (Comparative Example) formed from a curable epoxy resin composition that does not satisfy the provisions of the present invention has a low light reflectivity after heat aging and ultraviolet aging, and is inferior in heat resistance and light resistance. Furthermore, cracks were likely to occur during cutting and reflow, and the toughness was poor.
- Reflector (a reflector made of a cured product of the curable epoxy resin composition of the present invention) 2: Metal wiring 3: Optical semiconductor element 4: Bonding wire 5: Sealing resin 6: Package resin
- the curable epoxy resin composition of the present invention is used for LED packages (component materials for LED packages, such as reflector materials and housing materials in optical semiconductor devices), adhesive applications for electronic components, and liquid crystal display applications (for example, reflectors). ), White substrate ink, sealer and the like.
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Abstract
Description
また、本発明の他の目的は、上記硬化性エポキシ樹脂組成物を硬化してなる、高い光反射性を有し、耐熱性及び耐光性に優れ、なおかつ強靭であり、光反射性が経時で低下しにくい硬化物を提供することにある。
また、本発明の他の目的は、経時での光の輝度低下が抑制された光半導体装置を得ることができる光反射用硬化性樹脂組成物を提供することにある。
また、本発明の他の目的は、経時で光の輝度が低下しにくく、信頼性の高い光半導体装置を提供することにある。
で表されるモノアリルジグリシジルイソシアヌレート化合物(B)と、白色顔料(C)と、硬化剤(D)と、硬化促進剤(F)とを含むことを特徴とする硬化性エポキシ樹脂組成物を提供する。
で表されるモノアリルジグリシジルイソシアヌレート化合物(B)と、白色顔料(C)と、硬化触媒(E)とを含むことを特徴とする硬化性エポキシ樹脂組成物を提供する。
本発明の硬化性エポキシ樹脂組成物は、脂環式エポキシ化合物(A)と、下記式(1)
で表されるモノアリルジグリシジルイソシアヌレート化合物(B)と、白色顔料(C)と、硬化剤(D)と、硬化促進剤(F)とを必須成分として含む樹脂組成物、又は、脂環式エポキシ化合物(A)と、上記式(1)で表されるモノアリルジグリシジルイソシアヌレート化合物(B)と、白色顔料(C)と、硬化触媒(E)とを必須成分として含む樹脂組成物である。
本発明の硬化性エポキシ樹脂組成物を構成する脂環式エポキシ化合物(A)は、分子内(1分子内)に脂環(脂肪族環)構造とエポキシ基とを少なくとも有する化合物である。より具体的には、脂環式エポキシ化合物(A)には、例えば、(i)脂環を構成する隣接する2つの炭素原子と酸素原子とで構成されるエポキシ基(「脂環エポキシ基」と称する場合がある)を有する化合物、及び(ii)脂環にエポキシ基が直接単結合で結合している化合物等が含まれる。但し、脂環式エポキシ化合物(A)には、後述の分子内に2以上のエポキシ基を有するシロキサン誘導体(G)は含まれないものとする。
本発明の硬化性エポキシ樹脂組成物を構成するモノアリルジグリシジルイソシアヌレート化合物(B)は、下記の一般式(1)で表される。
本発明の硬化性エポキシ樹脂組成物の必須成分である白色顔料(C)は、上記硬化性エポキシ樹脂組成物を硬化して得られる硬化物に対し、高い光反射性を発揮させる役割を担う。白色顔料(C)としては、公知乃至慣用の白色顔料を使用することができ、特に限定されないが、例えば、ガラス、クレー、雲母、タルク、カオリナイト(カオリン)、ハロイサイト、ゼオライト、酸性白土、活性白土、ベーマイト、擬ベーマイト、無機酸化物、アルカリ土類金属塩等の金属塩などの無機白色顔料;スチレン系樹脂、ベンゾグアナミン系樹脂、尿素-ホルマリン系樹脂、メラミン-ホルマリン系樹脂、アミド系樹脂等の樹脂顔料などの有機白色顔料(プラスチックピグメントなど);中空構造(バルーン構造)を有する中空粒子などが挙げられる。これらの白色顔料は単独で、又は2種以上を組み合わせて使用することができる。
本発明の硬化性エポキシ樹脂組成物を構成する硬化剤(D)は、エポキシ基を有する化合物を硬化させる役割を担う。硬化剤(D)としては、エポキシ樹脂用硬化剤として公知乃至慣用の硬化剤を使用することができる。中でも、硬化剤(D)としては、25℃で液状の酸無水物が好ましく、より具体的には、例えば、メチルテトラヒドロ無水フタル酸、メチルヘキサヒドロ無水フタル酸、ドデセニル無水コハク酸、メチルエンドメチレンテトラヒドロ無水フタル酸などが挙げられる。また、例えば、無水フタル酸、テトラヒドロ無水フタル酸、ヘキサヒドロ無水フタル酸、メチルシクロヘキセンジカルボン酸無水物などの常温(約25℃)で固体状の酸無水物についても、常温(約25℃)で液状の酸無水物に溶解させて液状の混合物とすることで、硬化剤(D)として好ましく使用することができる。なお、硬化剤(D)は単独で、又は2種以上を組み合わせて使用することができる。硬化剤(D)としては、耐熱性、耐光性、耐クラック性の観点で、特に、飽和単環炭化水素ジカルボン酸の無水物(環にアルキル基等の置換基が結合したものも含む)が好ましい。
本発明の硬化性エポキシ樹脂組成物において硬化促進剤(F)は、エポキシ基を有する化合物が硬化剤(D)により硬化する際に、硬化速度を促進する機能を有する化合物である。硬化促進剤(F)としては、公知乃至慣用の硬化促進剤を使用することができ、特に限定されないが、例えば、1,8-ジアザビシクロ[5.4.0]ウンデセン-7(DBU)、及びその塩(例えば、フェノール塩、オクチル酸塩、p-トルエンスルホン酸塩、ギ酸塩、テトラフェニルボレート塩);1,5-ジアザビシクロ[4.3.0]ノネン-5(DBN)、及びその塩(例えば、フェノール塩、オクチル酸塩、p-トルエンスルホン酸塩、ギ酸塩、テトラフェニルボレート塩);ベンジルジメチルアミン、2,4,6-トリス(ジメチルアミノメチル)フェノール、N,N-ジメチルシクロヘキシルアミンなどの3級アミン;2-エチル-4-メチルイミダゾール、1-シアノエチル-2-エチル-4-メチルイミダゾールなどのイミダゾール類;リン酸エステル、トリフェニルホスフィンなどのホスフィン類;テトラフェニルホスホニウムテトラ(p-トリル)ボレートなどのホスホニウム化合物;オクチル酸スズ、オクチル酸亜鉛などの有機金属塩;金属キレートなどが挙げられる。なお、硬化促進剤(F)は単独で、又は2種以上を組み合わせて使用することができる。
