WO2021230143A1 - Organosilicon compound and method for producing same - Google Patents
Organosilicon compound and method for producing same Download PDFInfo
- Publication number
- WO2021230143A1 WO2021230143A1 PCT/JP2021/017462 JP2021017462W WO2021230143A1 WO 2021230143 A1 WO2021230143 A1 WO 2021230143A1 JP 2021017462 W JP2021017462 W JP 2021017462W WO 2021230143 A1 WO2021230143 A1 WO 2021230143A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- group
- organosilicon compound
- polyhydric alcohol
- formula
- carbon atoms
- Prior art date
Links
- 150000003961 organosilicon compounds Chemical class 0.000 title claims abstract description 46
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 10
- 229920001296 polysiloxane Polymers 0.000 claims abstract description 33
- 239000000203 mixture Substances 0.000 claims abstract description 29
- 150000005846 sugar alcohols Polymers 0.000 claims abstract description 22
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 17
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 16
- 239000000945 filler Substances 0.000 claims abstract description 12
- 125000003342 alkenyl group Chemical group 0.000 claims description 23
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 17
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 8
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 claims description 8
- 150000003377 silicon compounds Chemical class 0.000 claims description 7
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 6
- 239000003054 catalyst Substances 0.000 claims description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 5
- 150000003058 platinum compounds Chemical class 0.000 claims description 5
- 229910052710 silicon Inorganic materials 0.000 claims description 5
- 238000011049 filling Methods 0.000 claims description 4
- 239000010703 silicon Substances 0.000 claims description 3
- 125000001183 hydrocarbyl group Chemical group 0.000 claims 3
- 150000002430 hydrocarbons Chemical group 0.000 abstract description 11
- -1 group Chemical group 0.000 description 20
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 18
- 239000000853 adhesive Substances 0.000 description 12
- 230000001070 adhesive effect Effects 0.000 description 12
- 229920002379 silicone rubber Polymers 0.000 description 12
- 239000004945 silicone rubber Substances 0.000 description 12
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 11
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 9
- 238000006459 hydrosilylation reaction Methods 0.000 description 9
- 239000002904 solvent Substances 0.000 description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 7
- ZHNUHDYFZUAESO-UHFFFAOYSA-N Formamide Chemical compound NC=O ZHNUHDYFZUAESO-UHFFFAOYSA-N 0.000 description 6
- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 6
- 238000003786 synthesis reaction Methods 0.000 description 6
- 229940125904 compound 1 Drugs 0.000 description 5
- 239000004020 conductor Substances 0.000 description 5
- 235000011187 glycerol Nutrition 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- 229910052697 platinum Inorganic materials 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- ARXKVVRQIIOZGF-UHFFFAOYSA-N 1,2,4-butanetriol Chemical compound OCCC(O)CO ARXKVVRQIIOZGF-UHFFFAOYSA-N 0.000 description 4
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 4
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 4
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-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
- 239000001099 ammonium carbonate Substances 0.000 description 4
- 239000003426 co-catalyst Substances 0.000 description 4
- 229940125782 compound 2 Drugs 0.000 description 4
- 239000011231 conductive filler Substances 0.000 description 4
- 239000002270 dispersing agent Substances 0.000 description 4
- 239000004519 grease Substances 0.000 description 4
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 4
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- KDYFGRWQOYBRFD-UHFFFAOYSA-N succinic acid Chemical compound OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 4
