JP5314912B2 - Epoxy resin composition and molded article - Google Patents
Epoxy resin composition and molded article Download PDFInfo
- Publication number
- JP5314912B2 JP5314912B2 JP2008092280A JP2008092280A JP5314912B2 JP 5314912 B2 JP5314912 B2 JP 5314912B2 JP 2008092280 A JP2008092280 A JP 2008092280A JP 2008092280 A JP2008092280 A JP 2008092280A JP 5314912 B2 JP5314912 B2 JP 5314912B2
- Authority
- JP
- Japan
- Prior art keywords
- epoxy resin
- resin composition
- epoxy
- curing agent
- molding
- 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.)
- Expired - Fee Related
Links
- 239000003822 epoxy resin Substances 0.000 title claims description 128
- 229920000647 polyepoxide Polymers 0.000 title claims description 128
- 239000000203 mixture Substances 0.000 title claims description 55
- 239000003795 chemical substances by application Substances 0.000 claims description 48
- 229920005989 resin Polymers 0.000 claims description 29
- 239000011347 resin Substances 0.000 claims description 29
- 239000011256 inorganic filler Substances 0.000 claims description 28
- 229910003475 inorganic filler Inorganic materials 0.000 claims description 28
- 238000000465 moulding Methods 0.000 claims description 21
- 238000002844 melting Methods 0.000 claims description 14
- 230000008018 melting Effects 0.000 claims description 14
- 125000003700 epoxy group Chemical group 0.000 claims description 9
- 239000000463 material Substances 0.000 claims description 9
- 239000005011 phenolic resin Substances 0.000 claims description 9
- 239000004065 semiconductor Substances 0.000 claims description 9
- 229920001568 phenolic resin Polymers 0.000 claims description 8
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 claims description 7
- 238000004455 differential thermal analysis Methods 0.000 claims description 7
- 125000000524 functional group Chemical group 0.000 claims description 6
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical group C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 claims description 4
- 238000005538 encapsulation Methods 0.000 claims description 2
- 239000000835 fiber Substances 0.000 claims description 2
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 51
- 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 17
- 229920003986 novolac Polymers 0.000 description 17
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 16
- WQGWDDDVZFFDIG-UHFFFAOYSA-N pyrogallol Chemical compound OC1=CC=CC(O)=C1O WQGWDDDVZFFDIG-UHFFFAOYSA-N 0.000 description 16
- -1 t-butyl pyrogallol Chemical compound 0.000 description 16
- 238000000034 method Methods 0.000 description 15
- 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 14
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 13
- 239000004593 Epoxy Substances 0.000 description 12
- 238000007789 sealing Methods 0.000 description 11
- YBYIRNPNPLQARY-UHFFFAOYSA-N 1H-indene Chemical compound C1=CC=C2CC=CC2=C1 YBYIRNPNPLQARY-UHFFFAOYSA-N 0.000 description 10
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 description 10
- 238000002156 mixing Methods 0.000 description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 229940079877 pyrogallol Drugs 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 7
- 239000002585 base Substances 0.000 description 7
- VCCBEIPGXKNHFW-UHFFFAOYSA-N biphenyl-4,4'-diol Chemical compound C1=CC(O)=CC=C1C1=CC=C(O)C=C1 VCCBEIPGXKNHFW-UHFFFAOYSA-N 0.000 description 7
- 230000000694 effects Effects 0.000 description 7
- 150000002989 phenols Chemical class 0.000 description 7
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 6
- 230000001588 bifunctional effect Effects 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
- 239000002994 raw material Substances 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 6
- NZGQHKSLKRFZFL-UHFFFAOYSA-N 4-(4-hydroxyphenoxy)phenol Chemical compound C1=CC(O)=CC=C1OC1=CC=C(O)C=C1 NZGQHKSLKRFZFL-UHFFFAOYSA-N 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 5
- 150000008065 acid anhydrides Chemical class 0.000 description 5
- 239000007822 coupling agent Substances 0.000 description 5
- 238000011049 filling Methods 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- 238000005259 measurement Methods 0.000 description 5
- LVLNPXCISNPHLE-UHFFFAOYSA-N 2-[(4-hydroxyphenyl)methyl]phenol Chemical compound C1=CC(O)=CC=C1CC1=CC=CC=C1O LVLNPXCISNPHLE-UHFFFAOYSA-N 0.000 description 4
- VWGKEVWFBOUAND-UHFFFAOYSA-N 4,4'-thiodiphenol Chemical compound C1=CC(O)=CC=C1SC1=CC=C(O)C=C1 VWGKEVWFBOUAND-UHFFFAOYSA-N 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 4
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 4
- 150000001412 amines Chemical class 0.000 description 4
- GGNQRNBDZQJCCN-UHFFFAOYSA-N benzene-1,2,4-triol Chemical compound OC1=CC=C(O)C(O)=C1 GGNQRNBDZQJCCN-UHFFFAOYSA-N 0.000 description 4
- IMHDGJOMLMDPJN-UHFFFAOYSA-N biphenyl-2,2'-diol Chemical compound OC1=CC=CC=C1C1=CC=CC=C1O IMHDGJOMLMDPJN-UHFFFAOYSA-N 0.000 description 4
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical compound OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 description 4
- 239000000460 chlorine Substances 0.000 description 4
- 229910052801 chlorine Inorganic materials 0.000 description 4
- 229920006026 co-polymeric resin Polymers 0.000 description 4
- 229910002026 crystalline silica Inorganic materials 0.000 description 4
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical group C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 4
- RLSSMJSEOOYNOY-UHFFFAOYSA-N m-cresol Chemical compound CC1=CC=CC(O)=C1 RLSSMJSEOOYNOY-UHFFFAOYSA-N 0.000 description 4
- NXPPAOGUKPJVDI-UHFFFAOYSA-N naphthalene-1,2-diol Chemical compound C1=CC=CC2=C(O)C(O)=CC=C21 NXPPAOGUKPJVDI-UHFFFAOYSA-N 0.000 description 4
- XOOMNEFVDUTJPP-UHFFFAOYSA-N naphthalene-1,3-diol Chemical compound C1=CC=CC2=CC(O)=CC(O)=C21 XOOMNEFVDUTJPP-UHFFFAOYSA-N 0.000 description 4
- FZZQNEVOYIYFPF-UHFFFAOYSA-N naphthalene-1,6-diol Chemical compound OC1=CC=CC2=CC(O)=CC=C21 FZZQNEVOYIYFPF-UHFFFAOYSA-N 0.000 description 4
- QWVGKYWNOKOFNN-UHFFFAOYSA-N o-cresol Chemical compound CC1=CC=CC=C1O QWVGKYWNOKOFNN-UHFFFAOYSA-N 0.000 description 4
- IWDCLRJOBJJRNH-UHFFFAOYSA-N p-cresol Chemical compound CC1=CC=C(O)C=C1 IWDCLRJOBJJRNH-UHFFFAOYSA-N 0.000 description 4
- 235000012239 silicon dioxide Nutrition 0.000 description 4
- 238000001721 transfer moulding Methods 0.000 description 4
- BOKGTLAJQHTOKE-UHFFFAOYSA-N 1,5-dihydroxynaphthalene Chemical compound C1=CC=C2C(O)=CC=CC2=C1O BOKGTLAJQHTOKE-UHFFFAOYSA-N 0.000 description 3
- RXNYJUSEXLAVNQ-UHFFFAOYSA-N 4,4'-Dihydroxybenzophenone Chemical compound C1=CC(O)=CC=C1C(=O)C1=CC=C(O)C=C1 RXNYJUSEXLAVNQ-UHFFFAOYSA-N 0.000 description 3
- VPWNQTHUCYMVMZ-UHFFFAOYSA-N 4,4'-sulfonyldiphenol Chemical compound C1=CC(O)=CC=C1S(=O)(=O)C1=CC=C(O)C=C1 VPWNQTHUCYMVMZ-UHFFFAOYSA-N 0.000 description 3
- XSTITJMSUGCZDH-UHFFFAOYSA-N 4-(4-hydroxy-2,6-dimethylphenyl)-3,5-dimethylphenol Chemical group CC1=CC(O)=CC(C)=C1C1=C(C)C=C(O)C=C1C XSTITJMSUGCZDH-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-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
- SJRJJKPEHAURKC-UHFFFAOYSA-N N-Methylmorpholine Chemical compound CN1CCOCC1 SJRJJKPEHAURKC-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 238000013329 compounding Methods 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 239000000945 filler Substances 0.000 description 3
- 239000003063 flame retardant Substances 0.000 description 3
- 230000017525 heat dissipation Effects 0.000 description 3
- 239000011810 insulating material Substances 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000011159 matrix material Substances 0.000 description 3
- ZUVBIBLYOCVYJU-UHFFFAOYSA-N naphthalene-1,7-diol Chemical compound C1=CC=C(O)C2=CC(O)=CC=C21 ZUVBIBLYOCVYJU-UHFFFAOYSA-N 0.000 description 3
- MNZMMCVIXORAQL-UHFFFAOYSA-N naphthalene-2,6-diol Chemical compound C1=C(O)C=CC2=CC(O)=CC=C21 MNZMMCVIXORAQL-UHFFFAOYSA-N 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
- 239000002245 particle Substances 0.000 description 3
- 230000000704 physical effect Effects 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 239000011342 resin composition Substances 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- 229920001169 thermoplastic Polymers 0.000 description 3
- 239000004416 thermosoftening plastic Substances 0.000 description 3
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 2
- FRASJONUBLZVQX-UHFFFAOYSA-N 1,4-dioxonaphthalene Natural products C1=CC=C2C(=O)C=CC(=O)C2=C1 FRASJONUBLZVQX-UHFFFAOYSA-N 0.000 description 2
- IANQTJSKSUMEQM-UHFFFAOYSA-N 1-benzofuran Chemical compound C1=CC=C2OC=CC2=C1 IANQTJSKSUMEQM-UHFFFAOYSA-N 0.000 description 2
- FCEHBMOGCRZNNI-UHFFFAOYSA-N 1-benzothiophene Chemical compound C1=CC=C2SC=CC2=C1 FCEHBMOGCRZNNI-UHFFFAOYSA-N 0.000 description 2
- MQCPOLNSJCWPGT-UHFFFAOYSA-N 2,2'-Bisphenol F Chemical compound OC1=CC=CC=C1CC1=CC=CC=C1O MQCPOLNSJCWPGT-UHFFFAOYSA-N 0.000 description 2
- HTQNYBBTZSBWKL-UHFFFAOYSA-N 2,3,4-trihydroxbenzophenone Chemical compound OC1=C(O)C(O)=CC=C1C(=O)C1=CC=CC=C1 HTQNYBBTZSBWKL-UHFFFAOYSA-N 0.000 description 2
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 2
- CWLKGDAVCFYWJK-UHFFFAOYSA-N 3-aminophenol Chemical compound NC1=CC=CC(O)=C1 CWLKGDAVCFYWJK-UHFFFAOYSA-N 0.000 description 2
- JIGUICYYOYEXFS-UHFFFAOYSA-N 3-tert-butylbenzene-1,2-diol Chemical compound CC(C)(C)C1=CC=CC(O)=C1O JIGUICYYOYEXFS-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- 239000004721 Polyphenylene oxide Substances 0.000 description 2
- BGNXCDMCOKJUMV-UHFFFAOYSA-N Tert-Butylhydroquinone Chemical compound CC(C)(C)C1=CC(O)=CC=C1O BGNXCDMCOKJUMV-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- GTDPSWPPOUPBNX-UHFFFAOYSA-N ac1mqpva Chemical compound CC12C(=O)OC(=O)C1(C)C1(C)C2(C)C(=O)OC1=O GTDPSWPPOUPBNX-UHFFFAOYSA-N 0.000 description 2
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 2
- 150000008064 anhydrides Chemical class 0.000 description 2
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 description 2
- 150000004982 aromatic amines Chemical class 0.000 description 2
- 239000004305 biphenyl Substances 0.000 description 2
- 235000010290 biphenyl Nutrition 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- PMHQVHHXPFUNSP-UHFFFAOYSA-M copper(1+);methylsulfanylmethane;bromide Chemical compound Br[Cu].CSC PMHQVHHXPFUNSP-UHFFFAOYSA-M 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 150000004985 diamines Chemical class 0.000 description 2
- XXBDWLFCJWSEKW-UHFFFAOYSA-N dimethylbenzylamine Chemical compound CN(C)CC1=CC=CC=C1 XXBDWLFCJWSEKW-UHFFFAOYSA-N 0.000 description 2
- 238000006735 epoxidation reaction Methods 0.000 description 2
- 239000011888 foil Substances 0.000 description 2
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 2
- 150000002460 imidazoles Chemical class 0.000 description 2
- 230000001771 impaired effect Effects 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 239000012948 isocyanate Substances 0.000 description 2
- 150000002513 isocyanates Chemical class 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- PCILLCXFKWDRMK-UHFFFAOYSA-N naphthalene-1,4-diol Chemical compound C1=CC=C2C(O)=CC=C(O)C2=C1 PCILLCXFKWDRMK-UHFFFAOYSA-N 0.000 description 2
- OENHRRVNRZBNNS-UHFFFAOYSA-N naphthalene-1,8-diol Chemical compound C1=CC(O)=C2C(O)=CC=CC2=C1 OENHRRVNRZBNNS-UHFFFAOYSA-N 0.000 description 2
- JRNGUTKWMSBIBF-UHFFFAOYSA-N naphthalene-2,3-diol Chemical compound C1=CC=C2C=C(O)C(O)=CC2=C1 JRNGUTKWMSBIBF-UHFFFAOYSA-N 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- UTOPWMOLSKOLTQ-UHFFFAOYSA-N octacosanoic acid Chemical compound CCCCCCCCCCCCCCCCCCCCCCCCCCCC(O)=O UTOPWMOLSKOLTQ-UHFFFAOYSA-N 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 150000003003 phosphines Chemical class 0.000 description 2
- 229920000768 polyamine Polymers 0.000 description 2
- 229920000570 polyether Polymers 0.000 description 2
- 229920001451 polypropylene glycol Polymers 0.000 description 2
- 238000011417 postcuring Methods 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- WGYKZJWCGVVSQN-UHFFFAOYSA-N propylamine Chemical compound CCCN WGYKZJWCGVVSQN-UHFFFAOYSA-N 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 2
- 229960001755 resorcinol Drugs 0.000 description 2
- 239000003566 sealing material Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- USFPINLPPFWTJW-UHFFFAOYSA-N tetraphenylphosphonium Chemical compound C1=CC=CC=C1[P+](C=1C=CC=CC=1)(C=1C=CC=CC=1)C1=CC=CC=C1 USFPINLPPFWTJW-UHFFFAOYSA-N 0.000 description 2
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 description 2
- XFNJVJPLKCPIBV-UHFFFAOYSA-N trimethylenediamine Chemical compound NCCCN XFNJVJPLKCPIBV-UHFFFAOYSA-N 0.000 description 2
- 150000003739 xylenols Chemical class 0.000 description 2
- 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 1