本発明の硬化性エポキシ樹脂組成物は、上述の硬化剤(D)の代わりに、硬化触媒(E)を含んでいてもよい。硬化剤(D)を用いた場合と同様に、硬化触媒(E)を用いることにより、エポキシ基を有する化合物の硬化反応を進行させ、硬化物を得ることができる。上記硬化触媒(E)としては、特に限定されないが、例えば、紫外線照射又は加熱処理を施すことによりカチオン種を発生して、重合を開始させることができるカチオン触媒(カチオン重合開始剤)を使用できる。
上述のように、本発明の硬化性エポキシ樹脂組成物は、分子内(一分子中)に2以上のエポキシ基を有するシロキサン誘導体(G)を含んでいてもよい。分子内に2以上のエポキシ基を有するシロキサン誘導体(G)は、シロキサン骨格を有し、なおかつ分子内に2以上のエポキシ基を有する化合物である。分子内に2以上のエポキシ基を有するシロキサン誘導体(G)は、硬化物の耐熱性、耐光性、耐クラック性を向上させ、光半導体装置の光度低下を抑制する役割を担う。
上記脂環式ポリエステル樹脂(H)は、脂環構造(脂肪族環構造)を少なくとも有するポリエステル樹脂である。脂環式ポリエステル樹脂(H)は、硬化物の耐熱性、耐光性、耐クラック性を向上させ、光半導体装置の光度低下を抑制する役割を担う。特に、硬化物の耐熱性、耐光性、耐クラック性向上の観点で、脂環式ポリエステル樹脂(H)は、主鎖に脂環(脂環構造)を有する脂環式ポリエステルであることが好ましい。即ち、脂環式ポリエステル樹脂(H)は、脂環を構成する炭素原子の一部又は全部によりポリマー主鎖が構成されたポリエステル樹脂であることが好ましい。なお、脂環式ポリエステル樹脂(H)は単独で、又は2種以上を組み合わせて使用できる。
本発明の硬化性エポキシ樹脂組成物は、さらに、シリコーン系レベリング剤(ポリシロキサン系レベリング剤)及びフッ素系レベリング剤からなる群より選ばれた少なくとも1種のレベリング剤を含むことが好ましい。本発明の硬化性エポキシ樹脂組成物は、上記レベリング剤を含むことにより、より高度な耐熱性、耐光性、及び耐クラック性を示す硬化物を形成でき、該硬化物を用いて作製した光半導体装置は、経時での光度低下がいっそう生じにくい。
上記シリコーン系レベリング剤とは、ポリシロキサン骨格を有する化合物を含むレベリング剤である。上記シリコーン系レベリング剤としては、公知乃至慣用のシリコーン系レベリング剤を使用でき、特に限定されないが、例えば、商品名「BYK-300」、「BYK-301/302」、「BYK-306」、「BYK-307」、「BYK-310」、「BYK-315」、「BYK-313」、「BYK-320」、「BYK-322」、「BYK-323」、「BYK-325」、「BYK-330」、「BYK-331」、「BYK-333」、「BYK-337」、「BYK-341」、「BYK-344」、「BYK-345/346」、「BYK-347」、「BYK-348」、「BYK-349」、「BYK-370」、「BYK-375」、「BYK-377」、「BYK-378」、「BYK-UV3500」、「BYK-UV3510」、「BYK-UV3570」、「BYK-3550」、「BYK-SILCLEAN3700」、「BYK-SILCLEAN3720」(以上、ビックケミー・ジャパン(株)製)、商品名「AC FS 180」、「AC FS 360」、「AC S 20」(以上、Algin Chemie製)、商品名「ポリフローKL-400X」、「ポリフローKL-400HF」、「ポリフローKL-401」、「ポリフローKL-402」、「ポリフローKL-403」、「ポリフローKL-404」(以上、共栄社化学(株)製)、商品名「KP-323」、「KP-326」、「KP-341」、「KP-104」、「KP-110」、「KP-112」(以上、信越化学工業(株)製)、商品名「LP-7001」、「LP-7002」、「8032 ADDITIVE」、「57 ADDITIVE」、「L-7604」、「FZ-2110」、「FZ-2105」、「67 ADDITIVE」、「8618 ADDITIVE」、「3 ADDITIVE」、「56 ADDITIVE」(以上、東レ・ダウコーニング(株)製)などの市販品を使用することができる。
上記フッ素系レベリング剤とは、アルキル基の水素原子の一部又は全部がフッ素原子で置換されたフッ素化アルキル基を有する化合物を含むレベリング剤である。上記フッ素系レベリング剤としては、公知乃至慣用のフッ素系レベリング剤を使用でき、特に限定されないが、例えば、商品名「BYK-340」(ビックケミー・ジャパン(株)製)、商品名「AC 110a」、「AC 100a」(以上、Algin Chemie製)、商品名「メガファックF-114」、「メガファックF-410」、「メガファックF-444」、「メガファックEXP TP-2066」、「メガファックF-430」、「メガファックF-472SF」、「メガファックF-477」、「メガファックF-552」、「メガファックF-553」、「メガファックF-554」、「メガファックF-555」、「メガファックR-94」、「メガファックRS-72-K」、「メガファックRS-75」、「メガファックF-556」、「メガファックEXP TF-1367」、「メガファックEXP TF-1437」、「メガファックF-558」、「メガファックEXP TF-1537」(以上、DIC(株)製)、商品名「FC-4430」、「FC-4432」(以上、住友スリーエム(株)製)、商品名「フタージェント 100」、「フタージェント 100C」、「フタージェント 110」、「フタージェント 150」、「フタージェント 150CH」、「フタージェント A-K」、「フタージェント 501」、「フタージェント 250」、「フタージェント 251」、「フタージェント 222F」、「フタージェント 208G」、「フタージェント 300」、「フタージェント 310」、「フタージェント 400SW」(以上、(株)ネオス製)、商品名「PF-136A」、「PF-156A」、「PF-151N」、「PF-636」、「PF-6320」、「PF-656」、「PF-6520」、「PF-651」、「PF-652」(以上、北村化学産業(株)製)などの市販品を使用することもできる。
本発明の硬化性エポキシ樹脂組成物は、さらに、ポリオール化合物を含むことが好ましい。本発明の硬化性エポキシ樹脂組成物は、上記ポリオール化合物を含むことにより、より高度な耐熱性及び耐クラック性を示す硬化物を形成でき、該硬化物を用いて作製した光半導体装置は、経時での光度低下がいっそう生じにくい。上記ポリオール化合物とは、分子内(一分子中)に2個以上の水酸基を有する数平均分子量が200以上の重合体(オリゴマー又はポリマー)であり、例えば、ポリエーテルポリオール、ポリエステルポリオール、ポリカーボネートポリオール等が含まれる。なお、上記ポリオール化合物は単独で、又は2種以上を組み合わせて使用することができる。
