TW202409156A - Single-terminal modified organopolysiloxane and its manufacturing method, surface treatment agent and silicone composition - Google Patents
Single-terminal modified organopolysiloxane and its manufacturing method, surface treatment agent and silicone composition Download PDFInfo
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- TW202409156A TW202409156A TW112126533A TW112126533A TW202409156A TW 202409156 A TW202409156 A TW 202409156A TW 112126533 A TW112126533 A TW 112126533A TW 112126533 A TW112126533 A TW 112126533A TW 202409156 A TW202409156 A TW 202409156A
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- carbon atoms
- substituent
- silicone composition
- general formula
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- 229920001296 polysiloxane Polymers 0.000 title claims abstract description 113
- 239000000203 mixture Substances 0.000 title claims abstract description 83
- 239000012756 surface treatment agent Substances 0.000 title claims abstract description 9
- 238000004519 manufacturing process Methods 0.000 title claims description 8
- -1 polysiloxane Polymers 0.000 claims abstract description 65
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 56
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 38
- 125000001424 substituent group Chemical group 0.000 claims abstract description 37
- 239000000945 filler Substances 0.000 claims abstract description 21
- 125000000753 cycloalkyl group Chemical group 0.000 claims abstract description 14
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical group [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 27
- 239000000126 substance Substances 0.000 claims description 25
- 239000003054 catalyst Substances 0.000 claims description 20
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 16
- 229910052751 metal Inorganic materials 0.000 claims description 16
- 239000002184 metal Substances 0.000 claims description 16
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 14
- 125000001931 aliphatic group Chemical group 0.000 claims description 13
- 239000011231 conductive filler Substances 0.000 claims description 12
- 238000006459 hydrosilylation reaction Methods 0.000 claims description 11
- 239000002245 particle Substances 0.000 claims description 10
- 229930195735 unsaturated hydrocarbon Natural products 0.000 claims description 10
- 239000003795 chemical substances by application Substances 0.000 claims description 9
- 239000000843 powder Substances 0.000 claims description 8
- 238000007259 addition reaction Methods 0.000 claims description 5
- 229920006136 organohydrogenpolysiloxane Polymers 0.000 claims description 5
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 claims description 4
- 150000001875 compounds Chemical class 0.000 claims description 3
- 229910017464 nitrogen compound Inorganic materials 0.000 claims description 3
- 150000002830 nitrogen compounds Chemical class 0.000 claims description 3
- 150000004045 organic chlorine compounds Chemical class 0.000 claims description 3
- 150000002903 organophosphorus compounds Chemical class 0.000 claims description 3
- 125000001183 hydrocarbyl group Chemical group 0.000 claims 3
- 239000000463 material Substances 0.000 abstract description 21
- 239000000080 wetting agent Substances 0.000 abstract description 12
- 230000007774 longterm Effects 0.000 abstract description 5
- 238000003860 storage Methods 0.000 abstract description 5
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 63
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 25
- 238000006243 chemical reaction Methods 0.000 description 23
- 150000002430 hydrocarbons Chemical group 0.000 description 20
- 239000002253 acid Substances 0.000 description 16
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 16
- 238000011049 filling Methods 0.000 description 13
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 10
- 239000000377 silicon dioxide Substances 0.000 description 10
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 9
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 8
- 230000015572 biosynthetic process Effects 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 8
- 238000000034 method Methods 0.000 description 8
- 238000002156 mixing Methods 0.000 description 8
- 229910052697 platinum Inorganic materials 0.000 description 8
- 238000003786 synthesis reaction Methods 0.000 description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 7
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 7
- 239000004205 dimethyl polysiloxane Substances 0.000 description 7
- 235000013870 dimethyl polysiloxane Nutrition 0.000 description 7
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 7
- 229910052710 silicon Inorganic materials 0.000 description 7
- 125000001731 2-cyanoethyl group Chemical group [H]C([H])(*)C([H])([H])C#N 0.000 description 6
- 229910052794 bromium Inorganic materials 0.000 description 6
- 239000000460 chlorine Substances 0.000 description 6
- 229910052801 chlorine Inorganic materials 0.000 description 6
- 125000004093 cyano group Chemical group *C#N 0.000 description 6
- PEMATDLNMXTNGL-UHFFFAOYSA-N diethynyl(dimethyl)silane Chemical compound C#C[Si](C)(C)C#C PEMATDLNMXTNGL-UHFFFAOYSA-N 0.000 description 6
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 6
- 229910052731 fluorine Inorganic materials 0.000 description 6
- 125000005843 halogen group Chemical group 0.000 description 6
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- 125000000094 2-phenylethyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])C([H])([H])* 0.000 description 5
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Chemical group CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 5
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 5
- 125000003710 aryl alkyl group Chemical group 0.000 description 5
- 239000004020 conductor Substances 0.000 description 5
- 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 5
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 5
- 239000004615 ingredient Substances 0.000 description 5
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 5
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 5
- 125000001971 neopentyl group Chemical group [H]C([*])([H])C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])[H] 0.000 description 5
- 125000001400 nonyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 5
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 5
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 5
- 125000006201 3-phenylpropyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 4
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 4
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 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
- 125000001204 arachidyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 4
- 125000003118 aryl group Chemical group 0.000 description 4
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 4
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 4
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 4
- 238000011156 evaluation Methods 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 125000003187 heptyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 4
- 125000002960 margaryl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 4
- 125000001421 myristyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 4
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 4
- 125000001196 nonadecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 4
- 125000000962 organic group Chemical group 0.000 description 4
- 125000000913 palmityl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 4
- 125000002958 pentadecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 4
- 229910000077 silane Inorganic materials 0.000 description 4
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 4
- 125000002889 tridecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 4
- 125000002948 undecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 4
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 4
- 229920002554 vinyl polymer Polymers 0.000 description 4
- HMUNWXXNJPVALC-UHFFFAOYSA-N 1-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperazin-1-yl]-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)N1CCN(CC1)C(CN1CC2=C(CC1)NN=N2)=O HMUNWXXNJPVALC-UHFFFAOYSA-N 0.000 description 3
- VZSRBBMJRBPUNF-UHFFFAOYSA-N 2-(2,3-dihydro-1H-inden-2-ylamino)-N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]pyrimidine-5-carboxamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C(=O)NCCC(N1CC2=C(CC1)NN=N2)=O VZSRBBMJRBPUNF-UHFFFAOYSA-N 0.000 description 3
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 3
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 3
- 125000003342 alkenyl group Chemical group 0.000 description 3
- 125000004369 butenyl group Chemical group C(=CCC)* 0.000 description 3
- 238000001723 curing Methods 0.000 description 3
- 125000004122 cyclic group Chemical group 0.000 description 3
- 230000006866 deterioration Effects 0.000 description 3
- 230000017525 heat dissipation Effects 0.000 description 3
- 125000006038 hexenyl group Chemical group 0.000 description 3
- 239000011159 matrix material Substances 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
- 238000004806 packaging method and process Methods 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 235000012239 silicon dioxide Nutrition 0.000 description 3
- 125000003944 tolyl group Chemical group 0.000 description 3
- 125000005023 xylyl group Chemical group 0.000 description 3
- 239000011787 zinc oxide Substances 0.000 description 3
- QYLFHLNFIHBCPR-UHFFFAOYSA-N 1-ethynylcyclohexan-1-ol Chemical compound C#CC1(O)CCCCC1 QYLFHLNFIHBCPR-UHFFFAOYSA-N 0.000 description 2
- FRWYFWZENXDZMU-UHFFFAOYSA-N 2-iodoquinoline Chemical compound C1=CC=CC2=NC(I)=CC=C21 FRWYFWZENXDZMU-UHFFFAOYSA-N 0.000 description 2
- 229910052580 B4C Inorganic materials 0.000 description 2
- 229910052582 BN Inorganic materials 0.000 description 2
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 description 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 2
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 2
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 2
- 238000013006 addition curing Methods 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 2
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical compound [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- LTPBRCUWZOMYOC-UHFFFAOYSA-N beryllium oxide Inorganic materials O=[Be] LTPBRCUWZOMYOC-UHFFFAOYSA-N 0.000 description 2
- INAHAJYZKVIDIZ-UHFFFAOYSA-N boron carbide Chemical compound B12B3B4C32B41 INAHAJYZKVIDIZ-UHFFFAOYSA-N 0.000 description 2
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 229910021387 carbon allotrope Inorganic materials 0.000 description 2
- 229910000420 cerium oxide Inorganic materials 0.000 description 2
- 125000004218 chloromethyl group Chemical group [H]C([H])(Cl)* 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- PMHQVHHXPFUNSP-UHFFFAOYSA-M copper(1+);methylsulfanylmethane;bromide Chemical compound Br[Cu].CSC PMHQVHHXPFUNSP-UHFFFAOYSA-M 0.000 description 2
- 238000007872 degassing Methods 0.000 description 2
- 229910003460 diamond Inorganic materials 0.000 description 2
- 239000010432 diamond Substances 0.000 description 2
- UBHZUDXTHNMNLD-UHFFFAOYSA-N dimethylsilane Chemical compound C[SiH2]C UBHZUDXTHNMNLD-UHFFFAOYSA-N 0.000 description 2
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical compound [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 2
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- 239000011737 fluorine Substances 0.000 description 2
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- 239000000395 magnesium oxide Substances 0.000 description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 2
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 2
- 150000001247 metal acetylides Chemical class 0.000 description 2
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- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 2
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 2
- 229910052763 palladium Inorganic materials 0.000 description 2
- 125000002255 pentenyl group Chemical group C(=CCCC)* 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 230000009257 reactivity Effects 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
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- 239000010703 silicon Substances 0.000 description 2
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 2
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- QQQSFSZALRVCSZ-UHFFFAOYSA-N triethoxysilane Chemical compound CCO[SiH](OCC)OCC QQQSFSZALRVCSZ-UHFFFAOYSA-N 0.000 description 2
- YUYCVXFAYWRXLS-UHFFFAOYSA-N trimethoxysilane Chemical compound CO[SiH](OC)OC YUYCVXFAYWRXLS-UHFFFAOYSA-N 0.000 description 2
- 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 2
- 125000004417 unsaturated alkyl group Chemical group 0.000 description 2
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Abstract
本發明提供一種潤濕劑(表面處理劑)。其賦予能夠將填充材料高填充在矽酮組合物中，且即使長時間保存也黏度變化小的組合物。 所述矽酮組合物包含以下述通式(1)表示的單末端改質有機聚矽氧烷， (在通式(1)中，R 1相互獨立地、為可以具有取代基的碳原子數為1~20的一價烴基，R 2相互獨立地、為可以具有取代基的碳原子數為1~20的烷基或可以具有取代基的碳原子數為3~20的環烷基。a為1~3的整數。n為1~300的數。)或 包含所述單末端改質有機聚矽氧烷和填充材料。 The present invention provides a wetting agent (surface treatment agent). It can provide a composition that can highly fill a filler material in a silicone composition and has a small viscosity change even after long-term storage. The silicone composition comprises a single-terminal modified organic polysiloxane represented by the following general formula (1), (In the general formula (1), R1 is independently a monovalent alkyl group having 1 to 20 carbon atoms which may have a substituent, and R2 is independently an alkyl group having 1 to 20 carbon atoms which may have a substituent or a cycloalkyl group having 3 to 20 carbon atoms which may have a substituent. a is an integer of 1 to 3. n is a number of 1 to 300.) or comprises the single-terminal modified organic polysiloxane and a filler.
Description
本發明係關於單末端改質有機聚矽氧烷，特別是關於在單末端具有烷氧基甲矽烷基-伸乙烯基的直鏈有機聚矽氧烷及其製造方法、表面處理劑以及矽酮組合物。The present invention relates to a single-terminal modified organopolysiloxane, in particular to a linear organopolysiloxane having an alkoxysilyl-vinylidene group at a single end and its manufacturing method, surface treatment agent and silicone. composition.
