JP5741742B2 - Curable resin composition, cured product thereof and thermally conductive adhesive - Google Patents
Curable resin composition, cured product thereof and thermally conductive adhesive Download PDFInfo
- Publication number
- JP5741742B2 JP5741742B2 JP2014056368A JP2014056368A JP5741742B2 JP 5741742 B2 JP5741742 B2 JP 5741742B2 JP 2014056368 A JP2014056368 A JP 2014056368A JP 2014056368 A JP2014056368 A JP 2014056368A JP 5741742 B2 JP5741742 B2 JP 5741742B2
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- JP
- Japan
- Prior art keywords
- resin composition
- epoxy resin
- curable resin
- thermally conductive
- conductive filler
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- 239000011342 resin composition Substances 0.000 title claims description 51
- 239000000853 adhesive Substances 0.000 title claims description 25
- 230000001070 adhesive effect Effects 0.000 title claims description 25
- 239000003822 epoxy resin Substances 0.000 claims description 79
- 229920000647 polyepoxide Polymers 0.000 claims description 79
- 239000011231 conductive filler Substances 0.000 claims description 40
- 239000003795 chemical substances by application Substances 0.000 claims description 16
- LALXQOVGAFIPFI-UHFFFAOYSA-N 2-[[1-[2,7-bis(oxiran-2-ylmethoxy)naphthalen-1-yl]-7-(oxiran-2-ylmethoxy)naphthalen-2-yl]oxymethyl]oxirane Chemical compound C1OC1COC(C=C1C=2C=3C4=CC(OCC5OC5)=CC=C4C=CC=3OCC3OC3)=CC=C1C=CC=2OCC1CO1 LALXQOVGAFIPFI-UHFFFAOYSA-N 0.000 claims description 11
- 239000000463 material Substances 0.000 claims description 11
- LTPBRCUWZOMYOC-UHFFFAOYSA-N Beryllium oxide Chemical compound O=[Be] LTPBRCUWZOMYOC-UHFFFAOYSA-N 0.000 claims description 8
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 6
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 6
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 6
- 229910052582 BN Inorganic materials 0.000 claims description 5
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 claims description 5
- 229910052581 Si3N4 Inorganic materials 0.000 claims description 5
- PMHQVHHXPFUNSP-UHFFFAOYSA-M copper(1+);methylsulfanylmethane;bromide Chemical compound Br[Cu].CSC PMHQVHHXPFUNSP-UHFFFAOYSA-M 0.000 claims description 5
- 229910003460 diamond Inorganic materials 0.000 claims description 5
- 239000010432 diamond Substances 0.000 claims description 5
- 239000000395 magnesium oxide Substances 0.000 claims description 5
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 claims description 5
- 230000017525 heat dissipation Effects 0.000 claims description 4
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims description 4
- 229910052580 B4C Inorganic materials 0.000 claims description 3
- INAHAJYZKVIDIZ-UHFFFAOYSA-N boron carbide Chemical compound B12B3B4C32B41 INAHAJYZKVIDIZ-UHFFFAOYSA-N 0.000 claims description 3
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 claims description 3
- 229910010271 silicon carbide Inorganic materials 0.000 claims description 3
- MTPVUVINMAGMJL-UHFFFAOYSA-N trimethyl(1,1,2,2,2-pentafluoroethyl)silane Chemical compound C[Si](C)(C)C(F)(F)C(F)(F)F MTPVUVINMAGMJL-UHFFFAOYSA-N 0.000 claims description 3
- 239000011787 zinc oxide Substances 0.000 claims description 3
- 238000001723 curing Methods 0.000 description 24
- 239000000047 product Substances 0.000 description 24
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 22
- 239000000203 mixture Substances 0.000 description 21
- 239000002245 particle Substances 0.000 description 19
- 150000001875 compounds Chemical class 0.000 description 18
- 238000012360 testing method Methods 0.000 description 18
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 17
- 229920005989 resin Polymers 0.000 description 17
- 239000011347 resin Substances 0.000 description 17
- 229920003986 novolac Polymers 0.000 description 16
- 239000007788 liquid Substances 0.000 description 13
- 238000000034 method Methods 0.000 description 13
- 239000004593 Epoxy Substances 0.000 description 12
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 12
- -1 amine compounds Chemical class 0.000 description 12
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 11
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 10
- 238000002156 mixing Methods 0.000 description 10
- 239000000243 solution Substances 0.000 description 10
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 9
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 9
- 238000003786 synthesis reaction Methods 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- 230000015572 biosynthetic process Effects 0.000 description 8
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 8
- 239000000945 filler Substances 0.000 description 8
- 150000002989 phenols Chemical class 0.000 description 8
- NXPPAOGUKPJVDI-UHFFFAOYSA-N naphthalene-1,2-diol Chemical group C1=CC=CC2=C(O)C(O)=CC=C21 NXPPAOGUKPJVDI-UHFFFAOYSA-N 0.000 description 7
- 239000007787 solid Substances 0.000 description 7
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 6
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 6
- 238000005259 measurement Methods 0.000 description 6
- 239000003960 organic solvent Substances 0.000 description 6
- 239000000843 powder Substances 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- FUXWXKZEFOPVKY-UHFFFAOYSA-N 1-(2,7-dihydroxynaphthalen-1-yl)naphthalene-2,7-diol Chemical compound C1=C(O)C=C2C(C3=C(O)C=CC4=CC=C(C=C43)O)=C(O)C=CC2=C1 FUXWXKZEFOPVKY-UHFFFAOYSA-N 0.000 description 5
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 5
- 230000009477 glass transition Effects 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- 238000004898 kneading Methods 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- KBJFYLLAMSZSOG-UHFFFAOYSA-N n-(3-trimethoxysilylpropyl)aniline Chemical compound CO[Si](OC)(OC)CCCNC1=CC=CC=C1 KBJFYLLAMSZSOG-UHFFFAOYSA-N 0.000 description 5
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 5
- 239000004065 semiconductor Substances 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 description 4
- 208000019651 NDE1-related microhydranencephaly Diseases 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 238000005859 coupling reaction Methods 0.000 description 4
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 4
- 238000011156 evaluation Methods 0.000 description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 239000000758 substrate Substances 0.000 description 4
- 238000004381 surface treatment Methods 0.000 description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 3
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 3
- 239000007795 chemical reaction product Substances 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 229920001577 copolymer Polymers 0.000 description 3
- 239000007822 coupling agent Substances 0.000 description 3
- 239000000539 dimer Substances 0.000 description 3
- 229920001971 elastomer Polymers 0.000 description 3
- 125000003700 epoxy group Chemical group 0.000 description 3
- 238000011049 filling Methods 0.000 description 3
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 3
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 description 3
- DFQICHCWIIJABH-UHFFFAOYSA-N naphthalene-2,7-diol Chemical compound C1=CC(O)=CC2=CC(O)=CC=C21 DFQICHCWIIJABH-UHFFFAOYSA-N 0.000 description 3
- 125000001624 naphthyl group Chemical group 0.000 description 3
- 230000000704 physical effect Effects 0.000 description 3
- 235000013824 polyphenols Nutrition 0.000 description 3
- 238000010926 purge Methods 0.000 description 3
- 230000005855 radiation Effects 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 3
- 229960001755 resorcinol Drugs 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 238000010008 shearing Methods 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- MUTGBJKUEZFXGO-OLQVQODUSA-N (3as,7ar)-3a,4,5,6,7,7a-hexahydro-2-benzofuran-1,3-dione Chemical compound C1CCC[C@@H]2C(=O)OC(=O)[C@@H]21 MUTGBJKUEZFXGO-OLQVQODUSA-N 0.000 description 2
- RUEBPOOTFCZRBC-UHFFFAOYSA-N (5-methyl-2-phenyl-1h-imidazol-4-yl)methanol Chemical compound OCC1=C(C)NC(C=2C=CC=CC=2)=N1 RUEBPOOTFCZRBC-UHFFFAOYSA-N 0.000 description 2
- DHKHKXVYLBGOIT-UHFFFAOYSA-N 1,1-Diethoxyethane Chemical compound CCOC(C)OCC DHKHKXVYLBGOIT-UHFFFAOYSA-N 0.000 description 2
- OQOANOQNIDTIHS-UHFFFAOYSA-N 1-[(2,7-dihydroxynaphthalen-1-yl)methyl]naphthalene-2,7-diol Chemical compound C1=C(O)C=C2C(CC3=C(O)C=CC4=CC=C(C=C43)O)=C(O)C=CC2=C1 OQOANOQNIDTIHS-UHFFFAOYSA-N 0.000 description 2
- ZDZHCHYQNPQSGG-UHFFFAOYSA-N 1-naphthalen-1-ylnaphthalene Chemical compound C1=CC=C2C(C=3C4=CC=CC=C4C=CC=3)=CC=CC2=C1 ZDZHCHYQNPQSGG-UHFFFAOYSA-N 0.000 description 2
- KJCVRFUGPWSIIH-UHFFFAOYSA-N 1-naphthol Chemical compound C1=CC=C2C(O)=CC=CC2=C1 KJCVRFUGPWSIIH-UHFFFAOYSA-N 0.000 description 2
- WTYYGFLRBWMFRY-UHFFFAOYSA-N 2-[6-(oxiran-2-ylmethoxy)hexoxymethyl]oxirane Chemical compound C1OC1COCCCCCCOCC1CO1 WTYYGFLRBWMFRY-UHFFFAOYSA-N 0.000 description 2
- 125000000022 2-aminoethyl group Chemical group [H]C([*])([H])C([H])([H])N([H])[H] 0.000 description 2
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 2
- QTWJRLJHJPIABL-UHFFFAOYSA-N 2-methylphenol;3-methylphenol;4-methylphenol Chemical compound CC1=CC=C(O)C=C1.CC1=CC=CC(O)=C1.CC1=CC=CC=C1O QTWJRLJHJPIABL-UHFFFAOYSA-N 0.000 description 2
- GSKNLOOGBYYDHV-UHFFFAOYSA-N 2-methylphenol;naphthalen-1-ol Chemical compound CC1=CC=CC=C1O.C1=CC=C2C(O)=CC=CC2=C1 GSKNLOOGBYYDHV-UHFFFAOYSA-N 0.000 description 2
- MWSKJDNQKGCKPA-UHFFFAOYSA-N 6-methyl-3a,4,5,7a-tetrahydro-2-benzofuran-1,3-dione Chemical compound C1CC(C)=CC2C(=O)OC(=O)C12 MWSKJDNQKGCKPA-UHFFFAOYSA-N 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- 229920000049 Carbon (fiber) Polymers 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 239000004793 Polystyrene Substances 0.000 description 2
- 239000006087 Silane Coupling Agent Substances 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 2
- 125000003545 alkoxy group Chemical group 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 239000004305 biphenyl Substances 0.000 description 2
- 235000010290 biphenyl Nutrition 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000004917 carbon fiber Substances 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 229930003836 cresol Natural products 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- 230000032798 delamination Effects 0.000 description 2
- 239000003085 diluting agent Substances 0.000 description 2
- 229910001873 dinitrogen Inorganic materials 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 239000012530 fluid Substances 0.000 description 2
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 238000009413 insulation Methods 0.000 description 2
- NQXWGWZJXJUMQB-UHFFFAOYSA-K iron trichloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].Cl[Fe+]Cl NQXWGWZJXJUMQB-UHFFFAOYSA-K 0.000 description 2
- 239000010410 layer Substances 0.000 description 2
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- 238000000691 measurement method Methods 0.000 description 2
- 239000000155 melt Substances 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- VSWALKINGSNVAR-UHFFFAOYSA-N naphthalen-1-ol;phenol Chemical compound OC1=CC=CC=C1.C1=CC=C2C(O)=CC=CC2=C1 VSWALKINGSNVAR-UHFFFAOYSA-N 0.000 description 2
- 150000004780 naphthols Chemical class 0.000 description 2
- 239000012044 organic layer Substances 0.000 description 2
- 239000003444 phase transfer catalyst Substances 0.000 description 2
- 239000005011 phenolic resin Substances 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 229920001296 polysiloxane Polymers 0.000 description 2
- 229920002223 polystyrene Polymers 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 230000000717 retained effect Effects 0.000 description 2
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 description 1
- LTVUCOSIZFEASK-MPXCPUAZSA-N (3ar,4s,7r,7as)-3a-methyl-3a,4,7,7a-tetrahydro-4,7-methano-2-benzofuran-1,3-dione Chemical compound C([C@H]1C=C2)[C@H]2[C@H]2[C@]1(C)C(=O)OC2=O LTVUCOSIZFEASK-MPXCPUAZSA-N 0.000 description 1
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- KGSFMPRFQVLGTJ-UHFFFAOYSA-N 1,1,2-triphenylethylbenzene Chemical compound C=1C=CC=CC=1C(C=1C=CC=CC=1)(C=1C=CC=CC=1)CC1=CC=CC=C1 KGSFMPRFQVLGTJ-UHFFFAOYSA-N 0.000 description 1
- WBODDOZXDKQEFS-UHFFFAOYSA-N 1,2,3,4-tetramethyl-5-phenylbenzene Chemical group CC1=C(C)C(C)=CC(C=2C=CC=CC=2)=C1C WBODDOZXDKQEFS-UHFFFAOYSA-N 0.000 description 1