本発明の硬化性エポキシ樹脂組成物は、さらに、アクリルブロック共重合体を含むことが好ましい。より詳しくは、本発明の硬化性エポキシ樹脂組成物がアクリルブロック共重合体を含む場合、当該硬化性エポキシ樹脂組成物を用いて製造された光半導体装置は、特に高輝度・高出力の場合であっても光度が低下しにくい傾向にある。即ち、アクリルブロック共重合体を用いることにより、本発明の硬化性エポキシ樹脂組成物を硬化して得られる硬化物は、より高いレベルの耐熱性、耐光性、及び耐クラック性を発揮できる。
本発明の硬化性エポキシ樹脂組成物は、さらに、ゴム粒子を含んでいてもよい。上記ゴム粒子としては、例えば、粒子状NBR(アクリロニトリル-ブタジエンゴム)、反応性末端カルボキシル基NBR(CTBN)、メタルフリーNBR、粒子状SBR(スチレン-ブタジエンゴム)などのゴム粒子が挙げられる。上記ゴム粒子としては、ゴム弾性を有するコア部分と、該コア部分を被覆する少なくとも1層のシェル層とからなる多層構造(コアシェル構造)を有するゴム粒子が好ましい。上記ゴム粒子は、特に、(メタ)アクリル酸エステルを必須モノマー成分とするポリマー(重合体)で構成されており、表面に脂環式エポキシ化合物(A)などのエポキシ基を有する化合物と反応し得る官能基としてヒドロキシル基及び/又はカルボキシル基(ヒドロキシル基及びカルボキシル基のいずれか一方又は両方)を有するゴム粒子が好ましい。上記ゴム粒子の表面にヒドロキシル基及び/又はカルボキシル基が存在しない場合、硬化物にクラックが生じやすくなる場合がある。
本発明の硬化性エポキシ樹脂組成物は、上記以外にも、本発明の効果を損なわない範囲内で各種添加剤を使用することができる。添加剤として、例えば、エチレングリコール、ジエチレングリコール、プロピレングリコール、グリセリンなどの水酸基を有する化合物(上記ポリオール化合物を除く)を使用すると、反応(硬化反応)を緩やかに進行させることができる。その他にも、本発明の効果に悪影響を及ぼさない範囲内で、γ-グリシドキシプロピルトリメトキシシランなどのシランカップリング剤、界面活性剤、シリカ、アルミナなどの無機充填剤、難燃剤、着色剤、酸化防止剤、紫外線吸収剤、イオン吸着体、顔料、蛍光体、離型剤などの慣用の添加剤を使用することができる。
本発明の硬化性エポキシ樹脂組成物の製造方法としては、特に限定されず、公知乃至慣用の方法を適用することができる。具体的には、例えば、所定量の脂環式エポキシ化合物(A)、モノアリルジグリシジルイソシアヌレート化合物(B)、白色顔料(C)、硬化剤(D)、硬化促進剤(F)、及び任意の添加剤を配合して、又は、所定量の脂環式エポキシ化合物(A)、モノアリルジグリシジルイソシアヌレート化合物(B)、白色顔料(C)、硬化触媒(E)、及び任意の添加剤を配合して、ディゾルバー、ホモジナイザーなどの各種ミキサー、ニーダー、ロール、ビーズミル、自公転式撹拌装置などを用いて撹拌、混合する方法等が挙げられる。また、撹拌、混合後、減圧下や真空下にて脱泡してもよい。
本発明の硬化性エポキシ樹脂組成物は、加熱により、及び/又は紫外線などの光を照射して硬化させることにより、硬化物とすることができる。硬化の際の加熱温度(硬化温度)や加熱時間(硬化時間)としては、特に限定されないが、例えば、後述のリフレクター形成の際の条件を採用することができる。
本発明の光反射用硬化性エポキシ樹脂組成物は、本発明の硬化性エポキシ樹脂組成物からなる。なお、本明細書において「光反射用硬化性樹脂組成物」とは、硬化させることにより、高い光反射性を有する硬化物を形成可能な硬化性樹脂組成物を意味し、具体的には、例えば、波長450nmの光に対する反射率が80%以上である硬化物を形成可能な硬化性樹脂組成物を意味する。本発明の光反射用硬化性樹脂組成物を用いることにより、例えば、光反射性、耐熱性、耐光性、及び耐クラック性などの諸物性に優れた硬化物により形成されたリフレクターを備えた光半導体装置を得ることができる。上記リフレクターは、経時での反射率低下が生じにくいため、該リフレクターを備えた光半導体装置は、特に、高出力、高輝度の光半導体素子を備える場合であっても、光度が経時で低下しにくく、高い信頼性を発揮できる。
本発明の光半導体装置は、光源としての光半導体素子と、本発明の硬化性エポキシ樹脂組成物(光反射用硬化性樹脂組成物)の硬化物からなるリフレクターとを少なくとも備える光半導体装置である。なお、上記リフレクターとは、光半導体装置において光半導体素子から発せられた光を反射し、光の指向性及び輝度を高め、光の取り出し効率を向上させるための部材である。図1は、本発明の硬化性エポキシ樹脂組成物(光反射用硬化性樹脂組成物)の硬化物より形成されたリフレクターを有する光半導体装置(本発明の光半導体装置)の一例を示す概略図であり、(a)は斜視図、(b)は断面図を表す。図1における1はリフレクター、2は金属配線、3は光半導体素子(LED素子)、4はボンディングワイヤ、5は封止樹脂、6はパッケージ樹脂を示す。上記リフレクター1は、封止樹脂5の周囲を環状に取り囲み、上方に向かってその環の径が拡大するように傾斜した形状を有している。図1に示す光半導体装置においては、光半導体素子3から発せられた光をリフレクター1の表面(反射面)で反射することによって、高い効率で光半導体素子3からの光を取り出すことができる。
(白色顔料含有エポキシ樹脂の製造:実施例1~9)
モノアリルジグリシジルイソシアヌレート(四国化成工業(株)製、商品名「MA-DGIC」)、脂環式エポキシ化合物((株)ダイセル製、商品名「セロキサイド2021P」)を、表1に示す配合処方(配合割合)(単位:重量部)に従って混合し、80℃で1時間攪拌することで、モノアリルジグリシジルイソシアヌレートを溶解させ、エポキシ樹脂(混合物)を得た。次いで、上記エポキシ樹脂と白色顔料(酸化チタン;堺化学工業(株)製、商品名「TCR-52」)とを、表1に示す配合処方(配合割合)(単位:重量部)に従って、ディゾルバーを使用して均一に混合し、ロールミルによって所定条件下(ロールピッチ:0.2mm、回転数:25ヘルツ、3パス)で混練して、白色顔料含有エポキシ樹脂(エポキシ樹脂組成物)を得た。
(白色顔料含有エポキシ樹脂の製造:比較例1~8)
脂環式エポキシ化合物(商品名「セロキサイド2021P」、(株)ダイセル製;商品名「EHPE3150」、(株)ダイセル製)、トリスグリシジルイソシアヌレート(商品名「TEPIC-PAS B26」、日産化学工業(株)製)を、表1に示す配合処方(配合割合)(単位:重量部)に従って混合し、エポキシ樹脂(混合物)を得た(比較例1、2、4~6、8の場合には、エポキシ樹脂の成分が一種であるため当該混合を行わず、そのままエポキシ樹脂とした)。次いで、上記エポキシ樹脂と白色顔料(酸化チタン;商品名「TCR-52」、堺化学工業(株)製)とを、表1に示す配合処方(配合割合)(単位:重量部)に従って、ディゾルバーを使用して均一に混合し、ロールミルによって所定条件下(ロールピッチ:0.2mm、回転数:25ヘルツ、3パス)で混練して、白色顔料含有エポキシ樹脂(エポキシ樹脂組成物)を得た。
(硬化剤を少なくとも含む硬化剤組成物(以下、「K剤」と称する)の製造:実施例1~6、比較例1~4)
硬化剤(酸無水物)(新日本理化(株)製、商品名「リカシッド MH-700」)、硬化促進剤(サンアプロ(株)製、商品名「U-CAT 18X」)、添加剤(和光純薬工業(株)製、商品名「エチレングリコール」)を、表1に示す配合処方(配合割合)に従って、自公転式攪拌装置((株)シンキー製、商品名「あわとり練太郎AR-250」)を使用して均一に混合し、脱泡してK剤を得た。