- KMOUUZVZFBCRAM-OLQVQODUSA-N (3as,7ar)-3a,4,7,7a-tetrahydro-2-benzofuran-1,3-dione Chemical compound C1C=CC[C@@H]2C(=O)OC(=O)[C@@H]21 KMOUUZVZFBCRAM-OLQVQODUSA-N 0.000 description 1
- GEYOCULIXLDCMW-UHFFFAOYSA-N 1,2-phenylenediamine Chemical compound NC1=CC=CC=C1N GEYOCULIXLDCMW-UHFFFAOYSA-N 0.000 description 1
- WZCQRUWWHSTZEM-UHFFFAOYSA-N 1,3-phenylenediamine Chemical compound NC1=CC=CC(N)=C1 WZCQRUWWHSTZEM-UHFFFAOYSA-N 0.000 description 1
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 description 1
- BSZXAFXFTLXUFV-UHFFFAOYSA-N 1-phenylethylbenzene Chemical compound C=1C=CC=CC=1C(C)C1=CC=CC=C1 BSZXAFXFTLXUFV-UHFFFAOYSA-N 0.000 description 1
- HECLRDQVFMWTQS-RGOKHQFPSA-N 1755-01-7 Chemical class 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
- AHDSRXYHVZECER-UHFFFAOYSA-N 2,4,6-tris[(dimethylamino)methyl]phenol Chemical compound CN(C)CC1=CC(CN(C)C)=C(O)C(CN(C)C)=C1 AHDSRXYHVZECER-UHFFFAOYSA-N 0.000 description 1
- BGCSUUSPRCDKBQ-UHFFFAOYSA-N 2,4,8,10-tetraoxaspiro[5.5]undecane Chemical compound C1OCOCC21COCOC2 BGCSUUSPRCDKBQ-UHFFFAOYSA-N 0.000 description 1
- BAHPQISAXRFLCL-UHFFFAOYSA-N 2,4-Diaminoanisole Chemical compound COC1=CC=C(N)C=C1N BAHPQISAXRFLCL-UHFFFAOYSA-N 0.000 description 1
- VOZKAJLKRJDJLL-UHFFFAOYSA-N 2,4-diaminotoluene Chemical compound CC1=CC=C(N)C=C1N VOZKAJLKRJDJLL-UHFFFAOYSA-N 0.000 description 1
- YXOKJIRTNWHPFS-UHFFFAOYSA-N 2,5-dimethylhexane-1,6-diamine Chemical compound NCC(C)CCC(C)CN YXOKJIRTNWHPFS-UHFFFAOYSA-N 0.000 description 1
- KMRIWYPVRWEWRG-UHFFFAOYSA-N 2-(6-oxobenzo[c][2,1]benzoxaphosphinin-6-yl)benzene-1,4-diol Chemical compound OC1=CC=C(O)C(P2(=O)C3=CC=CC=C3C3=CC=CC=C3O2)=C1 KMRIWYPVRWEWRG-UHFFFAOYSA-N 0.000 description 1
- BYACHAOCSIPLCM-UHFFFAOYSA-N 2-[2-[bis(2-hydroxyethyl)amino]ethyl-(2-hydroxyethyl)amino]ethanol Chemical compound OCCN(CCO)CCN(CCO)CCO BYACHAOCSIPLCM-UHFFFAOYSA-N 0.000 description 1
- HJXPGCTYMKCLTR-UHFFFAOYSA-N 2-bromo-9,9-diethylfluorene Chemical compound C1=C(Br)C=C2C(CC)(CC)C3=CC=CC=C3C2=C1 HJXPGCTYMKCLTR-UHFFFAOYSA-N 0.000 description 1
- YTWBFUCJVWKCCK-UHFFFAOYSA-N 2-heptadecyl-1h-imidazole Chemical compound CCCCCCCCCCCCCCCCCC1=NC=CN1 YTWBFUCJVWKCCK-UHFFFAOYSA-N 0.000 description 1
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 description 1
- ZCUJYXPAKHMBAZ-UHFFFAOYSA-N 2-phenyl-1h-imidazole Chemical compound C1=CNC(C=2C=CC=CC=2)=N1 ZCUJYXPAKHMBAZ-UHFFFAOYSA-N 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- VEORPZCZECFIRK-UHFFFAOYSA-N 3,3',5,5'-tetrabromobisphenol A Chemical compound C=1C(Br)=C(O)C(Br)=CC=1C(C)(C)C1=CC(Br)=C(O)C(Br)=C1 VEORPZCZECFIRK-UHFFFAOYSA-N 0.000 description 1
- MBWYRMCXWROJMP-UHFFFAOYSA-N 3-(1-aminoethyl)aniline Chemical compound CC(N)C1=CC=CC(N)=C1 MBWYRMCXWROJMP-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
- ZDBWYUOUYNQZBM-UHFFFAOYSA-N 3-(aminomethyl)aniline Chemical compound NCC1=CC=CC(N)=C1 ZDBWYUOUYNQZBM-UHFFFAOYSA-N 0.000 description 1
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- 229940018563 3-aminophenol Drugs 0.000 description 1
- BLBSJBOFNFNGLV-UHFFFAOYSA-N 3-ethyl-oxacyclononadecane-2,19-dione Chemical compound CCC1CCCCCCCCCCCCCCCC(=O)OC1=O BLBSJBOFNFNGLV-UHFFFAOYSA-N 0.000 description 1
- XYUINKARGUCCQJ-UHFFFAOYSA-N 3-imino-n-propylpropan-1-amine Chemical compound CCCNCCC=N XYUINKARGUCCQJ-UHFFFAOYSA-N 0.000 description 1
- RDNPPYMJRALIIH-UHFFFAOYSA-N 3-methylcyclohex-3-ene-1,1,2,2-tetracarboxylic acid Chemical compound CC1=CCCC(C(O)=O)(C(O)=O)C1(C(O)=O)C(O)=O RDNPPYMJRALIIH-UHFFFAOYSA-N 0.000 description 1
- XTBGPYSCCALXIA-UHFFFAOYSA-N 3-phenyl-oxacycloheptadecane-2,17-dione Chemical compound O=C1OC(=O)CCCCCCCCCCCCCC1C1=CC=CC=C1 XTBGPYSCCALXIA-UHFFFAOYSA-N 0.000 description 1
- YBRVSVVVWCFQMG-UHFFFAOYSA-N 4,4'-diaminodiphenylmethane Chemical compound C1=CC(N)=CC=C1CC1=CC=C(N)C=C1 YBRVSVVVWCFQMG-UHFFFAOYSA-N 0.000 description 1
- WRYUIOMVOKUIHL-UHFFFAOYSA-N 4,5-dichloro-3-(dichloromethyl)-6-methylbenzene-1,2-diamine Chemical compound CC1=C(N)C(N)=C(C(Cl)Cl)C(Cl)=C1Cl WRYUIOMVOKUIHL-UHFFFAOYSA-N 0.000 description 1
- CDSPOZXUDJUBEZ-UHFFFAOYSA-N 4-(1-aminoethyl)aniline Chemical compound CC(N)C1=CC=C(N)C=C1 CDSPOZXUDJUBEZ-UHFFFAOYSA-N 0.000 description 1
- XFGDOQVDCBRDDP-UHFFFAOYSA-N 4-(benzenesulfonyl)benzene-1,3-diamine Chemical compound NC1=CC(N)=CC=C1S(=O)(=O)C1=CC=CC=C1 XFGDOQVDCBRDDP-UHFFFAOYSA-N 0.000 description 1
- AZZWZMUXHALBCQ-UHFFFAOYSA-N 4-[(4-hydroxy-3,5-dimethylphenyl)methyl]-2,6-dimethylphenol Chemical compound CC1=C(O)C(C)=CC(CC=2C=C(C)C(O)=C(C)C=2)=C1 AZZWZMUXHALBCQ-UHFFFAOYSA-N 0.000 description 1
- HDPBBNNDDQOWPJ-UHFFFAOYSA-N 4-[1,2,2-tris(4-hydroxyphenyl)ethyl]phenol Chemical compound C1=CC(O)=CC=C1C(C=1C=CC(O)=CC=1)C(C=1C=CC(O)=CC=1)C1=CC=C(O)C=C1 HDPBBNNDDQOWPJ-UHFFFAOYSA-N 0.000 description 1
- KXEPRLUGFAULQX-UHFFFAOYSA-N 4-[2,5-di(propan-2-yl)phenyl]aniline Chemical compound CC(C)C1=CC=C(C(C)C)C(C=2C=CC(N)=CC=2)=C1 KXEPRLUGFAULQX-UHFFFAOYSA-N 0.000 description 1
- UHNUHZHQLCGZDA-UHFFFAOYSA-N 4-[2-(4-aminophenyl)ethyl]aniline Chemical compound C1=CC(N)=CC=C1CCC1=CC=C(N)C=C1 UHNUHZHQLCGZDA-UHFFFAOYSA-N 0.000 description 1
- CJLPIPXJJJUBIV-UHFFFAOYSA-N 4-[3-(4-hydroxyphenoxy)phenoxy]phenol Chemical compound C1=CC(O)=CC=C1OC1=CC=CC(OC=2C=CC(O)=CC=2)=C1 CJLPIPXJJJUBIV-UHFFFAOYSA-N 0.000 description 1
- RLSMYIFSFZLJQZ-UHFFFAOYSA-N 4-[4-(4-hydroxyphenoxy)phenoxy]phenol Chemical compound C1=CC(O)=CC=C1OC(C=C1)=CC=C1OC1=CC=C(O)C=C1 RLSMYIFSFZLJQZ-UHFFFAOYSA-N 0.000 description 1
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- ULKLGIFJWFIQFF-UHFFFAOYSA-N 5K8XI641G3 Chemical compound CCC1=NC=C(C)N1 ULKLGIFJWFIQFF-UHFFFAOYSA-N 0.000 description 1
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- CSHJJWDAZSZQBT-UHFFFAOYSA-N 7a-methyl-4,5-dihydro-3ah-2-benzofuran-1,3-dione Chemical compound C1=CCCC2C(=O)OC(=O)C21C CSHJJWDAZSZQBT-UHFFFAOYSA-N 0.000 description 1
- IXCOKTMGCRJMDR-UHFFFAOYSA-N 9h-fluorene;phenol Chemical compound OC1=CC=CC=C1.OC1=CC=CC=C1.C1=CC=C2CC3=CC=CC=C3C2=C1 IXCOKTMGCRJMDR-UHFFFAOYSA-N 0.000 description 1
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- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical class [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
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- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 description 1
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- 239000002841 Lewis acid Substances 0.000 description 1
- 229920000106 Liquid crystal polymer Polymers 0.000 description 1
- 239000004977 Liquid-crystal polymers (LCPs) Substances 0.000 description 1
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- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000004642 Polyimide Substances 0.000 description 1
- 229910052581 Si3N4 Inorganic materials 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- 239000004809 Teflon Substances 0.000 description 1
- 229920006362 Teflon® Polymers 0.000 description 1
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- XZAHJRZBUWYCBM-UHFFFAOYSA-N [1-(aminomethyl)cyclohexyl]methanamine Chemical compound NCC1(CN)CCCCC1 XZAHJRZBUWYCBM-UHFFFAOYSA-N 0.000 description 1
- FDLQZKYLHJJBHD-UHFFFAOYSA-N [3-(aminomethyl)phenyl]methanamine Chemical compound NCC1=CC=CC(CN)=C1 FDLQZKYLHJJBHD-UHFFFAOYSA-N 0.000 description 1
- ISKQADXMHQSTHK-UHFFFAOYSA-N [4-(aminomethyl)phenyl]methanamine Chemical compound NCC1=CC=C(CN)C=C1 ISKQADXMHQSTHK-UHFFFAOYSA-N 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- LHIJANUOQQMGNT-UHFFFAOYSA-N aminoethylethanolamine Chemical compound NCCNCCO LHIJANUOQQMGNT-UHFFFAOYSA-N 0.000 description 1
- IMUDHTPIFIBORV-UHFFFAOYSA-N aminoethylpiperazine Chemical compound NCCN1CCNCC1 IMUDHTPIFIBORV-UHFFFAOYSA-N 0.000 description 1
- NIDNOXCRFUCAKQ-UHFFFAOYSA-N bicyclo[2.2.1]hept-5-ene-2,3-dicarboxylic acid Chemical compound C1C2C=CC1C(C(=O)O)C2C(O)=O NIDNOXCRFUCAKQ-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- MRNZSTMRDWRNNR-UHFFFAOYSA-N bis(hexamethylene)triamine Chemical compound NCCCCCCNCCCCCCN MRNZSTMRDWRNNR-UHFFFAOYSA-N 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 150000001642 boronic acid derivatives Chemical class 0.000 description 1
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 239000011889 copper foil Substances 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 239000002178 crystalline material Substances 0.000 description 1
- 229920006038 crystalline resin Polymers 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 229960002887 deanol Drugs 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical class C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 description 1
- PVAONLSZTBKFKM-UHFFFAOYSA-N diphenylmethanediol Chemical compound C=1C=CC=CC=1C(O)(O)C1=CC=CC=C1 PVAONLSZTBKFKM-UHFFFAOYSA-N 0.000 description 1
- GPAYUJZHTULNBE-UHFFFAOYSA-N diphenylphosphine Chemical compound C=1C=CC=CC=1PC1=CC=CC=C1 GPAYUJZHTULNBE-UHFFFAOYSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 239000012777 electrically insulating material Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000001125 extrusion Methods 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
- 239000005350 fused silica glass Substances 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 150000002430 hydrocarbons Chemical group 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- 150000007517 lewis acids Chemical class 0.000 description 1
- 229940018564 m-phenylenediamine Drugs 0.000 description 1
- UJNZOIKQAUQOCN-UHFFFAOYSA-N methyl(diphenyl)phosphane Chemical compound C=1C=CC=CC=1P(C)C1=CC=CC=C1 UJNZOIKQAUQOCN-UHFFFAOYSA-N 0.000 description 1
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 1
- VYKXQOYUCMREIS-UHFFFAOYSA-N methylhexahydrophthalic anhydride Chemical compound C1CCCC2C(=O)OC(=O)C21C VYKXQOYUCMREIS-UHFFFAOYSA-N 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 235000013872 montan acid ester Nutrition 0.000 description 1
- LSHROXHEILXKHM-UHFFFAOYSA-N n'-[2-[2-[2-(2-aminoethylamino)ethylamino]ethylamino]ethyl]ethane-1,2-diamine Chemical compound NCCNCCNCCNCCNCCN LSHROXHEILXKHM-UHFFFAOYSA-N 0.000 description 1
- ZETYUTMSJWMKNQ-UHFFFAOYSA-N n,n',n'-trimethylhexane-1,6-diamine Chemical compound CNCCCCCCN(C)C ZETYUTMSJWMKNQ-UHFFFAOYSA-N 0.000 description 1
- RIWRFSMVIUAEBX-UHFFFAOYSA-N n-methyl-1-phenylmethanamine Chemical compound CNCC1=CC=CC=C1 RIWRFSMVIUAEBX-UHFFFAOYSA-N 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 description 1
- RPGWZZNNEUHDAQ-UHFFFAOYSA-N phenylphosphine Chemical compound PC1=CC=CC=C1 RPGWZZNNEUHDAQ-UHFFFAOYSA-N 0.000 description 1
- 150000003014 phosphoric acid esters Chemical class 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229920005586 poly(adipic acid) Polymers 0.000 description 1
- 229920003207 poly(ethylene-2,6-naphthalate) Polymers 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920001707 polybutylene terephthalate Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 239000011112 polyethylene naphthalate Substances 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 238000003918 potentiometric titration Methods 0.000 description 1
- OVARTBFNCCXQKS-UHFFFAOYSA-N propan-2-one;hydrate Chemical compound O.CC(C)=O OVARTBFNCCXQKS-UHFFFAOYSA-N 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000007142 ring opening reaction Methods 0.000 description 1
- JIYNFFGKZCOPKN-UHFFFAOYSA-N sbb061129 Chemical compound O=C1OC(=O)C2C1C1C=C(C)C2C1 JIYNFFGKZCOPKN-UHFFFAOYSA-N 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 125000001174 sulfone group Chemical group 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 125000004434 sulfur atom Chemical group 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- BJQWBACJIAKDTJ-UHFFFAOYSA-N tetrabutylphosphanium Chemical compound CCCC[P+](CCCC)(CCCC)CCCC BJQWBACJIAKDTJ-UHFFFAOYSA-N 0.000 description 1
- FAGUFWYHJQFNRV-UHFFFAOYSA-N tetraethylenepentamine Chemical compound NCCNCCNCCNCCN FAGUFWYHJQFNRV-UHFFFAOYSA-N 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 238000003856 thermoforming Methods 0.000 description 1
- 230000000930 thermomechanical effect Effects 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
- 150000003626 triacylglycerols Chemical class 0.000 description 1
- TUQOTMZNTHZOKS-UHFFFAOYSA-N tributylphosphine Chemical compound CCCCP(CCCC)CCCC TUQOTMZNTHZOKS-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
- 239000002966 varnish Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Landscapes
- Epoxy Resins (AREA)
Description
本発明は、信頼性に優れた半導体封止、積層板、放熱基板等の電気・電子部品用絶縁材料に有用なエポキシ樹脂組成物及びそれを用いた成形物に関する。 The present invention relates to an epoxy resin composition useful as an insulating material for electrical and electronic parts such as a semiconductor sealing, a laminated plate, and a heat dissipation board having excellent reliability, and a molded article using the same.