- VDFVNEFVBPFDSB-UHFFFAOYSA-N 1,3-dioxane Chemical compound C1COCOC1 VDFVNEFVBPFDSB-UHFFFAOYSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- UWFRVQVNYNPBEF-UHFFFAOYSA-N 1-(2,4-dimethylphenyl)propan-1-one Chemical compound CCC(=O)C1=CC=C(C)C=C1C UWFRVQVNYNPBEF-UHFFFAOYSA-N 0.000 description 1
- CBOLARLSGQXRBB-UHFFFAOYSA-N 1-(oxiran-2-yl)-n,n-bis(oxiran-2-ylmethyl)methanamine Chemical compound C1OC1CN(CC1OC1)CC1CO1 CBOLARLSGQXRBB-UHFFFAOYSA-N 0.000 description 1
- OQILSTRGJVCFAG-UHFFFAOYSA-N 1-(oxiran-2-ylmethoxy)butan-1-ol Chemical compound CCCC(O)OCC1CO1 OQILSTRGJVCFAG-UHFFFAOYSA-N 0.000 description 1
- HECLRDQVFMWTQS-RGOKHQFPSA-N 1755-01-7 Chemical compound C1[C@H]2[C@@H]3CC=C[C@@H]3[C@@H]1C=C2 HECLRDQVFMWTQS-RGOKHQFPSA-N 0.000 description 1
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 description 1
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 1
- NQFUSWIGRKFAHK-UHFFFAOYSA-N 2,3-epoxypinane Chemical compound CC12OC1CC1C(C)(C)C2C1 NQFUSWIGRKFAHK-UHFFFAOYSA-N 0.000 description 1
- STMDPCBYJCIZOD-UHFFFAOYSA-N 2-(2,4-dinitroanilino)-4-methylpentanoic acid Chemical compound CC(C)CC(C(O)=O)NC1=CC=C([N+]([O-])=O)C=C1[N+]([O-])=O STMDPCBYJCIZOD-UHFFFAOYSA-N 0.000 description 1
- BBBUAWSVILPJLL-UHFFFAOYSA-N 2-(2-ethylhexoxymethyl)oxirane Chemical compound CCCCC(CC)COCC1CO1 BBBUAWSVILPJLL-UHFFFAOYSA-N 0.000 description 1
- YSUQLAYJZDEMOT-UHFFFAOYSA-N 2-(butoxymethyl)oxirane Chemical compound CCCCOCC1CO1 YSUQLAYJZDEMOT-UHFFFAOYSA-N 0.000 description 1
- VVHFXJOCUKBZFS-UHFFFAOYSA-N 2-(chloromethyl)-2-methyloxirane Chemical compound ClCC1(C)CO1 VVHFXJOCUKBZFS-UHFFFAOYSA-N 0.000 description 1
- SFRDXVJWXWOTEW-UHFFFAOYSA-N 2-(hydroxymethyl)propane-1,3-diol Chemical compound OCC(CO)CO SFRDXVJWXWOTEW-UHFFFAOYSA-N 0.000 description 1
- CUFXMPWHOWYNSO-UHFFFAOYSA-N 2-[(4-methylphenoxy)methyl]oxirane Chemical compound C1=CC(C)=CC=C1OCC1OC1 CUFXMPWHOWYNSO-UHFFFAOYSA-N 0.000 description 1
- SYEWHONLFGZGLK-UHFFFAOYSA-N 2-[1,3-bis(oxiran-2-ylmethoxy)propan-2-yloxymethyl]oxirane Chemical compound C1OC1COCC(OCC1OC1)COCC1CO1 SYEWHONLFGZGLK-UHFFFAOYSA-N 0.000 description 1
- HDPLHDGYGLENEI-UHFFFAOYSA-N 2-[1-(oxiran-2-ylmethoxy)propan-2-yloxymethyl]oxirane Chemical compound C1OC1COC(C)COCC1CO1 HDPLHDGYGLENEI-UHFFFAOYSA-N 0.000 description 1
- KUAUJXBLDYVELT-UHFFFAOYSA-N 2-[[2,2-dimethyl-3-(oxiran-2-ylmethoxy)propoxy]methyl]oxirane Chemical compound C1OC1COCC(C)(C)COCC1CO1 KUAUJXBLDYVELT-UHFFFAOYSA-N 0.000 description 1
- OZRVXYJWUUMVOW-UHFFFAOYSA-N 2-[[4-[4-(oxiran-2-ylmethoxy)phenyl]phenoxy]methyl]oxirane Chemical group C1OC1COC(C=C1)=CC=C1C(C=C1)=CC=C1OCC1CO1 OZRVXYJWUUMVOW-UHFFFAOYSA-N 0.000 description 1
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical class [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 1
- ZKPAGIWPCLTTAD-UHFFFAOYSA-N 2-methyl-n-(oxiran-2-ylmethyl)aniline Chemical compound CC1=CC=CC=C1NCC1OC1 ZKPAGIWPCLTTAD-UHFFFAOYSA-N 0.000 description 1
- RNLHGQLZWXBQNY-UHFFFAOYSA-N 3-(aminomethyl)-3,5,5-trimethylcyclohexan-1-amine Chemical compound CC1(C)CC(N)CC(C)(CN)C1 RNLHGQLZWXBQNY-UHFFFAOYSA-N 0.000 description 1
- SLJFKNONPLNAPF-UHFFFAOYSA-N 3-Vinyl-7-oxabicyclo[4.1.0]heptane Chemical group C1C(C=C)CCC2OC21 SLJFKNONPLNAPF-UHFFFAOYSA-N 0.000 description 1
- WVRNUXJQQFPNMN-VAWYXSNFSA-N 3-[(e)-dodec-1-enyl]oxolane-2,5-dione Chemical compound CCCCCCCCCC\C=C\C1CC(=O)OC1=O WVRNUXJQQFPNMN-VAWYXSNFSA-N 0.000 description 1
- ZYAASQNKCWTPKI-UHFFFAOYSA-N 3-[dimethoxy(methyl)silyl]propan-1-amine Chemical compound CO[Si](C)(OC)CCCN ZYAASQNKCWTPKI-UHFFFAOYSA-N 0.000 description 1
- OXYZDRAJMHGSMW-UHFFFAOYSA-N 3-chloropropyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)CCCCl OXYZDRAJMHGSMW-UHFFFAOYSA-N 0.000 description 1
- MECNWXGGNCJFQJ-UHFFFAOYSA-N 3-piperidin-1-ylpropane-1,2-diol Chemical compound OCC(O)CN1CCCCC1 MECNWXGGNCJFQJ-UHFFFAOYSA-N 0.000 description 1
- SJECZPVISLOESU-UHFFFAOYSA-N 3-trimethoxysilylpropan-1-amine Chemical compound CO[Si](OC)(OC)CCCN SJECZPVISLOESU-UHFFFAOYSA-N 0.000 description 1
- UUEWCQRISZBELL-UHFFFAOYSA-N 3-trimethoxysilylpropane-1-thiol Chemical compound CO[Si](OC)(OC)CCCS UUEWCQRISZBELL-UHFFFAOYSA-N 0.000 description 1
- XDLMVUHYZWKMMD-UHFFFAOYSA-N 3-trimethoxysilylpropyl 2-methylprop-2-enoate Chemical compound CO[Si](OC)(OC)CCCOC(=O)C(C)=C XDLMVUHYZWKMMD-UHFFFAOYSA-N 0.000 description 1
- CPXYLMJQRDHHCI-UHFFFAOYSA-N 4-(1,3-dioxan-2-yl)-7-oxabicyclo[4.1.0]heptane Chemical compound O1CCCOC1C1CC2OC2CC1 CPXYLMJQRDHHCI-UHFFFAOYSA-N 0.000 description 1
- CXXSQMDHHYTRKY-UHFFFAOYSA-N 4-amino-2,3,5-tris(oxiran-2-ylmethyl)phenol Chemical compound C1=C(O)C(CC2OC2)=C(CC2OC2)C(N)=C1CC1CO1 CXXSQMDHHYTRKY-UHFFFAOYSA-N 0.000 description 1
- GZVHEAJQGPRDLQ-UHFFFAOYSA-N 6-phenyl-1,3,5-triazine-2,4-diamine Chemical compound NC1=NC(N)=NC(C=2C=CC=CC=2)=N1 GZVHEAJQGPRDLQ-UHFFFAOYSA-N 0.000 description 1
- LQOPXMZSGSTGMF-UHFFFAOYSA-N 6004-79-1 Chemical compound C1CC2C3C(=O)OC(=O)C3C1C2 LQOPXMZSGSTGMF-UHFFFAOYSA-N 0.000 description 1
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- 239000004605 External Lubricant Substances 0.000 description 1
- 239000004610 Internal Lubricant Substances 0.000 description 1
- 239000002841 Lewis acid Substances 0.000 description 1
- 229920000877 Melamine resin Polymers 0.000 description 1
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- 239000006096 absorbing agent Substances 0.000 description 1
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- 238000007259 addition reaction Methods 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 229910000288 alkali metal carbonate Inorganic materials 0.000 description 1
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- 229910001860 alkaline earth metal hydroxide Inorganic materials 0.000 description 1
- NQFUSWIGRKFAHK-BDNRQGISSA-N alpha-Pinene epoxide Natural products C([C@@H]1O[C@@]11C)[C@@H]2C(C)(C)[C@H]1C2 NQFUSWIGRKFAHK-BDNRQGISSA-N 0.000 description 1
- DTOSIQBPPRVQHS-PDBXOOCHSA-N alpha-linolenic acid Chemical compound CC\C=C/C\C=C/C\C=C/CCCCCCCC(O)=O DTOSIQBPPRVQHS-PDBXOOCHSA-N 0.000 description 1
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- XFUOBHWPTSIEOV-UHFFFAOYSA-N bis(oxiran-2-ylmethyl) cyclohexane-1,2-dicarboxylate Chemical compound C1CCCC(C(=O)OCC2OC2)C1C(=O)OCC1CO1 XFUOBHWPTSIEOV-UHFFFAOYSA-N 0.000 description 1
- HGXHJQLDZPXEOG-UHFFFAOYSA-N bis(oxiran-2-ylmethyl) cyclohexane-1,4-dicarboxylate Chemical compound C1CC(C(=O)OCC2OC2)CCC1C(=O)OCC1CO1 HGXHJQLDZPXEOG-UHFFFAOYSA-N 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
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- 230000003197 catalytic effect Effects 0.000 description 1
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- 239000011353 cycloaliphatic epoxy resin Substances 0.000 description 1
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- AVKNGPAMCBSNSO-UHFFFAOYSA-N cyclohexylmethanamine Chemical compound NCC1CCCCC1 AVKNGPAMCBSNSO-UHFFFAOYSA-N 0.000 description 1
- 125000004210 cyclohexylmethyl group Chemical group [H]C([H])(*)C1([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C1([H])[H] 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 description 1
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 description 1
- 238000006471 dimerization reaction Methods 0.000 description 1
- ZZTCPWRAHWXWCH-UHFFFAOYSA-N diphenylmethanediamine Chemical compound C=1C=CC=CC=1C(N)(N)C1=CC=CC=C1 ZZTCPWRAHWXWCH-UHFFFAOYSA-N 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000010292 electrical insulation Methods 0.000 description 1
- GKIPXFAANLTWBM-UHFFFAOYSA-N epibromohydrin Chemical compound BrCC1CO1 GKIPXFAANLTWBM-UHFFFAOYSA-N 0.000 description 1
- 238000006735 epoxidation reaction Methods 0.000 description 1
- FWDBOZPQNFPOLF-UHFFFAOYSA-N ethenyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)C=C FWDBOZPQNFPOLF-UHFFFAOYSA-N 0.000 description 1
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
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- 230000001747 exhibiting effect Effects 0.000 description 1
- 239000003733 fiber-reinforced composite Substances 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- ANSXAPJVJOKRDJ-UHFFFAOYSA-N furo[3,4-f][2]benzofuran-1,3,5,7-tetrone Chemical compound C1=C2C(=O)OC(=O)C2=CC2=C1C(=O)OC2=O ANSXAPJVJOKRDJ-UHFFFAOYSA-N 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000001879 gelation Methods 0.000 description 1
- 238000007429 general method Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 description 1
- 150000002357 guanidines Chemical class 0.000 description 1
- 229940083094 guanine derivative acting on arteriolar smooth muscle Drugs 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- WJRBRSLFGCUECM-UHFFFAOYSA-N hydantoin Chemical compound O=C1CNC(=O)N1 WJRBRSLFGCUECM-UHFFFAOYSA-N 0.000 description 1
- 229940091173 hydantoin Drugs 0.000 description 1
- 150000002460 imidazoles Chemical class 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000013101 initial test Methods 0.000 description 1
- 150000002484 inorganic compounds Chemical class 0.000 description 1
- 239000011256 inorganic filler Substances 0.000 description 1
- 229910003475 inorganic filler Inorganic materials 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011810 insulating material Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 150000007517 lewis acids Chemical class 0.000 description 1
- 239000004611 light stabiliser Substances 0.000 description 1
- 229960004488 linolenic acid Drugs 0.000 description 1
- KQQKGWQCNNTQJW-UHFFFAOYSA-N linolenic acid Natural products CC=CCCC=CCC=CCCCCCCCC(O)=O KQQKGWQCNNTQJW-UHFFFAOYSA-N 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- VYKXQOYUCMREIS-UHFFFAOYSA-N methylhexahydrophthalic anhydride Chemical compound C1CCCC2C(=O)OC(=O)C21C VYKXQOYUCMREIS-UHFFFAOYSA-N 0.000 description 1
- 238000001471 micro-filtration Methods 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000002715 modification method Methods 0.000 description 1
- 239000012778 molding material Substances 0.000 description 1
- JAYXSROKFZAHRQ-UHFFFAOYSA-N n,n-bis(oxiran-2-ylmethyl)aniline Chemical compound C1OC1CN(C=1C=CC=CC=1)CC1CO1 JAYXSROKFZAHRQ-UHFFFAOYSA-N 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 239000004843 novolac epoxy resin Substances 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 150000003018 phosphorus compounds Chemical class 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 229920006122 polyamide resin Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 150000008442 polyphenolic compounds Chemical class 0.000 description 1
- 238000011417 postcuring Methods 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 239000012779 reinforcing material Substances 0.000 description 1
- 239000003566 sealing material Substances 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229920002545 silicone oil Polymers 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical class O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 1
- 239000008247 solid mixture Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000012756 surface treatment agent Substances 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- KCNSDMPZCKLTQP-UHFFFAOYSA-N tetraphenylen-1-ol Chemical compound C12=CC=CC=C2C2=CC=CC=C2C2=CC=CC=C2C2=C1C=CC=C2O KCNSDMPZCKLTQP-UHFFFAOYSA-N 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
- 125000003944 tolyl group Chemical group 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- GQIUQDDJKHLHTB-UHFFFAOYSA-N trichloro(ethenyl)silane Chemical compound Cl[Si](Cl)(Cl)C=C GQIUQDDJKHLHTB-UHFFFAOYSA-N 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
- AAAQKTZKLRYKHR-UHFFFAOYSA-N triphenylmethane Chemical compound C1=CC=CC=C1C(C=1C=CC=CC=1)C1=CC=CC=C1 AAAQKTZKLRYKHR-UHFFFAOYSA-N 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 239000005050 vinyl trichlorosilane Substances 0.000 description 1
- 230000004580 weight loss Effects 0.000 description 1
Landscapes
- Adhesives Or Adhesive Processes (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Epoxy Resins (AREA)
Description
本発明は、得られる硬化物の耐熱性、接着性、熱伝導性に優れる硬化性樹脂組成物、その硬化物および熱伝導性接着剤に関する。 The present invention relates to a curable resin composition excellent in heat resistance, adhesiveness, and thermal conductivity of a cured product to be obtained, the cured product, and a thermally conductive adhesive.
