JP2017019983A - Benzoxazine resin composition, method for producing the same, and use for the composition - Google Patents
Benzoxazine resin composition, method for producing the same, and use for the composition Download PDFInfo
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- JP2017019983A JP2017019983A JP2015201385A JP2015201385A JP2017019983A JP 2017019983 A JP2017019983 A JP 2017019983A JP 2015201385 A JP2015201385 A JP 2015201385A JP 2015201385 A JP2015201385 A JP 2015201385A JP 2017019983 A JP2017019983 A JP 2017019983A
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- formula
- benzoxazine resin
- resin composition
- atom
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- CMLFRMDBDNHMRA-UHFFFAOYSA-N 2h-1,2-benzoxazine Chemical compound C1=CC=C2C=CNOC2=C1 CMLFRMDBDNHMRA-UHFFFAOYSA-N 0.000 title claims abstract description 70
- 239000011342 resin composition Substances 0.000 title claims abstract description 42
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 10
- 239000000203 mixture Substances 0.000 title claims abstract description 7
- 229920005989 resin Polymers 0.000 claims abstract description 36
- 239000011347 resin Substances 0.000 claims abstract description 36
- 150000001875 compounds Chemical class 0.000 claims abstract description 29
- 125000003118 aryl group Chemical group 0.000 claims abstract description 19
- 125000003342 alkenyl group Chemical group 0.000 claims abstract description 16
- 125000002947 alkylene group Chemical group 0.000 claims abstract description 14
- 125000003161 (C1-C6) alkylene group Chemical group 0.000 claims abstract description 12
- 125000000753 cycloalkyl group Chemical group 0.000 claims abstract description 10
- 125000003710 aryl alkyl group Chemical group 0.000 claims abstract description 9
- 125000001183 hydrocarbyl group Chemical group 0.000 claims abstract 2
- 239000000463 material Substances 0.000 claims description 27
- 125000004430 oxygen atom Chemical group O* 0.000 claims description 22
- 239000008393 encapsulating agent Substances 0.000 claims description 17
- 125000004432 carbon atom Chemical group C* 0.000 claims description 14
- 125000004429 atom Chemical group 0.000 claims description 13
- 125000001424 substituent group Chemical group 0.000 claims description 13
- 239000002131 composite material Substances 0.000 claims description 11
- 239000003822 epoxy resin Substances 0.000 claims description 10
- 239000007788 liquid Substances 0.000 claims description 10
- 229920000647 polyepoxide Polymers 0.000 claims description 10
- 238000004382 potting Methods 0.000 claims description 9
- 239000004065 semiconductor Substances 0.000 claims description 9
- 125000004169 (C1-C6) alkyl group Chemical group 0.000 claims description 8
- 125000006702 (C1-C18) alkyl group Chemical group 0.000 claims description 7
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 7
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 7
- 229910052757 nitrogen Inorganic materials 0.000 claims description 7
- 229910052710 silicon Inorganic materials 0.000 claims description 7
- 229920000642 polymer Polymers 0.000 claims description 6
- 229910052799 carbon Inorganic materials 0.000 claims description 5
- 125000004433 nitrogen atom Chemical group N* 0.000 claims description 5
- 238000000034 method Methods 0.000 claims description 4
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims description 4
- 239000000565 sealant Substances 0.000 claims description 4
- 238000007142 ring opening reaction Methods 0.000 claims description 3
- 239000003566 sealing material Substances 0.000 claims description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Chemical group N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 2
- 229910052751 metal Inorganic materials 0.000 abstract description 8
- 239000002184 metal Substances 0.000 abstract description 8
- 125000000217 alkyl group Chemical group 0.000 abstract description 5
- -1 benzoxazine compound Chemical class 0.000 description 84
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 12
- 239000003054 catalyst Substances 0.000 description 10
- 229910052782 aluminium Inorganic materials 0.000 description 9
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 9
- 238000001723 curing Methods 0.000 description 9
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 9
- 239000002904 solvent Substances 0.000 description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 8
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 8
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 8
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 8
- 239000000853 adhesive Substances 0.000 description 7
- 230000001070 adhesive effect Effects 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 7
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 6
- 125000001118 alkylidene group Chemical group 0.000 description 6
- 239000003795 chemical substances by application Substances 0.000 description 6
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 6
- 125000003258 trimethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])[*:1] 0.000 description 5
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 5
- 125000006273 (C1-C3) alkyl group Chemical group 0.000 description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 4
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 4
- 150000001721 carbon Chemical group 0.000 description 4
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 238000006459 hydrosilylation reaction Methods 0.000 description 4
- 125000002950 monocyclic group Chemical group 0.000 description 4
- 125000000466 oxiranyl group Chemical group 0.000 description 4
- KJFMBFZCATUALV-UHFFFAOYSA-N phenolphthalein Chemical compound C1=CC(O)=CC=C1C1(C=2C=CC(O)=CC=2)C2=CC=CC=C2C(=O)O1 KJFMBFZCATUALV-UHFFFAOYSA-N 0.000 description 4
- 229910052697 platinum Inorganic materials 0.000 description 4
- 239000002210 silicon-based material Substances 0.000 description 4
- 125000004178 (C1-C4) alkyl group Chemical group 0.000 description 3
- 125000001140 1,4-phenylene group Chemical group [H]C1=C([H])C([*:2])=C([H])C([H])=C1[*:1] 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 229910052802 copper Inorganic materials 0.000 description 3
- 239000010949 copper Substances 0.000 description 3
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 3
- 239000012776 electronic material Substances 0.000 description 3
- 230000009477 glass transition Effects 0.000 description 3
- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 3
- 150000002430 hydrocarbons Chemical group 0.000 description 3
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 3
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 3
- 125000001624 naphthyl group Chemical group 0.000 description 3
- 125000004817 pentamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 3
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 3
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 3
- 239000002966 varnish Substances 0.000 description 3
- 125000000229 (C1-C4)alkoxy group Chemical group 0.000 description 2
- 125000006656 (C2-C4) alkenyl group Chemical group 0.000 description 2
- HECLRDQVFMWTQS-RGOKHQFPSA-N 1755-01-7 Chemical compound C1[C@H]2[C@@H]3CC=C[C@@H]3[C@@H]1C=C2 HECLRDQVFMWTQS-RGOKHQFPSA-N 0.000 description 2
- 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 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- 125000000882 C2-C6 alkenyl group Chemical group 0.000 description 2
- 229920000049 Carbon (fiber) Polymers 0.000 description 2
- ZRALSGWEFCBTJO-UHFFFAOYSA-N Guanidine Chemical compound NC(N)=N ZRALSGWEFCBTJO-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical group CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 150000001338 aliphatic hydrocarbons Chemical group 0.000 description 2
- 125000003545 alkoxy group Chemical group 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 230000003712 anti-aging effect Effects 0.000 description 2
- 125000002619 bicyclic group Chemical group 0.000 description 2
- 125000004369 butenyl group Chemical group C(=CCC)* 0.000 description 2
- 239000004917 carbon fiber Substances 0.000 description 2
- 238000013329 compounding Methods 0.000 description 2
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 2
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 2
- 239000003063 flame retardant Substances 0.000 description 2
- 239000003365 glass fiber Substances 0.000 description 2
- 125000006038 hexenyl group Chemical group 0.000 description 2
- 239000003112 inhibitor Substances 0.000 description 2
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 2
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 description 2
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 125000003506 n-propoxy group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])O* 0.000 description 2
- 125000003518 norbornenyl group Chemical group C12(C=CC(CC1)C2)* 0.000 description 2
- 125000004365 octenyl group Chemical group C(=CCCCCCC)* 0.000 description 2
- 125000002255 pentenyl group Chemical group C(=CCCC)* 0.000 description 2
- 229920001721 polyimide Polymers 0.000 description 2
- 239000012744 reinforcing agent Substances 0.000 description 2
- 229910052703 rhodium Inorganic materials 0.000 description 2
- 239000010948 rhodium Substances 0.000 description 2
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 2
- 239000012453 solvate Substances 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 125000003944 tolyl group Chemical group 0.000 description 2
- 239000008096 xylene Substances 0.000 description 2
- 125000005023 xylyl group Chemical group 0.000 description 2
- UHXCHUWSQRLZJS-UHFFFAOYSA-N (4-dimethylsilylidenecyclohexa-2,5-dien-1-ylidene)-dimethylsilane Chemical compound C[Si](C)C1=CC=C([Si](C)C)C=C1 UHXCHUWSQRLZJS-UHFFFAOYSA-N 0.000 description 1
- 125000000008 (C1-C10) alkyl group Chemical group 0.000 description 1