従来、ダイオード、トランジスタ、集積回路等の電気、電子部品や、半導体装置等の封止方法として、例えばエポキシ樹脂やシリコン樹脂等による封止方法やガラス、金属、セラミック等を用いたハーメチックシール法が採用されていたが、近年では信頼性の向上と共に大量生産が可能な、又、コストメリットのあるトランスファー成形による樹脂封止が主流を占めている。 Conventionally, as a sealing method for electrical and electronic parts such as diodes, transistors, and integrated circuits, and semiconductor devices, for example, a sealing method using an epoxy resin, a silicon resin, or the like, or a hermetic sealing method using glass, metal, ceramic, etc. In recent years, resin sealing by transfer molding, which can be mass-produced with improved reliability and cost-effective, has been the mainstream in recent years.
上記トランスファー成形による樹脂封止方法に用いられる樹脂組成物においては、エポキシ樹脂と、硬化剤としてフェノール樹脂を主成分とする樹脂組成物からなる封止材料が一般的に使用されている。 In the resin composition used for the resin sealing method by the transfer molding, a sealing material made of an epoxy resin and a resin composition mainly containing a phenol resin as a curing agent is generally used.
現在、パワーデバイスなどの素子を保護する目的で使用されるエポキシ樹脂組成物は、素子が放出する多量の熱に対応するため、結晶シリカなどの無機充填材を高密度に充填している。 Currently, an epoxy resin composition used for the purpose of protecting an element such as a power device is filled with an inorganic filler such as crystalline silica at a high density in order to cope with a large amount of heat released from the element.
さらには、近年、パワーデバイスは、ＩＣの技術を組み込んだワンチップで構成されるものやモジュール化されたものなどがあり、封止材料に対する熱放散性、熱膨張性の更なる向上が望まれている。 Furthermore, in recent years, power devices include one-chip devices incorporating IC technology and those made modular, and further improvements in heat dissipation and thermal expansion properties for sealing materials are desired. ing.
これらの要求に対応するべく、熱伝導率を向上するために結晶シリカ、窒化珪素、窒化アルミニウム、球状アルミナ粉末を使用するといった試みがなされているが（特許文献１、２）、無機充填材の含有率を上げていくと成形時の粘度上昇とともに流動性が低下し、成形性が損なわれるといった問題が生じる。従って、単に無機充填材の含有率を高める方法には限界があった。 In order to meet these requirements, attempts have been made to use crystalline silica, silicon nitride, aluminum nitride, and spherical alumina powder to improve thermal conductivity (Patent Documents 1 and 2). Increasing the content causes a problem that the fluidity decreases as the viscosity increases during molding, and the moldability is impaired. Therefore, there is a limit to the method of simply increasing the content of the inorganic filler.
上記背景から、マトリックス樹脂自体の高熱伝導率化による方法も検討されており、例えば、特許文献３および特許文献４には、剛直なメソゲン基を有する液晶性の樹脂を用いた樹脂組成物が提案されている。しかし、これらメソゲン基を有するエポキシ樹脂は、ビフェニル構造、アゾメチン構造等の剛直な構造を有する高結晶性で高融点のエポキシ化合物であるため、エポキシ樹脂組成物とする際の取扱い性に劣る欠点があった。さらには、硬化状態において分子を効率よく配向させるためには強力な磁場をかけて硬化させる等の特別な操作が必要であり、工業的に広く利用するためには設備上の大きな制約があった。また、無機充填材との配合系では、マトリックス樹脂の熱伝導率に比べて無機充填材の熱伝導率が圧倒的に大きく、マトリックス樹脂自体の熱伝導率を高くしても、複合材料としての熱伝導率向上には大きく寄与しないという現実があり、十分な熱伝導率向上効果は得られていなかった。 From the above background, a method of increasing the thermal conductivity of the matrix resin itself has also been studied. For example, Patent Document 3 and Patent Document 4 propose a resin composition using a liquid crystalline resin having a rigid mesogenic group. Has been. However, since these epoxy resins having a mesogenic group are highly crystalline and high melting point epoxy compounds having a rigid structure such as a biphenyl structure or an azomethine structure, they have a disadvantage of poor handling when making an epoxy resin composition. there were. Furthermore, in order to efficiently orient the molecules in the cured state, special operations such as curing by applying a strong magnetic field are necessary, and there are significant equipment limitations for wide industrial use. . In addition, in the compounding system with the inorganic filler, the thermal conductivity of the inorganic filler is overwhelmingly larger than that of the matrix resin, and even if the thermal conductivity of the matrix resin itself is increased, There is a reality that it does not greatly contribute to the improvement of thermal conductivity, and a sufficient effect of improving thermal conductivity has not been obtained.
特許文献５には、４，４’−ビスフェノールＦ型のエポキシ樹脂が示されているが、多官能性のフェノールノボラックを硬化剤として得られる硬化物が実施例として開示されるのみであり、高熱伝導性を発現する高次構造の制御された硬化物を与えるものではない。また、特許文献６には、４，４’−ビスフェノールＦ型エポキシ樹脂とビフェノールのエポキシ樹脂との混合物をビフェノールと反応させて得られる変性エポキシ樹脂が開示されているが、多官能性のフェノールノボラックを硬化剤として得られる硬化物が実施例として開示されるのみであり、高熱伝導率に加えて低吸水性、高耐熱性および低熱膨張性にも効果を発揮する高次構造の制御された硬化物を与えるものではなかった。特許文献７には、結晶性の４，４’−ビスフェノールＦ型のエポキシ樹脂が開示され、それを用いた硬化物は光学的異方性を有することが開示されているが、これは偏光顕微鏡観察において光学的異方性が確認できたものであり、液晶性を示すことを示唆するものではあるが、明確な融点を持つ結晶性の成形物を与えるものではなかった。 Patent Document 5 discloses a 4,4′-bisphenol F type epoxy resin, but only a cured product obtained using a polyfunctional phenol novolac as a curing agent is disclosed as an example, and high heat It does not give a cured product having a higher-order structure that exhibits conductivity. Patent Document 6 discloses a modified epoxy resin obtained by reacting a mixture of a 4,4′-bisphenol F type epoxy resin and a biphenol epoxy resin with biphenol, but it is a polyfunctional phenol novolak. Cured products obtained as a curing agent are only disclosed as examples, and controlled curing of a higher-order structure that exerts effects on low water absorption, high heat resistance and low thermal expansion in addition to high thermal conductivity It did not give anything. Patent Document 7 discloses a crystalline 4,4′-bisphenol F type epoxy resin, and it is disclosed that a cured product using the epoxy resin has optical anisotropy. Although optical anisotropy could be confirmed in the observation, suggesting that it exhibits liquid crystallinity, it did not give a crystalline molded product having a clear melting point.
従って、本発明の目的は、上記問題点を解消し、成形性に優れ、無機充填材と複合化させた場合の熱伝導率が高く、かつ低熱膨張性で耐熱性および耐湿性に優れた成形物を与えるエポキシ樹脂組成物を提供し、更にそれを用いた成形物を提供することである。 Therefore, the object of the present invention is to eliminate the above-mentioned problems, have excellent moldability, high thermal conductivity when combined with an inorganic filler, low thermal expansion, and excellent heat resistance and moisture resistance. It is to provide an epoxy resin composition that gives a product, and further to provide a molded product using the same.
上記課題を解決するために、本発明者らは種々検討を行ったところ、特定のエポキシ樹脂と特定の硬化剤を組み合わせた場合において、硬化後、高次構造の制御された成形物が得られ、高熱伝導性、低熱膨張性、高耐熱性および高耐湿性が特異的に向上することを見出し、本発明に到達した。 In order to solve the above-mentioned problems, the present inventors have made various studies. In the case where a specific epoxy resin and a specific curing agent are combined, a molded product having a higher-order structure is obtained after curing. The present inventors have found that high thermal conductivity, low thermal expansion, high heat resistance and high moisture resistance are specifically improved, and have reached the present invention.
本発明は、 （Ａ）エポキシ樹脂、（Ｂ）硬化剤及び無機充填材を含むエポキシ樹脂組成物において、無機充填材をエポキシ樹脂組成物中に５０〜９５ｗｔ％含有し、エポキシ樹脂の７５ｗｔ％以上を下記一般式（１）、
で表される４，４'−ジフェニルメタン構造を持つエポキシ樹脂とし、硬化剤の７５ｗｔ％以上を下記一般式（２）、
で表される４，４'−ジフェニルメタン構造を持つフェノール性樹脂を含むエポキシ樹脂組成物とし、エポキシ樹脂中のエポキシ基と硬化剤中の官能基が当量比で０．８〜１．５の範囲としたことを特徴とするエポキシ樹脂組成物である。上記当量比は、（エポキシ樹脂中のエポキシ基/硬化剤中の官能基）である。
In the epoxy resin composition containing (A) an epoxy resin , (B) a curing agent and an inorganic filler , the present invention contains 50 to 95 wt% of the inorganic filler in the epoxy resin composition, and 75 wt% or more of the epoxy resin. The following general formula (1),
An epoxy resin having a 4,4′-diphenylmethane structure represented by the following general formula (2): 75 wt% or more of the curing agent:
An epoxy resin composition containing a phenolic resin having a 4,4′-diphenylmethane structure represented by the formula, wherein the epoxy group in the epoxy resin and the functional group in the curing agent are in the range of 0.8 to 1.5 in terms of equivalent ratio An epoxy resin composition characterized by that. The equivalent ratio is (epoxy group in epoxy resin / functional group in curing agent).
上記エポキシ樹脂組成物は、無機充填材を含むことができ、その場合の含有量は５０〜９５ｗｔ％であることがよい。そして、このエポキシ樹脂組成物は、半導体封止用のエポキシ樹脂組成物として優れる。 The epoxy resin composition may contain an inorganic filler, and the content in that case is preferably 50 to 95 wt%. And this epoxy resin composition is excellent as an epoxy resin composition for semiconductor encapsulation.
また、本発明は、上記のエポキシ樹脂組成物をシート状の繊維基材に含浸し半硬化状態としてなるプリプレグである。 Moreover, this invention is a prepreg which impregnates said epoxy resin composition in a sheet-like fiber base material, and is made into a semi-hardened state.
更に、本発明は上記のエポキシ樹脂組成物を加熱、成形して得られる成形物である。この成形物は、次のいずれか１以上を満足することが好ましい。1）熱伝導率が３．５Ｗ／ｍ・Ｋ以上であること、2）走査示差熱分析における融点のピークが１２０℃から２８０℃の範囲にあること、3）走査示差熱分析における樹脂成分換算の吸熱量が５J/ｇ以上であること。 Furthermore, the present invention is a molded product obtained by heating and molding the above epoxy resin composition. This molded article preferably satisfies one or more of the following. 1) The thermal conductivity is 3.5 W / m · K or higher, 2) The melting point peak in the scanning differential thermal analysis is in the range of 120 ° C to 280 ° C, and 3) The resin component conversion in the scanning differential thermal analysis Endothermic amount of 5 J / g or more.