エポキシ樹脂およびその硬化剤を含有するエポキシ樹脂組成物は、耐熱性、低吸湿性等の諸物性に優れる点から、半積層板樹脂材料、電気絶縁材料、半導体封止材料、繊維強化複合材料、塗装材料、成型材料、接着材料等で広く用いられている。 The epoxy resin composition containing an epoxy resin and its curing agent is excellent in various physical properties such as heat resistance and low hygroscopicity, so that it is a semi-laminate resin material, an electrical insulating material, a semiconductor sealing material, a fiber reinforced composite material, Widely used in coating materials, molding materials, adhesive materials, etc.
近年、これらの各種用途、とりわけ先端材料分野において、耐熱性に代表される耐久性能の一層の向上が求められている。中でも、電子部品の小型化・高集積化に伴い、基板や回路、そしてモジュールを結合させるために、高い耐熱性を示す接着剤が求められている。特に、高熱化しやすい半導体モジュールを正常に作動させるためには、高い耐熱性に加えて、放熱性も有する熱伝導性接着剤が、近年特に求められている。
特に、パワー半導体と言われる次世代の半導体モジュールにおいては、２００℃を超える温度で作動することが予想されるため、２００℃以上の高温にも耐えうる熱伝導性接着剤の開発が急務になっている。
In recent years, in these various uses, particularly in the field of advanced materials, further improvement in durability performance typified by heat resistance has been demanded. In particular, as electronic components are miniaturized and highly integrated, an adhesive exhibiting high heat resistance is required for bonding substrates, circuits, and modules. In particular, in order to normally operate a semiconductor module that is easily heated, a heat conductive adhesive having heat dissipation in addition to high heat resistance has been particularly demanded in recent years.
In particular, next-generation semiconductor modules called power semiconductors are expected to operate at temperatures exceeding 200 ° C, so the development of thermally conductive adhesives that can withstand temperatures above 200 ° C is an urgent task. ing.
熱伝導性の接着剤としては、エポキシ化合物とエポキシ基含有アクリルポリマーと熱伝導性フィラーとを有する熱伝導性接着剤が開示されている（特許文献１）。しかし、１５０℃までの耐熱性は試験されているものの、２００℃を超えるような高温状態に対する耐熱性は課題として残されている。 As a heat conductive adhesive, a heat conductive adhesive having an epoxy compound, an epoxy group-containing acrylic polymer, and a heat conductive filler is disclosed (Patent Document 1). However, although heat resistance up to 150 ° C. has been tested, heat resistance to a high temperature state exceeding 200 ° C. remains as a problem.
一方で、高度な耐熱性の要求に対応できるエポキシ樹脂材料として、例えば、下記構造式１ On the other hand, as an epoxy resin material that can meet high heat resistance requirements, for example, the following structural formula 1
上記の四官能型ナフタレン系エポキシ樹脂は、一般的なフェノールノボラック型エポキシ樹脂と比較して、耐熱性および疎水性が高いナフタレン骨格を有すること、四官能であり、その硬化物の架橋密度が高いこと、対称性に優れる分子構造を持つことから、その硬化物は極めて優れた耐熱性を発現する。しかしながら、近年、耐熱性においてはより高い性能が求められ、一層の改善が必要となっている。 The tetrafunctional naphthalene-based epoxy resin has a naphthalene skeleton having high heat resistance and hydrophobicity compared to a general phenol novolac epoxy resin, is tetrafunctional, and has a high crosslinking density of the cured product. In addition, since it has a molecular structure with excellent symmetry, the cured product exhibits extremely excellent heat resistance. However, in recent years, higher performance is required in heat resistance, and further improvement is required.
前記の四官能型ナフタレン系エポキシ樹脂において、メチレン構造は高温に比較的弱いため、ナフタレン環がメチレン構造を介した結合ではなく直接の結合とする事が、耐熱性を向上する手段として有効であると考えられる。ジヒドロキシナフタレンの２量体において、メチレン構造を含まず、直接に単結合で繋がれたビ（ジヒドロキシナフタレン）構造のエポキシ樹脂の記載がある（特許文献３〜６）。ジヒドロキシナフタレンの水酸基の位置や２量体の結合位置は、それを用いたエポキシ樹脂の軟化点、溶剤溶解性、およびその硬化物の耐熱性等の物性に影響を与える重要因子であるが、特許文献３〜６はいずれも、ジヒドロキシナフタレンの水酸基の位置や２量体の結合位置が特定しておらず、具体的な化合物についての記載がない。 In the above-mentioned tetrafunctional naphthalene-based epoxy resin, the methylene structure is relatively weak at high temperatures. Therefore, it is effective for the naphthalene ring to be a direct bond rather than a bond via the methylene structure as a means for improving heat resistance. it is conceivable that. There is a description of an epoxy resin having a bi (dihydroxynaphthalene) structure that does not contain a methylene structure and is directly connected by a single bond in a dihydroxynaphthalene dimer (Patent Documents 3 to 6). The position of the hydroxyl group of dihydroxynaphthalene and the bonding position of the dimer are important factors that affect the physical properties such as the softening point of the epoxy resin, the solvent solubility, and the heat resistance of the cured product. In any of Literatures 3 to 6, the position of the hydroxyl group of dihydroxynaphthalene and the bonding position of the dimer are not specified, and no specific compound is described.
本発明が解決しようとする課題は、優れた耐熱性、接着性、熱伝導性を発現する硬化性樹脂組成物、その硬化物および熱伝導性接着剤を提供することにある。 The problem to be solved by the present invention is to provide a curable resin composition that exhibits excellent heat resistance, adhesiveness, and thermal conductivity, a cured product thereof, and a thermally conductive adhesive.
本発明者らは鋭意検討した結果、ジヒドロキシナフタレンの２量化反応において、２，７−ジヒドロキシナフタレンが、１，１’位で選択的にカップリング反応するため、高純度の１，１’−ビナフタレン−２，２’，７，７’−テトラオールを得ることが可能であり、それにエピハロヒドリンを反応させて得られる２，２’，７，７’−テトラグリシジルオキシ−１，１’−ビナフタレンを用いた熱伝導性エポキシ樹脂組成物の硬化物は、優れた耐熱性、接着性、熱伝導性を発現し、熱伝導性接着剤として有用であることを見出し、本発明を完成するに至った。 As a result of diligent dimerization reaction of dihydroxynaphthalene, the present inventors have conducted a selective coupling reaction of 2,7-dihydroxynaphthalene at the 1,1 ′ position, and therefore, high-purity 1,1′-binaphthalene. -2,2 ', 7,7'-tetraol can be obtained, and 2,2', 7,7'-tetraglycidyloxy-1,1'-binaphthalene obtained by reacting it with epihalohydrin can be obtained. The cured product of the thermally conductive epoxy resin composition used has found excellent heat resistance, adhesiveness, and thermal conductivity, and is found to be useful as a thermally conductive adhesive, leading to the completion of the present invention. .
すなわち、本発明の上記課題は以下の手段により解決される；
（１）２，２’，７，７’−テトラグリシジルオキシ−１，１’−ビナフタレンであるエポキシ樹脂と、熱伝導性フィラーと、硬化剤（C）および／または硬化促進剤と、を含有する硬化性樹脂組成物；
（２）熱伝導性フィラー（Ｂ）が１０Ｗ／ｍ・Ｋ以上の熱伝導率を有する、前記（１）に記載の硬化性樹脂組成物；
（３）熱伝導性フィラー（Ｂ）が、アルミナ、酸化マグネシウム、酸化亜鉛、ベリリア、窒化ホウ素、窒化アルミニウム、窒化ケイ素、炭化ケイ素、炭化ホウ素、炭化チタン、ダイヤモンドから選択される少なくとも１種である、前記（１）または（２）に記載の硬化性樹脂組成物；
（４）熱伝導性接着剤である、前記（１）〜（３）のいずれかに記載の硬化性樹脂組成物；
（５）前記（１）〜（４）のいずれかに記載の硬化性樹脂組成物を硬化することにより得られる、硬化物；
（６）前記（５）に記載の硬化物を有することを特徴とする、放熱材料。
That is, the above-mentioned problem of the present invention is solved by the following means;
(1) Contains an epoxy resin that is 2,2 ′, 7,7′-tetraglycidyloxy-1,1′-binaphthalene , a thermally conductive filler , a curing agent (C) and / or a curing accelerator. A curable resin composition ;
(2) The curable resin composition according to (1), wherein the thermally conductive filler (B) has a thermal conductivity of 10 W / m · K or more;
(3) The thermally conductive filler (B) is at least one selected from alumina, magnesium oxide, zinc oxide, beryllia, boron nitride, aluminum nitride, silicon nitride, silicon carbide, boron carbide, titanium carbide, and diamond. The curable resin composition according to (1) or (2) above;
(4) The curable resin composition according to any one of (1) to (3), which is a thermally conductive adhesive;
(5) Hardened | cured material obtained by hardening | curing the curable resin composition in any one of said (1)-(4);
(6) A heat dissipation material comprising the cured product according to (5).
本発明によれば、優れた耐熱性、接着性、熱伝導性を発現する硬化性樹脂組成物、その硬化物および熱伝導性接着剤を提供できる。 ADVANTAGE OF THE INVENTION According to this invention, the curable resin composition which expresses the outstanding heat resistance, adhesiveness, and heat conductivity, its hardened | cured material, and a heat conductive adhesive can be provided.
以下、本発明を詳細に説明する。
本発明に用いるエポキシ樹脂は、２，２’，７，７’−テトラグリシジルオキシ−１，１’−ビナフタレンを主成分とするものであり、次の構造式（２）で示されるものである。
Hereinafter, the present invention will be described in detail.
The epoxy resin used in the present invention has 2,2 ′, 7,7′-tetraglycidyloxy-1,1′-binaphthalene as a main component and is represented by the following structural formula (2). .
本発明に用いるエポキシ樹脂の原料となる１，１’−ビナフタレン−２，２’，７，７’−テトラオールは、ジヒロキシナフタレンのカップリング反応によって得られる。ジヒドロキシナフタレンのカップリング反応において、２，７−ジヒドロキシナフタレンが、１，１’位で選択的にカップリング反応を起こし、多量体化し難い上、類似構造の１，１’−メチレンビス（ナフタレン−２，７−ジオール）に比較して、低融点を有し、さらにそのグリシジルエーテル化物は、１，１’−メチレンビス（ナフタレン−２，７−ジオール）の四官能グリシジルエーテル化物に比べ、低軟化点で、低粘度である。
以下に、本発明に用いるエポキシ樹脂の製法を詳述するが、本発明のエポキシ樹脂の製造方法はこれらに限定されるものではない。
1,1′-Binaphthalene-2,2 ′, 7,7′-tetraol, which is a raw material for the epoxy resin used in the present invention, is obtained by a dihydroxynaphthalene coupling reaction. In the coupling reaction of dihydroxynaphthalene, 2,7-dihydroxynaphthalene selectively undergoes a coupling reaction at the 1,1 ′ position and is difficult to multimerize, and has a similar structure of 1,1′-methylenebis (naphthalene-2 , 7-diol) has a low melting point, and the glycidyl etherified product has a lower softening point than the tetrafunctional glycidyl etherified product of 1,1′-methylenebis (naphthalene-2,7-diol). And low viscosity.
Although the manufacturing method of the epoxy resin used for this invention is explained in full detail below, the manufacturing method of the epoxy resin of this invention is not limited to these.
すなわち、本発明に用いるエポキシ樹脂の製法は１，１’−ビナフタレン−２，２’，７，７’−テトラオールとエピハロヒドリンを反応させるものである。具体的には、例えばフェノール化合物中のフェノール性水酸基のモル数に対し、エピハロヒドリンを２〜１０倍量（モル基準）となる割合で添加し、更に、フェノール性水酸基のモル数に対し０．９〜２．０倍量（モル基準）の塩基性触媒を一括添加または徐々に添加しながら２０〜１２０℃の温度で０．５〜１０時間反応させる方法が挙げられる。この塩基性触媒は固形でもその水溶液を使用してもよく、水溶液を使用する場合は、連続的に添加すると共に、反応混合物中から減圧下、または常圧下、連続的に水及びエピハロヒドリン類を留出せしめ、更に分液して水は除去しエピハロヒドリンは反応混合物中に連続的に戻す方法でもよい。 That is, the method for producing the epoxy resin used in the present invention is to react 1,1'-binaphthalene-2,2 ', 7,7'-tetraol with epihalohydrin. Specifically, for example, epihalohydrin is added in a ratio of 2 to 10 times the amount (molar basis) with respect to the number of moles of the phenolic hydroxyl group in the phenolic compound, and further 0.9% relative to the number of moles of the phenolic hydroxyl group. A method of reacting at a temperature of 20 to 120 ° C. for 0.5 to 10 hours while adding or gradually adding up to 2.0 times (molar basis) of the basic catalyst is mentioned. The basic catalyst may be solid or an aqueous solution thereof. When an aqueous solution is used, it is continuously added and water and epihalohydrins are continuously distilled from the reaction mixture under reduced pressure or normal pressure. Alternatively, the solution may be separated and further separated to remove water and the epihalohydrin is continuously returned to the reaction mixture.
なお、工業生産を行う際、エポキシ樹脂生産の初バッチでは仕込みに用いるエピハロヒドリン類の全てが新しいものであるが、次バッチ以降は、粗反応生成物から回収されたエピハロヒドリン類と、反応で消費される分で消失する分に相当する新しいエピハロヒドリン類とを併用することが可能であり、経済的に好ましい。この時、使用するエピハロヒドリンは特に限定されないが、例えばエピクロルヒドリン、エピブロモヒドリン、β−メチルエピクロルヒドリン等が挙げられる。なかでも工業的入手が容易なことからエピクロルヒドリンが好ましい。 In the first batch of epoxy resin production, all of the epihalohydrins used for preparation are new in industrial production, but the subsequent batches are consumed by the reaction with epihalohydrins recovered from the crude reaction product. It is possible to use in combination with new epihalohydrins corresponding to the amount that disappears in part, which is economically preferable. At this time, the epihalohydrin used is not particularly limited, and examples thereof include epichlorohydrin, epibromohydrin, β-methylepichlorohydrin, and the like. Of these, epichlorohydrin is preferred because it is easily available industrially.