(硬化性エポキシ樹脂組成物の製造)
表1に示す配合処方(単位:重量部)となるように、製造例1で得られた白色顔料含有エポキシ樹脂、製造例2で得られた白色顔料含有エポキシ樹脂、製造例3で得られたK剤、硬化触媒(三新化学工業(株)製、商品名「サンエイド SI-100L」)を、自公転式攪拌装置((株)シンキー製、商品名「あわとり練太郎AR-250」)を使用して均一に混合し(2000rpm、5分間)、脱泡して、硬化性エポキシ樹脂組成物を得た。
上記硬化性エポキシ樹脂組成物を金型に注型し、オーブン(商品名「GPHH-201」、エスペック(株)製)に入れて、120℃で5時間加熱することによって、硬化物を得た。
(白色顔料含有エポキシ樹脂の製造:実施例10~21、比較例9~13)
モノアリルジグリシジルイソシアヌレート(商品名「MA-DGIC」、四国化成工業(株)製)、脂環式エポキシ化合物(商品名「セロキサイド2021P」、(株)ダイセル製;商品名「EHPE3150」、(株)ダイセル製)、トリスグリシジルイソシアヌレート(商品名「TEPIC-PAS B26」、日産化学工業(株)製)、分子内に2個のエポキシ基を有するシロキサン誘導体(商品名「X-40-2678」、信越化学工業(株)製)、分子内に3個のエポキシ基を有するシロキサン誘導体(商品名「X-40-2720」、信越化学工業(株)製)、分子内に4個のエポキシ基を有するシロキサン誘導体(商品名「X-40-2670」、信越化学工業(株)製)を、表2に示す配合処方(配合割合)(単位:重量部)に従って混合し、さらに80℃で1時間攪拌することでモノアリルジグリシジルイソシアヌレートを溶解させ、エポキシ樹脂(混合物)を得た(比較例9~13の場合には、エポキシ樹脂の成分が一種であるため当該混合を行わず、そのままエポキシ樹脂とした)。次いで、上記エポキシ樹脂と白色顔料(酸化チタン;商品名「TCR-52」、堺化学工業(株)製)とを、表2に示す配合処方(配合割合)(単位:重量部)に従って、ディゾルバーを使用して均一に混合し、ロールミルによって所定条件下(ロールピッチ:0.2mm、回転数:25ヘルツ、3パス)で混練して、白色顔料含有エポキシ樹脂(エポキシ樹脂組成物)を得た。
(硬化剤を少なくとも含む硬化剤組成物(K剤)の製造:実施例10~21、比較例9~13)
硬化剤(酸無水物)(商品名「リカシッド MH-700」、日立化成工業(株)製)、硬化剤(酸無水物)と脂環式ポリエステル樹脂の混合物(商品名「HN-7200」、日立化成工業(株)製)、硬化剤(酸無水物)と脂環式ポリエステル樹脂の混合物(商品名「HN-5700」、日立化成工業(株)製)、硬化促進剤(商品名「U-CAT 18X」、サンアプロ(株)製)、添加剤(商品名「エチレングリコール」、和光純薬工業(株)製)を、表2に示す配合処方(配合割合)(単位:重量部)に従って、自公転式攪拌装置(商品名「あわとり練太郎AR-250」、(株)シンキー製)を使用して均一に混合し、脱泡してK剤を得た。
(硬化性エポキシ樹脂組成物の製造)
表2に示す配合処方(単位:重量部)となるように、製造例4で得られた白色顔料含有エポキシ樹脂、製造例5で得られたK剤を、自公転式攪拌装置(商品名「あわとり練太郎AR-250」、(株)シンキー製)を使用して均一に混合し(2000rpm、5分間)、脱泡して、硬化性エポキシ樹脂組成物を得た。
上記で得た硬化性エポキシ樹脂組成物を、オーブン(商品名「GPHH-201」、エスペック(株)製)に入れて、120℃で5時間加熱することによって、硬化物を得た。
(ゴム粒子の製造)
還流冷却器付きの1L重合容器に、イオン交換水500g、及びジオクチルスルホコハク酸ナトリウム0.68gを仕込み、窒素気流下に撹拌しながら、80℃に昇温した。ここに、コア部分を形成するために必要とする量の約5重量%分に該当するアクリル酸ブチル9.5g、スチレン2.57g、及びジビニルベンゼン0.39gからなる単量体混合物を一括添加し、20分間撹拌して乳化させた後、ペルオキソ二硫酸カリウム9.5mgを添加し、1時間撹拌して最初のシード重合を行い、続いて、ペルオキソ二硫酸カリウム180.5mgを添加し、5分間撹拌した。ここに、コア部分を形成するために必要とする量の残り(約95重量%分)のアクリル酸ブチル180.5g、スチレン48.89g、ジビニルベンゼン7.33gにジオクチルスルホコハク酸ナトリウム0.95gを溶解させてなる単量体混合物を2時間かけて連続的に添加し、2度目のシード重合を行い、その後、1時間熟成してコア部分を得た。
次いで、ペルオキソ二硫酸カリウム60mgを添加して5分間撹拌し、ここに、メタクリル酸メチル60g、アクリル酸1.5g、及びアリルメタクリレート0.3gにジオクチルスルホコハク酸ナトリウム0.3gを溶解させてなる単量体混合物を30分かけて連続的に添加し、シード重合を行った。その後、1時間熟成し、コア部分を被覆するシェル層を形成した。
次いで、室温(25℃)まで冷却し、目開き120μmのプラスチック製網で濾過することにより、コアシェル構造を有するゴム粒子を含むラテックスを得た。得られたラテックスをマイナス30℃で凍結し、吸引濾過器で脱水洗浄した後、60℃で一昼夜送風乾燥してゴム粒子を得た。得られたゴム粒子の平均粒子径は254nm、最大粒子径は486nmであった。
(ゴム粒子分散エポキシ化合物の製造)
製造例6で得られたゴム粒子10重量部を、窒素気流下、60℃に加温した状態でディゾルバー(1000rpm、60分間)を使用して、セロキサイド2021P(3,4-エポキシシクロヘキシルメチル(3,4-エポキシ)シクロヘキサンカルボキシレート、(株)ダイセル製)48重量部に分散させ、真空脱泡して、ゴム粒子分散エポキシ化合物(25℃での粘度:1023mPa・s)を得た。
なお、製造例7で得られたゴム粒子分散エポキシ化合物(ゴム粒子10重量部をセロキサイド2021P((株)ダイセル製)48重量部に分散させたもの)の粘度(25℃における粘度)は、デジタル粘度計(商品名「DVU-EII型」、(株)トキメック製)を使用して測定した。
(白色顔料含有エポキシ樹脂の製造:実施例22~41)
モノアリルジグリシジルイソシアヌレート(商品名「MA-DGIC」、四国化成工業(株)製)、脂環式エポキシ化合物(商品名「セロキサイド2021P」、(株)ダイセル製)、分子内に2個のエポキシ基を有するシロキサン誘導体(商品名「X-40-2678」、信越化学工業(株)製)、分子内に3個のエポキシ基を有するシロキサン誘導体(商品名「X-40-2720」、信越化学工業(株)製)、分子内に4個のエポキシ基を有するシロキサン誘導体(商品名「X-40-2670」、信越化学工業(株)製)、シリコーン系レベリング剤(商品名「BYK-300」、ビックケミー・ジャパン(株)製;商品名「AC FS 180」、Algin Chemie製)、フッ素系レベリング剤(商品名「BYK-340」、ビックケミー・ジャパン(株)製;商品名「AC 110a」、Algin Chemie製)、ポリカーボネートジオール(商品名「プラクセル CD220PL」、(株)ダイセル製)、ポリテトラメチレンエーテルグリコール(商品名「PTMG2000」、三菱化学(株)製)、ポリカプロラクトンポリオール(商品名「プラクセル 308」、(株)ダイセル製)、フェノキシ樹脂(商品名「YP-70」、新日鐵化学(株)製)、水酸基含有長鎖エポキシ樹脂(商品名「エポトートYD-6020」、新日鐵化学(株)製)、アクリルブロック共重合体(商品名「ナノストレングス M52N」、アルケマ製)、製造例7で得られたゴム粒子分散エポキシ化合物を、表3に示す配合処方(配合割合)(単位:重量部)に従って混合し、80℃で1時間攪拌することでモノアリルジグリシジルイソシアヌレートを溶解させ、エポキシ樹脂(混合物)を得た。次いで、上記エポキシ樹脂と白色顔料(酸化チタン;商品名「TCR-52」、堺化学工業(株)製)とを、表3に示す配合処方(配合割合)(単位:重量部)に従って、ディゾルバーを使用して均一に混合し、ロールミルによって所定条件下(ロールピッチ:0.2mm、回転数:25ヘルツ、3パス)で混練して、白色顔料含有エポキシ樹脂(エポキシ樹脂組成物)を得た。