本発明のエポキシ樹脂組成物は、成形性、信頼性に優れ、かつ高熱伝導性、低吸水性、低熱膨張性、高耐熱性に優れた成形物を与え、半導体封止、積層板、放熱基板等の電気・電子部品用絶縁材料として好適に応用され、優れた高放熱性および寸法安定性が発揮される。 The epoxy resin composition of the present invention is excellent in moldability and reliability, and gives a molded product excellent in high thermal conductivity, low water absorption, low thermal expansion, and high heat resistance. It is suitably applied as an insulating material for electrical and electronic parts such as, and exhibits excellent high heat dissipation and dimensional stability.
上記一般式（１）で表されるエポキシ樹脂は、４，４’−ジヒドロキシジフェニルメタンとエピクロルヒドリンを反応させることにより製造することができる。ここで、原料に用いる４，４’−ジヒドロキシジフェニルメタンは、通常、フェノールとホルムアルデヒドとの縮合により合成されるが、その際に、２，４’−ジヒドロキシジフェニルメタン、２，２’−ジヒドロキシジフェニルメタン等の異性体、さらにはフェノール核を３つ以上含有する多量体が副生する。これらの異性体および多量体は許される範囲で含まれていても良いが、原料中の４，４’−ジヒドロキシジフェニルメタンの純度が高いものほど好ましく、通常、８５ｗｔ％以上、好ましくは９０ｗｔ％以上、より好ましくは９５ｗｔ％以上である。 The epoxy resin represented by the general formula (1) can be produced by reacting 4,4'-dihydroxydiphenylmethane and epichlorohydrin. Here, 4,4′-dihydroxydiphenylmethane used as a raw material is usually synthesized by the condensation of phenol and formaldehyde. At that time, 2,4′-dihydroxydiphenylmethane, 2,2′-dihydroxydiphenylmethane, etc. Isomers and multimers containing three or more phenol nuclei are by-produced. These isomers and multimers may be contained within the allowable range, but the higher the purity of 4,4′-dihydroxydiphenylmethane in the raw material, the more preferable, usually 85 wt% or more, preferably 90 wt% or more, More preferably, it is 95 wt% or more.
上記の反応は、通常のエポキシ化反応と同様に行うことができる。例えば、４，４’−ジヒドロキシジフェニルメタンを過剰のエピクロルヒドリンに溶解した後、水酸化ナトリウム、水酸化カリウム等のアルカリ金属水酸化物の存在下に、５０〜１５０℃、好ましくは、６０〜１００℃の範囲で１〜１０時間反応させる方法が挙げられる。この際の、アルカリ金属水酸化物の使用量は、４，４’−ジヒドロキシジフェニルメタン中の水酸基１モルに対して、０．８〜１．２モル、好ましくは、０．９〜１．０モルの範囲である。エピクロルヒドリンは、４，４’−ジヒドロキシジフェニルメタン中の水酸基に対して過剰量が用いられ、通常は、４，４’−ジヒドロキシジフェニルメタン中の水酸基１モルに対して、１．５から１５モルである。反応終了後、過剰のエピクロルヒドリンを留去し、残留物をトルエン、メチルイソブチルケトン等の溶剤に溶解し、濾過し、水洗して無機塩を除去し、次いで溶剤を留去することにより目的のエポキシ樹脂を得ることができる。 Said reaction can be performed similarly to normal epoxidation reaction. For example, after dissolving 4,4′-dihydroxydiphenylmethane in excess epichlorohydrin, in the presence of an alkali metal hydroxide such as sodium hydroxide or potassium hydroxide, 50 to 150 ° C., preferably 60 to 100 ° C. The method of making it react for 1 to 10 hours in the range is mentioned. In this case, the amount of the alkali metal hydroxide used is 0.8 to 1.2 mol, preferably 0.9 to 1.0 mol, based on 1 mol of the hydroxyl group in 4,4′-dihydroxydiphenylmethane. Range. Epichlorohydrin is used in an excess amount relative to the hydroxyl group in 4,4'-dihydroxydiphenylmethane, and is usually 1.5 to 15 mol per 1 mol of hydroxyl group in 4,4'-dihydroxydiphenylmethane. After completion of the reaction, excess epichlorohydrin is distilled off, the residue is dissolved in a solvent such as toluene, methyl isobutyl ketone, filtered, washed with water to remove inorganic salts, and then the target epoxy is removed by distilling off the solvent. A resin can be obtained.
上記一般式（１）において、ｎは０〜１５の数であるが、ｎの値はエポキシ樹脂の合成反応時に用いるエピクロルヒドリンの４，４’−ジヒドロキシジフェニルメタンに対するモル比を変えることにより、容易に調整することができる。ｎの値は、適用する用途に応じて、適宜、選択することができる。例えば、フィラーの高充填率化を求められる半導体封止の用途では、低粘度で結晶性を有するものが好ましく、ｎの平均値として、０．０１〜１．０の範囲にあるものが好適に選択される。これより大きいと粘度が高くなり取り扱い性が低下する。 In the above general formula (1), n is a number from 0 to 15, but the value of n can be easily adjusted by changing the molar ratio of epichlorohydrin to 4,4′-dihydroxydiphenylmethane used in the epoxy resin synthesis reaction. can do. The value of n can be appropriately selected according to the application to be applied. For example, in semiconductor sealing applications where a high filler filling rate is required, those having low viscosity and crystallinity are preferred, and those having an average value of n in the range of 0.01 to 1.0 are preferred. Selected. When larger than this, a viscosity will become high and a handleability will fall.
本発明に用いるエポキシ樹脂は、原料として４，４’−ジヒドロキシジフェニルメタンと別種のフェノール性化合物と混合させたものを用いて合成することができる。この場合の４，４’−ジヒドロキシジフェニルメタンの混合比率は７５ｗｔ％以上、好ましくは８０ｗｔ％以上である。別種のフェノール性化合物に特に制約はないが、一分子中に水酸基を２個有する二官能性のものが好ましい。 The epoxy resin used in the present invention can be synthesized using a raw material mixed with 4,4'-dihydroxydiphenylmethane and another kind of phenolic compound. In this case, the mixing ratio of 4,4'-dihydroxydiphenylmethane is 75 wt% or more, preferably 80 wt% or more. Although there is no restriction | limiting in particular in another kind of phenolic compound, The bifunctional thing which has two hydroxyl groups in 1 molecule is preferable.
本発明に用いるエポキシ樹脂は、一般式（１）で表されるエポキシ樹脂をエポキシ樹脂成分中７５ｗｔ％以上、好ましくは８０ｗｔ％以上、さらに好ましくは９０ｗｔ％以上含む。一般式（１）で表されるエポキシ樹脂のエポキシ当量は、通常１５０から２０，０００の範囲であるが、好適なエポキシ当量は用途に応じて、適宜、選択される。例えば、半導体封止の用途では、無機フィラーの高充填率化および流動性向上の観点からは低粘度性のものが良く、上記一般式（１）においてｎ＝０体を主成分とするエポキシ当量が１６０から２５０の範囲のものが好ましい。また、積層板等の用途においては、フィルム性、可撓性付与の観点から、好ましくは４００〜２０,０００の範囲である。 The epoxy resin used in the present invention contains the epoxy resin represented by the general formula (1) in an epoxy resin component of 75 wt% or more, preferably 80 wt% or more, more preferably 90 wt% or more. The epoxy equivalent of the epoxy resin represented by the general formula (1) is usually in the range of 150 to 20,000, but a suitable epoxy equivalent is appropriately selected according to the application. For example, in semiconductor sealing applications, low viscosity is preferable from the viewpoint of increasing the filling rate of inorganic filler and improving fluidity, and the epoxy equivalent mainly composed of n = 0 isomer in the above general formula (1) Is preferably in the range of 160 to 250. Moreover, in uses, such as a laminated board, Preferably it is the range of 400-20,000 from a viewpoint of film property and flexibility provision.
一般式（１）で表されるエポキシ樹脂の形態も用途に応じて、適宜、選択される。例えば、半導体封止の用途では、粉体で取り扱われる場合が多いため、常温で固形の結晶性のものが好ましく、望ましい融点は５０℃以上であり、好ましい１５０℃での溶融粘度は０．００５から０．１Ｐａ・ｓである。また、積層板等の用途においては、溶剤に溶解させて使用される場合が多いため、エポキシ樹脂の形態に特段の制約はない。 The form of the epoxy resin represented by the general formula (1) is also appropriately selected according to the application. For example, in semiconductor sealing applications, since it is often handled as a powder, a crystalline material that is solid at room temperature is preferable, a desirable melting point is 50 ° C. or higher, and a preferred melt viscosity at 150 ° C. is 0.005. To 0.1 Pa · s. Further, in applications such as laminates, there are many cases where they are used after being dissolved in a solvent, so that there are no particular restrictions on the form of the epoxy resin.
本発明に用いるエポキシ樹脂の純度、特に加水分解性塩素量は、適用する電子部品の信頼性向上の観点より少ない方がよい。特に限定するものではないが、好ましくは１０００ｐｐｍ以下、さらに好ましくは５００ｐｐｍ以下である。なお、本発明でいう加水分解性塩素とは、以下の方法により測定された値をいう。すなわち、試料０．５ｇをジオキサン３０ｍｌに溶解後、１Ｎ−ＫＯＨ、１０ｍｌを加え３０分間煮沸還流した後、室温まで冷却し、さらに８０％アセトン水１００ｍｌを加え、０．００２Ｎ−ＡｇＮＯ3水溶液で電位差滴定を行い得られる値である。 The purity of the epoxy resin used in the present invention, in particular the amount of hydrolyzable chlorine, is better from the viewpoint of improving the reliability of the applied electronic component. Although it does not specifically limit, Preferably it is 1000 ppm or less, More preferably, it is 500 ppm or less. In addition, the hydrolyzable chlorine as used in the field of this invention means the value measured by the following method. That is, the potential difference the sample 0.5g were dissolved in dioxane 30 ml, 1N-KOH, after the added boiled under reflux for 30 minutes 10 ml, cooled to room temperature, 80% aqueous acetone 100ml was added, with 0.002 N-AgNO 3 aqueous solution This is a value obtained by titration.
本発明のエポキシ樹脂組成物には、本発明の必須成分として使用される一般式（１）で表されるエポキシ樹脂以外に、エポキシ樹脂成分として分子中にエポキシ基を２個以上有する通常の他のエポキシ樹脂を併用してもよい。他のエポキシ樹脂の例を挙げれば、ビスフェノールＡ、３，３’，５，５’−テトラメチル−４，４’−ジヒドロキシジフェニルメタン、４，４’−ジヒドロキシジフェニルスルホン、４，４’−ジヒドロキシジフェニルスルフィド、４，４’−ジヒドロキシジフェニルケトン、フルオレンビスフェノール、４，４’−ビフェノール、３，３’，５，５’−テトラメチル−４，４’−ジヒドロキシビフェニル、２，２’−ビフェノール、レゾルシン、カテコール、ｔ−ブチルカテコール、ｔ−ブチルハイドロキノン、１，２−ジヒドロキシナフタレン、１，３−ジヒドロキシナフタレン、１，４−ジヒドロキシナフタレン、1,5‐ジヒドロキシナフタレン、１，６−ジヒドロキシナフタレン、１，７−ジヒドロキシナフタレン、１，８−ジヒドロキシナフタレン、２，３−ジヒドロキシナフタレン、２，４−ジヒドロキシナフタレン、２，５−ジヒドロキシナフタレン、２，６−ジヒドロキシナフタレン、２，７−ジヒドロキシナフタレン、２，８−ジヒドロキシナフタレン、上記ジヒドロキシナフタレンのアリル化物又はポリアリル化物、アリル化ビスフェノールＡ、アリル化ビスフェノールＦ、アリル化フェノールノボラック等の２価のフェノール類、あるいは、フェノールノボラック、ビスフェノールＡノボラック、ｏ−クレゾールノボラック、ｍ−クレゾールノボラック、ｐ−クレゾールノボラック、キシレノールノボラック、ポリ−ｐ−ヒドロキシスチレン、トリス−（４−ヒドロキシフェニル）メタン、１，１，２，２−テトラキス（４−ヒドロキシフェニル）エタン、フルオログリシノール、ピロガロール、ｔ−ブチルピロガロール、アリル化ピロガロール、ポリアリル化ピロガロール、１，２，４−ベンゼントリオール、２，３，４−トリヒドロキシベンゾフェノン、フェノールアラルキル樹脂、ナフトールアラルキル樹脂、ジシクロペンタジエン系樹脂等の３価以上のフェノール類、または、テトラブロモビスフェノールＡ等のハロゲン化ビスフェノール類から誘導されるグリシジルエーテル化物等がある。これら他のエポキシ樹脂は、１種または２種以上を混合して用いることができる。 In addition to the epoxy resin represented by the general formula (1) used as an essential component of the present invention, the epoxy resin composition of the present invention includes other ordinary epoxy resins having two or more epoxy groups in the molecule. These epoxy resins may be used in combination. Examples of other epoxy resins include bisphenol A, 3,3 ′, 5,5′-tetramethyl-4,4′-dihydroxydiphenylmethane, 4,4′-dihydroxydiphenyl sulfone, 4,4′-dihydroxydiphenyl Sulfide, 4,4′-dihydroxydiphenyl ketone, fluorene bisphenol, 4,4′-biphenol, 3,3 ′, 5,5′-tetramethyl-4,4′-dihydroxybiphenyl, 2,2′-biphenol, resorcin Catechol, t-butylcatechol, t-butylhydroquinone, 1,2-dihydroxynaphthalene, 1,3-dihydroxynaphthalene, 1,4-dihydroxynaphthalene, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 1, 7-dihydroxynaphthalene, 1,8-dihydride Xinaphthalene, 2,3-dihydroxynaphthalene, 2,4-dihydroxynaphthalene, 2,5-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, 2,7-dihydroxynaphthalene, 2,8-dihydroxynaphthalene, allyl of the above-mentioned dihydroxynaphthalene Divalent phenols such as fluorinated or polyallylated, allylated bisphenol A, allylated bisphenol F, allylated phenol novolak, or the like, or phenol novolak, bisphenol A novolak, o-cresol novolak, m-cresol novolak, p-cresol novolak Xylenol novolak, poly-p-hydroxystyrene, tris- (4-hydroxyphenyl) methane, 1,1,2,2-tetrakis (4-hydroxyphenyl) ethane, Luologlicinol, pyrogallol, t-butyl pyrogallol, allylated pyrogallol, polyallylated pyrogallol, 1,2,4-benzenetriol, 2,3,4-trihydroxybenzophenone, phenol aralkyl resin, naphthol aralkyl resin, dicyclopentadiene series Examples thereof include triglycerides such as resins and glycidyl ethers derived from halogenated bisphenols such as tetrabromobisphenol A. These other epoxy resins can be used alone or in combination of two or more.