また、前記の塩基性触媒は、具体的には、アルカリ土類金属水酸化物、アルカリ金属炭酸塩及びアルカリ金属水酸化物等が挙げられる。特にエポキシ樹脂合成反応の触媒活性に優れる点からアルカリ金属水酸化物が好ましく、例えば水酸化ナトリウム、水酸化カリウム等が挙げられる。使用に際しては、これらの塩基性触媒を１０〜５５質量％程度の水溶液の形態で使用してもよいし、固形の形態で使用しても構わない。また、有機溶媒を併用することにより、エポキシ樹脂の合成における反応速度を高めることができる。このような有機溶媒としては特に限定されないが、例えば、アセトン、メチルエチルケトン等のケトン類、メタノール、エタノール、１−プロピルアルコール、イソプロピルアルコール、１−ブタノール、セカンダリーブタノール、ターシャリーブタノール等のアルコール類、メチルセロソルブ、エチルセロソルブ等のセロソルブ類、テトラヒドロフラン、１、４−ジオキサン、１、３−ジオキサン、ジエトキシエタン等のエーテル類、アセトニトリル、ジメチルスルホキシド、ジメチルホルムアミド等の非プロトン性極性溶媒等が挙げられる。これらの有機溶媒は、それぞれ単独で使用してもよいし、また、極性を調整するために適宜２種以上を併用してもよい。 Specific examples of the basic catalyst include alkaline earth metal hydroxides, alkali metal carbonates and alkali metal hydroxides. In particular, alkali metal hydroxides are preferable from the viewpoint of excellent catalytic activity of the epoxy resin synthesis reaction, and examples thereof include sodium hydroxide and potassium hydroxide. In use, these basic catalysts may be used in the form of an aqueous solution of about 10 to 55% by mass, or in the form of a solid. Moreover, the reaction rate in the synthesis | combination of an epoxy resin can be raised by using an organic solvent together. Examples of such organic solvents include, but are not limited to, ketones such as acetone and methyl ethyl ketone, alcohols such as methanol, ethanol, 1-propyl alcohol, isopropyl alcohol, 1-butanol, secondary butanol, and tertiary butanol, methyl Examples include cellosolves such as cellosolve and ethyl cellosolve, ethers such as tetrahydrofuran, 1,4-dioxane, 1,3-dioxane and diethoxyethane, and aprotic polar solvents such as acetonitrile, dimethyl sulfoxide and dimethylformamide. These organic solvents may be used alone or in combination of two or more kinds in order to adjust the polarity.
前述のエポキシ化反応の反応物を水洗後、加熱減圧下、蒸留によって未反応のエピハロヒドリンや併用する有機溶媒を留去する。また更に加水分解性ハロゲンの少ないエポキシ樹脂とするために、得られたエポキシ樹脂を再びトルエン、メチルイソブチルケトン、メチルエチルケトンなどの有機溶媒に溶解し、水酸化ナトリウム、水酸化カリウムなどのアルカリ金属水酸化物の水溶液を加えてさらに反応を行うこともできる。この際、反応速度の向上を目的として、４級アンモニウム塩やクラウンエーテル等の相関移動触媒を存在させてもよい。相関移動触媒を使用する場合のその使用量としては、用いるエポキシ樹脂１００質量部に対して０．１〜３．０質量部となる割合であることが好ましい。反応終了後、生成した塩を濾過、水洗などにより除去し、更に、加熱減圧下にトルエン、メチルイソブチルケトンなどの溶剤を留去することにより目的とする本発明の必須成分であるエポキシ樹脂を得ることができる。 After the reaction product of the epoxidation reaction is washed with water, unreacted epihalohydrin and the organic solvent to be used in combination are distilled off by distillation under heating and reduced pressure. Further, in order to obtain an epoxy resin with less hydrolyzable halogen, the obtained epoxy resin is again dissolved in an organic solvent such as toluene, methyl isobutyl ketone, methyl ethyl ketone, and alkali metal hydroxide such as sodium hydroxide or potassium hydroxide. Further reaction can be carried out by adding an aqueous solution of the product. At this time, a phase transfer catalyst such as a quaternary ammonium salt or crown ether may be present for the purpose of improving the reaction rate. When the phase transfer catalyst is used, the amount used is preferably 0.1 to 3.0 parts by mass with respect to 100 parts by mass of the epoxy resin used. After completion of the reaction, the produced salt is removed by filtration, washing with water, etc., and further, a solvent such as toluene and methyl isobutyl ketone is distilled off under reduced pressure by heating to obtain the desired epoxy resin as an essential component of the present invention. be able to.
次に、本発明の硬化性樹脂組成物は、以上詳述したエポキシ樹脂と熱伝導性フィラーを含有するものであるが、該エポキシ樹脂は、オリゴマー成分を含有する製造時の反応生成物として用いて良い。 Next, the curable resin composition of the present invention contains the epoxy resin described above in detail and a thermally conductive filler, and the epoxy resin is used as a reaction product during production containing an oligomer component. Good.
さらに、本発明の硬化性組成物で用いられる熱伝導性フィラー（Ｂ）として、公知慣用の金属系ファイラー、無機化合物フィラー、炭素系フィラー等が使用される。具体的には、例えば、銀、銅、アルミニウム、鉄、ステンレス等の金属系フィラー、アルミナ、マグネシア、ベリリア、シリカ、窒化ホウ素、窒化アルミニウム、窒化ケイ素、炭化ケイ素、炭化ホウ素、炭化チタン等の無機系フィラー、ダイヤモンド、黒鉛、グラファイト、炭素繊維等の炭素系フィラーなどが挙げられる。少なくとも１種の熱伝導性フィラーが選択されて使用されるが、結晶形、粒子サイズ等が異なる１種あるいは複数種の熱伝導性フィラーを組み合わせて使用する事も可能である。電子機器等の用途で放熱性が必要とされる場合には、電気絶縁性が求められる事が多く、これらのフィラーの内、熱伝導性と体積固有抵抗のいずれも高い、アルミナ、酸化マグネシウム、酸化亜鉛、ベリリア、窒化ホウ素、窒化アルミニウム、窒化ケイ素、ダイヤモンドから選択される少なくとも１種の絶縁性の熱伝導性フィラーの使用が好ましい。硬化性組成物に対する熱伝導性フィラーの充填量に限りがあり、充填量が多くなりすぎると接着性等の物性を低下させてしまうため、熱伝導率の高い熱伝導フィラーの使用が好ましく、１０Ｗ／ｍ・Ｋ以上の熱伝導性フィラーの使用がより好ましい。 Further, as the heat conductive filler (B) used in the curable composition of the present invention, a known and commonly used metal-based filer, inorganic compound filler, carbon-based filler and the like are used. Specifically, for example, metallic fillers such as silver, copper, aluminum, iron, and stainless steel, alumina, magnesia, beryllia, silica, boron nitride, aluminum nitride, silicon nitride, silicon carbide, boron carbide, titanium carbide and the like And carbon fillers such as diamond filler, diamond, graphite, graphite, and carbon fiber. At least one type of thermally conductive filler is selected and used, but it is also possible to use one or more types of thermally conductive fillers having different crystal forms, particle sizes, and the like. When heat dissipation is required in applications such as electronic equipment, electrical insulation is often required, and among these fillers, both thermal conductivity and volume resistivity are high, alumina, magnesium oxide, The use of at least one insulating thermally conductive filler selected from zinc oxide, beryllia, boron nitride, aluminum nitride, silicon nitride, and diamond is preferred. The filling amount of the thermally conductive filler to the curable composition is limited, and if the filling amount is too large, physical properties such as adhesiveness are reduced. Therefore, it is preferable to use a thermally conductive filler with high thermal conductivity. It is more preferable to use a thermally conductive filler of at least / m · K.
中でもアルミナ、窒化アルミニウム、窒化ホウ素、窒化ケイ素、酸化マグネシウムが熱伝導性と絶縁性の確保の点で好ましく、特にアルミナが熱伝導性と絶縁性に加えて樹脂に対する充填性が良くなるのでより好ましい。 Among these, alumina, aluminum nitride, boron nitride, silicon nitride, and magnesium oxide are preferable from the viewpoint of ensuring thermal conductivity and insulation, and alumina is more preferable because the resin filling property is improved in addition to thermal conductivity and insulation. .
これらの熱伝導性フィラーとして、表面処理を行ったものを使用する事もできる。例えば、無機系フィラーなどは、シラン系、チタネート系およびアルミネート系カップリング剤などで、表面改質されたものを使用する事ができる。 As these thermally conductive fillers, those subjected to surface treatment can also be used. For example, as the inorganic filler, a silane-based, titanate-based, and aluminate-based coupling agent that has been surface-modified can be used.
硬化性樹脂組成物の流動性やその硬化物の熱伝導率をから、前記のカップリング剤で、処理した熱伝導性フィラーを用いた方が良い場合が多く、例えば、表面処理により、硬化物における樹脂と熱伝導性フィラーの密着性が更に高められ、樹脂と熱伝導性フィラーの間での界面熱抵抗が低下し、熱伝導性が向上する。 In view of the fluidity of the curable resin composition and the thermal conductivity of the cured product, it is often better to use a thermally conductive filler that has been treated with the above-mentioned coupling agent. In this case, the adhesion between the resin and the thermally conductive filler is further improved, the interfacial thermal resistance between the resin and the thermally conductive filler is lowered, and the thermal conductivity is improved.
カップリング剤の中でも、シラン系カップリング剤の使用が好ましく、例えば、シランカップリング剤としては、ビニルトリクロルシラン、ビニルトリエトキシシラン、ビニルトリメトキシシラン、γ−メタクリロキシプロピルトリメトキシシラン、β（３，４エポキシシンクロヘキシル）エチルトリメトキシシラン、γ−グリシドキシプロピルトリメトキシシラン、γ−グリシリメトキシプロピルメチルジエトキシシラン、Ｎ−β（アミノエチル）γ−アミノプロピルトリメトキシシラン、Ｎ−β（アミノエチル）γ−アミノプロピルメチルジメトキシシラン、γ−アミノプロピルトリエトキシシラン、Ｎ−フェニル−γ−アミノプロピルトリメトキシシラン、γ−メルカプトプロピルトリメトキシシラン、γ−クロロプロピルトリメトキシシラン等が挙げられる。 Among coupling agents, use of a silane coupling agent is preferable. For example, as a silane coupling agent, vinyltrichlorosilane, vinyltriethoxysilane, vinyltrimethoxysilane, γ-methacryloxypropyltrimethoxysilane, β ( 3,4 epoxy synchrohexyl) ethyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycylmethoxypropylmethyldiethoxysilane, N-β (aminoethyl) γ-aminopropyltrimethoxysilane, N- β (aminoethyl) γ-aminopropylmethyldimethoxysilane, γ-aminopropyltriethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-chloropropyltrimethoxysilane And the like.
表面処理は、公知慣用のフィラーの表面改質方法により行え、例えば、流体ノズルを用いた噴霧方式、せん断力のある攪拌、ボールミル、ミキサー等の乾式法、水系または有機溶剤系等の湿式法を採用することができる。せん断力を利用した表面処理は、熱伝導性フィラーの破壊が起こらない程度にして行うことが望ましい。 The surface treatment can be performed by a known and commonly used filler surface modification method, for example, a spray method using a fluid nozzle, a shearing stirring, a dry method such as a ball mill or a mixer, or a wet method such as an aqueous or organic solvent system. Can be adopted. It is desirable to perform the surface treatment using the shearing force so that the thermal conductive filler is not destroyed.
乾式法における系内温度ないしは湿式法における処理後の乾燥温度は、表面処理剤の種類に応じ熱分解しない領域で適宜決定される。例えば、γ−アミノプロピルトリエトキシシランで処理する場合は、８０〜１５０℃の温度が望ましい。 The system temperature in the dry method or the drying temperature after the treatment in the wet method is appropriately determined in a region where thermal decomposition does not occur depending on the type of the surface treatment agent. For example, when processing with (gamma) -aminopropyl triethoxysilane, the temperature of 80-150 degreeC is desirable.
上記の熱伝導性フィラーの平均粒子径は特に限定されないが、好ましい下限が０．２μｍ、好ましい上限が５０μｍである。上記の熱伝導性フィラーの平均粒子径が０．２μｍ未満であると、硬化性樹脂組成物の粘度が高くなって、作業性等が低下することがある。上記の熱伝導性フィラーの平均粒子径が５０μｍを超えたものを多量に使用すると、硬化性樹脂組成物の硬化物と基材との接着力が不足して、電子部品の反りが大きくなったり、冷熱サイクル下等においてクラック又は剥離が生じたり、接着界面で剥離が生じたりすることがある。上記の熱伝導性フィラーの平均粒子径のより好ましい下限は０．４μｍ、より好ましい上限は２０μｍである。 Although the average particle diameter of said heat conductive filler is not specifically limited, A preferable minimum is 0.2 micrometer and a preferable upper limit is 50 micrometers. When the average particle size of the above-mentioned heat conductive filler is less than 0.2 μm, the viscosity of the curable resin composition increases, and workability and the like may decrease. If a large amount of the above heat conductive filler having an average particle diameter of more than 50 μm is used, the adhesive force between the cured product of the curable resin composition and the substrate is insufficient, and the warpage of the electronic component is increased. Cracks or delamination may occur under a cooling / heating cycle, or delamination may occur at the bonding interface. The minimum with a more preferable average particle diameter of said heat conductive filler is 0.4 micrometer, and a more preferable upper limit is 20 micrometers.
上記の熱伝導性フィラーの形状は特に限定されないが、熱伝導性樹脂エポキシ組成物の流動性からは真球に近い方が好ましい。例えば、アスペクト比（粒子の短径の長さに対する粒子の長径の長さの比（長径の長さ／短径の長さ））は、特に限定されないが、１に近いほど好ましく、好ましくは、１〜８０であり、さらに好ましくは１〜１０である。 Although the shape of said heat conductive filler is not specifically limited, From the fluidity | liquidity of a heat conductive resin epoxy composition, the nearer one is preferable. For example, the aspect ratio (ratio of the length of the major axis of the particle to the length of the minor axis of the particle (length of major axis / length of minor axis)) is not particularly limited, but is preferably closer to 1, preferably It is 1-80, More preferably, it is 1-10.