由於多數的電子部件在使用中發熱，為了恰當地發揮該電子部件的功能，需要從該電子部件去除熱。尤其是被用於個人電腦和智慧手機的CPU、GPU等的積體電路元件，由於操作頻率的高速化和包裝的精細化導致熱值持續增大，從而相對於熱的對策、設計成為重要的課題。另外，近年來汽車的電動化也在發展，由於大多使用了電子部件，有時會在高溫高濕環境下等更為苛刻的條件下使用電子部件。Since most electronic components generate heat during use, in order to properly function the electronic components, it is necessary to remove heat from the electronic components. In particular, the heat value of integrated circuit components used in CPUs, GPUs, etc. of personal computers and smartphones continues to increase due to higher operating frequencies and refined packaging, so heat countermeasures and designs have become important. subject. In addition, the electrification of automobiles has also been developing in recent years. Since most electronic components are used, electronic components are sometimes used under more severe conditions such as high-temperature and high-humidity environments.
作為消除該熱的手段，人們提出了許多方法。特別是提出了在發熱量多的電子部件中，將熱傳導性潤滑脂或熱傳導性片材等熱傳導性材料介於電子部件和散熱器等構件之間來進行放熱的方法。特別是熱傳導性潤滑脂為無定形，由於在固化後與基材密合方面顯示出高熱傳導性，因此被優選使用。另外，作為這樣的熱傳導性材料，已知有將矽酮作為基質，再配合氧化鋅或鋁、氧化鋁粉的散熱黏合劑(專利文獻1)。As a means of eliminating this heat, many methods have been proposed. In particular, in electronic components that generate a lot of heat, a method has been proposed in which a thermally conductive material such as thermally conductive grease or a thermally conductive sheet is interposed between the electronic component and a member such as a radiator to release heat. In particular, thermally conductive grease is amorphous and exhibits high thermal conductivity in adhering closely to the base material after curing, so it is preferably used. In addition, as such a thermally conductive material, a heat dissipation adhesive is known which uses silicone as a matrix and further mixes zinc oxide, aluminum, and aluminum oxide powder (Patent Document 1).
為了將矽酮作為基質，從而作為具有高熱傳導性的熱傳導性材料，必須高填充熱傳導性填充材料。但是，如果僅僅是想要進行高填充，則會產生熱傳導性材料的流動性顯著降低，塗佈性(分配性、絲網印刷性)等操作性變差，進一步，不能與電子部件或散熱器表面的微細凹凸一致的問題。因此，為了解決該問題，人們提出了用潤濕劑表面處理熱傳導性填充材料，使其分散在為基質聚合物的矽酮中，從而保持熱傳導性材料的流動性的方法。 現在，作為被頻繁使用的潤濕劑，具有含有水解性基團的聚二甲基矽氧烷和含有水解性基團的低聚矽氧烷(專利文獻2、專利文獻3)。藉由使用這些潤濕劑，雖然可以獲得良好的流動性，但由於存在於材料中的未反應的水解性基團發生反應，則抑制在長期保存時的黏度增加(伴隨高黏度化的排出性的惡化)或由於長時間被暴露在高溫環境下而引發的硬度上升成為了課題。 現有技術文獻 專利文獻 In order to use silicone as a matrix and thus as a thermally conductive material with high thermal conductivity, it is necessary to highly fill the thermally conductive filler material. However, if only high filling is desired, the fluidity of the thermally conductive material will be significantly reduced, and workability such as coating properties (distribution properties, screen printing properties) will be deteriorated, and furthermore, it will not be compatible with electronic components or heat sinks. The problem of consistent fine unevenness on the surface. Therefore, in order to solve this problem, people have proposed a method of surface-treating the thermally conductive filler material with a wetting agent to disperse it in silicone as a matrix polymer, thereby maintaining the fluidity of the thermally conductive material. Currently, as wetting agents that are frequently used, there are hydrolyzable group-containing polydimethylsiloxane and hydrolyzable group-containing oligosiloxane (Patent Document 2, Patent Document 3). Although good fluidity can be obtained by using these wetting agents, unreacted hydrolyzable groups present in the material react, thereby suppressing an increase in viscosity during long-term storage (dischargeability associated with increased viscosity). Deterioration) or an increase in hardness caused by long-term exposure to high temperature environments have become issues. existing technical documents patent documents
[專利文獻1]:日本專利第3952184號公報 [專利文獻2]:日本專利第3543663號公報 [專利文獻3]:日本專利第4727017號公報 [Patent Document 1]: Japanese Patent No. 3952184 [Patent Document 2]: Japanese Patent No. 3543663 [Patent Document 3]: Japanese Patent No. 4727017
發明要解決的問題Invent the problem to be solved
因此，本發明的目的在於，提供一種潤濕劑(表面處理劑)，其能夠將填充材料高填充到矽酮組合物中，且能夠提供賦予一種即使長時間保存也黏度變化小的組合物。另外，本發明的目的還在於，提供一種潤濕劑，其在被添加到加成固化型的矽酮組合物中的情況下，能夠抑制在將所得到的固化物長時間暴露於高溫環境下時導致的硬度上升。 用於解決問題的方案 Therefore, an object of the present invention is to provide a wetting agent (surface treatment agent) capable of filling a silicone composition with a high filling material and providing a composition with little change in viscosity even when stored for a long time. In addition, another object of the present invention is to provide a wetting agent that, when added to an addition-curable silicone composition, can suppress the resulting cured product from being exposed to a high temperature environment for a long time. resulting in an increase in hardness. solutions to problems
為了達到上述目的，本發明人們依據精心研究的結果發現，被改質為單末端含有烷氧基甲矽烷基-伸乙烯基的結構的直鏈有機聚矽氧烷，作為對解決上述課題為有效的潤濕劑而發揮著作用，進而完成了本發明。In order to achieve the above object, the present inventors have discovered based on the results of careful research that linear organopolysiloxane modified into a structure containing an alkoxysilyl group and a vinylethylene group at one end is effective in solving the above problems. As a wetting agent, the present invention was completed.
即，本發明為提供下述的單末端改質有機聚矽氧烷等的發明。 ［1］一種單末端改質有機聚矽氧烷，其以下述通式(1)表示。 [化學式1] (在通式(1)中，R 1相互獨立地、為可以具有取代基的碳原子數為1~20的一價烴基，R 2相互獨立地、為可以具有取代基的碳原子數為1~20的烷基或可以具有取代基的碳原子數為3~20的環烷基，a為1~3的整數，n為1~300的數。) ［2］如［1］所述的單末端改質有機聚矽氧烷的製造方法，其以下述通式(1)表示， 所述製造方法具有使以下述通式(2)表示的雙矽烷化合物和以下述通式(3)表示的有機氫聚矽氧烷進行氫化矽烷化反應的步驟。 [化學式2] (在式中，R 1相互獨立地，為可以具有取代基的碳原子數為1~20的一價烴基，R 2相互獨立地，為可以具有取代基的碳原子數為1~20的烷基或可以具有取代基的碳原子數為3~20的環烷基，a為1~3的整數。n為1~300的數。) ［3］一種表面處理劑，其為由［1］所述的單末端改質有機聚矽氧烷構成的粉體。 ［4］一種矽酮組合物，其包含(A)單末端改質有機聚矽氧烷和(B)填充材料，其中， 所述單末端改質有機聚矽氧烷以下述通式(1)表示， [化學式3] (在通式(1)中，R 1相互獨立地、為可以具有取代基的碳原子數為1~20的一價烴基，R 2相互獨立地、為可以具有取代基的碳原子數為1~20的烷基或可以具有取代基的碳原子數為3~20的環烷基，a為1~3的整數，n為1~300的數。) ［5］如［4］所述的矽酮組合物，其中， 所述(B)成分的平均粒徑為0.01~150µm。 ［6］如［4］或［5］所述的矽酮組合物，更包含： (C)有機聚矽氧烷，其在1分子中具有至少2個與矽原子鍵結的脂肪族不飽和烴基，且在25℃條件下的運動黏度為60~100000mm 2/s； (D)有機氫聚矽氧烷，其在1分子中具有2個以上的與矽原子鍵結的氫原子，且相對於(A)成分和(C)成分中的脂肪族不飽和烴基的個數的合計，與矽原子鍵結的氫原子的個數為0.5~5的量； 以及， (E)鉑族金屬催化劑。 ［7］如［6］所述的矽酮組合物，更包含： (F)加成反應控制劑，其為選自由乙炔化合物、氮化合物、有機磷化合物、肟化合物和有機氯化合物所組成的群組中的1種以上。 ［8］如[4]~[7]中任意一項所述的矽酮組合物，更包含： (G)水解性有機聚矽氧烷，其以下述通式(w)表示，相對於組合物總量，為0.1~20質量%， [化學式4] 在通式(w)中，R 3相互獨立地、為氫原子或可以具有取代基的碳原子數為1~20的一價烴基，R 4相互獨立地、為可以具有取代基的碳原子數為1~20的烷基或可以具有取代基的碳原子數為3~20的環烷基，b為1~3的整數，m為1~200的數。 ［9］如[4]~[8]中任意一項所述的矽酮組合物，其中， 所述(B)成分的填充材料為熱傳導性填充材料。 發明的效果 That is, the present invention provides the following one-terminal modified organic polysiloxane and the like. [1] A one-terminal modified organic polysiloxane represented by the following general formula (1). [Chemical formula 1] (In the general formula (1), R1 is independently a monovalent alkyl group having 1 to 20 carbon atoms which may have a substituent, R2 is independently an alkyl group having 1 to 20 carbon atoms which may have a substituent or a cycloalkyl group having 3 to 20 carbon atoms which may have a substituent, a is an integer of 1 to 3, and n is a number of 1 to 300.) [2] A method for producing a single-terminal modified organic polysiloxane as described in [1], which is represented by the following general formula (1), wherein the production method comprises the step of subjecting a bissilane compound represented by the following general formula (2) and an organic hydropolysiloxane represented by the following general formula (3) to a hydrosilylation reaction. [Chemical formula 2] (In the formula, R1 is independently a monovalent alkyl group having 1 to 20 carbon atoms which may have a substituent, R2 is independently an alkyl group having 1 to 20 carbon atoms which may have a substituent or a cycloalkyl group having 3 to 20 carbon atoms which may have a substituent, a is an integer of 1 to 3, and n is a number of 1 to 300.) [3] A surface treatment agent, which is a powder composed of the single-terminal modified organic polysiloxane described in [1]. [4] A silicone composition, which comprises (A) a single-terminal modified organic polysiloxane and (B) a filler, wherein the single-terminal modified organic polysiloxane is represented by the following general formula (1): [Chemical Formula 3] (In the general formula (1), R1 is independently a monovalent alkyl group having 1 to 20 carbon atoms which may have a substituent, R2 is independently an alkyl group having 1 to 20 carbon atoms which may have a substituent or a cycloalkyl group having 3 to 20 carbon atoms which may have a substituent, a is an integer of 1 to 3, and n is a number of 1 to 300.) [5] The silicone composition as described in [4], wherein the average particle size of the component (B) is 0.01 to 150 µm. [6] The silicone composition as described in [4] or [5] further comprises: (C) an organic polysiloxane having at least two aliphatic unsaturated hydrocarbon groups bonded to silicon atoms in one molecule and having a kinematic viscosity of 60 to 100,000 mm2 /s at 25°C; (D) an organic hydropolysiloxane having two or more hydrogen atoms bonded to silicon atoms in one molecule and the number of hydrogen atoms bonded to silicon atoms is 0.5 to 5 relative to the total number of aliphatic unsaturated hydrocarbon groups in components (A) and (C); and (E) a platinum group metal catalyst. [7] The silicone composition as described in [6] further comprises: (F) an addition reaction control agent, which is one or more selected from the group consisting of acetylene compounds, nitrogen compounds, organic phosphorus compounds, oxime compounds and organic chlorine compounds. [8] The silicone composition as described in any one of [4] to [7] further comprises: (G) a hydrolyzable organopolysiloxane represented by the following general formula (w), which is 0.1 to 20% by weight relative to the total weight of the composition. [Chemical Formula 4] In the general formula (w), R3 is independently a hydrogen atom or a monovalent alkyl group having 1 to 20 carbon atoms which may have a substituent, R4 is independently an alkyl group having 1 to 20 carbon atoms which may have a substituent or a cycloalkyl group having 3 to 20 carbon atoms which may have a substituent, b is an integer of 1 to 3, and m is a number of 1 to 200. [9] The silicone composition as described in any one of [4] to [8], wherein the filler of the component (B) is a thermally conductive filler. Effect of the invention
本發明的單末端改質有機聚矽氧烷，由於具有與填充材料的反應性優異的烷氧基甲矽烷基-伸乙烯基(烷氧基甲矽烷基-乙烯撐基)，因此作為用於將填充材料高填充在矽酮組合物中的潤濕劑(表面處理劑)為有用，並且即使長期保存，也能夠提供黏度變化小的矽酮組合物。 進一步，在將本發明的單末端改質有機聚矽氧烷作為熱傳導性填充材料的潤濕劑添加到加成固化型的矽酮組合物中的情況下，由於能夠抑制在所得到的固化物被長時間暴露於高溫環境下時的硬度上升，因此，能夠提供適用於電子部件封裝或功率模組，且可靠性高的散熱材料。 The single-terminal modified organopolysiloxane of the present invention has an alkoxysilyl-vinylidene group (alkoxysilyl-vinylidene group) that has excellent reactivity with fillers, and therefore is used as a A wetting agent (surface treatment agent) in which a silicone composition is highly filled with a filler material is useful and can provide a silicone composition with little change in viscosity even when stored for a long period of time. Furthermore, when the single-terminal modified organopolysiloxane of the present invention is added to an addition-curable silicone composition as a wetting agent for a thermally conductive filler, it is possible to suppress The hardness increases when exposed to a high temperature environment for a long time. Therefore, it is possible to provide a highly reliable heat dissipation material suitable for electronic component packaging or power modules.