- 125000006681 (C2-C10) alkylene group Chemical group 0.000 description 1
- ZKZCHOVDCNLSKG-UHFFFAOYSA-N 1,2,3,4,5,6,7,8-octahydronaphthalene Chemical group C1CCCC2=C1CCCC2 ZKZCHOVDCNLSKG-UHFFFAOYSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- BLDLRWQLBOJPEB-UHFFFAOYSA-N 2-(2-hydroxyphenyl)sulfanylphenol Chemical compound OC1=CC=CC=C1SC1=CC=CC=C1O BLDLRWQLBOJPEB-UHFFFAOYSA-N 0.000 description 1
- OEPOKWHJYJXUGD-UHFFFAOYSA-N 2-(3-phenylmethoxyphenyl)-1,3-thiazole-4-carbaldehyde Chemical compound O=CC1=CSC(C=2C=C(OCC=3C=CC=CC=3)C=CC=2)=N1 OEPOKWHJYJXUGD-UHFFFAOYSA-N 0.000 description 1
- XAYDWGMOPRHLEP-UHFFFAOYSA-N 6-ethenyl-7-oxabicyclo[4.1.0]heptane Chemical compound C1CCCC2OC21C=C XAYDWGMOPRHLEP-UHFFFAOYSA-N 0.000 description 1
- 229930185605 Bisphenol Natural products 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical group [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- 125000006374 C2-C10 alkenyl group Chemical group 0.000 description 1
- LYGNXIFKMFKHPX-UHFFFAOYSA-L C=1C=CCCCCC=1[Ir](Cl)(Cl)C1=CC=CCCCC1 Chemical compound C=1C=CCCCCC=1[Ir](Cl)(Cl)C1=CC=CCCCC1 LYGNXIFKMFKHPX-UHFFFAOYSA-L 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- GXGJIOMUZAGVEH-UHFFFAOYSA-N Chamazulene Chemical group CCC1=CC=C(C)C2=CC=C(C)C2=C1 GXGJIOMUZAGVEH-UHFFFAOYSA-N 0.000 description 1
- 239000004641 Diallyl-phthalate Substances 0.000 description 1
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- CHJJGSNFBQVOTG-UHFFFAOYSA-N N-methyl-guanidine Natural products CNC(N)=N CHJJGSNFBQVOTG-UHFFFAOYSA-N 0.000 description 1
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- 239000004696 Poly ether ether ketone Substances 0.000 description 1
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- 229920001807 Urea-formaldehyde Polymers 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
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- DSVGQVZAZSZEEX-UHFFFAOYSA-N [C].[Pt] Chemical compound [C].[Pt] DSVGQVZAZSZEEX-UHFFFAOYSA-N 0.000 description 1
- ORILYTVJVMAKLC-UHFFFAOYSA-N adamantane Chemical group C1C(C2)CC3CC1CC2C3 ORILYTVJVMAKLC-UHFFFAOYSA-N 0.000 description 1
- 239000005456 alcohol based solvent Substances 0.000 description 1
- 125000005577 anthracene group Chemical group 0.000 description 1
- 125000005428 anthryl group Chemical group [H]C1=C([H])C([H])=C2C([H])=C3C(*)=C([H])C([H])=C([H])C3=C([H])C2=C1[H] 0.000 description 1
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- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- QUDWYFHPNIMBFC-UHFFFAOYSA-N bis(prop-2-enyl) benzene-1,2-dicarboxylate Chemical compound C=CCOC(=O)C1=CC=CC=C1C(=O)OCC=C QUDWYFHPNIMBFC-UHFFFAOYSA-N 0.000 description 1
- 238000009529 body temperature measurement Methods 0.000 description 1
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- 125000004855 decalinyl group Chemical group C1(CCCC2CCCCC12)* 0.000 description 1
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- SWSQBOPZIKWTGO-UHFFFAOYSA-N dimethylaminoamidine Natural products CN(C)C(N)=N SWSQBOPZIKWTGO-UHFFFAOYSA-N 0.000 description 1
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- LGEVRIFLFCVXDI-UHFFFAOYSA-N diphenylmethanediamine;phenol Chemical compound OC1=CC=CC=C1.C=1C=CC=CC=1C(N)(N)C1=CC=CC=C1 LGEVRIFLFCVXDI-UHFFFAOYSA-N 0.000 description 1
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- 229920000728 polyester Polymers 0.000 description 1
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- 229920002530 polyetherether ketone Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920006324 polyoxymethylene Polymers 0.000 description 1
- 229920001955 polyphenylene ether Polymers 0.000 description 1
- 229920000069 polyphenylene sulfide Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 125000004368 propenyl group Chemical group C(=CC)* 0.000 description 1
- 125000005581 pyrene group Chemical group 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 125000001973 tert-pentyl group Chemical group [H]C([H])([H])C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 125000005329 tetralinyl group Chemical group C1(CCCC2=CC=CC=C12)* 0.000 description 1
- 230000000930 thermomechanical effect Effects 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- 125000005425 toluyl group Chemical group 0.000 description 1
- 125000005580 triphenylene group Chemical group 0.000 description 1
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 1
- 229920006305 unsaturated polyester Polymers 0.000 description 1
- 229920001567 vinyl ester resin Polymers 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
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- Sealing Material Composition (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Epoxy Resins (AREA)
- Structures Or Materials For Encapsulating Or Coating Semiconductor Devices Or Solid State Devices (AREA)
Abstract
Description
本発明は、ベンゾオキサジン樹脂組成物、その製造方法、及び該組成物の用途に関する。 The present invention relates to a benzoxazine resin composition, a production method thereof, and a use of the composition.
ガラス繊維や炭素繊維などを用いた繊維強化複合材料は優れた力学物性を有することから、航空機、船舶、自動車、及びその他の一般産業用途などで用いられている。今後、複合材料のさらなる用途拡大に伴い、耐熱性の向上などのより高い特性が要求される。 Fiber reinforced composite materials using glass fibers, carbon fibers, and the like have excellent mechanical properties and are used in aircraft, ships, automobiles, and other general industrial applications. In the future, higher properties such as improved heat resistance will be required as composite materials are further expanded.
一方、電子材料分野においては、モジュールの高性能化に伴い、基板材料や封止材にも高い耐熱性が求められ、さらには、高周波特性を有する電子材料のニーズの高まりに伴い、構成部材の誘電特性の改善（低誘電率化及び低誘電正接化）が求められている。 On the other hand, in the field of electronic materials, as the performance of modules increases, substrate materials and sealing materials are also required to have high heat resistance. Furthermore, as the needs for electronic materials having high frequency characteristics increase, There is a need for improvement in dielectric properties (low dielectric constant and low dielectric loss tangent).
複合材料や電子材料に用いられるマトリックス樹脂としては、近年、ベンゾオキサジン樹脂が注目を浴びている。ベンゾオキサジン樹脂は、ベンゾオキサジン環を有する化合物であり、フェノール類とアミン類から合成され、硬化後の構造が、難燃性フェノール樹脂と似た構造であるために、難燃性が期待される。 In recent years, benzoxazine resins have attracted attention as matrix resins used for composite materials and electronic materials. A benzoxazine resin is a compound having a benzoxazine ring, which is synthesized from phenols and amines, and the structure after curing is similar to that of a flame retardant phenol resin. .
ベンゾオキサジン樹脂の適用分野の拡大を目指し、種々の新規ベンゾオキサジン樹脂が提案されている。（特許文献１及び２） Various new benzoxazine resins have been proposed with the aim of expanding the application fields of benzoxazine resins. (Patent Documents 1 and 2)
特許文献１及び２に記載のベンゾオキサジン樹脂は優れた特性を有しているものの、耐熱性、誘電特性、及び金属に対する接着性においては未だ不十分である。 Although the benzoxazine resins described in Patent Documents 1 and 2 have excellent properties, they are still insufficient in heat resistance, dielectric properties, and adhesion to metals.
本発明は、耐熱性、誘電特性、及び金属に対する接着性に優れたベンゾオキサジン樹脂組成物、その製造方法、及び該組成物の用途を提供することを課題とする。 An object of the present invention is to provide a benzoxazine resin composition excellent in heat resistance, dielectric properties, and adhesion to metals, a method for producing the same, and a use of the composition.
本発明者は、上記課題を解決するべく鋭意研究を行った結果、ベンゾオキサジン樹脂及び所定のケイ素原子を含有する化合物を含むベンゾオキサジン樹脂組成物が、上記の課題を解決できることを見出した。この知見に基づいてさらに研究を重ねた結果、本発明を完成するに至った。 As a result of intensive studies to solve the above problems, the present inventors have found that a benzoxazine resin composition containing a benzoxazine resin and a compound containing a predetermined silicon atom can solve the above problems. As a result of further research based on this knowledge, the present invention has been completed.
即ち、本発明は、ベンゾオキサジン樹脂及び下記に示すケイ素原子を含有する化合物を含むベンゾオキサジン樹脂組成物、その製造方法、及びその用途に関するものである。 That is, the present invention relates to a benzoxazine resin composition containing a benzoxazine resin and a compound containing a silicon atom shown below, a production method thereof, and an application thereof.
項１ ベンゾオキサジン樹脂、及び式（１）： Item 1 benzoxazine resin and formula (1):
（式中、Ｘは、炭化水素環から２個の水素原子を除いて得られる２価の基、又は式（２）： (Wherein X is a divalent group obtained by removing two hydrogen atoms from a hydrocarbon ring, or formula (2):
（式中、Ｙは、結合手、Ｃ１〜６のアルキレン基、酸素原子（−Ｏ−）又は式：−Ｓ（Ｏ）ｍ−（式中、ｍは０、１又は２を示す。）で示される基である。）で表される２価の基であり、
Ｒ１は同一又は異なって、Ｃ１〜１８のアルキル基、Ｃ２〜９のアルケニル基、シクロアルキル基、アリール基又はアラルキル基であり、これらの基は、一部の炭素原子が、酸素原子及び窒素原子からなる群より選ばれる少なくとも１種の原子で置換されていてもよく、
Ｒ２は同一又は異なって、Ｃ１〜１８のアルキレン基であり、この基は、ケイ素原子に直接結合した炭素原子を除く一部の炭素原子が、酸素原子及び窒素原子からなる群より選ばれる少なくとも１種の原子で置換されていてもよく、
Ｒ３は同一又は異なって、Ｃ１〜１８のアルキル基、Ｃ２〜９のアルケニル基、シクロアルキル基、アリール基又はアラルキル基であり、これらの基は、一部の炭素原子が、酸素原子及び窒素原子からなる群より選ばれる少なくとも１種の原子で置換されていてもよく、
ｎは同一又は異なって、０〜３の整数である。）
で表される化合物（エポキシ樹脂）を含有するベンゾオキサジン樹脂組成物。
Wherein Y is a bond, a C1-6 alkylene group, an oxygen atom (—O—) or a formula: —S (O) m — (wherein m represents 0, 1 or 2). A divalent group represented by:
R 1 may be the same or different and is a C1-18 alkyl group, a C2-9 alkenyl group, a cycloalkyl group, an aryl group or an aralkyl group, and these groups have some carbon atoms, oxygen atoms and nitrogens. May be substituted with at least one atom selected from the group consisting of atoms;
R 2 is the same or different and is a C1-18 alkylene group, and this group is a group in which some carbon atoms excluding the carbon atom directly bonded to the silicon atom are selected from the group consisting of an oxygen atom and a nitrogen atom. May be substituted with one atom,
R 3 is the same or different and is a C1-18 alkyl group, a C2-9 alkenyl group, a cycloalkyl group, an aryl group or an aralkyl group, and these groups have a part of carbon atoms, oxygen atom and nitrogen May be substituted with at least one atom selected from the group consisting of atoms;
n is the same or different and is an integer of 0-3. )
The benzoxazine resin composition containing the compound (epoxy resin) represented by these.