上記の熱伝導性フィラーの熱伝導性組成物中の含有量は特に限定されず、用途で求められる熱伝導率の程度に応じて配合されるが、好ましくは、硬化性樹脂組成物の１００重量部中、上記の熱伝導性フィラーの含有量は４０〜９０重量部である。上記の熱伝導性フィラーの含有量が４０重量部未満であると、硬化性樹脂組成物は充分な熱伝導性が得られない。上記の熱伝導性フィラーの含有量が９０重量部を超えると、熱伝導性樹脂組成物の硬化物と基材の接着力が不足して、電子部品の反りが大きくなったり、冷熱サイクル下等においてクラック又は電子部品の剥離が生じたり、接着界面で剥離が生じたりする。また、上記の熱伝導性フィラーの含有量が９０重量部を超えると、硬化性樹脂組成物の粘度が高くなって塗布性、作業性等が低下する。熱伝導性フィラーの機能を効果的に発現し、高い熱伝導性を得るためには、熱伝導性フィラーが高充填されている方が好ましく、６０〜９０重量部の使用が好ましい。硬化性樹脂組成物の流動性も考慮すると、より好ましくは、６０〜８５重量の使用である。 Content in the heat conductive composition of said heat conductive filler is not specifically limited, Although it mix | blends according to the grade of the heat conductivity calculated | required by use, Preferably, 100 weight of curable resin composition is used. In the part, the content of the heat conductive filler is 40 to 90 parts by weight. When the content of the heat conductive filler is less than 40 parts by weight, the curable resin composition cannot obtain sufficient heat conductivity. When the content of the above-mentioned heat conductive filler exceeds 90 parts by weight, the adhesive force between the cured product of the heat conductive resin composition and the substrate is insufficient, warping of the electronic component is increased, under a cooling / heating cycle, etc. In this case, cracks or peeling of electronic parts occurs, or peeling occurs at the adhesive interface. Moreover, when content of said heat conductive filler exceeds 90 weight part, the viscosity of curable resin composition will become high and applicability | paintability, workability | operativity, etc. will fall. In order to effectively express the function of the thermally conductive filler and to obtain high thermal conductivity, it is preferable that the thermally conductive filler is highly filled, and the use of 60 to 90 parts by weight is preferable. Considering the fluidity of the curable resin composition, the use of 60 to 85 weight is more preferable.
上記の熱伝導性フィラーは、２種類以上の粒子径の異なるものを混合して用いることが好ましく、これにより大粒子径の熱伝導性フィラーの空隙に小粒子径の熱伝導性フィラーがパッキングされることによって、単一粒子径の熱伝導性フィラーのみを使用するよりも密に充填されるために、より高い熱伝導率を発揮することが可能である。具体的には、酸化アルミニウムを使用した場合、熱伝導性フィラー中、平均粒子径５〜２０μｍ（大粒子径）を４５〜７５重量％、平均粒子径０．４〜１．０μｍ（小粒子径）を２５〜５５重量％の範囲の割合で混合すると、熱伝導率の温度依存性が小さくなるので好ましい。 It is preferable to use a mixture of two or more types having different particle diameters, so that the small particle diameter thermally conductive filler is packed in the voids of the large particle diameter thermally conductive filler. Therefore, since it is more densely packed than using only a single particle size thermal conductive filler, it is possible to exhibit higher thermal conductivity. Specifically, when aluminum oxide is used, the average particle diameter of 5 to 20 μm (large particle diameter) is 45 to 75% by weight and the average particle diameter is 0.4 to 1.0 μm (small particle diameter) in the thermally conductive filler. ) Is preferably mixed at a ratio in the range of 25 to 55% by weight, since the temperature dependence of the thermal conductivity becomes small.
本発明の樹脂組成物は、硬化剤を含有してもよい。硬化剤としては特に限定はなく、通常のエポキシ樹脂の硬化剤として常用されている化合物は何れも使用することができ、例えば、アミン系化合物、アミド系化合物、酸無水物系化合物、フェノ−ル系化合物などが挙げられる。具体的には、アミン系化合物としてはジアミノジフェニルメタン、ジエチレントリアミン、トリエチレンテトラミン、ジアミノジフェニルスルホン、イソホロンジアミン、イミダゾ−ル、ＢＦ３−アミン錯体、グアニジン誘導体等が挙げられ、アミド系化合物としては、ジシアンジアミド、リノレン酸の２量体とエチレンジアミンとより合成されるポリアミド樹脂等が挙げられ、酸無水物系化合物としては、無水フタル酸、無水トリメリット酸、無水ピロメリット酸、無水マレイン酸、テトラヒドロ無水フタル酸、メチルテトラヒドロ無水フタル酸、無水メチルナジック酸、ヘキサヒドロ無水フタル酸、メチルヘキサヒドロ無水フタル酸等が挙げられ、フェノール系化合物としては、フェノールノボラック樹脂、クレゾールノボラック樹脂、芳香族炭化水素ホルムアルデヒド樹脂変性フェノール樹脂、ジシクロペンタジエンフェノール付加型樹脂、フェノールアラルキル樹脂（ザイロック樹脂）、レゾルシンノボラック樹脂に代表される多価ヒドロキシ化合物とホルムアルデヒドから合成される多価フェノールノボラック樹脂、ナフトールアラルキル樹脂、トリメチロールメタン樹脂、テトラフェニロールエタン樹脂、ナフトールノボラック樹脂、ナフトール−フェノール共縮ノボラック樹脂、ナフトール−クレゾール共縮ノボラック樹脂、ビフェニル変性フェノール樹脂（ビスメチレン基でフェノール核が連結された多価フェノール化合物）、ビフェニル変性ナフトール樹脂（ビスメチレン基でフェノール核が連結された多価ナフトール化合物）、アミノトリアジン変性フェノール樹脂（メラミン、ベンゾグアナミンなどでフェノール核が連結された多価フェノール化合物）やアルコキシ基含有芳香環変性ノボラック樹脂（ホルムアルデヒドでフェノール核及びアルコキシ基含有芳香環が連結された多価フェノール化合物）等の多価フェノール化合物が挙げられる。これらの硬化剤は、単独でも２種類以上の併用でも構わない。 The resin composition of the present invention may contain a curing agent. There are no particular limitations on the curing agent, and any compound commonly used as a curing agent for ordinary epoxy resins can be used, such as amine compounds, amide compounds, acid anhydride compounds, phenols, and the like. System compounds and the like. Specifically, examples of the amine compound include diaminodiphenylmethane, diethylenetriamine, triethylenetetramine, diaminodiphenylsulfone, isophoronediamine, imidazole, BF3-amine complex, and guanidine derivatives. Examples of the amide compound include dicyandiamide, Examples include polyamide resins synthesized from dimer of linolenic acid and ethylenediamine. Examples of acid anhydride compounds include phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, maleic anhydride, and tetrahydrophthalic anhydride. , Methyltetrahydrophthalic anhydride, methyl nadic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, etc., and phenolic compounds include phenol novolac resins, cresol novolac resins, Aromatic hydrocarbon formaldehyde resin modified phenolic resin, dicyclopentadiene phenol addition type resin, phenol aralkyl resin (Zylok resin), polyhydric phenol novolak resin synthesized from formaldehyde and polyhydroxy compound represented by resorcin novolac resin, naphthol Aralkyl resin, trimethylol methane resin, tetraphenylol ethane resin, naphthol novolac resin, naphthol-phenol co-condensed novolac resin, naphthol-cresol co-condensed novolac resin, biphenyl-modified phenol resin (polyvalent polyphenol with bismethylene group linked to phenol nucleus) Phenolic compounds), biphenyl-modified naphthol resins (polyvalent naphthol compounds in which phenol nuclei are linked by bismethylene groups), aminotriazine-modified phenols Resin (polyhydric phenol compound in which phenol nucleus is linked by melamine, benzoguanamine, etc.) and alkoxy group-containing aromatic ring modified novolak resin (polyhydric phenol compound in which phenol nucleus and alkoxy group-containing aromatic ring are linked by formaldehyde) And monohydric phenol compounds. These curing agents may be used alone or in combination of two or more.
これらの中でも、高い接着性を発現するためには、接着面に硬化性樹脂組成物が均質に塗布された方が良く、液状あるいは固形であっても低温で高い流動性を示すものが求められるため、液状のものあるいは１００℃以下の低温で液状になる硬化剤の使用が好ましい。その様な硬化剤として、酸無水物系化合物が挙げられ、中でも、常温で液状のメチルテトラヒドロ無水フタル酸、メチルエンドメチレンテトラヒドロ無水フタル酸、メチルブテニルテトラヒドロ無水フタル酸、ドデセニル無水コハク酸、メチルヘキサヒドロ無水フタル酸の使用が好ましい。 Among these, in order to express high adhesiveness, it is better that the curable resin composition is uniformly applied to the adhesive surface, and even if it is liquid or solid, it must have high fluidity at low temperature. Therefore, it is preferable to use a curing agent that becomes liquid or becomes liquid at a low temperature of 100 ° C. or lower. Examples of such curing agents include acid anhydride compounds, among which methyltetrahydrophthalic anhydride, methylendomethylenetetrahydrophthalic anhydride, methylbutenyltetrahydrophthalic anhydride, dodecenyl succinic anhydride, methyl, which are liquid at room temperature. The use of hexahydrophthalic anhydride is preferred.
本発明の硬化性樹脂組成物におけるエポキシ樹脂と硬化剤の配合量としては、特に限定されるものではないが、得られる硬化物特性が良好である点から、エポキシ樹脂のエポキシ基の合計１当量に対して、硬化剤中の活性基が０．７〜１．５当量になる量が好ましい。 The blending amount of the epoxy resin and the curing agent in the curable resin composition of the present invention is not particularly limited, but from the viewpoint of good cured product properties, a total of 1 equivalent of epoxy groups of the epoxy resin. In contrast, the amount by which the active group in the curing agent is 0.7 to 1.5 equivalents is preferable.
また必要に応じて本発明の硬化性樹脂組成物に硬化促進剤を適宜併用することもできる。硬化促進剤としては種々のものが使用できるが、例えば、リン系化合物、第３級アミン、イミダゾール、有機酸金属塩、ルイス酸、アミン錯塩等が挙げられる。 Moreover, a hardening accelerator can also be suitably used together with the curable resin composition of this invention as needed. Various curing accelerators can be used, and examples thereof include phosphorus compounds, tertiary amines, imidazoles, organic acid metal salts, Lewis acids, and amine complex salts.
本発明の硬化性樹脂組成物において、エポキシ樹脂成分として、前記した２，２’，７，７’−テトラグリシジルオキシ−１，１’−ビナフタレンを単独で用いてもよいが、本発明の効果を損なわない範囲で他のエポキシ樹脂を併用して用いても良い。具体的には、エポキシ樹脂成分の全質量に対して前記のエポキシ樹脂が３０質量％以上、好ましくは４０質量％以上となる範囲で他のエポキシ樹脂を併用することができる。 In the curable resin composition of the present invention, the above-described 2,2 ′, 7,7′-tetraglycidyloxy-1,1′-binaphthalene may be used alone as an epoxy resin component. Other epoxy resins may be used in combination as long as the above is not impaired. Specifically, another epoxy resin can be used in combination in the range where the epoxy resin is 30% by mass or more, preferably 40% by mass or more with respect to the total mass of the epoxy resin component.
ここで前記の２，２’，７，７’−テトラグリシジルオキシ−１，１’−ビナフタレンと併用され得る他のエポキシ樹脂としては、種々のエポキシ樹脂を用いることができるが、例えば、ビスフェノールＡ型エポキシ樹脂、ビスフェノールＦ型エポキシ樹脂、レゾルシン型エポキシ樹脂、ビフェニル型エポキシ樹脂、テトラメチルビフェニル型エポキシ樹脂、フェノールノボラック型エポキシ樹脂、クレゾールノボラック型エポキシ樹脂、ビスフェノールＡノボラック型エポキシ樹脂、トリフェニルメタン型エポキシ樹脂、テトラフェニルエタン型エポキシ樹脂、ジシクロペンタジエン−フェノール付加反応型エポキシ樹脂、フェノールアラルキル型エポキシ樹脂、ナフトールノボラック型エポキシ樹脂、ナフトールアラルキル型エポキシ樹脂、ナフトール−フェノール共縮ノボラック型エポキシ樹脂、ナフトール−クレゾール共縮ノボラック型エポキシ樹脂、芳香族炭化水素ホルムアルデヒド樹脂変性フェノール樹脂型エポキシ樹脂、ビフェニルノボラック型エポキシ樹脂等が挙げられる。 Here, as the other epoxy resin that can be used in combination with the aforementioned 2,2 ′, 7,7′-tetraglycidyloxy-1,1′-binaphthalene, various epoxy resins can be used. For example, bisphenol A Type epoxy resin, bisphenol F type epoxy resin, resorcin type epoxy resin, biphenyl type epoxy resin, tetramethylbiphenyl type epoxy resin, phenol novolac type epoxy resin, cresol novolak type epoxy resin, bisphenol A novolak type epoxy resin, triphenylmethane type Epoxy resin, tetraphenylethane type epoxy resin, dicyclopentadiene-phenol addition reaction type epoxy resin, phenol aralkyl type epoxy resin, naphthol novolac type epoxy resin, naphthol aralkyl type epoxy resin , Naphthol - phenol co-condensed novolak type epoxy resin, naphthol - cresol co-condensed novolac type epoxy resin, aromatic hydrocarbon formaldehyde resin-modified phenol resin type epoxy resin, a biphenyl novolak type epoxy resins.