本発明のエポキシ樹脂組成物は、一般式（１）で表されるエポキシ樹脂のエポキシ樹脂組成物中の配合割合をエポキシ樹脂成分中７５ｗｔ％以上であれば、別種のエポキシ樹脂を含んでいても良いが、硬化物とした際の熱伝導率の向上の観点から、二官能性のエポキシ樹脂の合計量が好ましくは８０ｗｔ％以上、より好ましくは９０ｗｔ％以上とすることが良い。 The epoxy resin composition of the present invention may contain another type of epoxy resin as long as the blending ratio of the epoxy resin represented by the general formula (1) in the epoxy resin composition is 75 wt% or more in the epoxy resin component. Although it is good, from the viewpoint of improving the thermal conductivity when a cured product is used, the total amount of the bifunctional epoxy resin is preferably 80 wt% or more, more preferably 90 wt% or more.
一般式（１）のエポキシ樹脂以外のものとして特に好ましいものは、下記一般式（３）で表されるビスフェノール系エポキシ樹脂である。 Particularly preferred as other than the epoxy resin of the general formula (1) is a bisphenol-based epoxy resin represented by the following general formula (3).
上記のエポキシ樹脂は、４，４’−ジヒドロキシビフェニル、３，３’，５，５’−テトラメチル−４，４’−ジヒドロキシビフェニル、３，３’，５，５’−テトラメチル−4,4'−ジヒドロキシジフェニルメタン、４，４’−ジヒドロキシベンゾフェノン、４，４’−ジヒドロキシジフェニルエーテル、４，４’−ジヒドロキシジフェニルスルフィドを原料として、通常のエポキシ化反応を行うことで合成することができる。これらのエポキシ樹脂は、原料段階で４，４’−ジヒドロキシジフェニルメタンと混合させたものを用いて合成することができる。これらのなかで特に好ましいものは、４，４’−ジヒドロキシビフェニル、４，４’−ジヒドロキシジフェニルエーテルから合成されるエポキシ樹脂であり、取扱性に優れた結晶性のエポキシ樹脂を与えるとともに、熱伝導性にも優れた成形物を与えることができる。 The above epoxy resins are 4,4′-dihydroxybiphenyl, 3,3 ′, 5,5′-tetramethyl-4,4′-dihydroxybiphenyl, 3,3 ′, 5,5′-tetramethyl-4, It can be synthesized by performing a normal epoxidation reaction using 4′-dihydroxydiphenylmethane, 4,4′-dihydroxybenzophenone, 4,4′-dihydroxydiphenyl ether, and 4,4′-dihydroxydiphenyl sulfide as raw materials. These epoxy resins can be synthesized using those mixed with 4,4'-dihydroxydiphenylmethane at the raw material stage. Particularly preferred among these are epoxy resins synthesized from 4,4′-dihydroxybiphenyl and 4,4′-dihydroxydiphenyl ether, which gives a crystalline epoxy resin with excellent handling properties and thermal conductivity. In addition, an excellent molded product can be provided.
本発明のエポキシ樹脂組成物は、必須成分として、硬化剤として上記一般式（２）で表されるフェノール性樹脂を８０ｗｔ％以上含むもの使用する。ここで、好ましくはｍが０の４，４’−ジヒドロキシジフェニルメタンである。４，４’−ジヒドロキシジフェニルメタンは、エポキシ樹脂の原料として使用したものと同様に、２，４’−ジヒドロキシジフェニルメタン、２，２’−ジヒドロキシジフェニルメタン等の異性体、さらにはフェノール核を３つ以上含有する多量体を許される範囲で含まれていても良いが、硬化剤中の４，４’−ジヒドロキシジフェニルメタンの純度が高いものほど好ましく、通常、８５ｗｔ％以上、好ましくは９０ｗｔ％以上、より好ましくは９５ｗｔ％以上である。 The epoxy resin composition of the present invention uses, as an essential component, one containing 80 wt% or more of the phenolic resin represented by the general formula (2) as a curing agent. Here, m is preferably 4,4'-dihydroxydiphenylmethane having 0. 4,4'-dihydroxydiphenylmethane contains isomers such as 2,4'-dihydroxydiphenylmethane and 2,2'-dihydroxydiphenylmethane, and more than three phenol nuclei, similar to those used as raw materials for epoxy resins However, the higher the purity of 4,4′-dihydroxydiphenylmethane in the curing agent, the more preferable, usually 85 wt% or more, preferably 90 wt% or more, more preferably It is 95 wt% or more.
また、本発明のエポキシ樹脂組成物を積層材料用のプリプレグとして応用する場合は、上記一般式（２）において、平均値としてｍが０より大きい数のフェノール性樹脂が好適に使用される。この場合の好ましいｍの値は平均値として１〜１５であり、より好ましくは、２〜１５である。ｍの値が０より大きい数のフェノール性樹脂の製法は、限定されるものではないが、例えば、上記一般式（１）のエポキシ樹脂に対して、過剰量の４，４’−ジヒドロキシジフェニルメタンを反応させる手法を挙げることができる。あるいは、４，４’−ジヒドロキシジフェニルメタンと４，４’−ジヒドロキシジフェニルメタン中の水酸基１モルに対して、１モル以下のエピクロロヒドリンを反応させることにより合成することもできる。 Moreover, when applying the epoxy resin composition of this invention as a prepreg for laminated | multilayer material, in the said General formula (2), the number whose m is larger than 0 is suitably used as an average value. The preferable value of m in this case is 1 to 15 as an average value, and more preferably 2 to 15. The method for producing a phenolic resin having a value of m greater than 0 is not limited. For example, an excessive amount of 4,4′-dihydroxydiphenylmethane is added to the epoxy resin of the general formula (1). A method of reacting can be mentioned. Alternatively, it can be synthesized by reacting 1 mol or less of epichlorohydrin with 1 mol of hydroxyl group in 4,4'-dihydroxydiphenylmethane and 4,4'-dihydroxydiphenylmethane.
一般式（２）で表されるフェノール性樹脂の水酸基当量は、通常１００から２０，０００の範囲であるが、エポキシ樹脂と同様に、好適な水酸基当量は用途に応じて、適宜、選択される。例えば、半導体封止の用途では、無機フィラーの高充填率化および流動性向上の観点からは低粘度性のものが良く、上記一般式（２）においてｍ＝０体を主成分とする水酸基当量が１００から２００の範囲のものが好ましい。また、積層板等の用途においては、フィルム性、可撓性付与の観点から、好ましくは２００〜２０,０００の範囲である。この水酸基当量は、２種類以上のエポキシ樹脂を使用する場合においてもこれを満足することが好ましく、この場合、水酸基当量は、全重量（g）／水酸基（モル）で計算される。 The hydroxyl group equivalent of the phenolic resin represented by the general formula (2) is usually in the range of 100 to 20,000, but a suitable hydroxyl group equivalent is appropriately selected depending on the application, as with the epoxy resin. . For example, in semiconductor sealing applications, low viscosity is preferable from the viewpoint of increasing the filling rate of inorganic filler and improving fluidity. In the above general formula (2), the hydroxyl equivalent equivalent having m = 0 as the main component Is preferably in the range of 100 to 200. Moreover, in uses, such as a laminated board, Preferably it is the range of 200-20,000 from a viewpoint of film property and flexibility provision. This hydroxyl equivalent is preferably satisfied even when two or more types of epoxy resins are used. In this case, the hydroxyl equivalent is calculated by the total weight (g) / hydroxyl group (mol).
本発明のエポキシ樹脂組成物に用いる硬化剤としては、本発明の必須成分である一般式（２）で表されるフェノール性樹脂以外に、一般的にエポキシ樹脂硬化剤として知られているものを必要に応じて組み合わせることができるが、好ましくはフェノール性水酸基を有するフェノール系硬化剤が選択される。 As the curing agent used in the epoxy resin composition of the present invention, in addition to the phenolic resin represented by the general formula (2), which is an essential component of the present invention, what is generally known as an epoxy resin curing agent is used. Although it can combine as needed, Preferably the phenol type hardening | curing agent which has a phenolic hydroxyl group is selected.
その具体例として、ビスフェノールＡ、ビスフェノールＦ、４，４’−ジヒドロキシジフェニルエーテル、１，４−ビス（4−ヒドロキシフェノキシ）ベンゼン、１，３−ビス（４−ヒドロキシフェノキシ）ベンゼン、４，４’−ジヒドロキシジフェニルスルフィド、４，４’−ジヒドロキシジフェニルケトン、４，４’−ジヒドロキシジフェニルスルホン、４，４’−ジヒドロキシビフェニル、２，２’−ジヒドロキシビフェニル、１０−（２，５−ジヒドロキシフェニル）−１０Ｈ−９−オキサ−１０−ホスファフェナンスレン−１０−オキサイド、フェノールノボラック、ビスフェノールＡノボラック、ｏ−クレゾールノボラック、ｍ−クレゾールノボラック、ｐ−クレゾールノボラック、キシレノールノボラック、ポリ−ｐ−ヒドロキシスチレン、ハイドロキノン、レゾルシン、カテコール、ｔ−ブチルカテコール、ｔ−ブチルハイドロキノン、フルオログリシノール、ピロガロール、ｔ‐ブチルピロガロール、アリル化ピロガロール、ポリアリル化ピロガロール、１，２，４−ベンゼントリオール、２，３，４−トリヒドロキシベンゾフェノン、１，２−ジヒドロキシナフタレン、１，３−ジヒドロキシナフタレン、１，４−ジヒドロキシナフタレン、１，５−ジヒドロキシナフタレン、１，６−ジヒドロキシナフタレン、１，７−ジヒドロキシナフタレン、１，８−ジヒドロキシナフタレン、２，３−ジヒドロキシナフタレン、２，４−ジヒドロキシナフタレン、２，５−ジヒドロキシナフタレン、２，６−ジヒドロキシナフタレン、２，７−ジヒドロキシナフタレン、２，８−ジヒドロキシナフタレン、上記ジヒドロキシナフタレンのアリル化物又はポリアリル化物、アリル化ビスフェノールＡ、アリル化ビスフェノールＦ、アリル化フェノールノボラック、アリル化ピロガロール等を挙げることができる。 Specific examples thereof include bisphenol A, bisphenol F, 4,4′-dihydroxydiphenyl ether, 1,4-bis (4-hydroxyphenoxy) benzene, 1,3-bis (4-hydroxyphenoxy) benzene, 4,4′- Dihydroxydiphenyl sulfide, 4,4′-dihydroxydiphenyl ketone, 4,4′-dihydroxydiphenyl sulfone, 4,4′-dihydroxybiphenyl, 2,2′-dihydroxybiphenyl, 10- (2,5-dihydroxyphenyl) -10H -9-oxa-10-phosphaphenanthrene-10-oxide, phenol novolak, bisphenol A novolak, o-cresol novolak, m-cresol novolak, p-cresol novolak, xylenol novolak, poly-p-hydroxy Cystyrene, hydroquinone, resorcin, catechol, t-butylcatechol, t-butylhydroquinone, fluoroglycinol, pyrogallol, t-butyl pyrogallol, allylated pyrogallol, polyallylated pyrogallol, 1,2,4-benzenetriol, 2,3, 4-trihydroxybenzophenone, 1,2-dihydroxynaphthalene, 1,3-dihydroxynaphthalene, 1,4-dihydroxynaphthalene, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 1,7-dihydroxynaphthalene, 1, 8-dihydroxynaphthalene, 2,3-dihydroxynaphthalene, 2,4-dihydroxynaphthalene, 2,5-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, 2,7-dihydroxynaphthalene, , Mention may be made of 8-dihydroxynaphthalene, allylated or polyallyl compound of the dihydroxynaphthalene, allylated bisphenol A, allylated bisphenol F, allylated phenol novolak, allylated pyrogallol.
本発明のエポキシ樹脂組成物は、一般式（２）で表されるフェノール性樹脂の配合割合が硬化剤成分中７５ｗｔ％以上であれば、別種のフェノール性化合物（樹脂）を含んでいても良いが、硬化物とした際の熱伝導率の向上の観点から、二官能性のフェノール性化合物（樹脂）の合計量が好ましくは８０ｗｔ％以上、より好ましくは９０ｗｔ％以上とすることが良い。 The epoxy resin composition of the present invention may contain another type of phenolic compound (resin) as long as the blending ratio of the phenolic resin represented by the general formula (2) is 75 wt% or more in the curing agent component. However, from the viewpoint of improving the thermal conductivity when a cured product is obtained, the total amount of the bifunctional phenolic compound (resin) is preferably 80 wt% or more, more preferably 90 wt% or more.
一般式（２）以外のフェノール性化合物（樹脂）として特に好ましいものは、具体的にはヒドロキノン、４，４’−ジヒドロキシビフェニル、４，４’−ジヒドロキシジフェニルエーテル、１，４−ビス（４−ヒドロキシフェノキシ）ベンゼン、４，４’−ジヒドロキシジフェニルスルフィド、１，５−ナフタレンジオール、２，７−ナフタレンジオール、２，６−ナフタレンジオールを例示することができる。これら二官能性フェノール化合物あるいはフェノール性樹脂の使用量は、硬化剤成分中２５ｗｔ％以下であるが、好ましくは２０ｗｔ％以下である。 Particularly preferred as the phenolic compound (resin) other than the general formula (2) are specifically hydroquinone, 4,4′-dihydroxybiphenyl, 4,4′-dihydroxydiphenyl ether, 1,4-bis (4-hydroxy). Phenoxy) benzene, 4,4′-dihydroxydiphenyl sulfide, 1,5-naphthalenediol, 2,7-naphthalenediol, and 2,6-naphthalenediol can be exemplified. The amount of these bifunctional phenolic compounds or phenolic resins used is 25 wt% or less in the curing agent component, preferably 20 wt% or less.