以下，對本發明進一步詳細地進行說明。 [單末端改質有機聚矽氧烷] 本發明的單末端改質有機聚矽氧烷為以下述通式(1)表示的、單末端具有烷氧基甲矽烷基-伸乙烯基的結構所改質的直鏈有機聚矽氧烷。 The present invention is described in further detail below. [One-terminal modified organic polysiloxane] The one-terminal modified organic polysiloxane of the present invention is a linear organic polysiloxane represented by the following general formula (1) and modified to have an alkoxysilyl-vinylene group at one terminal.
[化學式5] (在通式(1)中，R 1相互獨立地、為可以具有取代基的碳原子數為1~20的一價烴基，R 2相互獨立地、為可以具有取代基的碳原子數為1~20的烷基或可以具有取代基的碳原子數為3~20的環烷基。a為1~3的整數。n為1~300的數。) [Chemical formula 5] (In the general formula (1), R1 is independently a monovalent alkyl group having 1 to 20 carbon atoms which may have a substituent, and R2 is independently an alkyl group having 1 to 20 carbon atoms which may have a substituent or a cycloalkyl group having 3 to 20 carbon atoms which may have a substituent. a is an integer of 1 to 3. n is a number of 1 to 300.)
在此，在上述通式(1)中，R 1作為碳原子數為1~20的取代或未取代的一價烴基可以為相同或也可以為不同，可例示出甲基、乙基、正丙基、異丙基、正丁基、異丁基、三級丁基、戊基、新戊基、己基、庚基、辛基、壬基、癸基、十一烷基、十二烷基、十三烷基、十四烷基、十五烷基、十六烷基、十七烷基、十八烷基、十九烷基、二十烷基等烷基；環戊基和環己基等環烷基；乙烯基、烯丙基、丁烯基、戊烯基和己烯基等烯基；苯基、甲苯基、二甲苯基、α-，β-萘基等芳基；苄基、2-苯基乙基和3-苯丙基等芳烷基；另外，這些基團的一部分氫原子或全部氫原子被F、Cl、Br等鹵素原子或被氰基等取代的基團，例如3-氯丙基、3,3,3-三氟丙基、2-氰乙基等。其中，較佳為碳原子數為1~10的一價烴基、特佳為碳原子數為1~6的一價烴基、特別更佳為甲基、乙基、苯基、從入手的容易性、生產性、成本方面考慮，更佳為甲基、苯基。 Here, in the above general formula (1), R 1 may be the same or different as a substituted or unsubstituted monovalent hydrocarbon group having 1 to 20 carbon atoms, and examples thereof include methyl, ethyl, n- Propyl, isopropyl, n-butyl, isobutyl, tertiary butyl, pentyl, neopentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl , tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl and other alkyl groups; cyclopentyl and cyclohexyl Cycloalkyl groups; alkenyl groups such as vinyl, allyl, butenyl, pentenyl, and hexenyl; aryl groups such as phenyl, tolyl, xylyl, α-, β-naphthyl, etc.; benzyl, Aralkyl groups such as 2-phenylethyl and 3-phenylpropyl; in addition, groups in which part or all of the hydrogen atoms of these groups are replaced by halogen atoms such as F, Cl, Br, or cyano groups, such as 3-chloropropyl, 3,3,3-trifluoropropyl, 2-cyanoethyl, etc. Among them, a monovalent hydrocarbon group having 1 to 10 carbon atoms is preferred, a monovalent hydrocarbon group having 1 to 6 carbon atoms is particularly preferred, and a methyl group, an ethyl group, and a phenyl group are particularly preferred. Ease of acquisition , productivity, and cost considerations, methyl and phenyl are more preferred.
R 2作為碳原子數為1~20的烷基，可列舉出甲基、乙基、正丙基、異丙基、正丁基、異丁基、三級丁基、戊基、新戊基、己基、庚基、辛基、壬基、癸基、十一烷基、十二烷基、十三烷基、十四烷基、十五烷基、十六烷基、十七烷基、十八烷基、十九烷基、二十烷基等。作為環烷基，可列舉出環戊基和環己基等；作為可以具有取代基的碳原子數為1~20的烷基，可列舉出苄基、2-苯基乙基和3-苯丙基等芳烷基。另外，這些的(取代)烷基的一部分氫原子或全部氫原子也可被F、Cl、Br等鹵素原子或被氰基等取代，其中，可列舉出例如，3-氯丙基、3,3,3-三氟丙基、2-氰乙基等。作為R 2，其中，較佳為碳原子數為1~6的烷基、特佳為碳原子數為1~4的烷基，特別更佳為甲基、乙基，從入手的容易性、生產性、成本方面考慮，更佳為甲基。 R2 is an alkyl group having 1 to 20 carbon atoms, and examples thereof include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tertiary butyl, pentyl, neopentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl, etc. Examples thereof include cyclopentyl and cyclohexyl, etc. Examples thereof include aralkyl groups having 1 to 20 carbon atoms that may have a substituent, such as benzyl, 2-phenylethyl, and 3-phenylpropyl. In addition, some or all of the hydrogen atoms of these (substituted) alkyl groups may be substituted by halogen atoms such as F, Cl, and Br, or by cyano, etc., and examples thereof include 3-chloropropyl, 3,3,3-trifluoropropyl, and 2-cyanoethyl, etc. R 2 is preferably an alkyl group having 1 to 6 carbon atoms, particularly preferably an alkyl group having 1 to 4 carbon atoms, more preferably a methyl group or an ethyl group, and more preferably a methyl group in view of availability, productivity and cost.
a為1~3的整數、較佳為2或3、更佳為3。a is an integer from 1 to 3, preferably 2 or 3, more preferably 3.
n為1~300的數、較佳為10~250的數、更佳為30~200的數。如果n小於1，則單末端改質有機聚矽氧烷變得容易滲出，有可能導致可靠性降低；如果n大於300，則有時填充材料的潤濕性變得不充分，或者有時組合物的黏度變高，從而導致流動性惡化。n is a number from 1 to 300, preferably from 10 to 250, more preferably from 30 to 200. If n is less than 1, the single-terminal modified organopolysiloxane may bleed out easily, possibly resulting in reduced reliability; if n is greater than 300, the wettability of the filling material may become insufficient, or a combination The viscosity of the material increases, resulting in deterioration of fluidity.
作為以本發明的通式(1)表示的單末端改質有機聚矽氧烷的具體例子，可列舉出例如，以下述結構式表示的單末端有機聚矽氧烷。Specific examples of the single-end modified organopolysiloxane represented by the general formula (1) of the present invention include, for example, a single-end organopolysiloxane represented by the following structural formula.
[化學式6] [Chemical formula 6]
＜單末端改質有機聚矽氧烷的製造方法＞ 本發明的單末端改質有機聚矽氧烷，可藉由例如，將在同一矽原子上具有2個乙炔基的矽烷(二乙炔基二有機矽烷)與烷氧基氫矽烷發生氫化矽烷化反應(下述反應式[1])所得到的雙矽烷化合物(2)，再與在單末端具有SiH基的直鏈有機聚矽氧烷(3)發生氫化矽烷化反應來進行製造(下述反應式[2])。 ＜Production method of single-end modified organopolysiloxane＞ The single-terminal modified organopolysiloxane of the present invention can be produced by, for example, hydrosilylation reaction between a silane having two ethynyl groups on the same silicon atom (diethynyl diorganosilane) and an alkoxyhydrosilane. The disilane compound (2) obtained (reaction formula [1] below) is further produced by hydrosilylation reaction with a linear organopolysiloxane (3) having a SiH group at one end (reaction below Formula [2]).
[化學式7] (在反應式中，R 1、R 2、a和n分別為如上所述相同。) [Chemical formula 7] (In the reaction formula, R 1 , R 2 , a and n are the same as described above.)
[化學式8] (在反應式中，R 1、R 2、a和n分別為如上所述相同。) [Chemical formula 8] (In the reaction formula, R 1 , R 2 , a and n are the same as described above.)
作為在所述氫化矽烷化中的催化劑，可列舉出鉑族金屬系催化劑，例如，鉑系催化劑、鈀系催化劑、銠系催化劑、釕系的催化劑，但特佳為鉑系催化劑。作為具體例子，可列舉出例如，鉑金黑、以及將固體鉑擔載在氧化鋁和二氧化矽等的載體上的鉑系催化劑、氯鉑酸、醇改質氯鉑酸、氯鉑酸和烯烴的錯合物、或氯鉑酸和乙烯基矽氧烷的錯合物等。鉑族金屬系催化劑可以單獨使用1種，也可以並用2種以上。這些鉑族金屬系催化劑的使用量，只要是所說的催化劑量即可，例如，相對於以式3表示的烷氧基氫化矽烷或者雙矽烷，以鉑族金屬換算可使用0.1~1000質量ppm、特別可使用0.5~100質量ppm。Examples of the catalyst used in the hydrosilylation include platinum group metal catalysts, such as platinum-based catalysts, palladium-based catalysts, rhodium-based catalysts, and ruthenium-based catalysts. Platinum-based catalysts are particularly preferred. Specific examples include platinum black, platinum-based catalysts in which solid platinum is supported on a carrier such as alumina and silica, chloroplatinic acid, alcohol-modified chloroplatinic acid, chloroplatinic acid, and olefins. The complex, or the complex of chloroplatinic acid and vinylsiloxane, etc. One type of platinum group metal catalyst may be used alone, or two or more types may be used in combination. The usage amount of these platinum group metal-based catalysts is sufficient as long as it is the catalyst amount. For example, 0.1 to 1000 mass ppm in terms of platinum group metal relative to the alkoxyhydrosilane or disilane represented by Formula 3 can be used. , especially 0.5~100 mass ppm can be used.