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 4
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 3
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- GXGJIOMUZAGVEH-UHFFFAOYSA-N Chamazulene Chemical group CCC1=CC=C(C)C2=CC=C(C)C2=C1 GXGJIOMUZAGVEH-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- 235000011054 acetic acid Nutrition 0.000 description 3
- 238000007259 addition reaction Methods 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 229940126214 compound 3 Drugs 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 125000000816 ethylene group Chemical group [H]C([H])([*:1])C([H])([H])[*:2] 0.000 description 3
- 238000005227 gel permeation chromatography Methods 0.000 description 3
- 150000002314 glycerols Chemical class 0.000 description 3
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 3
- HEBKCHPVOIAQTA-UHFFFAOYSA-N meso ribitol Natural products OCC(O)C(O)C(O)CO HEBKCHPVOIAQTA-UHFFFAOYSA-N 0.000 description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 3
- 230000009257 reactivity Effects 0.000 description 3
- 239000000377 silicon dioxide Substances 0.000 description 3
- 125000003258 trimethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])[*:1] 0.000 description 3
- 239000008096 xylene Substances 0.000 description 3
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 2
- DLFVBJFMPXGRIB-UHFFFAOYSA-N Acetamide Chemical compound CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 description 2
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- 238000004438 BET method Methods 0.000 description 2
- KXDAEFPNCMNJSK-UHFFFAOYSA-N Benzamide Chemical compound NC(=O)C1=CC=CC=C1 KXDAEFPNCMNJSK-UHFFFAOYSA-N 0.000 description 2
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Chemical compound CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- 239000004386 Erythritol Substances 0.000 description 2
- UNXHWFMMPAWVPI-UHFFFAOYSA-N Erythritol Natural products OCC(O)C(O)CO UNXHWFMMPAWVPI-UHFFFAOYSA-N 0.000 description 2
- AEMRFAOFKBGASW-UHFFFAOYSA-N Glycolic acid Chemical compound OCC(O)=O AEMRFAOFKBGASW-UHFFFAOYSA-N 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
- 239000004793 Polystyrene Substances 0.000 description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N Valeric acid Natural products CCCCC(O)=O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 125000002947 alkylene group Chemical group 0.000 description 2
- 235000012538 ammonium bicarbonate Nutrition 0.000 description 2
- 235000012501 ammonium carbonate Nutrition 0.000 description 2
- 150000003863 ammonium salts Chemical class 0.000 description 2
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 2
- 229910052794 bromium Inorganic materials 0.000 description 2
- 125000004369 butenyl group Chemical group C(=CCC)* 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 125000004093 cyano group Chemical group *C#N 0.000 description 2
- 238000010511 deprotection reaction Methods 0.000 description 2
- 239000004205 dimethyl polysiloxane Substances 0.000 description 2
- 235000013870 dimethyl polysiloxane Nutrition 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- UNXHWFMMPAWVPI-ZXZARUISSA-N erythritol Chemical compound OC[C@H](O)[C@H](O)CO UNXHWFMMPAWVPI-ZXZARUISSA-N 0.000 description 2
- 235000019414 erythritol Nutrition 0.000 description 2
- 229940009714 erythritol Drugs 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 235000019253 formic acid Nutrition 0.000 description 2
- 239000001530 fumaric acid Substances 0.000 description 2
- 125000005843 halogen group Chemical group 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000004310 lactic acid Substances 0.000 description 2
- 235000014655 lactic acid Nutrition 0.000 description 2
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 2
- 239000011976 maleic acid Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 150000007522 mineralic acids Chemical class 0.000 description 2