本発明のエポキシ樹脂組成物に用いる硬化剤としては、上記のフェノール系硬化剤以外に、硬化剤として一般的に知られている他の硬化剤を併用して用いることができる。例を挙げれば、アミン系硬化剤、酸無水物系硬化剤、フェノール系硬化剤、ポリメルカプタン系硬化剤、ポリアミノアミド系硬化剤、イソシアネート系硬化剤、ブロックイソシアネート系硬化剤等が挙げられる。これらの硬化剤の配合量は、上記範囲内であって、配合する硬化剤の種類や得られる熱伝導性エポキシ樹脂成形体の物性を考慮して適宜設定すればよい。 As a hardening | curing agent used for the epoxy resin composition of this invention, the other hardening | curing agent generally known as a hardening | curing agent other than said phenol type hardening | curing agent can be used together. Examples include amine curing agents, acid anhydride curing agents, phenolic curing agents, polymercaptan curing agents, polyaminoamide curing agents, isocyanate curing agents, block isocyanate curing agents, and the like. The blending amount of these curing agents is within the above range, and may be appropriately set in consideration of the kind of the curing agent to be blended and the physical properties of the obtained heat conductive epoxy resin molding.
アミン系硬化剤の具体例としては、脂肪族アミン類、ポリエーテルポリアミン類、脂環式アミン類、芳香族アミン類等が挙げられる。脂肪族アミン類としては、エチレンジアミン、１，３−ジアミノプロパン、１，４−ジアミノプロパン、ヘキサメチレンジアミン、２，５−ジメチルヘキサメチレンジアミン、トリメチルヘキサメチレンジアミン、ジエチレントリアミン、イミノビスプロピルアミン、ビス（ヘキサメチレン）トリアミン、トリエチレンテトラミン、テトラエチレンペンタミン、ペンタエチレンヘキサミン、Ｎ‐ヒドロキシエチルエチレンジアミン、テトラ（ヒドロキシエチル）エチレンジアミン等が挙げられる。ポリエーテルポリアミン類としては、トリエチレングリコールジアミン、テトラエチレングリコールジアミン、ジエチレングリコールビス（プロピルアミン）、ポリオキシプロピレンジアミン、ポリオキシプロピレントリアミン類等が挙げられる。脂環式アミン類としては、イソホロンジアミン、メタセンジアミン、Ｎ−アミノエチルピペラジン、ビス（４−アミノ−３−メチルジシクロヘキシル）メタン、ビス（アミノメチル）シクロヘキサン、３，９−ビス（3‐アミノプロピル）２，４，８，１０−テトラオキサスピロ（５，５）ウンデカン、ノルボルネンジアミン等が挙げられる。芳香族アミン類としては、テトラクロロ−ｐ−キシレンジアミン、ｍ−キシレンジアミン、ｐ−キシレンジアミン、ｍ−フェニレンジアミン、ｏ−フェニレンジアミン、ｐ−フェニレンジアミン、２，４−ジアミノアニゾール、２，４−トルエンジアミン、2,4‐ジアミノジフェニルメタン、４，４’−ジアミノジフェニルメタン、４，４’−ジアミノ−１，２−ジフェニルエタン、２，４−ジアミノジフェニルスルホン、４，４’−ジアミノジフェニルスルホン、ｍ−アミノフェノール、ｍ−アミノベンジルアミン、ベンジルジメチルアミン、２−ジメチルアミノメチル）フェノール、トリエタノールアミン、メチルベンジルアミン、α−（ｍ−アミノフェニル）エチルアミン、α−（ｐ−アミノフェニル）エチルアミン、ジアミノジエチルジメチルジフェニルメタン、α，α'−ビス（４−アミノフェニル）−ｐ−ジイソプロピルベンゼン等が挙げられる。 Specific examples of the amine curing agent include aliphatic amines, polyether polyamines, alicyclic amines, aromatic amines and the like. Aliphatic amines include ethylenediamine, 1,3-diaminopropane, 1,4-diaminopropane, hexamethylenediamine, 2,5-dimethylhexamethylenediamine, trimethylhexamethylenediamine, diethylenetriamine, iminobispropylamine, bis ( Hexamethylene) triamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, N-hydroxyethylethylenediamine, tetra (hydroxyethyl) ethylenediamine and the like. Examples of polyether polyamines include triethylene glycol diamine, tetraethylene glycol diamine, diethylene glycol bis (propylamine), polyoxypropylene diamine, and polyoxypropylene triamines. Cycloaliphatic amines include isophorone diamine, metacene diamine, N-aminoethylpiperazine, bis (4-amino-3-methyldicyclohexyl) methane, bis (aminomethyl) cyclohexane, 3,9-bis (3-amino). Propyl) 2,4,8,10-tetraoxaspiro (5,5) undecane, norbornenediamine and the like. Aromatic amines include tetrachloro-p-xylenediamine, m-xylenediamine, p-xylenediamine, m-phenylenediamine, o-phenylenediamine, p-phenylenediamine, 2,4-diaminoanisole, 2, 4-toluenediamine, 2,4-diaminodiphenylmethane, 4,4'-diaminodiphenylmethane, 4,4'-diamino-1,2-diphenylethane, 2,4-diaminodiphenylsulfone, 4,4'-diaminodiphenylsulfone , M-aminophenol, m-aminobenzylamine, benzyldimethylamine, 2-dimethylaminomethyl) phenol, triethanolamine, methylbenzylamine, α- (m-aminophenyl) ethylamine, α- (p-aminophenyl) Ethylamine, diaminodiethyldi Examples include methyldiphenylmethane, α, α′-bis (4-aminophenyl) -p-diisopropylbenzene.
酸無水物系硬化剤の具体例としては、ドデセニル無水コハク酸、ポリアジピン酸無水物、ポリアゼライン酸無水物、ポリセバシン酸無水物、ポリ（エチルオクタデカン二酸）無水物、ポリ（フェニルヘキサデカン二酸）無水物、メチルテトラヒドロ無水フタル酸、メチルヘキサヒドロ無水フタル酸、ヘキサヒドロ無水フタル酸、無水メチルハイミック酸、テトラヒドロ無水フタル酸、トリアルキルテトラヒドロ無水フタル酸、メチルシクロヘキセンジカルボン酸無水物、メチルシクロヘキセンテトラカルボン酸無水物、無水フタル酸、無水トリメリット酸、無水ピロメリット酸、ベンゾフェノンテトラカルボン酸無水物、エチレングリコールビストリメリテート、無水ヘット酸、無水ナジック酸、無水メチルナジック酸、５−（２，５−ジオキソテトラヒドロ−３−フラニル）−３−メチル−３−シクロヘキサン−１，２−ジカルボン酸無水物、３，４−ジカルボキシ−１，２，３，４−テトラヒドロ−１−ナフタレンコハク酸二無水物、１−メチル−ジカルボキシ−１，２，３，４−テトラヒドロ−１−ナフタレンコハク酸二無水物等が挙げられる。 Specific examples of acid anhydride curing agents include dodecenyl succinic anhydride, polyadipic acid anhydride, polyazeline acid anhydride, polysebacic acid anhydride, poly (ethyloctadecanedioic acid) anhydride, poly (phenylhexadecanedioic acid) Anhydride, Methyltetrahydrophthalic anhydride, Methylhexahydrophthalic anhydride, Hexahydrophthalic anhydride, Methylhymic anhydride, Tetrahydrophthalic anhydride, Trialkyltetrahydrophthalic anhydride, Methylcyclohexene dicarboxylic anhydride, Methylcyclohexene tetracarboxylic Acid anhydride, phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, benzophenone tetracarboxylic anhydride, ethylene glycol bistrimellitic acid, anhydrous het acid, anhydrous nadic acid, anhydrous methyl nadic acid, 5- (2,5 -Geo Sotetrahydro-3-furanyl) -3-methyl-3-cyclohexane-1,2-dicarboxylic anhydride, 3,4-dicarboxy-1,2,3,4-tetrahydro-1-naphthalene succinic dianhydride 1-methyl-dicarboxy-1,2,3,4-tetrahydro-1-naphthalene succinic dianhydride and the like.
本発明のエポキシ樹脂組成物では、エポキシ樹脂と硬化剤の配合比率は、エポキシ基と硬化剤中の官能基が当量比で０．８〜１．５の範囲である。この範囲外では硬化後も未反応のエポキシ基、又は硬化剤中の官能基が残留し、電気絶縁材料としての信頼性が低下するため好ましくない。 In the epoxy resin composition of this invention, the compounding ratio of an epoxy resin and a hardening | curing agent is the range of 0.8-1.5 by the equivalent ratio of the functional group in an epoxy group and a hardening | curing agent. Outside this range, an unreacted epoxy group or a functional group in the curing agent remains even after curing, which is not preferable because reliability as an electrical insulating material is lowered.
本発明のエポキシ樹脂組成物には、無機充填材を添加してもよい。無機充填材の添加量は、エポキシ樹脂組成物に対して５０〜９５ｗｔ％であるが、好ましくは８０〜９５ｗｔ％である。これより少ないと高熱伝導性、低熱膨張性、高耐熱性等の効果が十分に発揮されない。これらの効果は、無機充填材の添加量が多いほどよいが、その体積分率に応じて向上するものではなく、特定の添加量から飛躍的に向上する。これらの物性は、高分子状態での高次構造が制御された効果によるものであり、この高次構造が主に無機充填材表面で達成されることから、特定量の無機充填材を必要とするものであると考えられる。一方、無機充填材の添加量がこれより多いと粘度が高くなり、成形性が悪化するため好ましくない。 An inorganic filler may be added to the epoxy resin composition of the present invention. The addition amount of the inorganic filler is 50 to 95 wt% with respect to the epoxy resin composition, but preferably 80 to 95 wt%. If it is less than this, effects such as high thermal conductivity, low thermal expansion, and high heat resistance will not be sufficiently exhibited. These effects are better as the added amount of the inorganic filler is larger. However, the effect is not improved according to the volume fraction, but dramatically improved from a specific added amount. These physical properties are due to the effect of controlling the higher order structure in the polymer state, and since this higher order structure is achieved mainly on the surface of the inorganic filler, a specific amount of inorganic filler is required. It is thought to be. On the other hand, when the added amount of the inorganic filler is larger than this, the viscosity becomes high and the moldability deteriorates, which is not preferable.
本発明に用いる無機充填材は球状のものが好ましく、断面が楕円上であるものも含めて球状であれば特に限定されるものではないが、流動性改善の観点からは、極力真球状に近いものであることが特に好ましい。これにより、面心立方構造や六方稠密構造等の最密充填構造をとり易く、充分な充填量を得ることができる。球形でない場合、充填量が増えると充填材同士の摩擦が増え、上記の上限に達する前に流動性が極端に低下して粘度が高くなり、成形性が悪化する。 The inorganic filler used in the present invention is preferably spherical and is not particularly limited as long as it has a spherical shape including those having a cross section of an ellipse. However, from the viewpoint of improving fluidity, it is as close to a true sphere as possible. It is particularly preferable that Thereby, it is easy to take a close-packed structure such as a face-centered cubic structure or a hexagonal close-packed structure, and a sufficient filling amount can be obtained. When the amount is not spherical, the friction between the fillers increases as the filling amount increases, and before reaching the above upper limit, the fluidity is extremely lowered to increase the viscosity and the moldability is deteriorated.
熱伝導率向上の観点からは、無機充填材のうち、熱伝導率が５Ｗ／ｍ・Ｋ以上である無機充填材を５０ｗｔ％以上使用することが好ましく、アルミナ、窒化アルミニウム、結晶シリカ等が好適に使用される。これらの中で特に好ましいものは、球状アルミナである。その他、必要に応じて形状に関係なく無定形無機充填材、例えば溶融シリカ、結晶シリカなどを併用しても良い。 From the viewpoint of improving the thermal conductivity, it is preferable to use 50 wt% or more of an inorganic filler having a thermal conductivity of 5 W / m · K or more among inorganic fillers, and alumina, aluminum nitride, crystalline silica, etc. are preferable. Used for. Of these, spherical alumina is particularly preferable. In addition, an amorphous inorganic filler such as fused silica or crystalline silica may be used in combination, if necessary, regardless of the shape.
無機充填材の平均粒径は３０μｍ以下であることが好ましい。平均粒径がこれより大きいとエポキシ樹脂組成物の流動性が損なわれ、また強度も低下するため好ましくない。 The average particle size of the inorganic filler is preferably 30 μm or less. If the average particle size is larger than this, the fluidity of the epoxy resin composition is impaired, and the strength is also lowered, which is not preferable.
また、無機充填材は、ガラス繊維等の繊維状基材、あるいは繊維状基材と粒子状無機充填材を併用したものであっても良い。繊維状基材と複合化させる場合には、溶剤を使用しワニスとして、シート状とした繊維状基材に含浸し乾燥して本発明のプリプレグとすることができる。このようにして作成したプリプレグは、銅箔、アルミニウム箔、ステンレス箔等の金属基材、ポリエチレンテレフタレート、ポリブチレンテレフタレート、ポリエチレンナフタレート、液晶ポリマー、ポリアミド、ポリイミド、テフロン（登録商標）等の高分子基材と積層し、加熱成形させることにより、プリント配線板、放熱基板等として応用することができる。 The inorganic filler may be a fibrous base material such as glass fiber, or a combination of a fibrous base material and a particulate inorganic filler. In the case of compounding with a fibrous base material, it is possible to obtain a prepreg of the present invention by using a solvent as a varnish and impregnating the sheet-like fibrous base material and drying it. The prepreg thus prepared is made of a metal substrate such as copper foil, aluminum foil or stainless steel foil, or a polymer such as polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, liquid crystal polymer, polyamide, polyimide or Teflon (registered trademark). It can be applied as a printed wiring board, a heat radiating substrate, etc. by laminating with a base material and thermoforming.