項２ 前記ベンゾオキサジン樹脂が、式（５）： Item 2 The benzoxazine resin has the formula (5):
（式中、Ｒ４は、Ｃ１〜６のアルキレン基、酸素原子（−Ｏ−）、−ＣＯ−、式：−Ｓ（Ｏ）ｐ−（式中、ｐは０、１又は２を示す。）で示される基、式（７）： (In the formula, R 4 represents a C 1-6 alkylene group, an oxygen atom (—O—), —CO—, a formula: —S (O) p — (wherein p represents 0, 1 or 2). A group represented by formula (7):
で示される基、又は式（８）： Or a group represented by formula (8):
で示される基であり、Ｒ５は、置換基を有していてもよいアリール基である。）
で表される化合物及び／又はその開環重合体、或いは、式（６）：
R 5 is an aryl group which may have a substituent. )
And / or a ring-opened polymer thereof, or formula (6):
（式中、Ｒ６は、Ｃ１〜６のアルキレン基、酸素原子（−Ｏ−）、−ＣＯ−、式：−Ｓ（Ｏ）ｑ−（式中、ｑは０、１又は２を示す。）で示される基、又は式（９）： (In the formula, R 6 represents a C 1-6 alkylene group, an oxygen atom (—O—), —CO—, a formula: —S (O) q — (wherein q represents 0, 1 or 2). Or a group represented by formula (9):
で示される基であり、Ｒ７は、水素原子、又は置換基を有していてもよいＣ１〜６のアルキル基である。）
で表される化合物及び／又はその開環重合体である項１に記載のベンゾオキサジン樹脂組成物。
R 7 is a hydrogen atom or a C1-6 alkyl group which may have a substituent. )
Item 2. The benzoxazine resin composition according to Item 1, which is a compound represented by the formula: and / or a ring-opening polymer thereof.
項３ 前記項１に記載のベンゾオキサジン樹脂組成物の製造方法であって、前記ベンゾオキサジン樹脂及び前記式（１）で表される化合物を混合する工程を含む、製造方法。 Item 3 A method for producing the benzoxazine resin composition according to Item 1, comprising a step of mixing the benzoxazine resin and the compound represented by the formula (1).
項４ 前記項１又は２に記載のエポキシ樹脂組成物を硬化した物。 Item 4 A product obtained by curing the epoxy resin composition according to Item 1 or 2.
項５ 前記項１又は２に記載のベンゾオキサジン樹脂組成物、又はその硬化物（前記項４に記載のベンゾオキサジン樹脂組成物を硬化した物）が用いられている半導体封止体、液状封止材、ポッティング材、シール材、プリント基板材料又は複合材料。 Item 5 A semiconductor encapsulant, liquid encapsulation in which the benzoxazine resin composition according to Item 1 or 2 or a cured product thereof (a product obtained by curing the benzoxazine resin composition according to Item 4) is used. Materials, potting materials, sealing materials, printed circuit board materials or composite materials.
項６ 半導体封止体、液状封止材、ポッティング材、シール材、プリント基板材料又は複合材料の用途に用いられる前記項１又は２に記載のベンゾオキサジン樹脂組成物。 Item 6. The benzoxazine resin composition according to Item 1 or 2, which is used for a semiconductor encapsulant, a liquid encapsulant, a potting material, a sealant, a printed board material, or a composite material.
項７ 半導体封止体、液状封止材、ポッティング材、シール材、プリント基板材料又は複合材料を製造するための前記項１又は２に記載のベンゾオキサジン樹脂組成物の使用。 Item 7 Use of the benzoxazine resin composition according to Item 1 or 2 for producing a semiconductor encapsulant, a liquid encapsulant, a potting material, a sealant, a printed board material or a composite material.
本発明のベンゾオキサジン樹脂組成物は、その硬化物が優れた耐熱性、誘電特性（低誘電率及び低誘電正接）、及び金属に対する高い接着強度を有している。そのため、本発明のベンゾオキサジン樹脂組成物は、例えば、半導体封止体、液状封止材、ポッティング材、シール材、プリント基板材料、複合材料等の用途に好適に用いることができる。 In the benzoxazine resin composition of the present invention, the cured product has excellent heat resistance, dielectric properties (low dielectric constant and low dielectric loss tangent), and high adhesive strength to metal. Therefore, the benzoxazine resin composition of the present invention can be suitably used for applications such as a semiconductor encapsulant, a liquid encapsulant, a potting material, a seal material, a printed board material, and a composite material.
本明細書において、ある成分を「を含む」又は「を含有する」という表現には、当該成分を含みさらに他の成分を含んでいてもよい意味のほか、当該成分のみを含む意味の「のみからなる」、及び当該成分を必須として含む意味の「から必須としてなる」の概念も包含される。 In this specification, the expression “comprises” or “contains” a certain component includes the component and may include other components as well as “only” in the sense of including only the component. The concept of “consisting of” and “consisting of essential” including the component as an essential component is also included.
以下、本発明を詳細に説明する。 Hereinafter, the present invention will be described in detail.
本発明のベンゾオキサジン樹脂組成物は、ベンゾオキサジン樹脂及び式（１）で表される化合物を含有することを特徴とする。 The benzoxazine resin composition of the present invention contains a benzoxazine resin and a compound represented by the formula (1).
本発明のベンゾオキサジン樹脂組成物は、ベンゾオキサジン樹脂を含有する。ベンゾオキサジン樹脂とは、分子内にベンゾオキサジン環を有する化合物（以下「ベンゾオキサジン化合物」とも表記する。）及び／又はその開環重合体であれば特に限定されない。反応性と架橋密度の観点から、該化合物は、１分子内に２個以上のベンゾオキサジン環を有することが好ましい。 The benzoxazine resin composition of the present invention contains a benzoxazine resin. The benzoxazine resin is not particularly limited as long as it is a compound having a benzoxazine ring in the molecule (hereinafter also referred to as “benzoxazine compound”) and / or a ring-opened polymer thereof. From the viewpoint of reactivity and crosslink density, the compound preferably has two or more benzoxazine rings in one molecule.
ベンゾオキサジン化合物としては、例えば、式（５）： Examples of the benzoxazine compound include formula (5):
（式中、Ｒ４は、Ｃ１〜６のアルキレン基、酸素原子（−Ｏ−）、−ＣＯ−、式：−Ｓ（Ｏ）ｐ−（式中、ｐは０、１又は２を示す。）で示される基、式（７）： (In the formula, R 4 represents a C 1-6 alkylene group, an oxygen atom (—O—), —CO—, a formula: —S (O) p — (wherein p represents 0, 1 or 2). A group represented by formula (7):
で示される基、又は式（８）： Or a group represented by formula (8):
で示される基であり、Ｒ５は、置換基を有していてもよいアリール基である。）
で表される化合物、或いは、式（６）：
R 5 is an aryl group which may have a substituent. )
Or a compound represented by formula (6):
（式中、Ｒ６は、Ｃ１〜６のアルキレン基、酸素原子（−Ｏ−）、−ＣＯ−、式：−Ｓ（Ｏ）ｑ−（式中、ｑは０、１又は２を示す。）で示される基、又は式（９）： (In the formula, R 6 represents a C 1-6 alkylene group, an oxygen atom (—O—), —CO—, a formula: —S (O) q — (wherein q represents 0, 1 or 2). Or a group represented by formula (9):
で示される基であり、Ｒ７は、水素原子、又は置換基を有していてもよいＣ１〜６のアルキル基である。）
で表される化合物等が挙げられる。
R 7 is a hydrogen atom or a C1-6 alkyl group which may have a substituent. )
And the like.
式（５）において、Ｒ４で示されるＣ１〜６のアルキレン基は、直鎖又は分岐鎖状のアルキレン基であり、例えば、メチレン基、メチルメチレン基、エチルメチレン基、ジメチルメチレン基、ジエチルメチレン基、ジメチレン基（−ＣＨ２ＣＨ２−）、トリメチレン基（−ＣＨ２ＣＨ２ＣＨ２−）、テトラメチレン基、ペンタメチレン基、ヘキサメチレン基等が挙げられる。好ましくは、メチレン基、ジメチルメチレン基等のＣ１〜３のアルキレン基である。 In the formula (5), the C1-6 alkylene group represented by R 4 is a linear or branched alkylene group such as a methylene group, a methylmethylene group, an ethylmethylene group, a dimethylmethylene group, or diethylmethylene. Group, dimethylene group (—CH 2 CH 2 —), trimethylene group (—CH 2 CH 2 CH 2 —), tetramethylene group, pentamethylene group, hexamethylene group and the like. Preferably, it is a C1-3 alkylene group such as a methylene group or a dimethylmethylene group.