(K剤の製造:実施例22~41)
硬化剤(酸無水物)と脂環式ポリエステル樹脂の混合物(商品名「HN-7200」、日立化成工業(株)製)、硬化促進剤(商品名「U-CAT 18X」、サンアプロ(株)製)、添加剤(商品名「エチレングリコール」、和光純薬工業(株)製)を、表3に示す配合処方(配合割合)(単位:重量部)に従って、自公転式攪拌装置(商品名「あわとり練太郎AR-250」、(株)シンキー製)を使用して均一に混合し、脱泡してK剤を得た。
(硬化性エポキシ樹脂組成物の製造)
表3に示す配合処方(単位:重量部)となるように、製造例8で得られた白色顔料含有エポキシ樹脂、製造例9で得られたK剤を、自公転式攪拌装置(商品名「あわとり練太郎AR-250」、(株)シンキー製)を使用して均一に混合し(2000rpm、5分間)、脱泡して、硬化性エポキシ樹脂組成物を得た。
上記で得た硬化性エポキシ樹脂組成物を、オーブン(商品名「GPHH-201」、エスペック(株)製)に入れて、120℃で5時間加熱することによって、硬化物を得た。
(白色顔料含有エポキシ樹脂の製造:実施例42~60、比較例14~17)
モノアリルジグリシジルイソシアヌレート(商品名「MA-DGIC」、四国化成工業(株)製)、脂環式エポキシ化合物(商品名「セロキサイド2021P」、(株)ダイセル製;商品名「EHPE3150」、(株)ダイセル製)、トリスグリシジルイソシアヌレート(商品名「TEPIC-PAS B26」、日産化学工業(株)製)、分子内に2個のエポキシ基を有するシロキサン誘導体(商品名「X-40-2678」、信越化学工業(株)製)、分子内に3個のエポキシ基を有するシロキサン誘導体(商品名「X-40-2720」、信越化学工業(株)製)、分子内に4個のエポキシ基を有するシロキサン誘導体(商品名「X-40-2670」、信越化学工業(株)製)、シリコーン系レベリング剤(商品名「BYK-300」、ビックケミー・ジャパン(株)製;商品名「AC FS 180」、Algin Chemie製)、フッ素系レベリング剤(商品名「BYK-340」、ビックケミー・ジャパン(株)製;商品名「AC 110a」、Algin Chemie製)、ポリカーボネートジオール(商品名「プラクセル CD220PL」、(株)ダイセル製)、ポリテトラメチレンエーテルグリコール(商品名「PTMG2000」、三菱化学(株)製)、ポリカプロラクトンポリオール(商品名「プラクセル308」、(株)ダイセル製)、フェノキシ樹脂(商品名「YP-70」、新日鐵化学(株)製)、水酸基含有長鎖エポキシ樹脂(商品名「エポトートYD-6020」、新日鐵化学(株)製)、アクリルブロック共重合体(商品名「ナノストレングス M52N」、アルケマ製)、製造例7で得られたゴム粒子分散エポキシ化合物を、表4に示す配合処方(配合割合)(単位:重量部)に従って混合し、さらに80℃で1時間攪拌することでモノアリルジグリシジルイソシアヌレートを溶解させ、エポキシ樹脂(混合物)を得た(比較例14~17の場合には、エポキシ樹脂の成分が一種であるため当該混合を行わず、そのままエポキシ樹脂とした)。次いで、上記エポキシ樹脂と白色顔料(酸化チタン;商品名「TCR-52」、堺化学工業(株)製)とを、表4に示す配合処方(配合割合)(単位:重量部)に従って、ディゾルバーを使用して均一に混合し、ロールミルによって所定条件下(ロールピッチ:0.2mm、回転数:25ヘルツ、3パス)で混練して、白色顔料含有エポキシ樹脂(エポキシ樹脂組成物)を得た。
(脂環式ポリエステル樹脂の製造:実施例42~60、比較例14~17)
攪拌機、温度計及び還流冷却器を備えた反応容器に、1,4-シクロヘキサンジカルボン酸(東京化成工業(株)製)172重量部、ネオペンチルグリコール(東京化成工業(株)製)208重量部、テトラブチルチタネート(和光純薬工業(株)製)0.1重量部を仕込んで、160℃になるまで加熱し、さらに160℃から250℃まで4時間かけて昇温した。次いで、1時間かけて5mmHgまで減圧し、さらに0.3mmHg以下まで減圧してから250℃で1時間反応させ、脂環式ポリエステル樹脂を得た。
(硬化性エポキシ樹脂組成物の製造)
表4に示す配合処方(単位:重量部)となるように、製造例10で得られた白色顔料含有エポキシ樹脂、製造例11で得られた脂環式ポリエステル樹脂、硬化触媒(商品名「サンエイド SI-100L」、三新化学工業(株)製)を、自公転式攪拌装置(商品名「あわとり練太郎AR-250」、(株)シンキー製)を使用して均一に混合し(2000rpm、5分間)、脱泡して、硬化性エポキシ樹脂組成物を得た。
上記で得た硬化性エポキシ樹脂組成物を、オーブン(商品名「GPHH-201」、エスペック(株)製)に入れて、120℃で5時間加熱することによって、硬化物を得た。
実施例及び比較例で得られた硬化物について、下記の手順に従って、450nmの光に対する反射率を測定し、さらに成形(切削加工)時、リフロー時にクラックが生じるか否かの評価を行った。評価結果を表1~4に示す。
実施例及び比較例で得られた硬化物を切削加工して、厚み3mmの試験片を作製した。次いで、分光光度計(商品名「分光光度計 UV-2450」、(株)島津製作所製)を用いて、波長450nmの光に対する各試験片の反射率(「初期反射率」とする)を測定した。結果を表1~4の「初期反射率」の欄に示した。
初期反射率を測定した試験片(厚み3mm)を、120℃で250時間加熱した後、波長450nmの光に対する反射率(「加熱エージング(250時間)後の反射率」とする)を測定した。そして、下記式により、反射率保持率(加熱エージング前後;250時間)を算出した。結果を表1~4の「反射率保持率 加熱エージング前後(250時間)」の欄に示した。
[反射率保持率(加熱エージング前後;250時間)]=[加熱エージング(250時間)後の反射率]/[初期反射率]×100
初期反射率を測定した試験片(厚み3mm)を、120℃で500時間加熱した後、波長450nmの光に対する反射率(「加熱エージング(500時間)後の反射率」とする)を測定した。そして、下記式により、反射率保持率(加熱エージング前後;500時間)を算出した。結果を表1~4の「反射率保持率 加熱エージング前後(500時間)」の欄に示した。
[反射率保持率(加熱エージング前後;500時間)]=[加熱エージング(500時間)後の反射率]/[初期反射率]×100