この中でも基材の接着性の高い硬化性樹脂組成物を得るためには、液状あるいは比較的低温で液化するものの使用が好ましく、例えば、液状であるエポキシ樹脂としては、ビスフェノールＡ型エポキシ樹脂の平均分子量が約４００以下のもの；ｐ−グリシジルオキシフェニルジメチルトリスビスフェノールＡジグリシジルエーテルのような分岐状多官能ビスフェノールＡ型エポキシ樹脂；ビスフェノールＦ型エポキシ樹脂；レゾルシン型エポキシ樹脂；フェノールノボラック型エポキシ樹脂の平均分子量が約５７０以下のもの；ビニル（３，４−シクロヘキセン）ジオキシド、３，４−エポキシシクロヘキシルカルボン酸（３，４−エポキシシクロヘキシル）メチル、アジピン酸ビス（３，４−エポキシ−６−メチルシクロヘキシルメチル）、２−（３，４−エポキシシクロヘキシル）５，１−スピロ（３，４−エポキシシクロヘキシル）−ｍ−ジオキサンのような脂環式エポキシ樹脂；３，３’，５，５’−テトラメチル−４，４’−ジグリシジルオキシビフェニルのようなビフェニル型エポキシ樹脂；ヘキサヒドロフタル酸ジグリシジル、３−メチルヘキサヒドロフタル酸ジグリシジル、ヘキサヒドロテレフタル酸ジグリシジルのようなグリシジルエステル型エポキシ樹脂；ジグリシジルアニリン、ジグリシジルトルイジン、トリグリシジル−ｐ−アミノフェノール、テトラグリシジル−ｍ−キシリレンジアミン、テトラグリシジルビス（アミノメチル）シクロヘキサンのようなグリシジルアミン型エポキシ樹脂；ならびに１，３−ジグリシジル−５−メチル−５−エチルヒダントインのようなヒダントイン型エポキシ樹脂；ナフタレン環含有エポキシ樹脂、１，３−ビス（３−グリシドキシプロピル）−１，１，３，３−テトラメチルジシロキサンのようなシリコーン骨格をもつエポキシ樹脂などが挙げられる。 Among these, in order to obtain a curable resin composition having a high adhesion to the substrate, it is preferable to use a liquid or one that liquefies at a relatively low temperature. For example, as an epoxy resin that is liquid, the average of bisphenol A type epoxy resins Molecular weight of about 400 or less; branched polyfunctional bisphenol A type epoxy resin such as p-glycidyloxyphenyldimethyltrisbisphenol A diglycidyl ether; bisphenol F type epoxy resin; resorcin type epoxy resin; phenol novolac type epoxy resin Average molecular weight of about 570 or less; vinyl (3,4-cyclohexene) dioxide, 3,4-epoxycyclohexylcarboxylic acid (3,4-epoxycyclohexyl) methyl, bis (3,4-epoxy-6-methyl adipate) (Cyclohexylmethyl) Cycloaliphatic epoxy resins such as 2- (3,4-epoxycyclohexyl) 5,1-spiro (3,4-epoxycyclohexyl) -m-dioxane; 3,3 ′, 5,5′-tetramethyl-4 Biphenyl type epoxy resin such as 4,4'-diglycidyloxybiphenyl; Glycidyl ester type epoxy resin such as diglycidyl hexahydrophthalate, diglycidyl 3-methylhexahydrophthalate, diglycidyl hexahydroterephthalate; diglycidyl aniline, diglycidyl Glycidylamine type epoxy resins such as glycidyltoluidine, triglycidyl-p-aminophenol, tetraglycidyl-m-xylylenediamine, tetraglycidylbis (aminomethyl) cyclohexane; and 1,3-diglycidyl-5-methyl-5 Ethyl fold Hydantoin type epoxy resin such as Toin; Naphthalene ring-containing epoxy resin, Epoxy resin having a silicone skeleton such as 1,3-bis (3-glycidoxypropyl) -1,1,3,3-tetramethyldisiloxane Etc.
また、本発明の硬化性樹脂組成物を液状あるいは固形であっても低温で高い流動性を示すものにするために、エポキシ基を持つ液状の化合物、いわゆる反応性希釈剤を使用しても良く、その様な化合物として、ｎ−ブチルグリシジルエーテル、２−エチルヘキシルグリシジルエーテル、フェニルグリシジルエーテル、クレジルグリシジルエーテル、ｐ−ｓ−ブチルフェニルグリシジルエーテル、スチレンオキシド、α−ピネンオキシドのようなモノエポキシド化合物；（ポリ）エチレングリコールジグリシジルエーテル、（ポリ）プロピレングリコールジグルシジルエーテル、ブタンジオールグリシジルエーテル、ネオペンチルグリコールジグリシジルエーテルのようなジエポキシド化合物；トリメチロールプロパントリグリシジルエーテル、グリセリントリグリシジルエーテルのようなトリエポキシド化合物、アリルグリシジルエーテル、メタクリル酸グリシジル、１−ビニル−３，４−エポキシシクロヘキサンのような他の官能基を有するモノエポキシド化合物等が挙げられる。得られる硬化物の耐熱物性から、２官能性以上のものの使用が好ましい。 Further, in order to make the curable resin composition of the present invention liquid or solid and exhibit high fluidity at low temperature, a liquid compound having an epoxy group, so-called reactive diluent may be used. As such compounds, monoepoxide compounds such as n-butyl glycidyl ether, 2-ethylhexyl glycidyl ether, phenyl glycidyl ether, cresyl glycidyl ether, ps-butylphenyl glycidyl ether, styrene oxide, α-pinene oxide A diepoxide compound such as (poly) ethylene glycol diglycidyl ether, (poly) propylene glycol diglycidyl ether, butanediol glycidyl ether, neopentyl glycol diglycidyl ether; trimethylolpropane triglycidyl ether; Triepoxide compounds such as glycerin triglycidyl ether, allyl glycidyl ether, glycidyl methacrylate, monoepoxide compounds having other functional groups such as 1-vinyl-3,4-epoxycyclohexane, and the like. In view of the heat resistance of the resulting cured product, it is preferable to use a bifunctional or higher functional product.
本発明の硬化性樹脂組成物は、必要に応じてその他の配合物を含有してもよく、発明の効果を損ねない範囲で、外部滑剤、内部滑剤、酸化防止剤、難燃剤、光安定剤、紫外線吸収剤、ガラス繊維、カーボン繊維等の補強材、熱伝導性フィラー以外のフィラー、各種着色剤等を添加してもよい。また、接着性を調整するために、シリコーンオイル、液状ゴム、ゴム粉末、熱可塑性樹脂等のアクリル酸メチル−ブタジエン−スチレン共重合体、メタクリル酸メチル−ブタジエン−スチレン共重合体などのブタジエン系共重合体ゴムやシリコーン系化合物などの低応力化剤（応力緩和剤）の使用も可能である。 The curable resin composition of the present invention may contain other compounds as necessary, and within the range not impairing the effects of the invention, external lubricant, internal lubricant, antioxidant, flame retardant, light stabilizer In addition, reinforcing materials such as ultraviolet absorbers, glass fibers and carbon fibers, fillers other than heat conductive fillers, various colorants and the like may be added. In addition, in order to adjust the adhesion, butadiene-based copolymers such as silicone oil, liquid rubber, rubber powder, and thermoplastic resins such as methyl acrylate-butadiene-styrene copolymers and methyl methacrylate-butadiene-styrene copolymers. It is also possible to use a low stress agent (stress relaxation agent) such as a polymer rubber or a silicone compound.
本発明の硬化性樹脂組成物は、２，２’，７，７’−テトラグリシジルオキシ−１，１’−ビナフタレン、熱伝導性フィラーおよび／または硬化剤、さらに必要に応じてその他の配合物を混合することにより得られる。その混合方法に特に限定はなく、公知慣用の方法により、混合される。一般的な手法としては、所定の配合量の原材料をミキサー等によって充分に混合した後、三本ロール等で混練し、流動性ある液状の組成物として、あるいは、所定の配合量の原材料をミキサー等によって充分に混合した後、ミキシングロール、押出機等で、溶融混練した後、冷却、粉砕する事で、固形の組成物として得られる。その混合状態は、エポキシ化合物と硬化剤が充分に均一に混合されていれば良いが、熱伝導性フィラーも均一に分散混合された方がより好ましい。 The curable resin composition of the present invention comprises 2,2 ′, 7,7′-tetraglycidyloxy-1,1′-binaphthalene, a heat conductive filler and / or a curing agent, and, if necessary, other compounds. Is obtained by mixing. The mixing method is not particularly limited, and the mixing is performed by a known and common method. As a general method, a raw material of a predetermined blending amount is sufficiently mixed with a mixer or the like, and then kneaded with a three-roll roll or the like to form a fluid liquid composition, or a raw material of a predetermined blending amount is mixed with a mixer. After being sufficiently mixed by the above, etc., it is melt-kneaded with a mixing roll, an extruder, etc., and then cooled and pulverized to obtain a solid composition. The mixed state may be that the epoxy compound and the curing agent are sufficiently uniformly mixed, but it is more preferable that the thermally conductive filler is uniformly dispersed and mixed.
本発明の硬化性樹脂組成物から硬化物を得る方法としては、一般的な硬化性樹脂組成物の硬化方法に準拠すればよいが、例えば加熱温度条件は、組み合わせる硬化剤の種類や用途等によって、適宜選択すればよいが、上記方法によって得られた組成物を、室温〜２５０℃程度の温度範囲で加熱すればよい。 As a method for obtaining a cured product from the curable resin composition of the present invention, it may be in accordance with a general curing method for a curable resin composition. The composition obtained by the above method may be heated in a temperature range of room temperature to about 250 ° C.
本発明の熱伝導性組成物は接着剤として、パワーモジュールなどの電気・電子機器の放熱させたい部位と放熱部材（例えば、金属板やヒートシンク）を接着させ、良好な放熱を発現させるために使用される。その際の使用される熱伝導性組成物の形態には特に制限はないが、液状あるいはペースト状に設計した熱伝導性組成物の場合は、液状あるいはペースト状の熱伝導性組成物を接着面の界面に注入後、接着し、硬化させれば良い。固形状に設計されたものは、粉体状、チップ状あるいはシート状にしたものを、接着面の界面に置き、熱溶融させる事で接着し、硬化させれば良い。 The heat conductive composition of the present invention is used as an adhesive to bond a heat radiation part of an electric / electronic device such as a power module and a heat radiating member (for example, a metal plate or a heat sink) to develop good heat radiation. Is done. There are no particular restrictions on the form of the thermally conductive composition used at that time, but in the case of a thermally conductive composition designed in a liquid or paste form, the liquid or paste form thermally conductive composition is attached to the adhesive surface. After injecting into the interface, it may be adhered and cured. What is designed in a solid form may be a powder, chip, or sheet that is placed on the interface of the adhesive surface and bonded by heat melting and cured.
本発明を実施例、比較例により具体的に説明する。 The present invention will be specifically described with reference to examples and comparative examples.
尚、１５０℃における溶融粘度及びＧＰＣ、ＭＳスペクトルは以下の条件にて測定した。
１）１５０℃における溶融粘度：ＡＳＴＭ Ｄ４２８７に準拠
２）軟化点測定法：ＪＩＳ Ｋ７２３４
３）ＧＰＣ：測定条件は以下の通り。
測定装置 ：東ソー株式会社製「ＨＬＣ−８２２０ ＧＰＣ」、
カラム：東ソー株式会社製ガードカラム「ＨＸＬ−Ｌ」
＋東ソー株式会社製「ＴＳＫ−ＧＥＬ Ｇ２０００ＨＸＬ」
＋東ソー株式会社製「ＴＳＫ−ＧＥＬ Ｇ２０００ＨＸＬ」
＋東ソー株式会社製「ＴＳＫ−ＧＥＬ Ｇ３０００ＨＸＬ」
＋東ソー株式会社製「ＴＳＫ−ＧＥＬ Ｇ４０００ＨＸＬ」
検出器： ＲＩ（示差屈折率計）
データ処理：東ソー株式会社製「ＧＰＣ−８０２０モデルIIバージョン４．１０」
測定条件： カラム温度 ４０℃
移動相： テトラヒドロフラン
流速： １．０ｍｌ／分
標準 ： 前記「ＧＰＣ−８０２０モデルIIバージョン４．１０」の測定マニュアルに準拠して、分子量が既知の下記の単分散ポリスチレンを用いた。
（使用ポリスチレン）
東ソー株式会社製「Ａ−５００」
東ソー株式会社製「Ａ−１０００」
東ソー株式会社製「Ａ−２５００」
東ソー株式会社製「Ａ−５０００」
東ソー株式会社製「Ｆ−１」
東ソー株式会社製「Ｆ−２」
東ソー株式会社製「Ｆ−４」
東ソー株式会社製「Ｆ−１０」
東ソー株式会社製「Ｆ−２０」
東ソー株式会社製「Ｆ−４０」
東ソー株式会社製「Ｆ−８０」
東ソー株式会社製「Ｆ−１２８」
試料 ： 樹脂固形分換算で１．０質量％のテトラヒドロフラン溶液をマイクロフィルターでろ過したもの（５０μｌ）。
４）ＮＭＲ：日本電子株式会社製 ＮＭＲ ＬＡ３００
５）ＭＳ ：日本電子株式会社製 ガスクロマトグラフ飛行時間質量分析計ＪＭＳ−Ｔ１００ＧＣ
The melt viscosity at 150 ° C. and GPC and MS spectra were measured under the following conditions.
1) Melt viscosity at 150 ° C: according to ASTM D4287
2) Softening point measurement method: JIS K7234
3) GPC: The measurement conditions are as follows.
Measuring device: “HLC-8220 GPC” manufactured by Tosoh Corporation
Column: Guard column “HXL-L” manufactured by Tosoh Corporation
+ "TSK-GEL G2000HXL" manufactured by Tosoh Corporation
+ "TSK-GEL G2000HXL" manufactured by Tosoh Corporation
+ Tosoh Corporation “TSK-GEL G3000HXL”
+ Tosoh Corporation “TSK-GEL G4000HXL”
Detector: RI (differential refractometer)
Data processing: “GPC-8020 Model II version 4.10” manufactured by Tosoh Corporation
Measurement conditions: Column temperature 40 ° C
Mobile phase: Tetrahydrofuran
Flow rate: 1.0 ml / min
Standard: The following monodisperse polystyrene having a known molecular weight was used in accordance with the measurement manual of “GPC-8020 Model II version 4.10”.
(Polystyrene used)
“A-500” manufactured by Tosoh Corporation
"A-1000" manufactured by Tosoh Corporation
"A-2500" manufactured by Tosoh Corporation
"A-5000" manufactured by Tosoh Corporation
“F-1” manufactured by Tosoh Corporation
"F-2" manufactured by Tosoh Corporation
“F-4” manufactured by Tosoh Corporation
“F-10” manufactured by Tosoh Corporation
“F-20” manufactured by Tosoh Corporation
“F-40” manufactured by Tosoh Corporation
“F-80” manufactured by Tosoh Corporation
“F-128” manufactured by Tosoh Corporation
Sample: A 1.0 mass% tetrahydrofuran solution filtered in terms of resin solids and filtered through a microfilter (50 μl).
4) NMR: NMR LA300 manufactured by JEOL Ltd.
5) MS: Gas chromatograph time-of-flight mass spectrometer JMS-T100GC manufactured by JEOL Ltd.