上述氫化矽烷化反應，依照常規方法即可，可在較佳為50~120℃、特佳為在60~100℃的溫度條件下，且較佳為在0.5~12小時、特佳為在1~6小時的條件下進行。另外，也可在不使用溶劑的條件下進行，但根據需要也可以使用己烷、辛烷、甲苯、二甲苯等有機溶劑。 另外，在反應式[1]中，為了使1莫耳二乙炔基二有機矽烷與1莫耳烷氧基氫化矽烷進行反應，較佳為將過量的二乙炔基二有機矽烷與烷氧基氫化矽烷進行混合來進行氫化矽烷化反應。其中，較佳為用以二乙炔基二有機矽烷：烷氧基氫化矽烷=9：2~3：2(莫耳比)進行反應、更佳為以4：1~2：1(莫耳比)進行反應。 The above hydrosilylation reaction can be carried out according to conventional methods, preferably at a temperature of 50 to 120°C, particularly preferably at a temperature of 60 to 100°C, and preferably at a temperature of 0.5 to 12 hours, particularly preferably at 1 ~6 hours. In addition, it can also be carried out without using a solvent, but if necessary, organic solvents such as hexane, octane, toluene, and xylene can also be used. In addition, in the reaction formula [1], in order to react 1 mole of diethynyl diorganosilane and 1 mole of alkoxy hydrogenated silane, it is preferable to hydrogenate excess diethynyl diorganosilane and alkoxy hydrogenated silane. The silanes are mixed to perform the hydrosilylation reaction. Among them, the reaction is preferably carried out with diethynyl diorganosilane:alkoxyhydrosilane=9:2~3:2 (mol ratio), and more preferably 4:1~2:1 (mol ratio). ) to react.
在對乙炔基的加成反應中，被生成為例如，以下述反應式[3]表示的幾何異構體。其中，E體(trans體)的生成為高選擇性，且反應性也高。由於對所得到的雙矽烷化合物的特性沒有影響，因此，在本發明中，不用分離這些幾何異構體就可以使用。In the addition reaction to the ethynyl group, geometric isomers are generated, for example, as represented by the following reaction formula [3]. Among them, the E isomer (trans isomer) is generated with high selectivity and high reactivity. Since it has no effect on the properties of the obtained bisilane compound, these geometric isomers can be used without separation in the present invention.
[化學式9] (在反應式3中，R 1、R 2、a和n分別為如上所述相同。) 藉由以上述氫化矽烷化反應進行加成的步驟，雖能夠製造以通式(2)表示的雙矽烷化合物或者以通式(1)表示的單末端有機聚矽氧烷，但也可以在上述氫化矽烷化反應後，適當地按照常規方法進行精製。 [Chemical formula 9] (In Reaction Formula 3, R 1 , R 2 , a and n are each the same as above.) By performing the addition step through the above-mentioned hydrosilylation reaction, it is possible to produce a bis(2) represented by the general formula (2). The silane compound or the single-terminal organopolysiloxane represented by the general formula (1) may be appropriately purified according to a conventional method after the above-mentioned hydrosilylation reaction.
本發明的單末端改質有機聚矽氧烷可用作填充材料等粉體的表面處理劑(潤濕劑)、特別是可用作熱傳導性填充材料等粉體的表面處理劑(潤濕劑)。The single-terminal modified organopolysiloxane of the present invention can be used as a surface treatment agent (wetting agent) for powders such as fillers, and particularly can be used as a surface treatment agent (wetting agent) for powders such as thermally conductive fillers. ).
[矽酮組合物] 另外，在本發明中，提供一種矽酮組合物。所述矽酮組合物包含(A)以下述通式(1)表示的單末端改質有機聚矽氧烷 [化學式10] (在通式(1)中，R 1相互獨立地，為可以具有取代基的碳原子數為1~20的一價烴基，R 2相互獨立地，為可以具有取代基的碳原子數為1~20的烷基或可以具有取代基的碳原子數為3~20的環烷基。a為1~3的整數。n為1~300的數。) 和， (B)填充材料。 [Silicone Composition] In addition, the present invention provides a silicone composition. The silicone composition contains (A) a single-terminal modified organopolysiloxane [Chemical Formula 10] represented by the following general formula (1) (In the general formula (1), R 1 is a monovalent hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, and R 2 is a monovalent hydrocarbon group having a carbon number of 1 which may have a substituent. ~20 alkyl group or optionally substituted cycloalkyl group with 3 to 20 carbon atoms. a is an integer from 1 to 3. n is a number from 1 to 300.) and, (B) Filling material.
＜(A)成分＞ 在本發明的矽酮組合物中的(A)成分為以上述所述通式(1)表示的單末端改質有機聚矽氧烷。 ＜(A)Component＞ The component (A) in the silicone composition of the present invention is a single-terminal modified organopolysiloxane represented by the general formula (1) described above.
相對於組合物總量，(A)成分的配合量較佳為0.1~20質量%的範圍、更佳為0.5~15質量%的範圍、又更佳為1~10質量%的範圍。如果為在這樣的範圍內，則能夠對填充材料賦予充分的潤濕性，且能夠抑制本成分從組合物中滲出。The amount of component (A) is preferably in the range of 0.1 to 20 mass %, more preferably in the range of 0.5 to 15 mass %, and even more preferably in the range of 1 to 10 mass % relative to the total amount of the composition. Within such a range, sufficient wettability can be imparted to the filler and the leakage of this component from the composition can be suppressed.
＜(B)成分＞ 作為(B)成分的填充材料，可以使用公知的填充材料，可列舉出例如，鋁、銀、銅、金屬矽等金屬；礬土、氧化鋅、氧化鎂、氧化鈹、氧化鋁氧化鈦、氧化鉻、氧化鈰、氧化鐵等金屬氧化物；氣相二氧化矽(熱解法二氧化矽或乾式二氧化矽)、熔融二氧化矽、沉降性二氧化矽(濕式二氧化矽)、石英粉(結晶性二氧化矽)、用有機矽化合物對這些二氧化矽表面進行了疏水化處理的二氧化矽等二氧化矽系填充材料；玻璃纖維、玻璃珠、玻璃球等玻璃系填充材料；碳酸鈣、碳酸鎂、碳酸鋅等金屬碳酸鹽；氫化鋁、氫化鈰等金屬氫氧化物；氮化鋁、氮化硼等金屬氮化物；碳化硼、碳化矽等金屬碳化物；金剛石、石墨、碳奈米管、石墨烯、碳黑等碳的同素異形體；矽藻土、滑石、雲母、沸石、膨潤土等礦物系填充材料；聚苯乙烯、聚氯乙烯、聚丙烯等合成樹脂粉等，所述填充材料可為1種或也以為將2種以上進行混合。 藉由使用作為(B)成分的填充材料的熱傳導率高的熱傳導性填充材料，本發明的矽酮組合物成為能夠高填充熱傳導性填充材料的熱傳導性矽酮組合物，且塗佈性等操作性和流動性也優異，可適宜作為在長期保存後和在長期高溫保存後的黏度變化小、穩定性優異的散熱材料使用。作為熱傳導性填充材料，在所述中，可列舉出金屬、金屬氧化物、二氧化矽系填充材料、金屬氫氧化物、金屬氮化物、金屬碳化物、碳的同素異形體等，具體而言，可列舉出鋁、銀、銅、金屬矽、礬土、氧化鋅、氧化鎂、氧化鈹、氧化鋁、氧化鈦、氧化鉻、各種矽土(二氧化矽)、氧化鈰氧化鐵、氫化鋁、氫化鈰、氮化鋁、氮化硼、碳化硼粉、碳化矽、金剛石、石墨、碳奈米管、石墨烯等，所述填充材料可為1種或也以為將2種以上進行混合。 ＜(B)Component＞ As the filler of component (B), well-known fillers can be used, and examples thereof include metals such as aluminum, silver, copper, and metallic silicon; alumina, zinc oxide, magnesium oxide, beryllium oxide, aluminum oxide titanium oxide, and oxide Metal oxides such as chromium, cerium oxide, and iron oxide; fumed silica (pyrolytic silica or dry silica), fused silica, precipitated silica (wet silica), quartz powder (Crystalline silica), silica-based filling materials such as silica whose surface is hydrophobized with an organosilicon compound; glass-based filling materials such as glass fibers, glass beads, and glass spheres; carbonic acid Calcium, magnesium carbonate, zinc carbonate and other metal carbonates; aluminum hydride, cerium hydride and other metal hydroxides; aluminum nitride, boron nitride and other metal nitrides; boron carbide, silicon carbide and other metal carbides; diamond, graphite, carbon Allotropes of carbon such as nanotubes, graphene, and carbon black; mineral filling materials such as diatomaceous earth, talc, mica, zeolite, and bentonite; synthetic resin powders such as polystyrene, polyvinyl chloride, and polypropylene, etc. The filler material may be one type or two or more types may be mixed. By using a thermally conductive filler with a high thermal conductivity as the filler of component (B), the silicone composition of the present invention becomes a thermally conductive silicone composition that can be filled with a high thermal conductivity filler, and has improved applicability and other operations. It also has excellent properties and fluidity, making it suitable for use as a heat dissipation material with little viscosity change and excellent stability after long-term storage and long-term high-temperature storage. Examples of the thermally conductive filler include metals, metal oxides, silica-based fillers, metal hydroxides, metal nitrides, metal carbides, allotropes of carbon, and the like. Specifically, Examples include aluminum, silver, copper, metallic silicon, alumina, zinc oxide, magnesium oxide, beryllium oxide, aluminum oxide, titanium oxide, chromium oxide, various silicas (silicon dioxide), cerium oxide, iron oxide, hydrogenated Aluminum, cerium hydride, aluminum nitride, boron nitride, boron carbide powder, silicon carbide, diamond, graphite, carbon nanotubes, graphene, etc. The filling material can be one type or a mixture of two or more types. .
(B)成分的平均粒徑較佳為0.01~150µm的範圍、更佳為0.1~100µm的範圍。其原因在於，該平均粒徑如果大於0.01µm，則得到的組合物的延展性更優異，該平均粒徑如果小於150µm，則組合物的熱阻變小，性能提高。The average particle diameter of the component (B) is preferably in the range of 0.01 to 150 µm, more preferably in the range of 0.1 to 100 µm. The reason is that if the average particle diameter is greater than 0.01 µm, the resulting composition will have better ductility, and if the average particle diameter is less than 150 µm, the thermal resistance of the composition will become smaller and the performance will be improved.
需要說明的是，在本發明中，平均粒徑可以藉由日本日機裝股份有限公司製造的Microtrac MT3300EX進行測定，為體積基準的體積平均直徑。(B)成分的形狀可以為無定形，也可以為球形或可為任何形狀。It should be noted that in the present invention, the average particle diameter can be measured by Microtrac MT3300EX manufactured by Nikkiso Co., Ltd. and is a volume average diameter on a volume basis. The shape of component (B) may be amorphous, spherical, or may be any shape.
從組合物的延展性的觀點考慮，相對於上述(A)成分和後述的(C)成分的合計100質量份，(B)成分的配合量較佳為100~4000質量份、更佳為500~3500質量份。在使用導熱性填充材料作為(B)成分的情況下，從組合物的熱傳導率的觀點考慮，(B)成分的配合量較佳為在所述的範圍內。From the viewpoint of the ductility of the composition, the blending amount of component (B) is preferably 100 to 4000 parts by mass, more preferably 500 parts by mass, based on 100 parts by mass in total of the above-mentioned component (A) and component (C) described below. ~3500 parts by mass. When a thermally conductive filler is used as the component (B), the blending amount of the component (B) is preferably within the above range from the viewpoint of thermal conductivity of the composition.
本發明的矽酮組合物，進一步藉由含有下述(C)成分、(D)成分和(E)成分，從而能夠形成為加成固化型的矽酮組合物。The silicone composition of the present invention can be an addition-curing silicone composition by further containing the following components (C), (D) and (E).
＜(C)成分＞ (C)成分為有機聚矽氧烷，其具有在1分子中與至少2個、較佳為2~100個、更佳為2~50個的矽原子鍵結了的脂肪族不飽和烴基、且在25℃條件下的運動黏度為60~100000mm 2/s。 <Component (C)> Component (C) is an organopolysiloxane having an aliphatic unsaturated hydrocarbon group bonded to at least 2, preferably 2 to 100, more preferably 2 to 50 silicon atoms in one molecule and having a kinematic viscosity at 25°C of 60 to 100,000 mm2 /s.