初期反射率を測定した試験片(厚み3mm)に対し、強度10mW/cm2の紫外線を250時間照射した後、波長450nmの光に対する反射率(「紫外線エージング後の反射率」とする)を測定した。そして、下記式により、反射率保持率(紫外線エージング前後)を算出した。結果を表1~4の「反射率保持率 紫外線エージング前後」の欄に示した。
[反射率保持率(紫外線エージング前後)]=[紫外線エージング後の反射率]/[初期反射率]×100
実施例及び比較例で得られた硬化物を切削加工することによって、幅5mm×長さ5mm×厚さ3mmの試験片を作製した。上記硬化物の切削加工には、マイクロ・カッティング・マシン(商品名「BS-300CL」、メイワフォーシス(株)製)を使用し、切削加工の際に硬化物にクラックが生じたか否かを、デジタルマイクロスコープ(商品名「VHX-900」、(株)キーエンス製)を用いて観察し、確認した。表1~4の「切削加工時のクラック数」の欄には、1サンプルにつき10個の試験片を作製し、そのうちクラックの発生が確認された試験片の個数[個](「クラック数」と称する)を評価結果として示す。なお、表1~4においては、クラックの発生が確認された試験片の個数(クラック数)がn個である場合を、「n/10」のように示した。
上記切削加工により得られた試験片(幅5mm×長さ5mm×厚さ3mm)に対し、リフロー炉(商品名「UNI-5016F」、日本アントム(株)製)を用いて、260℃を最高温度として5秒間、全リフロー時間を90秒としてリフロー処理を施した。その後、当該リフロー処理により試験片にクラックが生じたか否かを、デジタルマイクロスコープ(商品名「VHX-900」、(株)キーエンス製)を用いて観察し、確認した。表1~4には、1サンプルにつき10個の試験片のリフロー処理を行い、そのうちクラックの発生が確認された試験片の個数[個](クラック数)を評価結果として示す。なお、表1~4の「リフロー時のクラック数」の欄には、クラックの発生が確認された試験片の個数(クラック数)がn個である場合を、「n/10」のように示した。
初期反射率が90%以上のもので、耐熱性試験(加熱エージング500時間)において反射率保持率が90%以上、耐光性試験において反射率保持率が90%以上、ならびに、切削加工時のクラック有無評価(強靭性評価)、及びリフロー時のクラック有無評価(強靭性評価)においてクラック数が0個となったものを、総合判定○(良好)とした。一方、これ以外のものを総合判定×(不良)とした。結果を表1~4の「総合判定」の欄に示す。
[エポキシ樹脂]
CEL2021P(セロキサイド 2021P):3,4-エポキシシクロヘキシルメチル(3,4-エポキシ)シクロヘキサンカルボキシレート、(株)ダイセル製
MA-DGIC:モノアリルジグリシジルイソシアヌレート、四国化成工業(株)製
EHPE3150:2,2-ビス(ヒドロキシメチル)-1-ブタノールの1,2-エポキシ-4-(2-オキシラニル)シクロヘキサン付加物、(株)ダイセル製
TEPIC-PAS B26:トリスグリシジルイソシアヌレート、日産化学工業(株)製
X-40-2678:分子内に2個のエポキシ基を有するシロキサン誘導体、信越化学工業(株)製
X-40-2720:分子内に3個のエポキシ基を有するシロキサン誘導体、信越化学工業(株)製
X-40-2670:分子内に4個のエポキシ基を有するシロキサン誘導体、信越化学工業(株)製
BYK-300:シリコーン系レベリング剤(シリコーン系重合体を含むレベリング剤)、ビックケミー・ジャパン(株)製
AC FS 180:シリコーン系レベリング剤(シリコーン系重合体を含むレベリング剤)、Algin Chemie製
BYK-340:フッ素系レベリング剤(含フッ素アクリル系重合体を含むレベリング剤)、ビックケミー・ジャパン(株)製
AC 110a:フッ素系レベリング剤(含フッ素ポリエーテル系重合体を含むレベリング剤)、Algin Chemie製
CD220PL(プラクセル CD220PL):ポリカーボネートジオール、(株)ダイセル製
PTMG2000:ポリテトラメチレンエーテルグリコール、三菱化学(株)製
プラクセル308:ポリカプロラクトンポリオール、(株)ダイセル製
YP-70:フェノキシ樹脂、新日鐵化学(株)製
エポトートYD-6020:水酸基含有長鎖エポキシ樹脂、新日鐵化学(株)製
M52N(ナノストレングス M52N):アクリルブロック共重合体、アルケマ製
[白色顔料]
酸化チタン、商品名「TCR-52」、堺化学工業(株)製
[K剤]
MH-700(リカシッド MH-700):4-メチルヘキサヒドロ無水フタル酸/ヘキサヒドロ無水フタル酸=70/30、新日本理化(株)製
HN-7200:4-メチルヘキサヒドロ無水フタル酸と脂環式ポリエステル樹脂の混合物、日立化成工業(株)製
HN-5700:4-メチルヘキサヒドロ無水フタル酸/3-メチルヘキサヒドロ無水フタル酸=70/30と脂環式ポリエステル樹脂の混合物、日立化成工業(株)製
18X(U-CAT 18X):硬化促進剤、サンアプロ(株)製
エチレングリコール:和光純薬工業(株)製
[硬化触媒]
サンエイド SI-100L:アリールスルホニウム塩、三新化学工業(株)製
一方、本発明の規定を満たさない硬化性エポキシ樹脂組成物より形成した硬化物(比較例)は、加熱エージング及び紫外線エージング後に光反射性が低下し、耐熱性及び耐光性に劣っていた。さらに、切削加工時やリフロー時にクラックが生じやすく、靭性にも劣っていた。
2: 金属配線
3: 光半導体素子
4: ボンディングワイヤ
5: 封止樹脂
6: パッケージ樹脂
Claims (14)
- 前記脂環式エポキシ化合物(A)が、シクロヘキセンオキシド基を有する化合物である請求項1又は2に記載の硬化性エポキシ樹脂組成物。
- さらに、分子内に2以上のエポキシ基を有するシロキサン誘導体(G)を含む請求項1~4のいずれか1項に記載の硬化性エポキシ樹脂組成物。
- さらに、脂環式ポリエステル樹脂(H)を含む請求項1~5のいずれか1項に記載の硬化性エポキシ樹脂組成物。
- 前記脂環式ポリエステル樹脂(H)が、主鎖に脂環を有する脂環式ポリエステル樹脂である請求項6に記載の硬化性エポキシ樹脂組成物。
- さらに、ゴム粒子を含む請求項1~7のいずれか1項に記載の硬化性エポキシ樹脂組成物。
- さらに、シリコーン系レベリング剤及びフッ素系レベリング剤からなる群より選ばれた少なくとも1種のレベリング剤を含む請求項1~8のいずれか1項に記載の硬化性エポキシ樹脂組成物。
- さらに、ポリオール化合物を含む請求項1~9のいずれか1項に記載の硬化性エポキシ樹脂組成物。
- さらに、アクリルブロック共重合体を含む請求項1~10のいずれか1項に記載の硬化性エポキシ樹脂組成物。
- 請求項1~11のいずれか1項に記載の硬化性エポキシ樹脂組成物を硬化してなる硬化物。
- 請求項1~11のいずれか1項に記載の硬化性エポキシ樹脂組成物からなる光反射用硬化性樹脂組成物。
- 光半導体素子と、請求項13に記載の光反射用硬化性樹脂組成物の硬化物からなるリフレクターとを少なくとも備えることを特徴とする光半導体装置。
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Citations (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2000344867A (ja) * | 1999-06-01 | 2000-12-12 | Shikoku Chem Corp | 熱硬化性エポキシ樹脂組成物 |