Ｒ５で示される置換基を有していてもよいアリール基のアリール基としては、単環、二環又は三環のアリール基が挙げられ、例えば、フェニル基、トルイル基、キシリル基、ナフチル基、アントリル基、フェナントリル基等が挙げられ、好ましくはフェニル基である。アリール基の置換基としては、例えば、アルキル基（例えば、メチル基、エチル基、ｎ−プロピル基等のＣ１〜４のアルキル基等）、アルコキシ基（例えば、メトキシ基、エトキシ基、ｎ−プロポキシ基等のＣ１〜４のアルコキシ基等）、アルケニル基（例えば、ビニル基、アリル基、クロチル基等のＣ２〜６のアルケニル基等）等が挙げられる。該アリール基は、１〜３個の該置換基を有していてもよい。 Examples of the aryl group of the aryl group which may have a substituent represented by R 5 include a monocyclic, bicyclic or tricyclic aryl group, for example, a phenyl group, a toluyl group, a xylyl group, a naphthyl group. , Anthryl group, phenanthryl group and the like, preferably a phenyl group. Examples of the substituent for the aryl group include an alkyl group (for example, a C1-4 alkyl group such as a methyl group, an ethyl group, and an n-propyl group), an alkoxy group (for example, a methoxy group, an ethoxy group, and an n-propoxy group). C1-4 alkoxy groups such as a group), alkenyl groups (for example, C2-6 alkenyl groups such as a vinyl group, an allyl group, a crotyl group, etc.) and the like. The aryl group may have 1 to 3 substituents.
ｐは０、１又は２であり、好ましくは０又は２である。 p is 0, 1 or 2, preferably 0 or 2.
式（５）において、Ｒ４がメチレン基、ジメチルメチレン基、酸素原子、−Ｓ−で示される基、式（７）で示される基、又は式（８）で示される基であり、Ｒ５がフェニル基であるものが好ましい。 In the formula (5), R 4 is a methylene group, a dimethylmethylene group, an oxygen atom, a group represented by —S—, a group represented by the formula (7), or a group represented by the formula (8), and R 5 Is preferably a phenyl group.
式（６）において、Ｒ６で示されるＣ１〜６のアルキレン基は、直鎖又は分岐鎖状のアルキレン基であり、例えば、メチレン基、メチルメチレン基、エチルメチレン基、ジメチルメチレン基、ジエチルメチレン基、ジメチレン基（−ＣＨ２ＣＨ２−）、トリメチレン基（−ＣＨ２ＣＨ２ＣＨ２−）、テトラメチレン基、ペンタメチレン基、ヘキサメチレン基、等が挙げられる。好ましくは、メチレン基、ジメチルメチレン基等のＣ１〜３のアルキレン基である。 In the formula (6), the C1-6 alkylene group represented by R 6 is a linear or branched alkylene group such as methylene group, methylmethylene group, ethylmethylene group, dimethylmethylene group, diethylmethylene group. Group, dimethylene group (—CH 2 CH 2 —), trimethylene group (—CH 2 CH 2 CH 2 —), tetramethylene group, pentamethylene group, hexamethylene group, and the like. Preferably, it is a C1-3 alkylene group such as a methylene group or a dimethylmethylene group.
ｑは０、１又は２であり、好ましくは０又は２である。 q is 0, 1 or 2, preferably 0 or 2.
Ｒ７で示される置換基を有していてもよいＣ１〜６のアルキル基のＣ１〜６のアルキル基としては、直鎖又は分岐鎖状のアルキル基であり、例えば、メチル基、エチル基、ｎ−プロピル基、イソプロピル基、ｎ−ブチル基、イソブチル基、ｔｅｒｔ−ブチル基、ｎ−ペンチル基等が挙げられる。好ましくは、メチル基、エチル基、イソプロピル基、又はｔｅｒｔ−ブチル基等のＣ１〜４アルキル基である。Ｃ１〜６のアルキル基の置換基としては、例えば、アルコキシ基（例えば、メトキシ基、エトキシ基、ｎ−プロポキシ基等のＣ１〜４のアルコキシ基等）、アルケニル基（例えば、ビニル基、アリル基、クロチル基等のＣ２〜６のアルケニル基等）、ハロゲン原子（例えば、フッ素原子、塩素原子、臭素原子等）等が挙げられる。該Ｃ１〜６のアルキル基は、１〜３個の該置換基を有していてもよい。 The C1-6 alkyl group of the C1-6 alkyl group which may have a substituent represented by R 7 is a linear or branched alkyl group, for example, a methyl group, an ethyl group, Examples include n-propyl group, isopropyl group, n-butyl group, isobutyl group, tert-butyl group, n-pentyl group and the like. Preferably, it is a C1-4 alkyl group such as a methyl group, an ethyl group, an isopropyl group, or a tert-butyl group. Examples of the substituent for the C1-6 alkyl group include an alkoxy group (for example, a C1-4 alkoxy group such as a methoxy group, an ethoxy group, and an n-propoxy group), an alkenyl group (for example, a vinyl group, an allyl group). And C2-6 alkenyl groups such as crotyl group), halogen atoms (for example, fluorine atom, chlorine atom, bromine atom and the like). The C1-6 alkyl group may have 1 to 3 substituents.
式（６）において、Ｒ６がメチレン基、ジメチルメチレン基、又は酸素原子であり、Ｒ７が水素原子であるものが好ましい。 In Formula (6), it is preferable that R 6 is a methylene group, a dimethylmethylene group, or an oxygen atom, and R 7 is a hydrogen atom.
上記式（５）及び式（６）で表される化合物は、公知の方法、例えば、特許文献１及び２、特開２０１０−２５４８９５号公報、国際公開第２０１２／０５７２９８号パンフレット等の記載に基づいて又は準じて製造することができる。 The compounds represented by the above formulas (5) and (6) are based on known methods such as Patent Documents 1 and 2, JP 2010-254895 A, International Publication No. 2012/057298 pamphlet and the like. Or can be produced according to the above.
上記式（５）で表される化合物は、一般に、ビスフェノール化合物とアミン化合物との反応によって製造することができ、その典型例として、ビスフェノールＡ型ベンゾオキサジン化合物、ビスフェノールＦ型ベンゾオキサジン化合物、チオジフェノール型ベンゾオキサジン化合物、フェノールフタレイン型ベンゾオキサジン化合物、ジシクロペンタジエン型ベンゾオキサジン化合物等が挙げられる。 The compound represented by the above formula (5) can generally be produced by a reaction between a bisphenol compound and an amine compound, and typical examples thereof include a bisphenol A type benzoxazine compound, a bisphenol F type benzoxazine compound, and a thiodioxide. Examples thereof include a phenol type benzoxazine compound, a phenolphthalein type benzoxazine compound, a dicyclopentadiene type benzoxazine compound, and the like.
上記式（６）で表される化合物は、一般に、フェニルジアミン化合物とフェノール化合物との反応によって製造することができ、その典型例としてジアミノジフェニルメタン型ベンゾオキサジン化合物等が挙げられる。 The compound represented by the above formula (6) can generally be produced by a reaction between a phenyldiamine compound and a phenol compound, and typical examples thereof include a diaminodiphenylmethane type benzoxazine compound.
本発明で用いるベンゾオキサジン樹脂としては、入手性の観点から、上記のベンゾオキサジン化合物及び／又はその開環重合体であることが好ましい。即ち、ビスフェノールＡ型ベンゾオキサジン化合物、ビスフェノールＦ型ベンゾオキサジン化合物、チオジフェノール型ベンゾオキサジン化合物、フェノールフタレイン型ベンゾオキサジン化合物、ジシクロペンタジエン型ベンゾオキサジン化合物を好適に用いることができる。 The benzoxazine resin used in the present invention is preferably the above benzoxazine compound and / or a ring-opening polymer thereof from the viewpoint of availability. That is, a bisphenol A type benzoxazine compound, a bisphenol F type benzoxazine compound, a thiodiphenol type benzoxazine compound, a phenolphthalein type benzoxazine compound, and a dicyclopentadiene type benzoxazine compound can be suitably used.
本発明で用いるベンゾオキサジン樹脂組成物は、式（１）で表される化合物（エポキシ樹脂）を含有する。式（１）において、Ｒ１は同一又は異なって、Ｃ１〜１８のアルキル基、Ｃ２〜９のアルケニル基、シクロアルキル基、アリール基又はアラルキル基であり、これらの基は、一部の炭素原子が、酸素原子及び窒素原子からなる群より選ばれる少なくとも１種の原子で置換されていてもよい。当該一部の炭素原子は、ケイ素原子に直接結合していない炭素原子であることが好ましい。 The benzoxazine resin composition used in the present invention contains a compound (epoxy resin) represented by the formula (1). In the formula (1), R 1 is the same or different and is a C1-18 alkyl group, a C2-9 alkenyl group, a cycloalkyl group, an aryl group or an aralkyl group, and these groups are a part of carbon atoms. May be substituted with at least one atom selected from the group consisting of an oxygen atom and a nitrogen atom. The partial carbon atoms are preferably carbon atoms that are not directly bonded to a silicon atom.
Ｒ１で示されるＣ１〜１８のアルキル基としては、直鎖又は分岐鎖状のアルキル基であり、例えば、メチル基、エチル基、ｎ−プロピル基、イソプロピル基、ｎ−ブチル基、イソブチル基、ｔｅｒｔ−ブチル基、ｎ−ペンチル基、ネオペンチル基、ｔｅｒｔ−ペンチル基、ｎ−ヘキシル基、ｎ−ヘプチル基、２，２，４−トリメチルペンチル基、ｎ−オクチル基、イソオクチル基、ｎ−ノニル基、ｎ−デシル基、ｎ−ドデシル基等が挙げられる。好ましくはＣ１〜１０のアルキル基であり、より好ましくはＣ１〜６のアルキル基であり、さらに好ましくはＣ１〜３のアルキル基であり、特に好ましくはメチル基である。 The C1-18 alkyl group represented by R 1 is a linear or branched alkyl group, for example, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, tert-butyl group, n-pentyl group, neopentyl group, tert-pentyl group, n-hexyl group, n-heptyl group, 2,2,4-trimethylpentyl group, n-octyl group, isooctyl group, n-nonyl group , N-decyl group, n-dodecyl group and the like. Preferably it is a C1-10 alkyl group, More preferably, it is a C1-6 alkyl group, More preferably, it is a C1-3 alkyl group, Most preferably, it is a methyl group.