合成例１
温度計、撹拌機、還流冷却器を取り付けたフラスコに、窒素ガスパージを施しながら、塩化鉄（ＩＩＩ）六水和物１３９ｇ（０．５モル）、水１３３０ｍＬを仕込み、攪拌しながら反応容器内を窒素置換した後、ナフタレン−２，７−ジオール８２ｇ（０．５モル）をイソプロピルアルコール１９０ｍＬにあらかじめ溶解した溶液を加え、４０℃で３０分撹拌した。塩化鉄（ＩＩＩ）六水和物１３９ｇ（０．５モル）及び水６６４ｍＬ、イソプロピルアルコール９４ｍＬの混合溶液を加え、４０℃まで昇温してから、さらに１時間撹拌した。反応液に酢酸エチル５００ｍＬを加え、１０分撹拌した。反応液を分液漏斗に移し、有機層を分離した後、さらに、水層を酢酸エチルで抽出した。合わせた有機層を飽和食塩水で洗浄した。真空下で溶媒を２００ｍＬ程度になるまで留去した後、溶液を温度計、攪拌機、ディーンスタークトラップを備えたＳＵＳ容器に移し、トルエン５Ｌを加えた後、溶媒を酢酸エチル及び水からトルエンに置換した。トルエン溶液を室温まで冷却した後、不溶物をろ別した。ろ液を温度計、攪拌機、ディーンスタークトラップを備えたＳＵＳ容器に移し、撹拌しながら、沸点以上の温度に加熱し、トルエンを５００ｍＬ程度になるまで留去することで濃縮し、１，１’−ビナフタレン−２，２’，７，７’−テトラオールの結晶を析出させた。析出物と溶媒を８０℃以上の温度での熱時ろ過でろ取した後、１１０℃で５時間乾燥させ、１，１’−ビナフタレン−２，２’，７，７’−テトラオールを収量５３ｇ（収率６８％）で得た。得られた１，１’−ビナフタレン−２，２’，７，７’−テトラオールは、ＧＰＣおよびＭＳにより、多量体化した成分を含まず、高純度であることを確認した。
Synthesis example 1
A flask equipped with a thermometer, a stirrer, and a reflux condenser was charged with 139 g (0.5 mol) of iron (III) chloride hexahydrate and 1330 mL of water while purging nitrogen gas, and the inside of the reaction vessel was stirred while stirring. After nitrogen substitution, a solution prepared by dissolving 82 g (0.5 mol) of naphthalene-2,7-diol in 190 mL of isopropyl alcohol in advance was added and stirred at 40 ° C. for 30 minutes. A mixed solution of 139 g (0.5 mol) of iron (III) chloride hexahydrate, 664 mL of water and 94 mL of isopropyl alcohol was added, the temperature was raised to 40 ° C., and the mixture was further stirred for 1 hour. Ethyl acetate 500mL was added to the reaction liquid, and it stirred for 10 minutes. The reaction solution was transferred to a separatory funnel, the organic layer was separated, and the aqueous layer was further extracted with ethyl acetate. The combined organic layers were washed with saturated brine. After the solvent was distilled off to about 200 mL under vacuum, the solution was transferred to a SUS container equipped with a thermometer, stirrer, and Dean-Stark trap, 5 L of toluene was added, and the solvent was replaced with toluene from ethyl acetate and water. did. After cooling the toluene solution to room temperature, insoluble matters were filtered off. The filtrate is transferred to a SUS vessel equipped with a thermometer, stirrer, and Dean-Stark trap, heated to a temperature higher than the boiling point while stirring, and concentrated by distilling off toluene to about 500 mL. -Crystals of binaphthalene-2,2 ', 7,7'-tetraol were precipitated. The precipitate and solvent were filtered by hot filtration at a temperature of 80 ° C. or higher and then dried at 110 ° C. for 5 hours to obtain 53 g of 1,1′-binaphthalene-2,2 ′, 7,7′-tetraol. (Yield 68%). The obtained 1,1′-binaphthalene-2,2 ′, 7,7′-tetraol was confirmed by GPC and MS to contain no multimerized component and high purity.
合成例２
温度計、滴下ロート、冷却管、撹拌機を取り付けたフラスコに、窒素ガスパージを施しながら、合成例１で得た１，１’−ビナフタレン−２，２’，７，７’−テトラオールの７９．５ｇ（０．２５モル）、エピクロルヒドリンの４６２ｇ（５．０モル）、ｎ−ブタノールの１２６ｇを仕込み溶解させた。４０℃に昇温した後に、４８％水酸化ナトリウム水溶液の１００ｇ（１．２０モル）を８時間要して添加し、その後更に５０℃に昇温し更に１時間反応させた。反応終了後、水１５０ｇを加えて静置した後、下層を棄却した。その後、１５０℃減圧下で未反応エピクロルヒドリンを留去した。それで得られた粗エポキシ樹脂にメチルイソブチルケトンの２３０ｇを加え溶解した。更にこの溶液に１０質量％水酸化ナトリウム水溶液の１００ｇを添加して８０℃で２時間反応させた後に洗浄液のｐＨが中性となるまで水洗を３回繰り返した。次いで共沸によって系内を脱水し、精密濾過を経た後に、溶媒を減圧下で留去して目的のエポキシ樹脂である２，２’，７，７’−テトラグリシジルオキシ−１，１’−ビナフタレン（Ａ−１）の１３５ｇを得た。得られたエポキシ樹脂（Ａ−１）の軟化点は６１℃（Ｂ＆Ｒ法）、溶融粘度（測定法：ＩＣＩ粘度計法、測定温度：１５０℃）は１．１ｄＰａ・ｓ、エポキシ当量は１４４ｇ／当量であった。ＧＰＣ測定により面積比で９０％以上が目的物であり、ＭＳ測定により、２，２’，７，７’−テトラグリシジルオキシ−１，１’−ビナフタレン（Ａ−１）を示す５４２のピークを確認した。
Synthesis example 2
79 of 1,1′-binaphthalene-2,2 ′, 7,7′-tetraol obtained in Synthesis Example 1 while purging a nitrogen gas purge to a flask equipped with a thermometer, a dropping funnel, a condenser, and a stirrer 0.5 g (0.25 mol), 462 g (5.0 mol) of epichlorohydrin, and 126 g of n-butanol were charged and dissolved. After the temperature was raised to 40 ° C., 100 g (1.20 mol) of a 48% aqueous sodium hydroxide solution was added over 8 hours, and then the temperature was further raised to 50 ° C. and reacted for another 1 hour. After completion of the reaction, 150 g of water was added and allowed to stand, and then the lower layer was discarded. Thereafter, unreacted epichlorohydrin was distilled off under reduced pressure at 150 ° C. Then, 230 g of methyl isobutyl ketone was added to the crude epoxy resin thus obtained and dissolved. Further, 100 g of a 10% by mass aqueous sodium hydroxide solution was added to this solution and reacted at 80 ° C. for 2 hours, and then washing with water was repeated three times until the pH of the washing solution became neutral. Next, the system was dehydrated by azeotropic distillation, and after microfiltration, the solvent was distilled off under reduced pressure to obtain the desired epoxy resin 2,2 ′, 7,7′-tetraglycidyloxy-1,1′-. 135 g of binaphthalene (A-1) was obtained. The resulting epoxy resin (A-1) had a softening point of 61 ° C. (B & R method), a melt viscosity (measurement method: ICI viscometer method, measurement temperature: 150 ° C.) of 1.1 dPa · s, and an epoxy equivalent of 144 g / Equivalent. 90% or more in area ratio is the target product by GPC measurement, and 542 peak indicating 2,2 ′, 7,7′-tetraglycidyloxy-1,1′-binaphthalene (A-1) is obtained by MS measurement. confirmed.
実施例１
合成例２で得られた本発明のエポキシ樹脂（Ａ−１）の１０ｇ、ＡＣ−９５００−ＳＣＸ（アドマテックス株式会社製、Ｎ−フェニル−γ−アミノプロピルトリメトキシシランで表面処理した平均粒径１０μｍの酸化アルミニウム粉末）の４．２ｇ、ＡＣ−２５００−ＳＸＱ（アドマテックス株式会社製、Ｎ−フェニル−γ−アミノプロピルトリメトキシシランで表面処理した平均粒径０．６μｍの酸化アルミニウム粉末）の２．８ｇ、ＭＨＡＣ−Ｐ(日立化成株式会社製、メチル−３，６−エンドメチレン−１，２，３，６−テトラヒドロ無水フタル酸、分子量１７８)の１０．５ｇ、キュアゾール２Ｐ４ＭＨＺ−ＰＷ（四国化成工業株式会社製、２−フェニル−４−メチル−５−ヒドロキシメチルイミダゾール）の０．１ｇを配合し、３本ロールで混練する事により、樹脂組成物を得た。得られた樹脂組成物を用いて、６０×１１０×０．８ｍｍの板状試験片を作成した（仮硬化条件１７０℃×２０分、本硬化条件１７０℃×２時間、２５０℃×８時間）。得られた板状試験片から、１０×４０ｍｍに切り出した試験片を２５０℃に保持した乾燥機に入れ、耐熱性を評価した結果、２４０時間後も９０％以上の重量を保持しており、高い耐熱性を示した。さらに、ガラス転移温度は２８５℃であった。
Example 1
10 g of the epoxy resin (A-1) of the present invention obtained in Synthesis Example 2, AC-9500-SCX (manufactured by Admatechs Co., Ltd., average particle diameter subjected to surface treatment with N-phenyl-γ-aminopropyltrimethoxysilane) Of 10 μm aluminum oxide powder), AC-2500-SXQ (manufactured by Admatechs Co., Ltd., aluminum oxide powder having an average particle diameter of 0.6 μm and surface-treated with N-phenyl-γ-aminopropyltrimethoxysilane) 2.8 g, 10.5 g of MHAC-P (manufactured by Hitachi Chemical Co., Ltd., methyl-3,6-endomethylene-1,2,3,6-tetrahydrophthalic anhydride, molecular weight 178), cureazole 2P4MHZ-PW (Shikoku 0.1 g of 2-phenyl-4-methyl-5-hydroxymethylimidazole (made by Kasei Kogyo Co., Ltd.) The resin composition was obtained by kneading with a slurry. A plate-shaped test piece of 60 × 110 × 0.8 mm was prepared using the obtained resin composition (temporary curing conditions 170 ° C. × 20 minutes, main curing conditions 170 ° C. × 2 hours, 250 ° C. × 8 hours). . From the obtained plate-like test piece, the test piece cut out to 10 × 40 mm was put in a dryer maintained at 250 ° C., and as a result of evaluating the heat resistance, the weight of 90% or more was maintained even after 240 hours. It showed high heat resistance. Furthermore, the glass transition temperature was 285 ° C.
実施例２
合成例２で得られた本発明のエポキシ樹脂（Ａ−１）の８ｇ、ＡＣ−９５００−ＳＣＸの４．３ｇ、ＡＣ−２５００−ＳＸＱの２．８ｇ、ＭＨＡＣ−Ｐの１０．８ｇ、ＳＲ−１６ＨＬ（坂本薬品工業株式会社製、１，６−ヘキサンジオールジグリシジルエーテル、エポキシ当量１２５）の２ｇ、キュアゾール２Ｐ４ＭＨＺ−ＰＷの０．１ｇを配合し、３本ロールで混練する事により、樹脂組成物を得た。得られた樹脂組成物を用いて、実施例１と同様の方法で、板状試験片を作成後、１０×４０ｍｍの試験片を切り出し、耐熱性を評価した。２４０時間後も９０％以上の重量を保持しており、高い耐熱性を示した。さらに、ガラス転移温度は２８０℃であった。
Example 2
8 g of the epoxy resin (A-1) of the present invention obtained in Synthesis Example 2, 4.3 g of AC-9500-SCX, 2.8 g of AC-2500-SXQ, 10.8 g of MHAC-P, SR- A resin composition was prepared by blending 2 g of 16HL (manufactured by Sakamoto Yakuhin Kogyo Co., Ltd., 1,6-hexanediol diglycidyl ether, epoxy equivalent 125) and 0.1 g of Curesol 2P4MHZ-PW, and kneading with 3 rolls Got. Using the obtained resin composition, a plate-shaped test piece was prepared in the same manner as in Example 1, and then a 10 × 40 mm test piece was cut out to evaluate heat resistance. Even after 240 hours, it retained a weight of 90% or more, and exhibited high heat resistance. Furthermore, the glass transition temperature was 280 ° C.
実施例３
合成例２で得られた本発明のエポキシ樹脂（Ａ−１）の２０ｇ、ＡＣ−９５００−ＳＣＸの４．３ｇ、ＡＣ−２５００−ＳＸＱの２．９ｇ、キュアゾール２Ｐ４ＭＨＺ−ＰＷの１．０ｇを配合し、３本ロールで配合物が溶融する温度で混練する事により、樹脂組成物を得た。得られた樹脂組成物を用いて、実施例１と同様の方法で、板状試験片を作成後、１０×４０ｍｍの試験片を切り出し、耐熱性を評価した。２４０時間後も９０％以上の重量を保持しており、高い耐熱性を示した。さらに、ガラス転移温度は２９５℃であった。
Example 3
20 g of the epoxy resin (A-1) of the present invention obtained in Synthesis Example 2, 4.3 g of AC-9500-SCX, 2.9 g of AC-2500-SXQ, 1.0 g of Curazole 2P4MHZ-PW And the resin composition was obtained by knead | mixing at the temperature which a compound melt | dissolves with 3 rolls. Using the obtained resin composition, a plate-shaped test piece was prepared in the same manner as in Example 1, and then a 10 × 40 mm test piece was cut out to evaluate heat resistance. Even after 240 hours, it retained a weight of 90% or more, and exhibited high heat resistance. Furthermore, the glass transition temperature was 295 ° C.
実施例４
表１に示した組成で、樹脂組成物、硬化物を実施例１と同様の方法で作製し、評価を行なった。評価結果は表１に纏めた。
Example 4
With the composition shown in Table 1, a resin composition and a cured product were produced in the same manner as in Example 1 and evaluated. The evaluation results are summarized in Table 1.
実施例５、６
表２に示した組成で、樹脂組成物、硬化物を実施例１と同様の方法で作製し、評価を行なった。評価結果は表２に纏めた。
Examples 5 and 6
With the composition shown in Table 2, a resin composition and a cured product were produced in the same manner as in Example 1 and evaluated. The evaluation results are summarized in Table 2.