- WWZKQHOCKIZLMA-UHFFFAOYSA-N octanoic acid Chemical compound CCCCCCCC(O)=O WWZKQHOCKIZLMA-UHFFFAOYSA-N 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- CLSUSRZJUQMOHH-UHFFFAOYSA-L platinum dichloride Chemical compound Cl[Pt]Cl CLSUSRZJUQMOHH-UHFFFAOYSA-L 0.000 description 2
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 2
- 229920002223 polystyrene Polymers 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 239000001384 succinic acid Substances 0.000 description 2
- 239000011787 zinc oxide Substances 0.000 description 2
- BSSNZUFKXJJCBG-UPHRSURJSA-N (z)-but-2-enediamide Chemical compound NC(=O)\C=C/C(N)=O BSSNZUFKXJJCBG-UPHRSURJSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical group CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 1
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 description 1
- 125000001731 2-cyanoethyl group Chemical group [H]C([H])(*)C([H])([H])C#N 0.000 description 1
- 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 1
- 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 1
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 1
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 description 1
- 229910052582 BN Inorganic materials 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 description 1
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 description 1
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- FBPFZTCFMRRESA-KVTDHHQDSA-N D-Mannitol Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-KVTDHHQDSA-N 0.000 description 1
- HEBKCHPVOIAQTA-QWWZWVQMSA-N D-arabinitol Chemical compound OC[C@@H](O)C(O)[C@H](O)CO HEBKCHPVOIAQTA-QWWZWVQMSA-N 0.000 description 1
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- NHTMVDHEPJAVLT-UHFFFAOYSA-N Isooctane Chemical compound CC(C)CC(C)(C)C NHTMVDHEPJAVLT-UHFFFAOYSA-N 0.000 description 1
- 229930195725 Mannitol Natural products 0.000 description 1
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 1
- OHLUUHNLEMFGTQ-UHFFFAOYSA-N N-methylacetamide Chemical compound CNC(C)=O OHLUUHNLEMFGTQ-UHFFFAOYSA-N 0.000 description 1
- MXRIRQGCELJRSN-UHFFFAOYSA-N O.O.O.[Al] Chemical compound O.O.O.[Al] MXRIRQGCELJRSN-UHFFFAOYSA-N 0.000 description 1
- JVWLUVNSQYXYBE-UHFFFAOYSA-N Ribitol Natural products OCC(C)C(O)C(O)CO JVWLUVNSQYXYBE-UHFFFAOYSA-N 0.000 description 1
- 229910052581 Si3N4 Inorganic materials 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- TVXBFESIOXBWNM-UHFFFAOYSA-N Xylitol Natural products OCCC(O)C(O)C(O)CCO TVXBFESIOXBWNM-UHFFFAOYSA-N 0.000 description 1
- DSVGQVZAZSZEEX-UHFFFAOYSA-N [C].[Pt] Chemical compound [C].[Pt] DSVGQVZAZSZEEX-UHFFFAOYSA-N 0.000 description 1
- FNIUGHSZXXYXER-UHFFFAOYSA-N [Pt].ClC1=C(Cl)C=CCCCC1 Chemical compound [Pt].ClC1=C(Cl)C=CCCCC1 FNIUGHSZXXYXER-UHFFFAOYSA-N 0.000 description 1
- RGCDNCWAAGEBOU-UHFFFAOYSA-N acetonitrile;platinum Chemical compound [Pt].CC#N RGCDNCWAAGEBOU-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000012790 adhesive layer Substances 0.000 description 1
- 125000004450 alkenylene group Chemical group 0.000 description 1
- OBETXYAYXDNJHR-UHFFFAOYSA-N alpha-ethylcaproic acid Natural products CCCCC(CC)C(O)=O OBETXYAYXDNJHR-UHFFFAOYSA-N 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- 235000019270 ammonium chloride Nutrition 0.000 description 1
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 description 1
- 229910000148 ammonium phosphate Inorganic materials 0.000 description 1
- ZRIUUUJAJJNDSS-UHFFFAOYSA-N ammonium phosphates Chemical compound [NH4+].[NH4+].[NH4+].[O-]P([O-])([O-])=O ZRIUUUJAJJNDSS-UHFFFAOYSA-N 0.000 description 1
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 1
- UYJXRRSPUVSSMN-UHFFFAOYSA-P ammonium sulfide Chemical compound [NH4+].[NH4+].[S-2] UYJXRRSPUVSSMN-UHFFFAOYSA-P 0.000 description 1
- 235000011130 ammonium sulphate Nutrition 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 125000003710 aryl alkyl group Chemical group 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 229920005601 base polymer Polymers 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- SNCZNSNPXMPCGN-UHFFFAOYSA-N butanediamide Chemical compound NC(=O)CCC(N)=O SNCZNSNPXMPCGN-UHFFFAOYSA-N 0.000 description 1