Ｒ１で示されるＣ２〜９のアルケニル基としては、直鎖又は分岐鎖状のアルケニル基であり、例えば、ビニル基、アリル基、２−プロペニル基、ブテニル基、ペンテニル基、ヘキセニル基、ヘプテニル基、オクテニル基、ノネニル基等が挙げられる。好ましくはＣ２〜４のアルケニル基である。 The C2-9 alkenyl group represented by R 1 is a linear or branched alkenyl group, for example, vinyl group, allyl group, 2-propenyl group, butenyl group, pentenyl group, hexenyl group, heptenyl group. Octenyl group, nonenyl group and the like. Preferably it is a C2-4 alkenyl group.
Ｒ１で示されるシクロアルキル基としては、３〜８員環のシクロアルキル基が挙げられ、例えば、シクロペンチル基、シクロヘキシル基、シクロヘプチル基、メチルシクロヘキシル基等が挙げられる。 Examples of the cycloalkyl group represented by R 1 include a 3- to 8-membered cycloalkyl group, and examples thereof include a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, and a methylcyclohexyl group.
Ｒ１で示されるアリール基としては、単環又は二環のアリール基が挙げられ、例えば、フェニル基、トリル基、キシリル基、エチルフェニル基、ナフチル基等が挙げられる。中でも、フェニル基が好ましい。 Examples of the aryl group represented by R 1 include a monocyclic or bicyclic aryl group, and examples thereof include a phenyl group, a tolyl group, a xylyl group, an ethylphenyl group, and a naphthyl group. Of these, a phenyl group is preferred.
Ｒ１で示されるアラルキル基としては、アリール基（特にフェニル基）で置換されたＣ１〜４アルキル基が挙げられ、例えば、ベンジル基、α−フェネチル基、β−フェネチル基、β−メチルフェネチル基等が挙げられる。 Examples of the aralkyl group represented by R 1 include a C1-4 alkyl group substituted with an aryl group (particularly a phenyl group), such as a benzyl group, an α-phenethyl group, a β-phenethyl group, and a β-methylphenethyl group. Etc.
Ｒ１として、好ましくはＣ１〜３のアルキル基であり、より好ましくはメチル基である。 R 1 is preferably a C 1-3 alkyl group, and more preferably a methyl group.
式（１）において、Ｒ３は同一又は異なって、Ｃ１〜１８のアルキル基、Ｃ２〜９のアルケニル基、シクロアルキル基、アリール基又はアラルキル基であり、これらの基は、一部の炭素原子が、酸素原子及び窒素原子からなる群より選ばれる少なくとも１種の原子で置換されていてもよい。Ｒ３がオキシラン環と直接結合する場合、当該一部の炭素原子は、オキシラン環に直接結合していない炭素原子であることが好ましい。 In the formula (1), R 3 is the same or different and is a C1-18 alkyl group, a C2-9 alkenyl group, a cycloalkyl group, an aryl group or an aralkyl group, and these groups are a part of carbon atoms. May be substituted with at least one atom selected from the group consisting of an oxygen atom and a nitrogen atom. When R 3 is directly bonded to the oxirane ring, the partial carbon atom is preferably a carbon atom that is not directly bonded to the oxirane ring.
Ｒ３で示されるＣ１〜１８のアルキル基、Ｃ２〜９のアルケニル基、シクロアルキル基、アリール基及びアラルキル基はそれぞれ、上記Ｒ１で示される対応する置換基と同様のものが挙げられる。 Alkyl group C1~18 represented by R 3, an alkenyl group of C2～9, cycloalkyl group, each aryl group and aralkyl group, those similar to the corresponding substituents represented by R 1 can be mentioned.
Ｒ３として、好ましくはＣ１〜３のアルキル基であり、より好ましくはメチル基である。 R 3 is preferably a C 1-3 alkyl group, more preferably a methyl group.
式（１）において、ｎは同一又は異なって、０〜３の整数である。好ましくは、０又は１であり、より好ましくは０である。 In Formula (1), n is the same or different and is an integer of 0-3. Preferably, it is 0 or 1, more preferably 0.
式（１）において、Ｒ２は同一又は異なって、Ｃ１〜１８のアルキレン基であり、直鎖又は分岐鎖状のアルキレン基であり、例えば、メチレン基、メチルメチレン基、エチルメチレン基、ジメチルメチレン基、ジエチルメチレン基、ジメチレン基（−ＣＨ２ＣＨ２−）、トリメチレン基（−ＣＨ２ＣＨ２ＣＨ２−）、テトラメチレン基、ペンタメチレン基、ヘキサメチレン基、ヘプタメチレン基、オクタメチレン基、ノナメチレン基、デカメチレン基、ウンデカメチレン基、ドデカメチレン基、トリデカメチレン基等が挙げられる。好ましくはＣ２〜１０のアルキレン基であり、より好ましくはＣ２〜４のアルキレン基であり、さらに好ましくはＣ２又は３のアルキレン基（特にジメチレン基又はトリメチレン基）であり、特に好ましくはＣ２のアルキレン基（特にジメチレン基）である。 In the formula (1), R 2 is the same or different and is a C1-18 alkylene group, which is a linear or branched alkylene group, such as a methylene group, a methylmethylene group, an ethylmethylene group, or a dimethylmethylene group. Group, diethylmethylene group, dimethylene group (—CH 2 CH 2 —), trimethylene group (—CH 2 CH 2 CH 2 —), tetramethylene group, pentamethylene group, hexamethylene group, heptamethylene group, octamethylene group, Nonamethylene group, decamethylene group, undecamethylene group, dodecamethylene group, tridecamethylene group and the like can be mentioned. Preferred is a C2-10 alkylene group, more preferred is a C2-4 alkylene group, still more preferred is a C2 or 3 alkylene group (particularly a dimethylene group or trimethylene group), and particularly preferred is a C2 alkylene group. (Especially dimethylene group).
このＣ１〜１８のアルキレン基は、ケイ素原子に直接結合した炭素原子を除く一部の炭素原子が、酸素原子及び窒素原子からなる群より選ばれる少なくとも１種の原子で置換されていてもよい。当該一部の炭素原子は、Ｒ２がオキシラン環と直接結合する場合、オキシラン環に直接結合していない炭素原子であることが好ましい。 In the C1-18 alkylene group, a part of carbon atoms excluding a carbon atom directly bonded to a silicon atom may be substituted with at least one atom selected from the group consisting of an oxygen atom and a nitrogen atom. The some carbon atoms are preferably carbon atoms not directly bonded to the oxirane ring when R 2 is directly bonded to the oxirane ring.
式（１）において、Ｘで示される炭化水素環から２個の水素原子を除いて得られる２価の基の「炭化水素環」としては、単環若しくは多環（特に２又は３環）の脂肪族炭化水素環又は単環若しくは多環の芳香族炭化水素環が挙げられる。例えば、シクロペンタン環、シクロヘキサン環、テトラリン環、デカヒドロナフタレン環、１，２，３，４，５，６，７，８−オクタヒドロナフタレン環、ノルボルネン環、アダマンタン環、ベンゼン環、トルエン環、キシレン環、ナフタレン環、フェナントレン環、アントラセン環、ピレン環、トリフェニレン環等が挙げられる。好ましくはシクロヘキサン環、ベンゼン環である。Ｘで示される２価の基として、好ましくはシクロヘキサン−１，４−ジイル基、１，４−フェニレン基が挙げられ、より好ましくは１，４−フェニレン基である。 In the formula (1), the “hydrocarbon ring” of the divalent group obtained by removing two hydrogen atoms from the hydrocarbon ring represented by X is monocyclic or polycyclic (particularly 2 or 3 rings). Examples thereof include an aliphatic hydrocarbon ring and a monocyclic or polycyclic aromatic hydrocarbon ring. For example, cyclopentane ring, cyclohexane ring, tetralin ring, decahydronaphthalene ring, 1,2,3,4,5,6,7,8-octahydronaphthalene ring, norbornene ring, adamantane ring, benzene ring, toluene ring, Examples include a xylene ring, a naphthalene ring, a phenanthrene ring, an anthracene ring, a pyrene ring, and a triphenylene ring. Of these, a cyclohexane ring and a benzene ring are preferable. The divalent group represented by X is preferably a cyclohexane-1,4-diyl group or a 1,4-phenylene group, more preferably a 1,4-phenylene group.
式（２）において、Ｙで示されるＣ１〜６のアルキレン基としては、鎖状又は分岐鎖状のアルキレン基であり、例えば、メチレン基、メチルメチレン基、エチルメチレン基、ジメチルメチレン基、ジエチルメチレン基、ジメチレン基（−ＣＨ２ＣＨ２−）、トリメチレン基（−ＣＨ２ＣＨ２ＣＨ２−）等が挙げられる。 In the formula (2), the C1-6 alkylene group represented by Y is a chain or branched alkylene group, for example, a methylene group, a methylmethylene group, an ethylmethylene group, a dimethylmethylene group, a diethylmethylene group. Group, dimethylene group (—CH 2 CH 2 —), trimethylene group (—CH 2 CH 2 CH 2 —) and the like.
式（２）において、ｍは０、１又は２であり、好ましくは０又は２である。
Ｙは好ましくは、結合手、酸素原子、メチレン基、ジメチルメチレン基、−Ｓ−、−ＳＯ２−であり、より好ましくは、結合手、ジメチルメチレン基、酸素原子、−ＳＯ２−である。
In the formula (2), m is 0, 1 or 2, preferably 0 or 2.
Y is preferably a bond, an oxygen atom, a methylene group, dimethylmethylene group, -S -, - SO 2 -, more preferably an a bond, a dimethylmethylene group, an oxygen atom, -SO 2 - is.
式（２）で表される２価の基のうち好ましくは、式（２ａ）： Of the divalent groups represented by the formula (2), the formula (2a):
（式中、Ｙは前記に同じ。）
で表される基である。
(Wherein Y is the same as above)
It is group represented by these.