本発明のエポキシ樹脂組成物には、従来より公知の硬化促進剤を配合することができる。例を挙げれば、アミン類、イミダゾール類、有機ホスフィン類、ルイス酸等があり、具体的には、1，8−ジアザビシクロ（５，４，０）ウンデセン−７、トリエチレンジアミン、ベンジルジメチルアミン、トリエタノールアミン、ジメチルアミノエタノール、トリス（ジメチルアミノメチル）フェノールなどの三級アミン、２−メチルイミダゾール、２−フェニルイミダゾール、２−フェニル−４−メチルイミダゾール、２−へプタデシルイミダゾールなどのイミダゾール類、トリブチルホスフィン、メチルジフェニルホスフイン、トリフェニルホスフィン、ジフェニルホスフィン、フェニルホスフィンなどの有機ホスフィン類、テトラフェニルホスホニウム・テトラフェニルボレート、テトラフェニルホスホニウム・エチルトリフェニルボレート、テトラブチルホスホニウム・テトラブチルボレートなどのテトラ置換ホスホニウム・テトラ置換ボレート、２−エチル−４−メチルイミダゾール・テトラフェニルポレート、Ｎ−メチルモルホリン・テトラフェニルポレートなどのテトラフェニルボロン塩などがある。添加量としては、通常、エポキシ樹脂１００重量部に対して、０．２〜１０重量部の範囲である。これらは単独で用いても良く、併用しても良い。 A conventionally well-known hardening accelerator can be mix | blended with the epoxy resin composition of this invention. Examples include amines, imidazoles, organic phosphines, Lewis acids, etc., specifically 1,8-diazabicyclo (5,4,0) undecene-7, triethylenediamine, benzyldimethylamine, Tertiary amines such as ethanolamine, dimethylaminoethanol, tris (dimethylaminomethyl) phenol, imidazoles such as 2-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 2-heptadecylimidazole, Organic phosphines such as tributylphosphine, methyldiphenylphosphine, triphenylphosphine, diphenylphosphine, phenylphosphine, tetraphenylphosphonium / tetraphenylborate, tetraphenylphosphonium / ethyltriphenylborate Tetra-substituted phosphonium / tetra-substituted borate such as tetrabutylphosphonium / tetrabutyl borate, tetraphenylboron salts such as 2-ethyl-4-methylimidazole / tetraphenylporate, N-methylmorpholine / tetraphenylporate, etc. . As addition amount, it is the range of 0.2-10 weight part normally with respect to 100 weight part of epoxy resins. These may be used alone or in combination.
上記硬化触媒の添加量は、エポキシ樹脂（難燃剤としての含ハロゲンエポキシ樹脂を含む）と硬化剤の合計に対して、０．１〜１０．０ｗｔ％が好ましい。０．１ｗｔ％未満では成形時間が長くなって成形時の剛性低下による作業性の低下をもたらし、逆に１０．０ｗｔ％を超えると成形途中で硬化が進んでしまい、未充填が発生し易くなる。 The addition amount of the curing catalyst is preferably 0.1 to 10.0 wt% with respect to the total of the epoxy resin (including the halogen-containing epoxy resin as a flame retardant) and the curing agent. If it is less than 0.1 wt%, the molding time becomes long, resulting in a decrease in workability due to a reduction in rigidity at the time of molding. Conversely, if it exceeds 10.0 wt%, curing proceeds during molding and unfilling is likely to occur. .
本発明のエポキシ樹脂組成物においては、エポキシ樹脂組成物に一般的に用いられる離型剤としてワックスが使用できる。ワックスとしては、例えばステアリン酸、モンタン酸、モンタン酸エステル、リン酸エステル等が使用可能である。 In the epoxy resin composition of the present invention, a wax can be used as a release agent generally used in an epoxy resin composition. As the wax, for example, stearic acid, montanic acid, montanic acid ester, phosphoric acid ester and the like can be used.
本発明のエポキシ樹脂組成物においては、無機充填材と樹脂成分の接着力を向上させるため、エポキシ樹脂組成物に一般的に用いられるカップリング剤を用いることができる。カップリング剤としては、例えばエポキシシランが使用可能である。カップリング剤の添加量は、エポキシ樹脂組成物に対して、０．１〜２．０ｗｔ％が好ましい。０．１ｗｔ％未満では樹脂と基材のなじみが悪く成形性が悪くなり、逆に２．０ｗｔ％を超えると連続成形性での成形品汚れが生じる。 In the epoxy resin composition of this invention, in order to improve the adhesive force of an inorganic filler and a resin component, the coupling agent generally used for an epoxy resin composition can be used. As the coupling agent, for example, epoxy silane can be used. The addition amount of the coupling agent is preferably 0.1 to 2.0 wt% with respect to the epoxy resin composition. If it is less than 0.1 wt%, the resin and the base material will not be well-matched, and the moldability will be poor. Conversely, if it exceeds 2.0 wt%, the molded product will become dirty with continuous moldability.
また本発明のエポキシ樹脂組成物には、成形時の流動性改良およびリードフレーム等の基材との密着性向上の観点より、熱可塑性のオリゴマー類を添加することができる。熱可塑性のオリゴマー類としては、Ｃ５系およびＣ９系の石油樹脂、スチレン樹脂、インデン樹脂、インデン・スチレン共重合樹脂、インデン・スチレン・フェノール共重合樹脂、インデン・クマロン共重合樹脂、インデン・ベンゾチオフェン共重合樹脂等が例示さえる。添加量としては、通常、エポキシ樹脂１００重量部に対して、２〜３０重量部の範囲である。 In addition, thermoplastic oligomers can be added to the epoxy resin composition of the present invention from the viewpoint of improving fluidity during molding and improving adhesion to a substrate such as a lead frame. Thermoplastic oligomers include C5 and C9 petroleum resins, styrene resins, indene resins, indene / styrene copolymer resins, indene / styrene / phenol copolymer resins, indene / coumarone copolymer resins, indene / benzothiophene. Examples thereof include copolymer resins. As addition amount, it is the range of 2-30 weight part normally with respect to 100 weight part of epoxy resins.
さらに本発明のエポキシ樹脂組成物には、一般的にエポキシ樹脂組成物に使用可能なものを適宜配合して用いることができる。例えば、リン系難燃剤、ブロム化合物や三酸化アンチモン等の難燃剤、及びカーボンブラックや有機染料等の着色剤等を使用することができる。 Furthermore, what can generally be used for an epoxy resin composition can be suitably mix | blended and used for the epoxy resin composition of this invention. For example, phosphorus-based flame retardants, flame retardants such as bromine compounds and antimony trioxide, and colorants such as carbon black and organic dyes can be used.
本発明のエポキシ樹脂組成物は、エポキシ樹脂、硬化剤、無機充填材と、カップリング剤以外のその他の成分をミキサー等によって均一に混合した後、カップリング剤を添加し、加熱ロール、ニーダー等によって混練して製造する。これらの成分の配合順序には特に制限はない。更に又、混練後に溶融混練物の粉砕を行い、パウダー化することやタブレット化することも可能である。 The epoxy resin composition of the present invention is prepared by uniformly mixing an epoxy resin, a curing agent, an inorganic filler, and other components other than the coupling agent with a mixer, and then adding a coupling agent, a heating roll, a kneader, etc. Kneaded and manufactured. There is no restriction | limiting in particular in the mixing | blending order of these components. Furthermore, after kneading, the melt-kneaded product can be pulverized to be powdered or tableted.
本発明のエポキシ樹脂組成物は、エポキシ樹脂、硬化剤を樹脂成分の主成分とする。好ましくは、樹脂成分中、エポキシ樹脂と硬化剤を６０ｗｔ％以上、好ましくは８０ｗｔ％以上含む。なお、樹脂成分には、エポキシ樹脂、硬化剤、その他の樹脂の他に、熱をかけて成形することにより樹脂となるモノマーを含む。 The epoxy resin composition of the present invention comprises an epoxy resin and a curing agent as main components of the resin component. Preferably, the resin component contains an epoxy resin and a curing agent in an amount of 60 wt% or more, preferably 80 wt% or more. In addition to the epoxy resin, the curing agent, and other resins, the resin component includes a monomer that becomes a resin by molding by applying heat.
本発明のエポキシ樹脂組成物は、電気絶縁材料として有用であり、特に半導体装置に封止用として好適に用いられる。 The epoxy resin composition of the present invention is useful as an electrically insulating material, and is particularly suitably used for sealing in semiconductor devices.
本発明のエポキシ樹脂組成物を用いて成形物を得るためには、例えば、トランスファー成形、プレス成形、注型成形、射出成形、押出成形等の方法が適用されるが、量産性の観点からは、トランスファー成形が好ましい。この成形の際、重合が生じて硬化して、熱硬化樹脂となる。
In order to obtain a molded product using the epoxy resin composition of the present invention, for example, methods such as transfer molding, press molding, cast molding, injection molding, and extrusion molding are applied, but from the viewpoint of mass productivity. Transfer molding is preferred. During this molding, polymerization occurs and cures to become a thermosetting resin.
本発明の成形物は、三次元架橋をしたものである。二官能性エポキシ樹脂を二官能性硬化剤と反応させた場合、通常は、エポキシ基の開環反応で生成する二級水酸基がさらにエポキシ基と反応することにより三次元架橋体となるが、硬化条件を選択することで熱可塑性の二次元高分子成形体とすることができる。高熱伝導性の観点から結晶性の成形物とすることが望ましいが、三次元架橋は、一般的に結晶性を阻害するため、架橋を少なくして二次元高分子が主体の成形体とすることが良い。成形物の結晶性の発現は、走査示差熱分析で結晶の融解に伴う吸熱ピークを融点として観測により確認することができる。好ましい融点は１２０℃から２８０℃の範囲であり、より好ましくは１５０℃から２２０℃の範囲である。
The molded product of the present invention is three-dimensionally crosslinked . When a bifunctional epoxy resin is reacted with a bifunctional curing agent, usually a secondary hydroxyl group generated by a ring-opening reaction of the epoxy group further reacts with the epoxy group to form a three-dimensional crosslinked product. By selecting the conditions, a thermoplastic two-dimensional polymer molded body can be obtained. From the viewpoint of high thermal conductivity, it is desirable to use a crystalline molded product, but three-dimensional crosslinking generally inhibits crystallinity. Is good. The expression of the crystallinity of the molded product can be confirmed by observing the endothermic peak accompanying melting of the crystal as a melting point by scanning differential thermal analysis. A preferred melting point is in the range of 120 ° C. to 280 ° C., more preferably in the range of 150 ° C. to 220 ° C.
本発明の成形物の結晶化度は高いものほどよく、結晶化の程度は走査示差熱分析での結晶の融解に伴う吸熱量から評価することができる。好ましい吸熱量は、充填材を除いた樹脂成分の単位重量あたり５J/ｇ以上である。より好ましくは１０J/ｇ以上であり、特に好ましくは２０J/ｇ以上である。これより小さいと成形物としての熱伝導率向上効果が小さい。また、低熱膨張性および耐熱性向上の観点からも結晶性が高いほど好ましい。なお、ここでいう吸熱量は、示差熱分析計により、約１０ｍｇを精秤した試料を用いて、窒素気流下、昇温速度１０℃／分の条件で測定して得られる吸熱量を指す。 The higher the degree of crystallinity of the molded product of the present invention, the better, and the degree of crystallization can be evaluated from the endothermic amount accompanying the melting of the crystal in the scanning differential thermal analysis. A preferable endothermic amount is 5 J / g or more per unit weight of the resin component excluding the filler. More preferably, it is 10 J / g or more, and particularly preferably 20 J / g or more. If it is smaller than this, the effect of improving the thermal conductivity as a molded product is small. Also, higher crystallinity is preferable from the viewpoint of low thermal expansion and improved heat resistance. In addition, the endothermic amount here refers to the endothermic amount obtained by measuring with a differential thermal analyzer under the condition of a heating rate of 10 ° C./min under a nitrogen stream using a sample that is precisely weighed about 10 mg.
本発明の成形物は、上記成形方法により加熱成形させることにより得ることができるが、通常、成形温度としては８０℃から２５０℃であるが、成形物の結晶化度を上げるためには、成形物の融点よりも低い温度で成形することが望ましい。好ましい成形温度は１００℃から２００℃の範囲であり、より好ましくは１３０℃から１８０℃である。また、好ましい成形時間は３０秒から１時間であり、より好ましくは１分から３０分である。さらに成形後、ポストキュアにより、さらに結晶化度を上げることができる。通常、ポストキュア温度は１３０℃から２５０℃であり、時間は１時間から２０時間の範囲であるが、好ましくは、示差熱分析における吸熱ピーク温度よりも５℃から４０℃低い温度で、１時間から２４時間かけてポストキュアを行うことが望ましい。また、成形物の好ましい熱伝導率は３．５Ｗ／ｍ・Ｋ以上であり、特に好ましくは６Ｗ／ｍ・Ｋ以上である。 The molded product of the present invention can be obtained by heat molding using the above molding method. Usually, the molding temperature is 80 ° C. to 250 ° C. However, in order to increase the crystallinity of the molded product, molding is performed. It is desirable to mold at a temperature lower than the melting point of the product. A preferable molding temperature is in the range of 100 ° C to 200 ° C, more preferably 130 ° C to 180 ° C. The preferable molding time is 30 seconds to 1 hour, more preferably 1 minute to 30 minutes. Further, after molding, the crystallinity can be further increased by post-cure. Usually, the post-cure temperature is 130 ° C. to 250 ° C., and the time is in the range of 1 hour to 20 hours, but preferably 1 hour at a temperature 5 ° C. to 40 ° C. lower than the endothermic peak temperature in differential thermal analysis. It is desirable to perform post-cure over 24 hours from the beginning. Moreover, the preferable heat conductivity of a molded object is 3.5 W / m * K or more, Most preferably, it is 6 W / m * K or more.
以下実施例により本発明をさらに具体的に説明する。 Hereinafter, the present invention will be described more specifically with reference to examples.
参考例１
４，４’−ジヒドロキシジフェニルメタン１０００ｇをエピクロルヒドリン６５００ｇに溶解し、６０℃にて減圧下（約１３０Ｔｏｒｒ）、４８％水酸化ナトリウム水溶液８０８ｇを４時間かけて滴下した。この間、生成する水はエピクロルヒドリンとの共沸により系外に除き、留出したエピクロルヒドリンは系内に戻した。滴下終了後、さらに１時間反応を継続して脱水後、エピクロルヒドリンを留去し、メチルイソブチルケトン３５００ｇを加えた後、水洗を行い塩を除いた。その後、８０℃にて２０％水酸化ナトリウムを１００ｇ添加して２時間攪拌し、温水１０００ｍＬで水洗した。その後、分液により水を除去後、メチルイソブチルケトンを減圧留去し、淡黄色結晶状のエポキシ樹脂１４６０ｇを得た（エポキシ樹脂Ａ）。
Reference example 1
1,000 g of 4,4′-dihydroxydiphenylmethane was dissolved in 6500 g of epichlorohydrin, and 808 g of a 48% sodium hydroxide aqueous solution was added dropwise over 4 hours at 60 ° C. under reduced pressure (about 130 Torr). During this time, the generated water was removed from the system by azeotropy with epichlorohydrin, and the distilled epichlorohydrin was returned to the system. After completion of the dropwise addition, the reaction was further continued for 1 hour, followed by dehydration. Then, epichlorohydrin was distilled off, and 3500 g of methyl isobutyl ketone was added, followed by washing with water to remove the salt. Thereafter, 100 g of 20% sodium hydroxide was added at 80 ° C., stirred for 2 hours, and washed with 1000 mL of warm water. Then, after removing water by liquid separation, methyl isobutyl ketone was distilled off under reduced pressure to obtain 1460 g of a light yellow crystalline epoxy resin (epoxy resin A).