- 125000005569 butenylene group Chemical group 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 150000008280 chlorinated hydrocarbons Chemical class 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- PMHQVHHXPFUNSP-UHFFFAOYSA-M copper(1+);methylsulfanylmethane;bromide Chemical compound Br[Cu].CSC PMHQVHHXPFUNSP-UHFFFAOYSA-M 0.000 description 1
- 125000000753 cycloalkyl group Chemical group 0.000 description 1
- 125000002993 cycloalkylene group Chemical group 0.000 description 1
- HPXRVTGHNJAIIH-UHFFFAOYSA-N cyclohexanol Chemical compound OC1CCCCC1 HPXRVTGHNJAIIH-UHFFFAOYSA-N 0.000 description 1
- 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 1
- 125000004956 cyclohexylene group Chemical group 0.000 description 1
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- 125000004979 cyclopentylene group Chemical group 0.000 description 1
- 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 1
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 description 1
- 229910000388 diammonium phosphate Inorganic materials 0.000 description 1
- 235000019838 diammonium phosphate Nutrition 0.000 description 1
- JVSWJIKNEAIKJW-UHFFFAOYSA-N dimethyl-hexane Natural products CCCCCC(C)C JVSWJIKNEAIKJW-UHFFFAOYSA-N 0.000 description 1
- 229920005645 diorganopolysiloxane polymer Polymers 0.000 description 1
- 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 1
- 230000000694 effects Effects 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 239000003759 ester based solvent Substances 0.000 description 1
- BITPLIXHRASDQB-UHFFFAOYSA-N ethenyl-[ethenyl(dimethyl)silyl]oxy-dimethylsilane Chemical compound C=C[Si](C)(C)O[Si](C)(C)C=C BITPLIXHRASDQB-UHFFFAOYSA-N 0.000 description 1
- RCNRJBWHLARWRP-UHFFFAOYSA-N ethenyl-[ethenyl(dimethyl)silyl]oxy-dimethylsilane;platinum Chemical compound [Pt].C=C[Si](C)(C)O[Si](C)(C)C=C RCNRJBWHLARWRP-UHFFFAOYSA-N 0.000 description 1
- 125000005678 ethenylene group Chemical group [H]C([*:1])=C([H])[*:2] 0.000 description 1
- 239000004210 ether based solvent Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- MNWFXJYAOYHMED-UHFFFAOYSA-N heptanoic acid Chemical compound CCCCCCC(O)=O MNWFXJYAOYHMED-UHFFFAOYSA-N 0.000 description 1
- 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 1
- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 1
- 125000006038 hexenyl group Chemical group 0.000 description 1
- 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 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 238000013101 initial test Methods 0.000 description 1
- 239000011256 inorganic filler Substances 0.000 description 1
- 229910003475 inorganic filler Inorganic materials 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- WRIRWRKPLXCTFD-UHFFFAOYSA-N malonamide Chemical compound NC(=O)CC(N)=O WRIRWRKPLXCTFD-UHFFFAOYSA-N 0.000 description 1
- 239000000594 mannitol Substances 0.000 description 1
- 235000010355 mannitol Nutrition 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- RMIODHQZRUFFFF-UHFFFAOYSA-N methoxyacetic acid Chemical compound COCC(O)=O RMIODHQZRUFFFF-UHFFFAOYSA-N 0.000 description 1
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 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 1
- LYRFLYHAGKPMFH-UHFFFAOYSA-N octadecanamide Chemical compound CCCCCCCCCCCCCCCCCC(N)=O LYRFLYHAGKPMFH-UHFFFAOYSA-N 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 150000001451 organic peroxides Chemical class 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- 125000004817 pentamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 1
- 125000002255 pentenyl group Chemical group C(=CCCC)* 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- NAYYNDKKHOIIOD-UHFFFAOYSA-N phthalamide Chemical compound NC(=O)C1=CC=CC=C1C(N)=O NAYYNDKKHOIIOD-UHFFFAOYSA-N 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 125000004368 propenyl group Chemical group C(=CC)* 0.000 description 1
- QLNJFJADRCOGBJ-UHFFFAOYSA-N propionamide Chemical compound CCC(N)=O QLNJFJADRCOGBJ-UHFFFAOYSA-N 0.000 description 1