JP2004131553A (ja) * | 2002-10-09 | 2004-04-30 | Yokohama Tlo Co Ltd | エポキシ樹脂組成物 |
JP2008007782A (ja) * | 2006-06-27 | 2008-01-17 | Lumination Llc | オプトエレクトロニックデバイス |
JP2008143954A (ja) * | 2006-12-06 | 2008-06-26 | Jsr Corp | イソシアヌル環含有重合体、その製造法およびそれを含有する組成物 |
JP2008260853A (ja) * | 2007-04-12 | 2008-10-30 | Hitachi Chem Co Ltd | 新規硬化性樹脂とその製造方法、及びエポキシ樹脂組成物、電子部品装置 |
WO2009088059A1 (ja) * | 2008-01-09 | 2009-07-16 | Hitachi Chemical Company, Ltd. | 熱硬化性樹脂組成物、エポキシ樹脂成形材料及び多価カルボン酸縮合体 |
WO2009096374A1 (ja) * | 2008-01-28 | 2009-08-06 | Kaneka Corporation | 脂環式エポキシ樹脂組成物、その硬化物、及びその製造方法、並びにゴム状重合体含有樹脂組成物 |
JP2009227849A (ja) * | 2008-03-24 | 2009-10-08 | Sanyo Chem Ind Ltd | 光半導体素子封止用エポキシ樹脂組成物 |
JP2009256604A (ja) * | 2008-03-28 | 2009-11-05 | Shin Etsu Chem Co Ltd | 光半導体素子封止用エポキシ・シリコーン混成樹脂組成物及びそれからなるトランスファー成型用タブレット |
WO2010092947A1 (ja) * | 2009-02-10 | 2010-08-19 | 日産化学工業株式会社 | 長鎖アルキレン基含有エポキシ化合物 |
Family Cites Families (12)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
SG63803A1 (en) * | 1997-01-23 | 1999-03-30 | Toray Industries | Epoxy-resin composition to seal semiconductors and resin-sealed semiconductor device |
US6180696B1 (en) * | 1997-02-19 | 2001-01-30 | Georgia Tech Research Corporation | No-flow underfill of epoxy resin, anhydride, fluxing agent and surfactant |
JP4560982B2 (ja) * | 2000-04-17 | 2010-10-13 | 三菱電機株式会社 | 高圧回転機用絶縁コイルの製造方法 |
JP2003277591A (ja) * | 2002-03-26 | 2003-10-02 | Sumitomo Bakelite Co Ltd | エポキシ樹脂組成物、プリプレグ及び積層板 |
KR100799146B1 (ko) * | 2003-08-21 | 2008-01-29 | 아사히 가세이 케미칼즈 가부시키가이샤 | 감광성 조성물 및 그 경화물 |
JP4852893B2 (ja) * | 2005-05-31 | 2012-01-11 | 住友ベークライト株式会社 | プリアプライド用封止樹脂組成物及びそれを用いた半導体装置の製造方法 |
EP1939233A1 (en) * | 2005-10-18 | 2008-07-02 | Nippon Kayaku Kabushiki Kaisha | Epoxy resin, epoxy resin composition, photosensitive resin composition, and cured object obtained therefrom |
US20070295983A1 (en) * | 2006-06-27 | 2007-12-27 | Gelcore Llc | Optoelectronic device |
CN102408543B (zh) * | 2006-11-15 | 2014-10-29 | 日立化成工业株式会社 | 光反射用热固化性树脂组合物、用该组合物的光半导体元件搭载用基板及其光半导体装置 |
US8042976B2 (en) * | 2007-11-30 | 2011-10-25 | Taiyo Holdings Co., Ltd. | White hardening resin composition, hardened material, printed-wiring board and reflection board for light emitting device |
WO2010013407A1 (ja) * | 2008-07-31 | 2010-02-04 | ダイセル化学工業株式会社 | 光半導体封止用樹脂組成物とこれを使用した光半導体装置 |
JP5638812B2 (ja) * | 2010-02-01 | 2014-12-10 | 株式会社ダイセル | 硬化性エポキシ樹脂組成物 |
-
2012
- 2012-07-03 KR KR1020137028933A patent/KR101923244B1/ko active IP Right Grant
- 2012-07-03 CN CN201280034269.0A patent/CN103649218B/zh not_active Expired - Fee Related
- 2012-07-03 JP JP2013523900A patent/JP5938040B2/ja active Active
- 2012-07-03 WO PCT/JP2012/066966 patent/WO2013008680A1/ja active Application Filing
- 2012-07-12 TW TW101125029A patent/TWI555769B/zh not_active IP Right Cessation
Patent Citations (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2000344867A (ja) * | 1999-06-01 | 2000-12-12 | Shikoku Chem Corp | 熱硬化性エポキシ樹脂組成物 |
JP2004131553A (ja) * | 2002-10-09 | 2004-04-30 | Yokohama Tlo Co Ltd | エポキシ樹脂組成物 |
JP2008007782A (ja) * | 2006-06-27 | 2008-01-17 | Lumination Llc | オプトエレクトロニックデバイス |