エポキシ樹脂Ａのキャピラリー法による融点は５９℃から６５℃であり、１５０℃での粘度は６．２ｍＰａ・ｓであった。エポキシ当量は１６４であり、加水分解性塩素は２８０ｐｐｍ、得られた樹脂のＧＰＣ測定より求められた一般式（１）における各成分比は、ｎ＝０が９１．５％、ｎ＝１が７．２％であった。ここで、加水分解性塩素とは、試料０．５ｇをジオキサン３０ｍｌに溶解後、１Ｎ−ＫＯＨ、１０ｍｌを加え３０分間煮沸還流した後、室温まで冷却し、さらに８０％アセトン水１００ｍｌを加えたものを、０．００２Ｎ−ＡｇＮＯ3水溶液で電位差滴定を行うことにより測定された値である。また融点とは、キャピラリー法により昇温速度２℃／分で得られる値である。粘度はＢＲＯＯＫＦＩＥＬＤ製、ＣＡＰ２０００Ｈで測定し、軟化点はＪＩＳ Ｋ−６９１１に従い環球法で測定した。また、ＧＰＣ測定は、装置；日本ウォーターズ（株）製、５１５Ａ型、カラム；ＴＳＫ−ＧＥＬ２０００×３本およびＴＳＫ−ＧＥＬ４０００×１本（いずれも東ソー（株）製）、溶媒；テトラヒドロフラン、流量；１ ｍｌ／ｍｉｎ、温度；３８℃、検出器；ＲＩの条件に従った。 The melting point of the epoxy resin A according to the capillary method was 59 ° C. to 65 ° C., and the viscosity at 150 ° C. was 6.2 mPa · s. Epoxy equivalent is 164, hydrolyzable chlorine is 280 ppm, and each component ratio in the general formula (1) obtained by GPC measurement of the obtained resin is 91.5% for n = 0 and 7 for n = 1. 2%. Here, hydrolyzable chlorine is obtained by dissolving 0.5 g of a sample in 30 ml of dioxane, adding 1 N-KOH, 10 ml, boiling and refluxing for 30 minutes, cooling to room temperature, and further adding 100 ml of 80% acetone water. Is a value measured by performing potentiometric titration with a 0.002N-AgNO 3 aqueous solution. The melting point is a value obtained by a capillary method at a heating rate of 2 ° C./min. Viscosity was measured with a product manufactured by BROOKFIELD, CAP2000H, and softening point was measured by a ring and ball method according to JIS K-6911. In addition, GPC measurement was carried out using a device: Nippon Waters Co., Ltd., Model 515A, column: TSK-GEL2000 × 3 and TSK-GEL4000 × 1 (both manufactured by Tosoh Corporation), solvent: tetrahydrofuran, flow rate: ml / min, temperature; 38 ° C., detector; RI conditions were followed.
参考例２
攪拌機、温度計、冷却管、窒素導入管のついた１Ｌ、４口セパラブルフラスコに、合成例１で合成したエポキシ樹脂４００ｇと４，４’−ジヒドロキシジフェニルメタン６１．０ｇを仕込み、窒素気流下、攪拌しながら１５０℃にて溶融混合した後、トリフェニルホスフィン０．２ｇを加え、２時間反応を行った。反応後、得られたエポキシ樹脂（エポキシ樹脂Ｂ）は、室温に放冷することにより、結晶性を示し固化した。得られたエポキシ樹脂Ｂのエポキシ当量は２６４ｇ／ｅｑ．、融点は９０から１１２℃、１５０℃での粘度は０．０４１Ｐａ・ｓであった。また、得られた樹脂のＧＰＣ測定より求められた一般式（１）における各成分比は、ｎ＝０が４６．８%、ｎ＝２が２７．０％、ｎ＝４が１２．１％、ｎ≧６が１３．７％であった。ここで、粘度はコントラバス社製レオマット１１５で測定した。また、ＧＰＣ測定は、装置；ＨＬＣ−８２Ａ（東ソー（株）製）、カラム；ＴＳＫ−ＧＥＬ２０００×３本およびＴＳＫ−ＧＥＬ４０００×１本（いずれも東ソー（株）製）、溶媒；テトラヒドロフラン、流量；１ ｍｌ／ｍｉｎ、温度；３８℃、検出器；ＲＩの条件に従った。
Reference example 2
400 g of epoxy resin synthesized in Synthesis Example 1 and 61.0 g of 4,4′-dihydroxydiphenylmethane were charged into a 1 L, 4-neck separable flask equipped with a stirrer, thermometer, cooling tube, and nitrogen introduction tube. After stirring and mixing at 150 ° C. with stirring, 0.2 g of triphenylphosphine was added and the reaction was performed for 2 hours. After the reaction, the obtained epoxy resin (epoxy resin B) was allowed to cool to room temperature, thereby showing crystallinity and solidifying. The epoxy equivalent of the obtained epoxy resin B was 264 g / eq. The melting point was 90 to 112 ° C., and the viscosity at 150 ° C. was 0.041 Pa · s. Moreover, each component ratio in General formula (1) calculated | required from GPC measurement of the obtained resin is 46.8% where n = 0, 27.0% where n = 2, and 12.1% where n = 4. N ≧ 6 was 13.7%. Here, the viscosity was measured with Rheomatt 115 manufactured by Contrabass. In addition, GPC measurement was performed by using an apparatus; HLC-82A (manufactured by Tosoh Corp.), column; TSK-GEL2000 × 3 and TSK-GEL4000 × 1 (both manufactured by Tosoh Corp.), solvent; 1 ml / min, temperature; 38 ° C., detector; RI conditions were followed.
実施例１〜６、比較例１〜７
エポキシ樹脂成分として、参考例１、２のエポキシ樹脂（エポキシ樹脂Ａ、Ｂ）、ビフェニル系エポキシ樹脂（エポキシ樹脂Ｃ：ジャパンエポキシレジン製、ＹＬ−６１２１（４，４'−ジヒドロキシビフェニルのエポキシ化物と３，３'，５，５'−テトラメチル−４，４'−ジヒドロキシビフェニルのエポキシ化物との１：１の混合物）、３，３'，５，５'−テトラメチル−４，４'−ジヒドロキシジフェニルメタンのエポキシ化物（エポキシ樹脂Ｄ：東都化成製、ＹＳＬＶ−８０ＸＹ、エポキシ当量１９２）、ビスフェノールＦ型エポキシ樹脂（エポキシ樹脂Ｅ：東都化成製、ＹＤＦ−１７０；エポキシ当量１７１）又はビスフェノールＡ型エポキシ樹脂（エポキシ樹脂Ｆ：東都化成製、ＹＤ−１２８；エポキシ当量１８９）を使用した。硬化剤として４，４'−ジヒドロキシジフェニルメタン（硬化剤Ａ）、ビスフェノールＡ（硬化剤Ｂ）、４，４'−ジヒドロキシビフェニル（硬化剤Ｃ）、４，４'−ジヒドロキシジフェニルエーテル（硬化剤Ｄ）又はフェノールノボラック（硬化剤Ｅ：群栄化学製、ＰＳＭ−４２６１；ＯＨ当量１０３、軟化点 ８２℃）を使用した。硬化促進剤としてトリフェニルホスフィン、無機充填材として、球状アルミナ（平均粒径１２．２μｍ）を使用した。
Examples 1-6, Comparative Examples 1-7
As an epoxy resin component, epoxy resins of Reference Examples 1 and 2 (epoxy resins A and B), biphenyl epoxy resin (epoxy resin C: manufactured by Japan Epoxy Resin, YL-6121 (epoxidized product of 4,4′-dihydroxybiphenyl) 3,3 ′, 5,5′-tetramethyl-4,4′-dihydroxybiphenyl 1: 1 mixture with epoxidized product), 3,3 ′, 5,5′-tetramethyl-4,4′- Epoxy product of dihydroxydiphenylmethane (epoxy resin D: Toto Kasei, YSLV-80XY, epoxy equivalent 192), bisphenol F type epoxy resin (epoxy resin E: Toto Kasei, YDF-170; epoxy equivalent 171) or bisphenol A type epoxy Resin (epoxy resin F: manufactured by Tohto Kasei, YD-128; epoxy equivalent 189) was used. 4,4′-dihydroxydiphenylmethane (curing agent A), bisphenol A (curing agent B), 4,4′-dihydroxybiphenyl (curing agent C), 4,4′-dihydroxydiphenyl ether (curing agent D) or phenol Novolak (curing agent E: manufactured by Gunei Chemical Co., PSM-4261; OH equivalent 103, softening point 82 ° C.) Triphenylphosphine as curing accelerator, spherical alumina (average particle size 12.2 μm) as inorganic filler )It was used.
表１に示す成分を配合し、ミキサーで十分混合した後、加熱ロールで約５分間混練したものを冷却し、粉砕してそれぞれ実施例１〜６、比較例１〜３のエポキシ樹脂組成物を得た。このエポキシ樹脂組成物を用いて表１に示す条件で成形およびポストキュアを行い、成形物の物性を評価した。結果をまとめて表１に示す。なお、表１中の各配合物の数字は重量部を表す。また、評価は次により行った。 After blending the components shown in Table 1 and thoroughly mixing with a mixer, the mixture kneaded for about 5 minutes with a heating roll was cooled and ground to obtain the epoxy resin compositions of Examples 1 to 6 and Comparative Examples 1 to 3, respectively. Obtained. Using this epoxy resin composition, molding and post-curing were performed under the conditions shown in Table 1, and the physical properties of the molded product were evaluated. The results are summarized in Table 1. In addition, the number of each compound in Table 1 represents parts by weight. The evaluation was performed as follows.
（１）熱伝導率：ＮＥＴＺＳＣＨ製ＬＦＡ４４７型熱伝導率計を用いて非定常熱線法により測定した。
（２）融点、融解熱の測定（ＤＳＣ法）：示差走査熱量分析装置（セイコーインスツル製ＤＳＣ６２００型）を用い、昇温速度１０℃／分で測定した。
（３）線膨張係数、ガラス転移温度：セイコーインスツル（株）製ＴＭＡ１２０Ｃ型熱機械測定装置を用いて、昇温速度１０℃／分にて測定した。
（４）吸水率：直径５０mm、厚さ３ｍｍの円盤を成形し、ポストキュア後、８５℃、相対湿度８５％の条件で１００時間吸湿させた後の重量変化率とした。
(1) Thermal conductivity: Measured by the unsteady hot wire method using an LFA447 type thermal conductivity meter manufactured by NETZSCH.
(2) Measurement of melting point and heat of fusion (DSC method): Using a differential scanning calorimeter (DSC6200, manufactured by Seiko Instruments Inc.), the temperature was increased at a rate of 10 ° C./min.
(3) Linear expansion coefficient, glass transition temperature: Measured using a TMA120C thermomechanical measuring device manufactured by Seiko Instruments Inc. at a rate of temperature increase of 10 ° C./min.
(4) Water absorption: A disk having a diameter of 50 mm and a thickness of 3 mm was formed, and after post-curing, the weight change rate was obtained after moisture absorption at 85 ° C. and a relative humidity of 85% for 100 hours.
Claims (6)
で表される４，４'−ジフェニルメタン構造を持つエポキシ樹脂とし、硬化剤の７５ｗｔ％以上を下記一般式（２）、
で表される４，４'−ジフェニルメタン構造を持つフェノール性樹脂とし、エポキシ樹脂中のエポキシ基と硬化剤中の官能基が当量比（エポキシ基/硬化剤中の官能基）で０．８〜１．５の範囲としたことを特徴とするエポキシ樹脂組成物。 (A) Epoxy resin , (B) In the epoxy resin composition containing a curing agent and an inorganic filler, the inorganic filler is contained in the epoxy resin composition in an amount of 50 to 95 wt%, and 75 wt% or more of the epoxy resin is represented by the following general formula. (1),
An epoxy resin having a 4,4′-diphenylmethane structure represented by the following general formula (2): 75 wt% or more of the curing agent:
The phenolic resin having a 4,4′-diphenylmethane structure represented by the formula (1) , the epoxy group in the epoxy resin and the functional group in the curing agent have an equivalent ratio (epoxy group / functional group in the curing agent) of 0.8 to An epoxy resin composition having a range of 1.5.
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| JP2008092280A Expired - Fee Related JP5314912B2 (en) | 2008-03-31 | 2008-03-31 | Epoxy resin composition and molded article |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| WO2012050400A2 (en) | 2010-10-14 | 2012-04-19 | 주식회사 엘지화학 | Resin blend for melting process |
| WO2013015577A1 (en) * | 2011-07-22 | 2013-01-31 | 주식회사 엘지화학 | Heat-curable resin composition, and prepreg and metal foil-stacked plate using same |
| TWI594882B (en) * | 2011-07-22 | 2017-08-11 | Ｌｇ化學股份有限公司 | Thermosetting resin composition and prepreg and metal clad laminate using the same |
| WO2024029602A1 (en) * | 2022-08-05 | 2024-02-08 | 日鉄ケミカル＆マテリアル株式会社 | Resin composition, and cured product |
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| JP3384472B2 (en) * | 1994-12-26 | 2003-03-10 | 住友ベークライト株式会社 | Conductive resin paste |
| JPH1135659A (en) * | 1997-07-16 | 1999-02-09 | Matsushita Electric Ind Co Ltd | Resin composition, prepreg and printed wiring base board and production of these |
| JP4124004B2 (en) * | 2002-03-26 | 2008-07-23 | 日本ゼオン株式会社 | Hydrogenated conjugated diene polymer latex, process for producing the same, and hydrogenated conjugated diene polymer rubber |
| JP2007177180A (en) * | 2005-12-28 | 2007-07-12 | Nippon Kayaku Co Ltd | Epoxy resin varnish, photosensitive resin composition and its cured product |
| JP2008195751A (en) * | 2007-02-08 | 2008-08-28 | Nitto Denko Corp | Epoxy resin composition for sealing semiconductor and semiconductor device obtained using the same |
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