- 229940080818 propionamide Drugs 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- MWWATHDPGQKSAR-UHFFFAOYSA-N propyne Chemical group CC#C MWWATHDPGQKSAR-UHFFFAOYSA-N 0.000 description 1
- 125000006239 protecting group Chemical group 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000002683 reaction inhibitor Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- HEBKCHPVOIAQTA-ZXFHETKHSA-N ribitol Chemical compound OC[C@H](O)[C@H](O)[C@H](O)CO HEBKCHPVOIAQTA-ZXFHETKHSA-N 0.000 description 1
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 229940095064 tartrate Drugs 0.000 description 1
- 125000000999 tert-butyl group Chemical group [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
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- WYXIGTJNYDDFFH-UHFFFAOYSA-Q triazanium;borate Chemical compound [NH4+].[NH4+].[NH4+].[O-]B([O-])[O-] WYXIGTJNYDDFFH-UHFFFAOYSA-Q 0.000 description 1
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 description 1
- 239000000811 xylitol Substances 0.000 description 1
- 235000010447 xylitol Nutrition 0.000 description 1
- HEBKCHPVOIAQTA-SCDXWVJYSA-N xylitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)CO HEBKCHPVOIAQTA-SCDXWVJYSA-N 0.000 description 1
- 229960002675 xylitol Drugs 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
- C07B61/00—Other general methods
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/18—Compounds having one or more C—Si linkages as well as one or more C—O—Si linkages
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K3/00—Materials not provided for elsewhere
Definitions
- the present invention relates to a novel organosilicon compound, and is particularly suitably used as a wetter (dispersant) capable of highly filling a silicone composition (organopolysiloxane composition) with a filler such as a heat conductive filler.
- a wetter dispenser
- the present invention relates to an organosilicon compound which can be used and a method for producing the same.
- Patent Documents Many methods have been proposed as a means of removing this heat.
- a method has been proposed in which a heat conductive material such as a heat conductive grease or a heat conductive sheet is interposed between the electronic parts and a member such as a heat sink to dissipate heat (Patent Documents). 1, 2).
- the heat conductive grease has an amorphous shape and is preferably used because it exhibits high heat conductivity by adhering to the base material after curing.
- a heat radiating grease or a heat radiating adhesive which is based on silicone (organopolysiloxane) and contains zinc oxide or alumina powder is known (Patent Documents 3 and 4).
- heat conductive filler In order to make a heat conductive material based on silicone and having high heat conductivity, it is necessary to highly fill the heat conductive filler. However, if only a high filling is attempted, the fluidity of the heat conductive material is significantly reduced, workability such as coatability (dispensability, screen printability) is deteriorated, and the surface of electronic parts and heat sinks is fine. There is a problem that it cannot follow the unevenness. Therefore, in order to solve this problem, the heat conductive filler surface-treated with a wetter (dispersant) is dispersed in the base polymer silicone (organopolysiloxane) to maintain the fluidity of the heat conductive material. The method is proposed.
- Patent Documents 5 and 6 Currently, as wetters frequently used, there are methylpolysiloxane having a hydrolyzable group and oligosiloxane having a hydrolyzable group (Patent Documents 5 and 6). Although good fluidity can be obtained by using these wetters, unreacted hydrolyzable groups have a great influence on the adhesiveness between electronic components and substrates under high temperature and high humidity conditions, and the adhesive strength changes. As a result, when movement is applied to the electronic components, stress is also generated on the base material, which causes the electronic components and the substrate to crack or shift.