作為與矽原子鍵結了的脂肪族不飽和烴基，較佳為具有脂肪族不飽和鍵的碳原子數為2~8的一價烴基、更佳為碳原子數為2~6的一價烴基，可列舉出例如，乙烯基、烯丙基、丙烯基、異丙烯基、丁烯基、己烯基、環己烯基和辛烯基等烯基，特佳為乙烯基。 脂肪族不飽和烴基可以與分子鏈末端的矽原子、分子鏈中端的矽原子中的任一者鍵結，也可以與兩者鍵結。 As the aliphatic unsaturated alkyl group bonded to the silicon atom, preferably a monovalent alkyl group having 2 to 8 carbon atoms and having an aliphatic unsaturated bond, more preferably a monovalent alkyl group having 2 to 6 carbon atoms, for example, vinyl, allyl, propenyl, isopropenyl, butenyl, hexenyl, cyclohexenyl and octenyl, etc., and vinyl is particularly preferred. The aliphatic unsaturated alkyl group may be bonded to either the silicon atom at the end of the molecular chain or the silicon atom in the middle of the molecular chain, or may be bonded to both.
作為與矽原子鍵結了的脂肪族不飽和烴基以外的有機基團，可列舉出碳原子數為1~18、較佳為碳原子數為1~10、更佳為碳原子數為1~8的、未取代或取代的一價烴基。 作為這樣的一價烴基，可列舉出例如，甲基、乙基、丙基、異丙基、丁基、異丁基、三級丁基、戊基、新戊基、己基、環己基、辛基、壬基、癸基等烷基；苯基、甲苯基、二甲苯基、萘基等芳基；苄基、苯基乙基、苯丙基等芳烷基，或這些基團的一部分氫原子或全部氫原子被氟、溴、氯等鹵原子、氰基等取代的基團，例如氯甲基、氯丙基、溴乙基、三氟丙基、氰乙基等，特佳為甲基、苯基。 Examples of organic groups other than aliphatic unsaturated hydrocarbon groups bonded to silicon atoms include carbon atoms of 1 to 18, preferably 1 to 10 carbon atoms, more preferably 1 to 18 carbon atoms. 8, unsubstituted or substituted monovalent hydrocarbon group. Examples of such monovalent hydrocarbon groups include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tertiary butyl, pentyl, neopentyl, hexyl, cyclohexyl, and octyl. Alkyl groups such as base, nonyl, and decyl; aryl groups such as phenyl, tolyl, xylyl, and naphthyl; aralkyl groups such as benzyl, phenylethyl, and phenylpropyl, or part of the hydrogen of these groups A group in which atoms or all hydrogen atoms are replaced by halogen atoms such as fluorine, bromine, chlorine, or cyano groups, such as chloromethyl, chloropropyl, bromoethyl, trifluoropropyl, cyanoethyl, etc., especially methyl base, phenyl.
(C)成分在25℃條件下的運動黏度為60~100000mm 2/s、較佳為100~300000mm 2/s。該運動黏度如果小於60mm 2/s，則矽酮組合物的物理特性降低，該運動黏度如果超過100000mm 2/s，則有時矽酮組合物會缺乏延展性。 在本發明中，運動黏度為用奧斯特瓦爾德黏度計黏度計測定的在25℃條件下的值(以下相同)。 The kinematic viscosity of the component (C) at 25°C is 60 to 100,000 mm2 /s, preferably 100 to 300,000 mm2 /s. If the kinematic viscosity is less than 60 mm2 /s, the physical properties of the silicone composition are deteriorated, and if the kinematic viscosity exceeds 100,000 mm2 /s, the silicone composition may lack ductility. In the present invention, the kinematic viscosity is a value measured at 25°C using an Ostwald viscometer (the same applies hereinafter).
對(C)成分的分子結構沒有特別的限定，可列舉出直鏈結構、支鏈結構和具有部分支鏈結構或環狀結構的直鏈結構等，特佳為具有主鏈由二有機矽氧烷單元的重複構成，分子鏈兩末端用三有機甲矽烷氧基封端的直鏈結構的分子結構。具有該直鏈結構的有機聚矽氧烷也可以具有部分的支鏈結構或環狀結構。 (C)成分可以單獨使用1種或將2種以上組合進行使用。 There is no particular limitation on the molecular structure of the component (C), and examples thereof include a linear structure, a branched structure, and a linear structure having a partial branched structure or a ring structure. A particularly preferred molecular structure is a linear structure having a main chain composed of a repeating diorganosiloxane unit and a molecular chain end-capped with triorganosiloxy groups. The organic polysiloxane having the linear structure may also have a partial branched structure or a ring structure. The component (C) may be used alone or in combination of two or more.
＜(D)成分＞ (D)成分為在1分子中具有2個以上、特佳為2~100個、又更佳為2~50個與矽原子鍵結的氫原子(SiH基)的有機氫聚矽氧烷。該有機氫聚矽氧烷只要是分子中的SiH基在鉑催化劑的存在下，能夠與上述(A)成分和(C)成分所具有的脂肪族不飽和烴基進行加成反應，形成交聯結構的有機氫聚矽氧烷即可。 ＜(D)Component＞ The component (D) is an organohydrogen polysiloxane having 2 or more, particularly preferably 2 to 100, and more preferably 2 to 50 hydrogen atoms (SiH groups) bonded to silicon atoms in one molecule. As long as the SiH group in the molecule of this organohydrogen polysiloxane is in the presence of a platinum catalyst, it can undergo an addition reaction with the aliphatic unsaturated hydrocarbon group contained in the component (A) and component (C) to form a cross-linked structure. of organohydrogenpolysiloxane.
作為與SiH基以外的矽原子鍵結了的有機基團，可列舉出脂肪族不飽和烴基以外的未取代或取代的一價烴基。特別是碳原子數為1~12、較佳為碳原子數為1~10的未取代或取代的一價烴基。可列舉出例如，甲基、乙基、丙基、丁基、己基、十二烷基等烷基；苯基等芳基；2-苯基乙基、2-苯基丙基等芳烷基；這些的一部分的氫原子或全部的氫原子被氟、溴、氯等鹵原子，氰基、含有環氧環的有機基團(縮水甘油基或縮水甘油氧基取代的烷基)等取代的基團，例如，氯甲基、氯丙基、氰乙基、2-環氧丙氧基乙基、3-環氧丙氧基丙基和4-環氧丙氧基丁基等。其中，較佳為甲基、3-環氧丙氧基丙基。As the organic group bonded to the silicon atom other than the SiH group, there can be listed unsubstituted or substituted monovalent hydrocarbon groups other than aliphatic unsaturated hydrocarbon groups. In particular, unsubstituted or substituted monovalent hydrocarbon groups having 1 to 12 carbon atoms, preferably 1 to 10 carbon atoms, can be listed. For example, alkyl groups such as methyl, ethyl, propyl, butyl, hexyl, and dodecyl; aryl groups such as phenyl; aralkyl groups such as 2-phenylethyl and 2-phenylpropyl; groups in which some or all of the hydrogen atoms are substituted by halogen atoms such as fluorine, bromine, and chlorine, cyano groups, and organic groups containing epoxy rings (alkyl groups substituted with glycidyl or glycidyloxy groups), such as chloromethyl, chloropropyl, cyanoethyl, 2-glycidoxyethyl, 3-glycidoxypropyl, and 4-glycidoxybutyl. Among them, methyl and 3-glycidoxypropyl are preferred.
(D)成分在25℃條件下的運動黏度較佳為1~1000mm 2/s、更佳為10~300mm 2/s。如果該運動黏度為1mm 2/s以上，則不用擔心矽酮組合物的物理特性會降低，如果該運動黏度為1000mm 2/s以下，則不用擔心矽酮組合物會缺乏延展性。 The kinematic viscosity of the component (D) at 25°C is preferably 1 to 1000 mm2 /s, more preferably 10 to 300 mm2 /s. If the kinematic viscosity is 1 mm2 /s or more, there is no concern about reduction in physical properties of the silicone composition, and if the kinematic viscosity is 1000 mm2 /s or less, there is no concern about lack of ductility of the silicone composition.
對(D)成分的分子結構沒有特別的限定，可列舉出直鏈結構、支鏈結構、環狀結構、具有部分支鏈結構或環狀結構的直鏈結構等。較佳為直鏈結構、環狀結構。 (D)成分可以單獨使用1種或也可以將2種以上組合進行使用。 The molecular structure of component (D) is not particularly limited, and examples include a linear structure, a branched chain structure, a cyclic structure, a linear structure having a partially branched chain structure or a cyclic structure, and the like. Preferred are linear structures and cyclic structures. (D) Component may be used individually by 1 type, or may be used in combination of 2 or more types.
相對於上述(A)成分和(C)成分中的脂肪族不飽和烴基的合計，(D)成分的配合量為(D)成分中的SiH基的個數(以下也簡稱為「(D)成分的量」)為0.5~5的量、較佳為0.7~4.5的量、更佳為0.9~4的量。如果上述(D)成分的量小於0.5，則有時加成反應不能充分地進行，交聯不充分，從而導致固化不良。另外，在上述(D)成分的量超過5的情況下，有時交聯結構會變得不均勻，或有時組合物的保存性顯著惡化。The compounding amount of component (D) is the number of SiH groups in component (D) (hereinafter also referred to as "(D)") relative to the total aliphatic unsaturated hydrocarbon groups in component (A) and (C). The amount of ingredients") is an amount of 0.5 to 5, preferably an amount of 0.7 to 4.5, more preferably an amount of 0.9 to 4. If the amount of the component (D) is less than 0.5, the addition reaction may not proceed sufficiently and crosslinking may be insufficient, resulting in poor curing. In addition, when the amount of the component (D) exceeds 5, the crosslinked structure may become uneven, or the storage stability of the composition may significantly deteriorate.
＜(E)成分＞ (E)成分為促進上述(C)成分中的脂肪族不飽和烴基與上述(D)成分中的SiH基團進行氫化矽烷化反應的鉑族金屬系催化劑。 作為鉑族金屬系催化劑，可列舉出鉑系、鈀系、銠系、釕系的催化劑，特佳為鉑系的催化劑。作為具體例子，可列舉出例如，鉑黑或將固體鉑擔載在氧化鋁或矽土等載體上的催化劑、氯鉑酸、醇改質氯鉑酸、氯鉑酸與烯烴的錯合物或氯鉑酸與乙烯基矽氧烷的錯合物等。 (E)成分的使用量可以是所說的催化劑量，例如，相對於上述(C)成分，以鉑族金屬換算可以使用0.1~1000質量ppm、特別是可以使用0.5~100質量ppm。 <Component (E)> Component (E) is a platinum group metal catalyst that promotes the hydrosilylation reaction between the aliphatic unsaturated hydrocarbon group in the above-mentioned component (C) and the SiH group in the above-mentioned component (D). As the platinum group metal catalyst, platinum-based, palladium-based, rhodium-based, and ruthenium-based catalysts can be listed, and platinum-based catalysts are particularly preferred. As specific examples, for example, platinum black or a catalyst in which solid platinum is supported on a carrier such as alumina or silica, chloroplatinic acid, alcohol-modified chloroplatinic acid, a complex of chloroplatinic acid and olefin, or a complex of chloroplatinic acid and vinylsiloxane can be listed. The amount of component (E) used can be the amount of the catalyst mentioned above. For example, relative to the above-mentioned component (C), 0.1 to 1000 mass ppm can be used in terms of platinum group metals, and in particular 0.5 to 100 mass ppm can be used.
本發明的矽酮組合物，除了添加上述(A)~(E)成分以外，根據需要還可以添加以下的任意成分。In addition to the above-mentioned components (A) to (E), the silicone composition of the present invention may also add any of the following components as necessary.