式（２ａ）において、Ｙが結合手、ジメチルメチレン基、酸素原子、−ＳＯ２−であるものが好ましい。 In formula (2a), it is preferable that Y is a bond, a dimethylmethylene group, an oxygen atom, or —SO 2 —.
上記式（１）で表されるエポキシ樹脂のうち好ましくは、式（１ａ）： Of the epoxy resins represented by the formula (1), the formula (1a):
（式中、各記号は前記に同じ。）
で表される化合物である。
(In the formula, each symbol is the same as above.)
It is a compound represented by these.
式（１ａ）において、Ｒ１がいずれもＣ１〜３アルキル基（特にメチル基）であり、ｎが共に０であり、Ｒ２が共にジメチレン基であり、Ｘが１，４−フェニレン基であるものが好ましい。 In formula (1a), R 1 is any C1-3 alkyl group (particularly methyl group), n is both 0, R 2 is both dimethylene group, and X is 1,4-phenylene group. Those are preferred.
式（１）で表されるエポキシ樹脂（式（１ａ）で表されるエポキシ樹脂を包含する）は、公知の方法、例えば、特開２０１２−１６６８号公報、及び英国特許第１２３９６０号公報等の記載に基づいて又は準じて製造することができる。具体例の１つとして、次の反応式により製造することができる。 The epoxy resin represented by the formula (1) (including the epoxy resin represented by the formula (1a)) is a known method such as those disclosed in JP2012-1668A and British Patent No.123960. It can be produced based on or according to the description. As one specific example, it can be produced by the following reaction formula.
（式中、Ｒ２Ａは、Ｃ１〜１８のアルキリデン基又はＣ２〜１８のアルケニル基であり、他の記号は前記に同じ。）
Ｒ２Ａで示されるＣ１〜１８のアルキリデン基としては、直鎖又は分岐鎖状のアルキリデン基であり、例えば、メチリデン基、プロピリデン基、イソプロピリデン基、ブチリデン基、イソブチリデン基、ｓｅｃ−ブチリデン基、ペンチリデン基、イソペンチリデン基、オクチリデン基、イソオクチリデン基等が挙げられる。好ましくはＣ１〜１０のアルキリデン基であり、より好ましくはＣ１〜４のアルキリデン基であり、さらに好ましくはＣ１〜３のアルキリデン基であり、特に好ましくはメチリデン基又はエチリデン基である。
(In the formula, R 2A is a C1-18 alkylidene group or a C2-18 alkenyl group, and other symbols are the same as above.)
The C1-18 alkylidene group represented by R 2A is a linear or branched alkylidene group, such as a methylidene group, a propylidene group, an isopropylidene group, a butylidene group, an isobutylidene group, a sec-butylidene group, or a pentylidene group. Group, isopentylidene group, octylidene group, isooctylidene group and the like. Preferably it is a C1-10 alkylidene group, more preferably a C1-4 alkylidene group, still more preferably a C1-3 alkylidene group, and particularly preferably a methylidene group or an ethylidene group.
Ｒ２Ａで示されるＣ２〜１８のアルケニル基としては、直鎖又は分岐鎖状のアルケニル基であり、例えば、ビニル基、アリル基、プロペニル基、ブテニル基、ペンテニル基、ヘキセニル基、ヘプテニル基、オクテニル基、ノルボルネニル基、シクロヘキセニル基等が挙げられる。好ましくはＣ２〜１０のアルケニル基であり、より好ましくはＣ２〜４のアルケニル基であり、さらに好ましくはＣ２又は３のアルケニル基であり、特に好ましくはビニル基又はアリル基である。 The C2-18 alkenyl group represented by R 2A is a linear or branched alkenyl group, for example, vinyl group, allyl group, propenyl group, butenyl group, pentenyl group, hexenyl group, heptenyl group, octenyl. Group, norbornenyl group, cyclohexenyl group and the like. Preferred is a C2-10 alkenyl group, more preferred is a C2-4 alkenyl group, still more preferred is a C2 or 3 alkenyl group, and particularly preferred is a vinyl group or an allyl group.
式（３）で表される化合物と式（４）で表される化合物をヒドロシリル化反応させて製造することができる。ヒドロシリル化反応は、通常、触媒の存在下、溶媒の存在下又は非存在下で実施することができる。 The compound represented by the formula (3) and the compound represented by the formula (4) can be produced by a hydrosilylation reaction. The hydrosilylation reaction can usually be carried out in the presence of a catalyst, in the presence or absence of a solvent.
ヒドロシリル化反応に用いられる触媒は、公知の触媒でよく、例えば、白金カーボン、塩化白金酸、白金のオレフィン錯体、白金のアルケニルシロキサン錯体、白金のカルボニル錯体等の白金系触媒；トリス(トリフェニルフォスフィン)ロジウム等のロジウム系触媒；ビス(シクロオクタジエニル)ジクロロイリジウム等のイリジウム系触媒が挙げられる。上記の触媒は溶媒和物（例えば、水和物、アルコール和物等）の形態であってもよく、また使用にあたり触媒をアルコール（例えば、エタノール等）に溶解して溶液の形態で用いることもできる。 The catalyst used in the hydrosilylation reaction may be a known catalyst, for example, platinum-based catalysts such as platinum carbon, chloroplatinic acid, platinum olefin complexes, platinum alkenylsiloxane complexes, platinum carbonyl complexes; Examples include rhodium-based catalysts such as (fin) rhodium; and iridium-based catalysts such as bis (cyclooctadienyl) dichloroiridium. The above catalyst may be in the form of a solvate (for example, hydrate, alcohol solvate, etc.). In use, the catalyst may be dissolved in an alcohol (for example, ethanol) and used in the form of a solution. it can.
触媒の使用量は、触媒としての有効量でよく特に限定されないが、通常、上記式（３）で表される化合物と式（４）で表される化合物の合計量１００質量部に対して ０．００００１〜２０質量部、好ましくは０．０００５〜５質量部である。 The amount of the catalyst used may be an effective amount as a catalyst, and is not particularly limited. 0.0001 to 20 parts by mass, preferably 0.0005 to 5 parts by mass.
前記ヒドロシリル化反応は溶媒を用いなくても進行するが、溶媒を用いることにより穏和な条件で反応を行うことができる。溶媒としては、例えば、トルエン、キシレンなどの芳香族炭化水素溶媒；ヘキサン、オクタンなどの脂肪族炭化水素溶媒；テトラヒドロフラン、ジオキサンなどのエーテル系溶媒；エタノール、イソプロパノールなどのアルコール系溶媒などが挙げられ、これらは単独であるいは２種以上組み合わせてもよい。 The hydrosilylation reaction proceeds without using a solvent, but the reaction can be performed under mild conditions by using a solvent. Examples of the solvent include aromatic hydrocarbon solvents such as toluene and xylene; aliphatic hydrocarbon solvents such as hexane and octane; ether solvents such as tetrahydrofuran and dioxane; alcohol solvents such as ethanol and isopropanol; These may be used alone or in combination of two or more.
式（４）で表される化合物の使用量は、式（３）で表される化合物中のＳｉ−Ｈ基１モルに対して、通常、０．５〜２モル、好ましくは０．６〜１．５モル、さらに好ましくは０．８〜１．２モルである。 The amount of the compound represented by the formula (4) is usually 0.5 to 2 mol, preferably 0.6 to the mol of the Si—H group in the compound represented by the formula (3). The amount is 1.5 mol, more preferably 0.8 to 1.2 mol.
反応温度は２０℃〜１５０℃、好ましくは５０℃〜１２０℃であり、反応時間は１時間〜２４時間程度である。 The reaction temperature is 20 ° C. to 150 ° C., preferably 50 ° C. to 120 ° C., and the reaction time is about 1 to 24 hours.
反応終了後、反応液から溶媒を留去するなどして、式（１）で表される化合物を得ることができる。 After completion of the reaction, the compound represented by the formula (1) can be obtained by evaporating the solvent from the reaction solution.
式（１）で表される化合物の配合量は、ベンゾオキサジン樹脂１００質量部に対して、通常、５〜５００質量部、好ましくは１０〜２００質量部、より好ましくは１５〜１５０質量部、特に好ましくは２０〜１００質量部である。 The compounding amount of the compound represented by the formula (1) is usually 5 to 500 parts by mass, preferably 10 to 200 parts by mass, more preferably 15 to 150 parts by mass, particularly 100 parts by mass of the benzoxazine resin. Preferably it is 20-100 mass parts.
本発明のベンゾオキサジン樹脂組成物は、必要に応じて、ベンゾオキサジン樹脂及び式（１）で表される化合物以外のその他の樹脂を含有してもよい。上記その他の樹脂としては、例えば、エポキシ樹脂、ユリア樹脂、メラミン樹脂、不飽和ポリエステル、ビニルエステル樹脂、ジアリルフタレート樹脂、ポリウレタン、ケイ素樹脂、ポリイミド、塩化ビニル樹脂、塩化ビニリデン樹脂、酢酸ビニル樹脂、ポリスチレン、メタクリル樹脂、ポリエチレン、ポリプロピレン、フッ素樹脂、ポリアミド、ポリアセタール、ポリカーボネート、ポリエステル、ポリフェニレンエーテル、ポリフェニレンスルフィド、ポリアリレート、ポリスルホン、ポリエーテルスルホン、ポリエーテルエーテルケトン、液晶性ポリマー等が挙げられる。 The benzoxazine resin composition of the present invention may contain other resins other than the benzoxazine resin and the compound represented by the formula (1) as necessary. Examples of the other resin include epoxy resin, urea resin, melamine resin, unsaturated polyester, vinyl ester resin, diallyl phthalate resin, polyurethane, silicon resin, polyimide, vinyl chloride resin, vinylidene chloride resin, vinyl acetate resin, polystyrene. Methacrylic resin, polyethylene, polypropylene, fluororesin, polyamide, polyacetal, polycarbonate, polyester, polyphenylene ether, polyphenylene sulfide, polyarylate, polysulfone, polyethersulfone, polyetheretherketone, liquid crystalline polymer and the like.