比較例１ エポキシ樹脂（Ａ−２） Comparative Example 1 Epoxy resin (A-2)
上記構造式で表されるエピクロンＨＰ−４７１０（ＤＩＣ株式会社製４官能型ナフタレン系エポキシ樹脂、軟化点９５℃１５０℃溶融粘度９ｄＰａ・ｓ、エポキシ当量１７０ｇ／当量）をエポキシ樹脂（Ａ−２）とした。該エポキシ樹脂（Ａ−２）を４．０ｇ、ＡＣ−９５００−ＳＣＸの４．３ｇ、ＡＣ−２５００−ＳＸＱの２．９ｇ、ＭＨＡＣ−Ｐの１１．１ｇ、ＳＲ−ＴＭＰ（坂本薬品工業株式会社製トリメチロールプロパンポリグリシジエーテル、エポキシ当量１３７）の６．０ｇ、キュアゾール２Ｐ４ＭＨＺ−ＰＷの０．１ｇを配合し、３本ロールで混練する事により、樹脂組成物を得た。得られた樹脂組成物を用いて、実施例１と同様の方法で、板状試験片を作成後、１０×４０ｍｍの試験片を切り出し、耐熱性を評価した。１２０時間後に９０％まで重量減少し、さらに、２４０時間後は９０％以下にまで重量が減少した。 Epiklon HP-4710 represented by the above structural formula (tetrafunctional naphthalene type epoxy resin manufactured by DIC Corporation, softening point 95 ° C. 150 ° C. melt viscosity 9 dPa · s, epoxy equivalent 170 g / equivalent) epoxy resin (A-2) It was. 4.0 g of the epoxy resin (A-2), 4.3 g of AC-9500-SCX, 2.9 g of AC-2500-SXQ, 11.1 g of MHAC-P, SR-TMP (Sakamoto Pharmaceutical Co., Ltd.) A resin composition was obtained by blending 6.0 g of trimethylolpropane polyglycidyl ether manufactured, epoxy equivalent 137) and 0.1 g of Curesol 2P4MHZ-PW, and kneading with three rolls. Using the obtained resin composition, a plate-shaped test piece was prepared in the same manner as in Example 1, and then a 10 × 40 mm test piece was cut out to evaluate heat resistance. After 120 hours, the weight decreased to 90%, and after 240 hours, the weight decreased to 90% or less.
比較例２
エポキシ樹脂（Ａ−２）の２０ｇ、ＡＣ−９５００−ＳＣＸの４．３ｇ、ＡＣ−２５００−ＳＸＱの２．９ｇ、キュアゾール２Ｐ４ＭＨＺ−ＰＷの１．０ｇを配合し、３本ロールで配合物が溶融する温度で混練する事で、樹脂組成物の作製を行なったが、混練中にゲル化し、樹脂組成物は得られなかった。
Comparative Example 2
20g of epoxy resin (A-2), 4.3g of AC-9500-SCX, 2.9g of AC-2500-SXQ, 1.0g of Curezol 2P4MHZ-PW are blended. Although the resin composition was prepared by kneading at a temperature at which the resin composition was kneaded, gelation occurred during the kneading and the resin composition was not obtained.
比較例３
表２に示した組成で、樹脂組成物、硬化物を実施例１と同様の方法で作製し、評価を行なった。評価結果は表２に纏めた。
Comparative Example 3
With the composition shown in Table 2, a resin composition and a cured product were produced in the same manner as in Example 1 and evaluated. The evaluation results are summarized in Table 2.
＜評価＞
＜耐熱性（重量保持率（％））＞
得られた熱伝導性組成物を硬化する事で得た板状試験片から切り出した、１０×４０×０．８ｍｍの試料片を、２５０℃に保持した乾燥機に保持し、時間ごとに取り出した試験片の重量を測定し、初期の試験片の重量に対する重量保持率を計算により求めた。
＜ガラス転移温度（℃）＞
粘弾性測定装置（ＤＭＡ：レオメトリック社製固体粘弾性測定装置ＲＳＡＩＩ、レクタンギュラーテンション法；周波数１Ｈｚ、昇温速度３℃／ｍｉｎ）を用いて、弾性率変化が最大となる（ｔａｎδ変化率が最も大きい）温度をガラス転移温度として評価した。
＜熱伝導性＞
得られた熱伝導性組成物を硬化する事で得た板状試験片から切り出した、６０×１１０×０．８ｍｍの板状試験片を作成した（プレ硬化条件１７０℃×２０分、ポスト硬化条件１７０℃×２時間＋２５０℃×８時間）。得られた板状試験片の１０×１０ｍｍに切り出した試験片について、熱伝導率測定装置（ＬＦＡ４４７ｎａｎｏｆｌａｓｈ、ＮＥＴＺＳＣＨ社製）を用いて熱伝導率の測定を行った。
＜接着強度＞
得られた液状樹脂組成物を用いて、引っ張り剪断接着強さの測定を行った。被着体は幅２５ｍｍ×長さ１００ｍｍ×厚み１．５ｍｍのアルミ板（Ａ１０５０）を用いて、ＪＩＳ Ｋ６８５０に準拠して試験片を作製した（硬化条件１７０℃×２時間＋２５０℃×８時間）。
作製した試験片を用いて、引っ張り剪断接着強さの測定を行い、初期の接着強度を測定した。次に、同時に作製した試験片を、２５０℃に保持した乾燥機に保持し、時間ごとに取り出した試験片の引っ張り剪断接着強さの測定を行い、耐熱の接着強度として評価した。
<Evaluation>
<Heat resistance (weight retention (%))>
A 10 × 40 × 0.8 mm sample piece cut out from a plate-like test piece obtained by curing the obtained heat conductive composition is held in a dryer maintained at 250 ° C. and taken out every hour. The weight of the test piece was measured, and the weight retention with respect to the weight of the initial test piece was calculated.
<Glass transition temperature (℃)>
Using a viscoelasticity measuring device (DMA: solid viscoelasticity measuring device RSAII manufactured by Rheometric, rectangular tension method; frequency 1 Hz, heating rate 3 ° C./min), the elastic modulus change is maximized (tan δ change rate is the highest). The (large) temperature was evaluated as the glass transition temperature.
<Thermal conductivity>
A plate-like test piece of 60 × 110 × 0.8 mm cut out from the plate-like test piece obtained by curing the obtained heat conductive composition was prepared (pre-curing conditions 170 ° C. × 20 minutes, post-curing. Condition 170 ° C. × 2 hours + 250 ° C. × 8 hours). About the test piece cut out to 10x10 mm of the obtained plate-shaped test piece, the heat conductivity was measured using the heat conductivity measuring apparatus (LFA447 nanoflash, the product made from NETZSCH).
<Adhesive strength>
Using the obtained liquid resin composition, the tensile shear bond strength was measured. The adherend was prepared using a 25 mm width × 100 mm length × 1.5 mm thickness aluminum plate (A1050) in accordance with JIS K6850 (curing conditions 170 ° C. × 2 hours + 250 ° C. × 8 hours). .
Using the prepared test piece, the tensile shear bond strength was measured, and the initial bond strength was measured. Next, the test piece produced simultaneously was hold | maintained at the dryer hold | maintained at 250 degreeC, the tensile shearing adhesive strength of the test piece taken out for every time was measured, and it evaluated as heat resistant adhesive strength.
表１、２の表記は以下の通りである。
（１）エポキシ化合物（Ａ）
（Ａ−１） ２，２’，７，７’−テトラグリシジルオキシ−１，１’−ビナフタレン（前記の合成例２で得られた化合物）
（Ａ−２）下記構造式で表される構造を主成分とするエポキシ樹脂、エピクロンＨＰ−４７１０（ＤＩＣ株式会社製、４官能型ナフタレン系エポキシ樹脂、軟化点９５℃、１５０℃溶融粘度９ｄＰａ・ｓ、エポキシ当量１７０ｇ／当量）
The notations in Tables 1 and 2 are as follows.
(1) Epoxy compound (A)
(A-1) 2,2 ′, 7,7′-tetraglycidyloxy-1,1′-binaphthalene (compound obtained in Synthesis Example 2)
(A-2) Epoxy resin whose main component is a structure represented by the following structural formula, Epicron HP-4710 (manufactured by DIC Corporation, tetrafunctional naphthalene epoxy resin, softening point 95 ° C., 150 ° C., melt viscosity 9 dPa · s, epoxy equivalent 170 g / equivalent)
（２）熱伝導性フィラー（Ｂ）
（Ｂ−１）ＡＣ９５００−ＳＸＣ（商品名、アドマテックス株式会社製、Ｎ−フェニル−γ−アミノプロピルトリメトキシシランで表面処理した平均粒径１０μｍの酸化アルミニウム粉末）
（Ｂ−２）ＡＣ２５００−ＳＸＱ（商品名、アドマテックス株式会社製、Ｎ−フェニル−γ−アミノプロピルトリメトキシシランで表面処理した平均粒径０．６μｍの酸化アルミニウム粉末）
(2) Thermally conductive filler (B)
(B-1) AC9500-SXC (trade name, manufactured by Admatechs Co., Ltd., aluminum oxide powder having an average particle diameter of 10 μm and surface-treated with N-phenyl-γ-aminopropyltrimethoxysilane)
(B-2) AC2500-SXQ (trade name, manufactured by Admatechs Co., Ltd., aluminum oxide powder having an average particle diameter of 0.6 μm and surface-treated with N-phenyl-γ-aminopropyltrimethoxysilane)
（３）硬化剤
（Ｃ−１） ＭＨＡＣ−Ｐ(日立化成株式会社製、メチル−３，６−エンドメチレン−１，２，３，６−テトラヒドロ無水フタル酸、分子量１７８)
（Ｃ−２）リカシッド ＨＮＡ−１００（新日本理化株式会社製、メチルビシクロ［２．２．１］ヘプタン−２，３−ジカルボン酸無水物/ビシクロ［２．２．１］ヘプタン−２，３−ジカルボン酸無水物）
(3) Curing agent (C-1) MHAC-P (manufactured by Hitachi Chemical Co., Ltd., methyl-3,6-endomethylene-1,2,3,6-tetrahydrophthalic anhydride, molecular weight 178)
(C-2) Ricacid HNA-100 (manufactured by Shin Nippon Rika Co., Ltd., methylbicyclo [2.2.1] heptane-2,3-dicarboxylic anhydride / bicyclo [2.2.1] heptane-2,3 -Dicarboxylic acid anhydride)
（４）反応性希釈剤
（ＴＭＰＬ）ＳＲ−ＴＭＰＬ（坂本薬品工業株式会社製、トリメチロールプロパンポリグリシジエーテル、エポキシ当量１３７）
（１６ＨＬ）ＳＲ−１６ＨＬ（坂本薬品工業株式会社製、１，６−ヘキサンジオールジグリシジルエーテル、エポキシ当量１２５）
(4) Reactive diluent (TMPL) SR-TMPL (manufactured by Sakamoto Pharmaceutical Co., Ltd., trimethylolpropane polyglycidyl ether, epoxy equivalent 137)
(16HL) SR-16HL (Sakamoto Pharmaceutical Co., Ltd., 1,6-hexanediol diglycidyl ether, epoxy equivalent 125)
（５）硬化促進剤
（２Ｐ４ＭＨＺ）キュアゾール２Ｐ４ＭＨＺ−ＰＷ（四国化成工業株式会社製、２−フェニル−４−メチル−５−ヒドロキシメチルイミダゾール）
(5) Curing accelerator (2P4MHZ) Curesol 2P4MHZ-PW (manufactured by Shikoku Chemicals Co., Ltd., 2-phenyl-4-methyl-5-hydroxymethylimidazole)
本発明の硬化性樹脂組成物、その硬化物および熱伝導性接着剤は、高い熱伝導性を有しており、２５０℃でも重量減少が小さく、接着強度の低下も少なく、さらに硬化物のガラス転移温度も高い事から、パワーモジュールなどの電気・電子機器の放熱をさせたい部位と放熱部材（例えば、金属板やヒートシンク）との接着など、様々な用途に使用することができ、特に半導体モジュールに好適に使用できる。 The curable resin composition of the present invention, the cured product thereof, and the thermally conductive adhesive have high thermal conductivity, have a small weight loss even at 250 ° C., have a small decrease in adhesive strength, and are further cured glass. Because of its high transition temperature, it can be used for various applications such as bonding of heat radiation parts (such as metal plates and heat sinks) to parts that want to dissipate electrical and electronic equipment such as power modules, especially semiconductor modules. Can be suitably used.
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| KR101784148B1 (en) * | 2015-12-31 | 2017-10-11 | 동의대학교 산학협력단 | Thermal conductive epoxy composites, preparation method thereof and thermal conductive adhesives |
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| KR101837512B1 (en) * | 2015-04-08 | 2018-03-12 | 주식회사 아모그린텍 | Heat radiation coating composite and heat radiator coated with the same |
| WO2016163830A1 (en) * | 2015-04-08 | 2016-10-13 | 주식회사 아모그린텍 | Heat dissipating coating composition and heat dissipating unit formed using same |
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| WO2017191801A1 (en) * | 2016-05-06 | 2017-11-09 | Dic株式会社 | Resin composition, molded article, layered body, and adhesive |
| WO2019230969A1 (en) * | 2018-05-31 | 2019-12-05 | 積水化学工業株式会社 | Heat dissipation composition, heat dissipation member, and filler aggregate for heat dissipation member |
| JP7231363B2 (en) * | 2018-09-20 | 2023-03-01 | 日東シンコー株式会社 | resin composition |
| EP3919540A4 (en) * | 2019-02-01 | 2022-02-16 | FUJIFILM Corporation | Composition for forming thermally conductive material, and thermally conductive material |
| CN118715262A (en) * | 2022-01-07 | 2024-09-27 | 太阳控股株式会社 | Curable resin composition |
| CN116063252A (en) * | 2022-12-26 | 2023-05-05 | 北京智芯微电子科技有限公司 | Binaphthyl monomer and preparation method thereof, epoxy resin and preparation method and application thereof |
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| JP2845410B2 (en) * | 1991-05-15 | 1999-01-13 | 日本化薬株式会社 | New epoxy resin, resin composition and cured product thereof |
| JP3735911B2 (en) * | 1995-11-30 | 2006-01-18 | 大日本インキ化学工業株式会社 | Epoxy resin composition and laminate using the same |
| JP2001089644A (en) * | 1999-09-22 | 2001-04-03 | Dainippon Ink & Chem Inc | Interlaminar insulating material for multilayer printed- wiring board |
| TW575631B (en) * | 2001-05-23 | 2004-02-11 | Agi Corp | Photosensitive resin composition containing hetero atoms |
| JP2007308640A (en) * | 2006-05-19 | 2007-11-29 | Kyocera Chemical Corp | Resin composition for laminate, organic substrate prepreg, metal foil-clad laminate and printed circuit board |
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