＜(F)成分＞ (F)成分為抑制氫化矽烷化反應的進程的反應控制劑，添加(F)成分可以延長保質期、適用期。該反應控制劑可以使用被使用在加成固化型矽酮組合物中的以往公知的反應控制劑。由此，可列舉出例如，乙炔醇類(例如，乙炔基甲基癸基碳醇(ethynylmethyldecylcarbinol)、1-乙炔基-1-環己醇、3，5-二甲基-1-己炔-3-醇)等乙炔化合物；三丁基胺、四甲基乙二胺、苯並三唑等各種氮化合物；三苯基膦等有機磷化合物；肟化合物；有機氯化合物。 <Component (F)> Component (F) is a reaction control agent that inhibits the progress of the hydrosilylation reaction. Adding component (F) can extend the shelf life and the applicable period. The reaction control agent can use a conventionally known reaction control agent used in addition-curing silicone compositions. For example, acetylene compounds such as acetylene alcohols (e.g., ethynylmethyldecylcarbinol, 1-ethynyl-1-cyclohexanol, 3,5-dimethyl-1-hexyn-3-ol); various nitrogen compounds such as tributylamine, tetramethylethylenediamine, and benzotriazole; organic phosphorus compounds such as triphenylphosphine; oxime compounds; and organic chlorine compounds.
在配合(F)成分時的配合量，相對於(C)成分100質量份，較佳為0.05~5質量份、更佳為0.1~2質量份。如果反應控制劑的量小於0.05質量份，則有可能得不到所希望的充分的保質期、適用期，另外，反應控制劑的量在大於5質量份的情況下，則矽酮組合物的固化性有可能會降低。 另外，為了提高對矽酮組合物的分散性，也可以用有機聚矽氧烷或甲苯等將反應控制劑稀釋，然後進行使用。 The amount of component (F) to be added is preferably 0.05 to 5 parts by mass, more preferably 0.1 to 2 parts by mass, relative to 100 parts by mass of component (C). If the amount of the reaction control agent is less than 0.05 parts by mass, the desired shelf life and application period may not be achieved. In addition, if the amount of the reaction control agent is greater than 5 parts by mass, the curability of the silicone composition may be reduced. In addition, in order to improve the dispersibility of the silicone composition, the reaction control agent can be diluted with an organic polysiloxane or toluene and then used.
＜(G)成分＞ (G)成分為以下述通式(w)表示的水解性有機聚矽氧烷。本成分為用於處理填充材料的表面的成分，起到輔助填充材料的高填充化的作用。 [化學式11] (在通式(w)中，R 3相互獨立地，為氫原子或可以具有取代基的碳原子數為1~20的一價烴基，R 4相互獨立地，為可以具有取代基的碳原子數為1~20的烷基或可以具有取代基的碳原子數為3~20的環烷基。b為1~3的整數。m為1~200的數。) <Component (G)> Component (G) is a hydrolyzable organopolysiloxane represented by the following general formula (w). This component is used to treat the surface of the filler and plays a role in assisting the high filling of the filler. [Chemical formula 11] (In the general formula (w), R3 is independently a hydrogen atom or a monovalent alkyl group having 1 to 20 carbon atoms which may have a substituent, and R4 is independently an alkyl group having 1 to 20 carbon atoms which may have a substituent or a cycloalkyl group having 3 to 20 carbon atoms which may have a substituent. b is an integer of 1 to 3. m is a number of 1 to 200.)
在此，在上述通式(w)中，作為R 3的碳原子數為1~20的取代或未取代的一價烴基，可以為相同或也可以為不同，可例示出甲基、乙基、正丙基、異丙基、正丁基、異丁基、三級丁基、戊基、新戊基、己基、庚基、辛基、壬基、癸基、十一烷基、十二烷基、十三烷基、十四烷基、十五烷基、十六烷基、十七烷基、十八烷基、十九烷基、二十烷基等烷基；環戊基、環己基等環烷基；乙烯基、烯丙基、丁烯基、戊烯基和己烯基等烯基；苯基、甲苯基、二甲苯基、α-，β-萘基等芳基；苄基、2-苯基乙基和3-苯基丙基等芳烷基；另外，這些基團的一部分氫原子或全部氫原子被用F、Cl、Br等鹵素原子或氰基等取代的基團，例如3-氯丙基、3,3,3-三氟丙基、2-氰乙基等。其中，較佳為碳原子數為1~10的一價烴基、特佳為碳原子數為1~6的一價烴基，特佳為甲基、乙基、苯基，從入手的容易性、生產性、成本方面考慮，更佳為甲基、苯基。b各自獨立地，為1~3的整數、較佳為2或3、更佳為3。 Here, in the above general formula (w), the substituted or unsubstituted monovalent hydrocarbon group having 1 to 20 carbon atoms as R 3 may be the same or different, and examples thereof include methyl and ethyl. , n-propyl, isopropyl, n-butyl, isobutyl, tertiary butyl, pentyl, neopentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl Alkyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl and other alkyl groups; cyclopentyl, Cycloalkyl groups such as cyclohexyl; alkenyl groups such as vinyl, allyl, butenyl, pentenyl, and hexenyl; aryl groups such as phenyl, tolyl, xylyl, α-, β-naphthyl, etc.; benzyl aralkyl groups such as 2-phenylethyl group and 3-phenylpropyl group; in addition, some or all of the hydrogen atoms of these groups are substituted with halogen atoms such as F, Cl, Br, or cyano groups. Groups, such as 3-chloropropyl, 3,3,3-trifluoropropyl, 2-cyanoethyl, etc. Among them, a monovalent hydrocarbon group having 1 to 10 carbon atoms is preferred, a monovalent hydrocarbon group having 1 to 6 carbon atoms is particularly preferred, and a methyl group, an ethyl group, and a phenyl group are particularly preferred, in terms of ease of acquisition, In terms of productivity and cost, methyl and phenyl are more preferred. b is each independently an integer of 1 to 3, preferably 2 or 3, more preferably 3.
作為R 4的碳原子數為1~20的烷基，可列舉出甲基、乙基、正丙基、異丙基、正丁基、異丁基、三級丁基、戊基、新戊基、己基、庚基、辛基、壬基、癸基、十一烷基、十二烷基、十三烷基、十四烷基、十五烷基、十六烷基、十七烷基、十八烷基、十九烷基、二十烷基等。作為環烷基，可列舉出環戊基、環己基等。作為也可以具有取代基的碳原子數為1~20的烷基，可列舉出苄基、2-苯基乙基和3-苯基丙基等的芳烷基；另外，這些(取代)烷基的一部分氫原子或全部氫原子也可以被用F、Cl、Br等鹵素原子或氰基等取代，在此，可列舉出例如，3-氯丙基、3,3,3-三氟丙基、2-氰乙基等。作為R 4，其中，較佳為碳原子數為1~16的烷基、特佳為碳原子數為1~4的烷基、特別更佳為甲基、乙基，從入手的容易性、生產性、成本方面考慮，又更佳為甲基。 Examples of the alkyl group having 1 to 20 carbon atoms in R 4 include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tertiary butyl, pentyl, and neopentyl Base, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl , octadecyl, nonadecyl, eicosyl, etc. Examples of the cycloalkyl group include cyclopentyl group, cyclohexyl group, and the like. Examples of the alkyl group having 1 to 20 carbon atoms that may have a substituent include aralkyl groups such as benzyl, 2-phenylethyl, and 3-phenylpropyl; in addition, these (substituted) alkyl groups Some or all of the hydrogen atoms of the group may be substituted with halogen atoms such as F, Cl, Br, or cyano groups. Here, examples include 3-chloropropyl and 3,3,3-trifluoropropyl. base, 2-cyanoethyl, etc. As R 4 , among them, an alkyl group having 1 to 16 carbon atoms is preferred, an alkyl group having 1 to 4 carbon atoms is particularly preferred, and a methyl group and an ethyl group are particularly preferred, in terms of ease of acquisition, In terms of productivity and cost, methyl is more preferred.
m為1~200的數、較佳為3~100的數、更佳為5~50的數。如果m小於1，則有可能由於本成分容易滲出，會導致可靠性降低，如果m大於200，則有時組合物的黏度變高，流動性惡化。m is a number of 1 to 200, preferably 3 to 100, and more preferably 5 to 50. If m is less than 1, the component may easily ooze out, which may result in reduced reliability, while if m is greater than 200, the viscosity of the composition may increase, and fluidity may deteriorate.
從填充材料的潤濕性和防止本成分滲出的觀點考慮，相對於組合物總體，在配合(G)成分的時的配合量較佳為0.1~20質量%的範圍、更佳為1~15質量的範圍、又更佳為1~10質量%的範圍。From the viewpoint of wettability of the filling material and prevention of bleed-out of this component, the blending amount of component (G) is preferably in the range of 0.1 to 20 mass %, more preferably 1 to 15 mass %, based on the entire composition. The mass range is preferably in the range of 1 to 10 mass %.
＜其他成分＞ 為了調整組合物的強度和黏度，本發明的矽酮組合物也可以含有二甲基聚矽氧烷等不具有反應性的有機(聚)矽氧烷。進一步，以提高填充材料的填充性為目的或以對組合物賦予黏合性為目的，也可以配合水解性有機聚矽氧烷、各種改質矽酮和水解性有機矽烷。此外，還可以配合用於調整組合物的黏度的溶劑。並且，為了防止矽酮組合物的劣化，根據需要，還可以含有2,6-二三級丁基-4-甲基苯酚等以往公知的抗氧化劑。此外，根據需要，還可以配合染料、顏料、阻燃劑、防沉降劑或觸變性改進劑等。 ＜Other ingredients＞ In order to adjust the strength and viscosity of the composition, the silicone composition of the present invention may also contain non-reactive organo(poly)siloxane such as dimethylpolysiloxane. Furthermore, for the purpose of improving the filling property of the filling material or for the purpose of imparting adhesiveness to the composition, hydrolyzable organopolysiloxane, various modified silicones and hydrolyzable organosilane may be blended. In addition, a solvent for adjusting the viscosity of the composition may be blended. In addition, in order to prevent deterioration of the silicone composition, conventionally known antioxidants such as 2,6-ditertiary butyl-4-methylphenol may be included as necessary. In addition, dyes, pigments, flame retardants, anti-settling agents or thixotropy improvers can also be added as needed.
對本發明的矽酮組合物的製造方法沒有特別的限定，可列舉出例如，使用三輥混合機、雙輥混合機、行星式攪拌機(全部為日本井上製作所股份有限公司製造的混合機的註冊商標)、高速攪拌機(日本瑞穗工業股份有限公司製造的混合機、註冊商標)、HIVIS MIX (日本譜萊密克司股份有限公司製造的混合機的註冊商標)等混合機等混合上述(A)成分和(B)成分、以及根據需要混合(C)~(G)成分和其他成分的方法。另外，在混合時，也可以邊加熱邊混合。對加熱條件沒有特別的限制，溫度通常為25~220℃、較佳為40~200℃、特佳為50~180℃；時間通常為3分鐘~24小時、較佳為5分鐘~12小時、特佳為10分鐘~6小時。另外，也可以在加熱時進行脫氣。 在本發明中，較佳為預先在20~220℃條件下加熱混合(A)成分~(C)成分和(G)成分，然後再混合(D)成分~(F)成分。另外，也可以在混合時進行脫氣。 There is no particular limitation on the method for producing the silicone composition of the present invention. For example, a method of mixing the above-mentioned component (A) and component (B), and mixing components (C) to (G) and other components as needed, using a three-roll mixer, a double-roll mixer, a planetary mixer (all registered trademarks of mixers manufactured by Inoue Seisakusho Co., Ltd., Japan), a high-speed mixer (mixer, registered trademark manufactured by Mizuho Industries Co., Ltd., Japan), HIVIS MIX (registered trademark of mixer manufactured by Promix Co., Ltd., Japan) and other mixers can be cited. In addition, the mixing can be performed while heating. There is no particular restriction on the heating conditions. The temperature is usually 25 to 220°C, preferably 40 to 200°C, and particularly preferably 50 to 180°C; the time is usually 3 minutes to 24 hours, preferably 5 minutes to 12 hours, and particularly preferably 10 minutes to 6 hours. In addition, degassing can also be performed during heating. In the present invention, it is preferred to heat and mix the components (A) to (C) and (G) at 20 to 220°C in advance, and then mix the components (D) to (F). In addition, degassing can also be performed during mixing.