本発明のベンゾオキサジン樹脂組成物は、更に硬化促進剤を含有していてもよい。これにより、硬化物の耐熱性、金属への接着性、耐薬品性等を更に向上させることができる。硬化促進剤としては、特に限定されないが、例えば、アミン系硬化促進剤、グアニジン系硬化促進剤、イミダゾール系硬化促進剤、ホスホニウム系硬化促進剤、金属系硬化促進剤等が挙げられる。これらは１種又は２種以上組み合わせて使用してもよい。 The benzoxazine resin composition of the present invention may further contain a curing accelerator. Thereby, the heat resistance of a hardened | cured material, the adhesiveness to a metal, chemical-resistance, etc. can be improved further. Although it does not specifically limit as a hardening accelerator, For example, an amine type hardening accelerator, a guanidine type hardening accelerator, an imidazole type hardening accelerator, a phosphonium type hardening accelerator, a metal type hardening accelerator etc. are mentioned. These may be used alone or in combination of two or more.
前記硬化促進剤の配合量は特に限定されないが、硬化物の耐熱性、金属への接着性等がより優れたベンゾオキサジン樹脂組成物が得られることから、ベンゾオキサジン樹脂及び式（１）で表される化合物の合計量１００質量部に対して、好ましくは０．１〜５．０質量部であり、より好ましくは０．５〜２質量部である。 Although the compounding quantity of the said hardening accelerator is not specifically limited, Since the benzoxazine resin composition which was excellent in the heat resistance of hardened | cured material, the adhesiveness to a metal, etc. is obtained, it represents with a benzoxazine resin and Formula (1). Preferably it is 0.1-5.0 mass part with respect to 100 mass parts of total amounts of the compound made, More preferably, it is 0.5-2 mass part.
本発明のベンゾオキサジン樹脂組成物は、本発明の目的や効果を損なわない範囲で、必要に応じて添加剤を含有してもよい。前記添加剤としては、例えば、無機フィラー、繊維状強化剤、エラストマー成分、酸化防止剤、無機蛍光体、滑剤、紫外線吸収剤、熱光安定剤、分散剤、帯電防止剤、重合禁止剤、消泡剤、硬化促進剤、溶剤、老化防止剤、ラジカル禁止剤、接着性改良剤、難燃剤、界面活性剤、保存安定性改良剤、オゾン老化防止剤、増粘剤、可塑剤、放射線遮断剤、核剤、カップリング剤、導電性付与剤、リン系過酸化物分解剤、顔料、金属不活性化剤、物性調整剤等が挙げられる。 The benzoxazine resin composition of the present invention may contain an additive as necessary within a range that does not impair the object and effect of the present invention. Examples of the additive include an inorganic filler, a fibrous reinforcing agent, an elastomer component, an antioxidant, an inorganic phosphor, a lubricant, an ultraviolet absorber, a heat-light stabilizer, a dispersant, an antistatic agent, a polymerization inhibitor, a quencher. Foaming agent, curing accelerator, solvent, anti-aging agent, radical inhibitor, adhesion improver, flame retardant, surfactant, storage stability improving agent, ozone anti-aging agent, thickener, plasticizer, radiation blocker , Nucleating agent, coupling agent, conductivity imparting agent, phosphorus peroxide decomposing agent, pigment, metal deactivator, physical property adjusting agent and the like.
本発明のベンゾオキサジン樹脂組成物は、ベンゾオキサジン樹脂、及び式（１）で表される化合物、さらに必要に応じて他の成分を混合することにより製造することができる。混合方法は、均一に混合できる方法であれば特に限定はない。 The benzoxazine resin composition of the present invention can be produced by mixing a benzoxazine resin, a compound represented by the formula (1), and other components as necessary. The mixing method is not particularly limited as long as it can be uniformly mixed.
本発明のベンゾオキサジン樹脂組成物を硬化することにより硬化物を得ることができる。硬化の方法は、特に限定されず、例えば、該組成物を加熱硬化することで実施できる。また、ベンゾオキサジン樹脂組成物を溶剤（例えば、トルエン、アセトン等）に溶解させてワニスを調製し、該ワニスを基材（例えば、銅箔、アルミ箔、ポリイミドフィルム等）上に塗布し加熱することによりフィルム状の硬化物を得ることができる。また、該ワニスを、繊維状強化剤（ガラス繊維、カーボン線維等）の基材に含浸させて乾燥したプリプレグを、加熱加圧してシート状の硬化物にすることもできる。硬化温度は、通常１２０〜２５０℃であり、硬化時間は、通常１〜１２時間である。 A cured product can be obtained by curing the benzoxazine resin composition of the present invention. The curing method is not particularly limited, and can be carried out, for example, by heat curing the composition. Moreover, a benzoxazine resin composition is dissolved in a solvent (eg, toluene, acetone, etc.) to prepare a varnish, and the varnish is applied onto a substrate (eg, copper foil, aluminum foil, polyimide film, etc.) and heated. Thus, a film-like cured product can be obtained. Further, a prepreg dried by impregnating the varnish into a base material of a fibrous reinforcing agent (glass fiber, carbon fiber, etc.) can be heated and pressed to obtain a sheet-like cured product. The curing temperature is usually 120 to 250 ° C., and the curing time is usually 1 to 12 hours.
本発明のベンゾオキサジン樹脂組成物は、硬化後の硬化物が優れた耐熱性及び接着性を有することから、例えば、半導体封止体、液状封止材、ポッティング材、シール材、プリント基板材料、複合材料等の用途に好適に用いることができる。また、本発明には、当該ベンゾオキサジン樹脂組成物又はその硬化物が用いられた半導体封止体、液状封止材、ポッティング材、シール材、プリント基板材料、及び複合材も包含される。 Since the benzoxazine resin composition of the present invention has excellent heat resistance and adhesiveness after cured, for example, a semiconductor encapsulant, a liquid encapsulant, a potting material, a seal material, a printed circuit board material, It can use suitably for uses, such as a composite material. The present invention also includes a semiconductor encapsulant, a liquid encapsulant, a potting material, a seal material, a printed board material, and a composite material using the benzoxazine resin composition or a cured product thereof.
以下に実施例を掲げて本発明を更に詳しく説明するが、本発明はこれら実施例のみに限定されない。 Hereinafter, the present invention will be described in more detail with reference to examples. However, the present invention is not limited to these examples.
製造例１（式（１）で表されるケイ素含有化合物の製造）
攪拌機、温度計及び冷却器を備え付けた５００ｍＬ容の四つ口フラスコに、窒素雰囲気下で、ビニルシクロヘキセンオキシド２５ｇ、ヘキサクロロ白金酸六水和物の２ｗｔ％エタノール溶液０．２５ｇ、トルエン２５０ｇを仕込み、７０℃まで昇温させた後、１，４−ビス（ジメチルシリル）ベンゼン２０ｇをゆっくりと滴下し、その後、９０℃で４時間攪拌した。トルエンを濃縮後、微黄色液体（ケイ素含有化合物：１，４−ジ［２−（３，４−エポキシシクロヘキシルエチル）ジメチルシリル］ベンゼン）４２ｇを取得した。
Production Example 1 (Production of silicon-containing compound represented by formula (1))
A 500 mL four-necked flask equipped with a stirrer, a thermometer and a condenser was charged with 25 g of vinylcyclohexene oxide, 0.25 g of a 2 wt% ethanol solution of hexachloroplatinic acid hexahydrate, and 250 g of toluene under a nitrogen atmosphere. After raising the temperature to 70 ° C., 20 g of 1,4-bis (dimethylsilyl) benzene was slowly added dropwise and then stirred at 90 ° C. for 4 hours. After concentrating toluene, 42 g of a slightly yellow liquid (silicon-containing compound: 1,4-di [2- (3,4-epoxycyclohexylethyl) dimethylsilyl] benzene) was obtained.
実施例１〜４、比較例１〜２
表１に記載した配合量の各成分を均一に加温混合し、その後、充分に脱気することでベンゾオキサジン樹脂組成物を調製した。
Examples 1-4, Comparative Examples 1-2
A benzoxazine resin composition was prepared by uniformly warming and mixing the components in the amounts shown in Table 1 and then thoroughly degassing.
表１中の各成分は以下の通りである。
・ベンゾオキサジン樹脂：フェノール−ジアミノジフェニルメタン型（Ｐ−ｄ型）ベンゾオキサジン樹脂（四国化成（株）製）
・ビスフェノールＡ型エポキシ樹脂：ＪＥＲ８２８（三菱化学（株）製）
Each component in Table 1 is as follows.
Benzoxazine resin: phenol-diaminodiphenylmethane type (Pd type) benzoxazine resin (manufactured by Shikoku Kasei Co., Ltd.)
・ Bisphenol A type epoxy resin: JER828 (manufactured by Mitsubishi Chemical Corporation)
（１）アルミニウムＡに対する引張せん断接着強度
実施例１〜４及び比較例１〜２で得られた各ベンゾオキサジン樹脂組成物を、接着部が１２．５×２５ｍｍの長方形になるようにアルミニウムＡ：アルミニウム板（ＪＩＳ Ｈ４０００、Ａ１０５０Ｐ）（サイズ２×２５×１００ｍｍ）に塗布し、もう一枚のアルミニウム板を貼り合わせ、１８０℃で２時間、２００℃で３時間加熱して硬化させ、引張せん断接着試験片とした。
(1) Tensile shear adhesive strength to aluminum A Aluminum A: The benzoxazine resin compositions obtained in Examples 1 to 4 and Comparative Examples 1 and 2 were bonded to each other in a rectangular shape with an adhesive part of 12.5 × 25 mm. Apply to aluminum plate (JIS H4000, A1050P) (size 2 × 25 × 100mm), and paste another aluminum plate and cure by heating at 180 ° C for 2 hours and 200 ° C for 3 hours, tensile shear bonding A test piece was obtained.