JP2008143954A (ja) * | 2006-12-06 | 2008-06-26 | Jsr Corp | イソシアヌル環含有重合体、その製造法およびそれを含有する組成物 |
JP2008260853A (ja) * | 2007-04-12 | 2008-10-30 | Hitachi Chem Co Ltd | 新規硬化性樹脂とその製造方法、及びエポキシ樹脂組成物、電子部品装置 |
WO2009088059A1 (ja) * | 2008-01-09 | 2009-07-16 | Hitachi Chemical Company, Ltd. | 熱硬化性樹脂組成物、エポキシ樹脂成形材料及び多価カルボン酸縮合体 |
WO2009096374A1 (ja) * | 2008-01-28 | 2009-08-06 | Kaneka Corporation | 脂環式エポキシ樹脂組成物、その硬化物、及びその製造方法、並びにゴム状重合体含有樹脂組成物 |
JP2009227849A (ja) * | 2008-03-24 | 2009-10-08 | Sanyo Chem Ind Ltd | 光半導体素子封止用エポキシ樹脂組成物 |
JP2009256604A (ja) * | 2008-03-28 | 2009-11-05 | Shin Etsu Chem Co Ltd | 光半導体素子封止用エポキシ・シリコーン混成樹脂組成物及びそれからなるトランスファー成型用タブレット |
WO2010092947A1 (ja) * | 2009-02-10 | 2010-08-19 | 日産化学工業株式会社 | 長鎖アルキレン基含有エポキシ化合物 |
Cited By (29)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2014095039A (ja) * | 2012-11-09 | 2014-05-22 | Shin Etsu Chem Co Ltd | 熱硬化性エポキシ樹脂組成物及び光半導体装置 |
JP2014172990A (ja) * | 2013-03-08 | 2014-09-22 | Nippon Zeon Co Ltd | エポキシ樹脂組成物、封止材、および光半導体装置 |
WO2015030089A1 (ja) * | 2013-08-30 | 2015-03-05 | 株式会社ダイセル | 硬化性樹脂組成物、粉体成形用硬化性樹脂組成物、及び光半導体装置 |
EP3045508A4 (en) * | 2013-09-13 | 2017-04-12 | Dexerials Corporation | Adhesive and light-emitting device |
US9994743B2 (en) | 2013-09-13 | 2018-06-12 | Dexerials Corporation | Adhesive and light-emitting device |
CN103641998A (zh) * | 2013-12-24 | 2014-03-19 | 江苏华海诚科新材料有限公司 | Led反射杯用的白色环氧树脂组合物 |
WO2015146988A1 (ja) * | 2014-03-28 | 2015-10-01 | 株式会社ダイセル | 熱硬化性樹脂組成物及びその硬化物、光半導体素子搭載用基板、並びに光半導体装置 |
WO2016017531A1 (ja) * | 2014-07-31 | 2016-02-04 | 株式会社ダイセル | 硬化性樹脂組成物及びその硬化物、光半導体素子搭載用基板、並びに光半導体装置 |
JP2016045448A (ja) * | 2014-08-26 | 2016-04-04 | 中国塗料株式会社 | 光硬化性樹脂組成物、該組成物から形成される硬化被膜および防眩フィルム、画像表示装置、並びに硬化被膜および防眩フィルムの製造方法 |
JP2016164254A (ja) * | 2015-02-10 | 2016-09-08 | 株式会社ダイセル | 光学材料用硬化性エポキシ樹脂組成物 |
CN105907038A (zh) * | 2015-02-20 | 2016-08-31 | 信越化学工业株式会社 | Led反光装置用白色热固性环氧树脂组合物 |
CN105907038B (zh) * | 2015-02-20 | 2019-08-20 | 信越化学工业株式会社 | Led反光装置用白色热固性环氧树脂组合物 |
JP2016153447A (ja) * | 2015-02-20 | 2016-08-25 | 信越化学工業株式会社 | Ledリフレクター用白色熱硬化性エポキシ樹脂組成物 |
US9884960B2 (en) * | 2015-02-20 | 2018-02-06 | Shin-Etsu Chemical Co., Ltd. | White heat-curable epoxy resin composition, optical semiconductor element case made of the white heat-curable epoxy resin composition and optical semiconductor device comprised of the case |
JP2017071708A (ja) * | 2015-10-08 | 2017-04-13 | 信越化学工業株式会社 | 熱硬化性エポキシ樹脂組成物及び光半導体装置 |
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WO2019124476A1 (ja) * | 2017-12-21 | 2019-06-27 | 株式会社ダイセル | 硬化性エポキシ樹脂組成物及びその硬化物、並びに光半導体装置 |
WO2022148103A1 (zh) * | 2021-01-07 | 2022-07-14 | 天津德高化成光电科技有限责任公司 | 一种预聚体、含有该预聚体的封装树脂及封装树脂的应用 |
WO2022219308A1 (en) * | 2021-04-13 | 2022-10-20 | Johnson Matthey Public Limited Company | Uv-curable ethylene scavenging compositions |
KR102556932B1 (ko) * | 2023-04-18 | 2023-07-19 | 주식회사 유환 | 인쇄회로기판의 개별 엘이디 소자 주변부에 반사 성형체를 형성시키는 방법 |
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TWI555769B (zh) | 2016-11-01 |
KR20140034777A (ko) | 2014-03-20 |
CN103649218A (zh) | 2014-03-19 |
JPWO2013008680A1 (ja) | 2015-02-23 |
TW201307423A (zh) | 2013-02-16 |
JP5938040B2 (ja) | 2016-06-22 |
KR101923244B1 (ko) | 2018-11-28 |
CN103649218B (zh) | 2016-05-11 |
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