本發明的矽酮組合物在25℃條件下測定的絕對黏度較佳為10~1000Pa·s、更佳為20~700Pa·s、又更佳為30~500Pa·s。如果絕對黏度為10Pa·s以上，則形狀保持變得容易、填充材料不會沉降等，因此不會有操作性變差的擔心。另外，如果絕對黏度為1000Pa·s以下，則排出或塗佈變得容易等，不會有操作性變差的擔心。藉由調整上述各成分的配合量，能夠得到所述絕對黏度。可以使用例如瑪律科姆(MALCOM)黏度計(型號PC-1T)在25℃條件下測定絕對黏度。 另外，在使用導熱性填充材料作為(B)成分的填充材料的情況下，本發明的矽酮組合物較佳為具有0.5~20W/m·K的熱傳導率。需要說明的是，熱傳導率為用熱盤法測定的在25℃條件下的值。 實施例 The absolute viscosity of the silicone composition of the present invention measured at 25°C is preferably 10~1000Pa·s, more preferably 20~700Pa·s, and even more preferably 30~500Pa·s. If the absolute viscosity is 10Pa·s or more, the shape is easy to maintain and the filler material does not settle, so there is no worry about poor operability. In addition, if the absolute viscosity is less than 1000Pa·s, discharge or coating becomes easy, and there is no worry about poor operability. The absolute viscosity can be obtained by adjusting the amount of each component. The absolute viscosity can be measured at 25°C using, for example, a Malcom viscometer (model PC-1T). In addition, when a thermally conductive filler is used as the filler of component (B), the silicone composition of the present invention preferably has a thermal conductivity of 0.5 to 20 W/m·K. It should be noted that the thermal conductivity is a value measured by a hot plate method at 25°C. Example
以下，使用實施例和比較例，對本發明具體地進行說明，但本發明並不被限定於這些實施例。Hereinafter, the present invention will be specifically described using Examples and Comparative Examples, but the present invention is not limited to these Examples.
[合成例1] 將90.9g(0.840莫耳)二乙炔基二甲基矽烷、0.25g氯鉑酸(H 2PtCl 6·6H 2O)的0.5質量%甲苯溶液和50mL甲苯加入到具備機械攪拌器、溫度計和滴液漏斗的500mL四口可分離燒瓶中，又滴加了51.3g(0.420莫耳)三甲氧基矽烷。然後，在85℃條件下攪拌了6小時後，進行蒸餾，回收未反應原料的二乙炔基二甲基矽烷，從而得到了91.9g(三甲氧基矽烷的反應率為95%)以下述結構式(4)表示的乙炔基(三甲氧基甲矽烷基-伸乙烯基)二甲基矽烷。 [Synthesis Example 1] 90.9 g (0.840 mol) of diethynyldimethylsilane, 0.25 g of a 0.5 mass % toluene solution of chloroplatinic acid (H 2 PtCl 6 ·6H 2 O) and 50 mL of toluene were added to a 500 mL four-necked separable flask equipped with a mechanical stirrer, a thermometer and a dropping funnel, and 51.3 g (0.420 mol) of trimethoxysilane was added dropwise. The mixture was stirred at 85° C. for 6 hours and then distilled to recover the unreacted raw material diethynyldimethylsilane, thereby obtaining 91.9 g (reaction rate of trimethoxysilane: 95%) of ethynyl (trimethoxysilyl-vinylene) dimethylsilane represented by the following structural formula (4).
【化學式12】 【Chemical Formula 12】
[合成例2] 將212.1g(1.959莫耳)二乙炔基二甲基矽烷、0.58g氯鉑酸(H 2PtCl 6·6H 2O)的0.5質量%甲苯溶液和50mL甲苯加入到具備機械攪拌器、溫度計和滴液漏斗的500mL四口可分離燒瓶中，又滴加了53.6g(0.506莫耳)二甲氧基甲基矽烷。然後，在85℃條件下攪拌了6小時後，進行蒸餾，回收未反應原料的二乙炔基二甲基矽烷，從而得到了102.9g(二甲氧基矽烷的反應率為95%)以下述結構式(7)表示的乙炔基(二甲氧基甲基甲矽烷基-伸乙烯基)二甲基矽烷。 [Synthesis Example 2] 212.1g (1.959 mol) diethynyldimethylsilane, 0.58g 0.5 mass% toluene solution of chloroplatinic acid (H 2 PtCl 6 ·6H 2 O) and 50 mL toluene were added to a machine equipped with mechanical stirring 53.6g (0.506 mol) of dimethoxymethylsilane was added dropwise to a 500mL four-necked separable flask with a thermometer, a thermometer and a dropping funnel. Then, after stirring at 85° C. for 6 hours, distillation was performed to recover unreacted raw material diethynyldimethylsilane, thereby obtaining 102.9 g (reaction rate of dimethoxysilane: 95%) with the following structure Ethynyl(dimethoxymethylsilyl-vinylidene)dimethylsilane represented by formula (7).
[化學13] [Chemistry 13]
[合成例3] 將90.9g(0.840莫耳)二乙炔基二甲基矽烷、0.25g氯鉑酸(H 2PtCl 6·6H 2O)的0.5質量%甲苯溶液和50mL甲苯加入到具備機械攪拌器、溫度計和滴液漏斗的500mL四口可分離燒瓶中，又滴加了35.6g(0.271莫耳)三乙氧基矽烷。然後，在85℃條件下攪拌了6小時後，進行蒸餾，回收未反應原料的二乙炔基二甲基矽烷，從而得到了56.2g(三乙氧基矽烷的反應率為95%)以下述結構式(9)表示的乙炔基(三乙氧基甲矽烷基-伸乙烯基)二甲基矽烷。 [Synthesis Example 3] 90.9 g (0.840 mol) of diethynyldimethylsilane, 0.25 g of a 0.5 mass % toluene solution of chloroplatinic acid (H 2 PtCl 6 ·6H 2 O) and 50 mL of toluene were added to a 500 mL four-necked separable flask equipped with a mechanical stirrer, a thermometer and a dropping funnel, and 35.6 g (0.271 mol) of triethoxysilane was added dropwise. The mixture was stirred at 85° C. for 6 hours and then distilled to recover the unreacted raw material diethynyldimethylsilane, thereby obtaining 56.2 g (reaction rate of triethoxysilane: 95%) of ethynyl (triethoxysilyl-vinylene) dimethylsilane represented by the following structural formula (9).
[化學式14] [Chemical formula 14]
[實施例1-1] 將在合成例1中得到的以上述結構式(4)表示的41.6g(0.181莫耳)乙炔基(三甲氧基甲矽烷基-伸乙烯基)二甲基矽烷、0.5g氯鉑酸(H 2PtCl 6· 6H 2O)的0.5質量%甲苯溶液和200mL甲苯加入到具備機械攪拌器、溫度計和滴液漏斗的500mL四口可分離燒瓶中，又滴加了以下述結構式(5)表示的375g(Si-H，0.181莫耳)有機聚矽氧烷，然後，在85℃條件下攪拌了6小時後，蒸餾去除甲苯，從而得到了以下述結構式(6)表示的396g(收率為95%)單末端改質有機聚矽氧烷(A-1)。將該反應表示在下述反應式(4)。 [Example 1-1] 41.6 g (0.181 mol) of ethynyl(trimethoxysilyl-vinylene)dimethylsilane represented by the above structural formula (4) obtained in Synthesis Example 1, 0.5 g of a 0.5 mass % toluene solution of chloroplatinic acid (H 2 PtCl 6 · 6 H 2 O) and 200 mL of toluene were added to a 500 mL four-necked separable flask equipped with a mechanical stirrer, a thermometer and a dropping funnel, and 375 g (Si-H, 0.181 mol) of an organopolysiloxane represented by the following structural formula (5) was added dropwise. After stirring at 85° C. for 6 hours, toluene was distilled off to obtain 396 g (yield: 95%) of a single-terminal modified organopolysiloxane (A-1) represented by the following structural formula (6). This reaction is represented by the following reaction formula (4).
[化學式15] [Chemical formula 15]
[實施例1-2] 將在合成例2中得到的以上述結構式(7)表示的25.8g(0.121莫耳)乙炔基(二甲氧基甲基甲矽烷基-伸乙烯基)二甲基矽烷、0.5g氯鉑酸(H 2PtCl 6· 6H 2O)的0.5質量%甲苯溶液和150mL甲苯加入到具備機械攪拌器、溫度計和滴液漏斗的500mL四口可分離燒瓶中，又滴加了以下述結構式(5)表示的250g(Si-H，0.121莫耳)有機聚矽氧烷，然後，在85℃條件下攪拌了6小時後，蒸餾去除甲苯，從而得到了以下述(8)表示的262g(收率為95%)單末端改質有機聚矽氧烷(A-2)。 [Example 1-2] 25.8 g (0.121 mol) of ethynyl(dimethoxymethylsilyl-vinylene)dimethylsilane represented by the above structural formula (7) obtained in Synthesis Example 2, 0.5 g of a 0.5 mass % toluene solution of chloroplatinic acid (H 2 PtCl 6 · 6 H 2 O) and 150 mL of toluene were added to a 500 mL four-necked separable flask equipped with a mechanical stirrer, a thermometer and a dropping funnel, and 250 g (Si-H, 0.121 mol) of an organopolysiloxane represented by the following structural formula (5) was added dropwise. After stirring at 85° C. for 6 hours, toluene was distilled off to obtain 262 g (yield: 95%) of a single-terminal modified organopolysiloxane (A-2) represented by the following (8).
[化學式16] [Chemical formula 16]
[實施例1-3] 將在合成例3中得到的以上述結構式(9)表示的28.3g(0.104莫耳)的乙炔基(三乙氧基甲矽烷基-伸乙烯基)二甲基矽烷、0.5g氯鉑酸(H 2PtCl 6· 6H 2O)的0.5質量%甲苯溶液和150mL甲苯加入到具備機械攪拌器、溫度計和滴液漏斗的500mL四口可分離燒瓶中，又滴加了以下述結構式(5)表示的224g(Si-H，0.104莫耳)有機聚矽氧烷，然後，在85℃條件下攪拌了6小時後，蒸餾去除甲苯，從而得到了以下述式(10)表示的239g(收率為95%)單末端改質有機聚矽氧烷(A-3)。將該反應表示在下述反應式(6)。 [Example 1-3] 28.3 g (0.104 mol) of ethynyl(triethoxysilyl-vinylidene)dimethyl represented by the above structural formula (9) obtained in Synthesis Example 3 Silane, 0.5g 0.5 mass% toluene solution of chloroplatinic acid (H 2 PtCl 6 · 6 H 2 O) and 150 mL toluene were added to a 500 mL four-neck detachable flask equipped with a mechanical stirrer, a thermometer and a dropping funnel, and then dripped 224 g (Si-H, 0.104 mol) of organopolysiloxane represented by the following structural formula (5) was added, and then, after stirring at 85°C for 6 hours, toluene was distilled off to obtain the following formula: 239 g (yield 95%) of single-end modified organopolysiloxane (A-3) represented by (10). This reaction is represented by the following reaction formula (6).
[化學式17] [Chemical formula 17]
[實施例1-4] 將在合成例2中得到的以上述結構式(7)表示的11.3g(0.051莫耳)乙炔基(二甲氧基甲基甲矽烷基-伸乙烯基)二甲基矽烷、0.5g氯鉑酸(H 2PtCl 6· 6H 2O)的0.5質量%甲苯溶液和150mL甲苯加入到具備機械攪拌器、溫度計和滴液漏斗的500mL四口可分離燒瓶中，又滴加了以下述結構式(11)表示的650g(Si-H，0.051莫耳)有機聚矽氧烷，然後，在85℃條件下攪拌了6小時後，蒸餾去除甲苯，從而得到了以下述式(12)表示的628g(收率為95%)單末端改質有機聚矽氧烷(A-4)。將該反應表示在下述反應式(7)。 [Example 1-4] 11.3 g (0.051 mol) of ethynyl(dimethoxymethylsilyl-vinylidene)dimethyl represented by the above structural formula (7) obtained in Synthesis Example 2 Silane, 0.5g 0.5 mass% toluene solution of chloroplatinic acid (H 2 PtCl 6 · 6 H 2 O) and 150mL toluene were added to a 500mL four-necked separable flask equipped with a mechanical stirrer, thermometer and dropping funnel, and 650 g (Si-H, 0.051 mol) of organopolysiloxane represented by the following structural formula (11) was added dropwise, and then, after stirring at 85° C. for 6 hours, toluene was distilled off to obtain the following product: 628 g (yield 95%) of single-terminal modified organopolysiloxane (A-4) represented by formula (12). This reaction is represented by the following reaction formula (7).