得られた接着試験片について、引張試験機（ＡＧＳ−Ｘ、島津製作所（株）製）を用いて、つかみ具間距離１００ｍｍ、試験速度５ｍｍ／ｍｉｎの条件で引張せん断接着試験を行い、最大破断強度の測定値と接着面積から、引張せん断接着強度を算出した。 Using the tensile tester (AGS-X, manufactured by Shimadzu Corporation), the obtained adhesion test piece was subjected to a tensile shear adhesion test under the conditions of a distance between grips of 100 mm and a test speed of 5 mm / min. The tensile shear bond strength was calculated from the measured strength value and the bonding area.
（２）アルミニウムＢに対する引張せん断接着強度
実施例１〜４及び比較例１〜２で得られた各ベンゾオキサジン樹脂組成物を、接着部が１２．５×２５ｍｍの長方形になるようにアルミニウムＢ：アルミニウム板（ＪＩＳ Ｈ４０００、Ａ５０５２Ｐ）（サイズ２×２５×１００ｍｍ）に塗布し、もう一枚のアルミニウム板を貼り合わせ、１８０℃で２時間、２００℃で３時間加熱して硬化させ、引張せん断接着試験片とした。
(2) Tensile shear adhesive strength to aluminum B Aluminum B: Each of the benzoxazine resin compositions obtained in Examples 1 to 4 and Comparative Examples 1 to 2 has a rectangular shape of 12.5 × 25 mm. Apply to aluminum plate (JIS H4000, A5052P) (size 2 × 25 × 100mm), and paste another aluminum plate, heat and cure at 180 ° C for 2 hours and 200 ° C for 3 hours, tensile shear bonding A test piece was obtained.
得られた接着試験片について、引張試験機（ＡＧＳ−Ｘ、島津製作所（株）製）を用いて、つかみ具間距離１００ｍｍ、試験速度５ｍｍ／ｍｉｎの条件で引張せん断接着試験を行い、最大破断強度の測定値と接着面積から、引張せん断接着強度を算出した。 Using the tensile tester (AGS-X, manufactured by Shimadzu Corporation), the obtained adhesion test piece was subjected to a tensile shear adhesion test under the conditions of a distance between grips of 100 mm and a test speed of 5 mm / min. The tensile shear bond strength was calculated from the measured strength value and the bonding area.
（３）銅に対する引張せん断接着強度
実施例１〜４及び比較例１〜２で得られた各ベンゾオキサジン樹脂組成物を、接着部が１２．５×２５ｍｍの長方形になるように無酸素銅板（ＪＩＳ Ｈ３１００、１０２０Ｐ）（サイズ２×２５×１００ｍｍ）に塗布し、もう一枚の無酸素銅板を貼り合わせ、１８０℃で２時間、２００℃で３時間加熱して硬化させ、引張せん断接着試験片とした。
(3) Tensile shear adhesive strength to copper Each of the benzoxazine resin compositions obtained in Examples 1 to 4 and Comparative Examples 1 to 2 is an oxygen-free copper plate so that the bonded portion has a rectangular shape of 12.5 × 25 mm ( JIS H3100, 1020P) (size 2 × 25 × 100mm), another oxygen-free copper plate is bonded together, cured by heating at 180 ° C. for 2 hours and 200 ° C. for 3 hours, and a tensile shear adhesion test piece It was.
得られた接着試験片について、引張試験機（ＡＧＳ−Ｘ、島津製作所（株）製）を用いて、つかみ具間距離１００ｍｍ、試験速度５ｍｍ／ｍｉｎの条件で引張せん断接着試験を行い、最大破断強度の測定値と接着面積から、引張せん断接着強度を算出した。 Using the tensile tester (AGS-X, manufactured by Shimadzu Corporation), the obtained adhesion test piece was subjected to a tensile shear adhesion test under the conditions of a distance between grips of 100 mm and a test speed of 5 mm / min. The tensile shear bond strength was calculated from the measured strength value and the bonding area.
（４）電気特性（誘電特性）
実施例１〜４及び比較例１〜２で得られた各ベンゾオキサジン樹脂組成物を樹脂製モールド（厚さ２ｍｍ）に流し込み、１００℃で１時間、１２０℃で２時間、１５０℃で２時間加熱して硬化させ、誘電率測定用試験片とした。
(4) Electrical characteristics (dielectric characteristics)
Each benzoxazine resin composition obtained in Examples 1 to 4 and Comparative Examples 1 to 2 was poured into a resin mold (thickness 2 mm), and was 100 ° C. for 1 hour, 120 ° C. for 2 hours, and 150 ° C. for 2 hours. It was cured by heating to obtain a dielectric constant measurement specimen.
得られた試験片について、誘電率測定装置（インピーダンスアナライザー、アジレント（株）製）を用いて、ＰＴＦＥで校正した後、比誘電率（１ＧＨｚ）及び誘電正接（１ＧＨｚ）を測定した。その結果を表１に示す。 About the obtained test piece, after calibrating with PTFE using the dielectric constant measuring apparatus (impedance analyzer, the Agilent make), the dielectric constant (1 GHz) and the dielectric loss tangent (1 GHz) were measured. The results are shown in Table 1.
（５）ガラス転移温度
実施例１〜４及び比較例１〜２で得られた各ベンゾオキサジン樹脂組成物を樹脂製モールドに流し込み、１８０℃で２時間、２００℃で３時間加熱して硬化させ、ガラス転移温度測定用試験片としたとした。
(5) Glass transition temperature Each benzoxazine resin composition obtained in Examples 1 to 4 and Comparative Examples 1 and 2 was poured into a resin mold and cured by heating at 180 ° C. for 2 hours and 200 ° C. for 3 hours. A glass transition temperature measurement specimen was obtained.
得られた試験片について、熱機械分析装置（ＳＳＣ５２００、エスアイアイ・ナノテクノロジー社製、ＳＳＣ５２００）を用いて、圧縮モード、荷重５０ｍＮ、５℃／ｍｉｎで、ガラス転移温度を測定した。 About the obtained test piece, the glass transition temperature was measured by the compression mode, the load of 50 mN, and 5 degree-C / min using the thermomechanical analyzer (SSC5200, the SII nanotechnology company make, SSC5200).
実施例１〜４に記載の式（１）で表されるケイ素含有化合物を含むベンゾオキサジン樹脂組成物は、金属に対する優れた接着性及び高耐熱性を有している。さらに、低誘電率、低誘電正接であり優れた誘電特性を有している。 The benzoxazine resin composition containing the silicon-containing compound represented by the formula (1) described in Examples 1 to 4 has excellent adhesion to metal and high heat resistance. Furthermore, it has a low dielectric constant and a low dielectric loss tangent and has excellent dielectric properties.
一方で、ベンゾオキサジン樹脂のみの場合（比較例１）は、接着強度及び耐熱性に劣っている。また、ケイ素含有化合物に代えて、ビスフェノールＡ型エポキシ樹脂を含むベンゾオキサジン樹脂組成物（比較例２）は、接着強度及び電気特性の点で劣っている。 On the other hand, when only the benzoxazine resin is used (Comparative Example 1), the adhesive strength and heat resistance are poor. Moreover, it replaced with the silicon containing compound and the benzoxazine resin composition (Comparative Example 2) containing a bisphenol A type epoxy resin is inferior in terms of adhesive strength and electrical characteristics.
Claims (7)
Ｒ１は同一又は異なって、Ｃ１〜１８のアルキル基、Ｃ２〜９のアルケニル基、シクロアルキル基、アリール基又はアラルキル基であり、これらの基は、一部の炭素原子が、酸素原子及び窒素原子からなる群より選ばれる少なくとも１種の原子で置換されていてもよく、
Ｒ２は同一又は異なって、Ｃ１〜１８のアルキレン基であり、この基は、ケイ素原子に直接結合した炭素原子を除く一部の炭素原子が、酸素原子及び窒素原子からなる群より選ばれる少なくとも１種の原子で置換されていてもよく、
Ｒ３は同一又は異なって、Ｃ１〜１８のアルキル基、Ｃ２〜９のアルケニル基、シクロアルキル基、アリール基又はアラルキル基であり、これらの基は、一部の炭素原子が、酸素原子及び窒素原子からなる群より選ばれる少なくとも１種の原子で置換されていてもよく、
ｎは同一又は異なって、０〜３の整数である。）
で表される化合物を含有するベンゾオキサジン樹脂組成物。 Benzoxazine resin and formula (1):
R 1 may be the same or different and is a C1-18 alkyl group, a C2-9 alkenyl group, a cycloalkyl group, an aryl group or an aralkyl group, and these groups have some carbon atoms, oxygen atoms and nitrogens. May be substituted with at least one atom selected from the group consisting of atoms;
R 2 is the same or different and is a C1-18 alkylene group, and this group is a group in which some carbon atoms excluding the carbon atom directly bonded to the silicon atom are selected from the group consisting of an oxygen atom and a nitrogen atom. May be substituted with one atom,
R 3 is the same or different and is a C1-18 alkyl group, a C2-9 alkenyl group, a cycloalkyl group, an aryl group or an aralkyl group, and these groups have a part of carbon atoms, oxygen atom and nitrogen May be substituted with at least one atom selected from the group consisting of atoms;
n is the same or different and is an integer of 0-3. )
The benzoxazine resin composition containing the compound represented by these.
で表される化合物及び／又はその開環重合体、或いは、式（６）：
で表される化合物及び／又はその開環重合体である請求項１に記載のベンゾオキサジン樹脂組成物。 The benzoxazine resin has the formula (5):
And / or a ring-opened polymer thereof, or formula (6):
The benzoxazine resin composition according to claim 1, which is a compound represented by the formula: and / or a ring-opening polymer thereof.
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