[化學式18] [Chemical formula 18]
[實施例1-5] 將在合成例2中得到的以上述結構式(7)表示的5.57g(0.025莫耳)的乙炔基(二甲氧基甲基甲矽烷基-伸乙烯基)二甲基矽烷、0.5g氯鉑酸(H 2PtCl 6· 6H 2O)的0.5質量%甲苯溶液和150mL甲苯加入到具備機械攪拌器、溫度計和滴液漏斗的500mL四口可分離燒瓶中，又滴加了以下述結構式(13)表示的325g(Si-H，0.025莫耳)有機聚矽氧烷，然後，在85℃條件下攪拌了6小時後，蒸餾去除甲苯，從而得到了以下述式(14)表示的310g(收率為94%)單末端改質有機聚矽氧烷(A-5)。將該反應表示在下述反應式(8)。 [Example 1-5] 5.57 g (0.025 mol) of ethynyl (dimethoxymethylsilyl-vinylene) dimethylsilane represented by the above structural formula (7) obtained in Synthesis Example 2 and 0.5 g of chloroplatinic acid (H 2 PtCl 6 · 6 H 2 A 0.5 mass% toluene solution of 1,2-dihydro-1,4 ...
[化學式19] [Chemical formula 19]
[實施例2-1~實施例2-4、比較例2-1、比較例2-2] 使用混合機，以表1所示的配合量(質量份)混合下述各成分，從而得到了矽酮組合物。 [Example 2-1 to Example 2-4, Comparative Example 2-1, Comparative Example 2-2] The following components were mixed in the amounts (parts by mass) shown in Table 1 using a mixer to obtain a silicone composition.
(A)成分 (A-1)：在實施例1-1中得到的以上述式(6)表示的單末端改質有機聚矽氧烷 (A-2)：在實施例1-2中得到的以上述式(8)表示的單末端改質有機聚矽氧烷 (A)Ingredients (A-1): Single-terminal modified organopolysiloxane represented by the above formula (6) obtained in Example 1-1 (A-2): Single-terminal modified organopolysiloxane represented by the above formula (8) obtained in Example 1-2
(B)成分 (B-1)：平均粒徑為0.3µm的無定形氧化鋅粉 (B) Ingredients (B-1): Amorphous zinc oxide powder with an average particle size of 0.3µm
(G)成分 (G-1)：以下述式(15)表示的有機聚矽氧烷 [化學式20] (G) Component (G-1): Organopolysiloxane [Chemical Formula 20] represented by the following formula (15)
(H)成分 (H-1)：以旋轉黏度計測定的在25℃條件下的黏度為1000mPa·s的以三甲基甲矽烷氧基封端分子鏈兩末端的二甲基聚矽氧烷 (H) Component (H-1): Dimethylpolysiloxane with trimethylsiloxy groups capped at both ends of the molecular chain, with a viscosity of 1000 mPa·s at 25°C as measured by a rotational viscometer
將對得到的矽酮組合物進行下述測定的結果表示在表1。Table 1 shows the results of the following measurements on the obtained silicone composition.
[黏度] 使用瑪律科姆黏度計(型號PC-1TL)，在25℃條件下測定了矽酮組合物在剛混合之後(初期)、在25℃條件下的5天後和在25℃條件下14天後的絕對黏度(為轉子A，10rpm，剪切速率6[1/s])。另外，算出了相對於初期黏度的在25℃條件下14天後的黏度之比。 [熱傳導率] 用保鮮膜包覆各組合物，並使用日本京都電子工業股份有限公司公司製造的TPS-2500S，測定了各組合物的熱傳導率。 [viscosity] Using a Malcom viscometer (model PC-1TL), the silicone composition was measured immediately after mixing (initial stage) at 25°C, after 5 days at 25°C, and after 14 days at 25°C. The final absolute viscosity (for rotor A, 10rpm, shear rate 6[1/s]). In addition, the ratio of the viscosity after 14 days at 25° C. to the initial viscosity was calculated. [Thermal conductivity] Each composition was covered with plastic wrap, and the thermal conductivity of each composition was measured using TPS-2500S manufactured by Kyoto Electronics Co., Ltd., Japan.
[表1]
由表1的評價結果顯示出，實施例2-1~實施例2-4與比較例2-1、比較例2-2相比，初期的黏度與14天後的黏度變化小，本發明的單末端改質有機聚矽氧烷作為減少矽酮組合物的黏度變化的潤濕劑為有效。The evaluation results in Table 1 show that the initial viscosity and the viscosity after 14 days of Examples 2-1 to 2-4 are less different from those of Comparative Examples 2-1 and 2-2, and the single-terminal modified organopolysiloxane of the present invention is effective as a wetting agent for reducing the viscosity change of the silicone composition.
[實施例3-1~實施例3-4、比較例3-1~比較例3-4] 按表2所示的配合(質量份)且按下述所示方法配合下述(A)成分~(G)成分，從而製備了矽酮組合物。 將(A)成分、(B)成分、(C)成分以及(G)成分添加在5公升行星式攪拌機(日本井上製作所股份有限公司製造)內，從25℃開始攪拌，邊脫氣邊升溫至150℃，且在150℃條件下混合了1小時。然後，將其冷卻至40℃以下，並根據需要再添加(F)成分、(E)成分和(D)成分，並將其在25℃條件下混合至均勻，從而製備了矽酮組合物。需要說明的是，運動黏度為使用奧斯特瓦爾德黏度計所測定的在25℃條件下的值，SiH/SiVi為相對於(A)成分中的烯基的個數的合計的(D)成分的SiH基的個數的合計之比。 [Example 3-1~Example 3-4, Comparative Example 3-1~Comparative Example 3-4] The following components (A) to (G) were blended according to the formula (parts by mass) shown in Table 2 and the method shown below, thereby preparing a silicone composition. Add component (A), component (B), component (C) and component (G) to a 5-liter planetary mixer (manufactured by Inoue Manufacturing Co., Ltd., Japan), start stirring at 25°C, and raise the temperature to 150°C and mixed at 150°C for 1 hour. Then, this was cooled to 40° C. or lower, and (F) component, (E) component, and (D) component were added as necessary, and the mixture was mixed until uniform at 25° C., thereby preparing a silicone composition. In addition, the kinematic viscosity is the value measured at 25°C using an Ostwald viscometer, and SiH/SiVi is (D) relative to the total number of alkenyl groups in the component (A). The ratio of the total number of SiH groups in the components.
(A)成分 (A-5)：在實施例1-5中得到的以上述式(14)表示的單末端改質有機聚矽氧烷(在25℃條件下的運動黏度：395mm 2/s) (A) Component (A-5): One-terminal modified organopolysiloxane represented by the above formula (14) obtained in Example 1-5 (kinematic viscosity at 25°C: 395 mm 2 /s)
(B)成分 (B-1)：平均粒徑為0.3µm的無定形的氧化鋅粉 (B-2)：平均粒徑為2µm的鋁粉：平均粒徑為10µm的鋁粉=1：1(質量比)的混合物 (B)Ingredients (B-1): Amorphous zinc oxide powder with an average particle size of 0.3µm (B-2): A mixture of aluminum powder with an average particle size of 2µm: aluminum powder with an average particle size of 10µm = 1:1 (mass ratio)
(C)成分 (C-1)：兩末端用二甲基乙烯基甲矽烷基封端，在25℃條件下的運動黏度為600mm 2/s的二甲基聚矽氧烷 (C-2)：兩末端用二甲基乙烯基甲矽烷基封端，在25℃條件下的運動黏度為30000mm 2/s的二甲基聚矽氧烷 (C) Component (C-1): Dimethylpolysiloxane (C-2) with both ends capped with dimethylvinylsilyl groups and a kinematic viscosity of 600 mm 2 /s at 25°C. : Dimethylpolysiloxane with both ends capped with dimethylvinylsilyl groups and a kinematic viscosity of 30000mm 2 /s at 25°C
(D)成分 (D-1)：以下述式(16)表示的甲基氫二甲基聚矽氧烷(在25℃條件下的運動黏度為30mm 2/s，在式中，矽氧烷單元的排列順序為嵌段或無規。) [化學式21] (D-2)：以下述式(17)表示的甲基氫二甲基聚矽氧烷(在25℃條件下的運動黏度為40mm 2/s，在式中，矽氧烷單元的排列順序為嵌段或無規。) [化學式22] (D) Component (D-1): methylhydrogendimethylpolysiloxane represented by the following formula (16) (kinematic viscosity at 25°C is 30 mm 2 /s, in which siloxane The arrangement order of the units is block or random.) [Chemical Formula 21] (D-2): Methyl hydrogen dimethyl polysiloxane represented by the following formula (17) (kinematic viscosity at 25°C is 40 mm 2 /s, in the formula, the order of the siloxane units Be block or random.) [Chemical Formula 22]
(E)成分 (E-1)：將鉑-二乙烯基四甲基二矽氧烷錯合物溶解在與上述(C-1)相同的二甲基聚矽氧烷中的溶液(鉑原子含量：1質量%) (E) Component (E-1): A solution in which platinum-divinyltetramethyldisiloxane complex is dissolved in the same dimethylpolysiloxane as (C-1) above (platinum atom content: 1 mass %)
(F)成分 (F-1)：1-乙炔基-1-環己醇 (F) Component (F-1): 1-ethynyl-1-cyclohexanol
(G)成分 (G-1)：以上述式(15)表示的有機聚矽氧烷 (G) Component (G-1): Organic polysiloxane represented by the above formula (15)
按照上述方法測定了所得到的矽酮組合物的絕對黏度、熱傳導率，按照下述方法測定了所得到的矽酮組合物的硬度。將結果表示在表2。The absolute viscosity and thermal conductivity of the obtained silicone composition were measured according to the above method, and the hardness of the obtained silicone composition was measured according to the following method. The results are shown in Table 2.
[硬度] 對將藉由在150℃條件下將矽酮組合物加熱1小時使之固化而製備的2片6mm厚的固化物進行重疊的試驗片，進一步使用Asker C硬度計測定了在150℃的環境中暴露了0小時(初期)、250小時、500小時、1000小時後的硬度。 [hardness] Two test pieces of 6 mm thick cured material prepared by heating and curing the silicone composition at 150°C for 1 hour were stacked, and further measured using an Asker C hardness meter in an environment of 150°C. Hardness after exposure for 0 hours (initial), 250 hours, 500 hours, and 1000 hours.
[表2]
由表2的評價結果可知，在實施例3-1~實施例3-4的矽酮組合物中，與不含(A)成分的比較例3-1~比較例3-4的矽酮組合物相比，在藉由配合大量的熱傳導性填充材料而具有高熱傳導率的同時，還能夠抑制在150℃耐熱試驗後的硬度上升。即，明確了本發明的矽酮組合物為，在使用熱傳導性填充材料作為填充材料的情況下，特別是作為在電子部件封裝或功率模組中使用的散熱材料可以得到高可靠性的矽酮組合物。From the evaluation results in Table 2, it can be seen that the silicone compositions of Examples 3-1 and 3-4 have high thermal conductivity by incorporating a large amount of thermally conductive filler, and can suppress the increase in hardness after a 150°C heat resistance test, compared to the silicone compositions of Comparative Examples 3-1 and 3-4 that do not contain the component (A). That is, it was found that the silicone composition of the present invention is a silicone composition that can obtain high reliability when a thermally conductive filler is used as a filler, especially as a heat sink used in electronic component packaging or power modules.
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