- the present invention makes it possible to highly fill a silicone composition with a filler, and there is little change in adhesiveness even under high temperature and high humidity conditions, and in particular, the amount of change in tensile shear adhesive strength from the initial value is doubled. It is an object of the present invention to provide an organosilicon compound suitable as a wetter having a composition of less than or less than that, and a method for producing the same.
- an organosilicon compound having a specific polyhydric alcohol structure is useful for solving the above-mentioned problems, and completed the present invention.
- the present invention provides the following organosilicon compound and a method for producing the same.
- R 1 is an unsubstituted or substituted monovalent hydrocarbon group having 1 to 12 carbon atoms
- R 2 is an unsubstituted or substituted divalent hydrocarbon group having 1 to 12 carbon atoms.
- A is a polyhydric alcohol residue having two or more residual hydroxyl groups, and n is a number having a viscosity of this organic silicon compound at 23 ° C. of 1 to 1,000 mPa ⁇ s.
- the polyhydric alcohol residue of A is a residue derived from a polyhydric alcohol having at least 3 hydroxyl groups, and at least one hydroxyl group in the polyhydric alcohol forms an ether bond with an adjacent R 2.
- [3] The organosilicon compound according to [2], wherein the polyhydric alcohol residue of A is a residue of glycerol or pentaerythritol.
- [4] The organosilicon compound according to any one of [1] to [3], which is a wetter for highly filling a curable silicone composition with a filler.
- [5] The following formula (II) (In the formula, A is a polyhydric alcohol residue having two or more residual hydroxyl groups, and Y is an alkenyl group having 2 to 10 carbon atoms.)
- R 1 is a heterologous or homogeneous unsubstituted or substituted monovalent hydrocarbon group having 1 to 12 carbon atoms independently of each other, and n is the viscosity of this organopolysiloxane at 23 ° C. of 1 to 1, It is a number of 000 mPa ⁇ s.
- the organosilicon compound of the present invention makes it possible to highly fill a silicone composition with a filler such as a heat conductive filler, and provides a composition having little change in adhesiveness even under high temperature and high humidity conditions. It is useful as a wetter for.
- the organosilicon compound according to the present invention is represented by the following formula (I).
- R 1 is an unsubstituted or substituted monovalent hydrocarbon group having 1 to 12 carbon atoms
- R 2 is an unsubstituted or substituted divalent hydrocarbon group having 1 to 12 carbon atoms.
- A is a group
- A is a polyhydric alcohol residue having two or more residual hydroxyl groups
- n is a number having a viscosity of this organic silicon compound at 23 ° C. of 1 to 1,000 mPa ⁇ s.
- Examples of the unsubstituted or substituted monovalent hydrocarbon group having 1 to 12 carbon atoms of R 1 include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a tert-butyl group, a pentyl group and a hexyl.
- Alkyl group such as group, heptyl group, octyl group, nonyl group, decyl group, dodecyl group; cycloalkyl group such as cyclopentyl group and cyclohexyl group; alkenyl group such as vinyl group, allyl group, butenyl group, pentenyl group and hexenyl group.
- Aryl groups such as phenyl group, trill group, xsilyl group, ⁇ -, ⁇ -naphthyl group; aralkyl groups such as benzyl group, 2-phenylethyl group and 3-phenylpropyl group; and hydrogen atoms of these groups
- an alkyl group such as a methyl group or an ethyl group is preferable, and a methyl group is particularly preferable.
- Examples of the unsubstituted or substituted divalent hydrocarbon group having 1 to 12 carbon atoms of R 2 include a methylene group, an ethylene group (dimethylene group), a propylene group (ethylmethylene group, trimethylene group), an isopropylene group and a butylene group.
- an alkylene group such as an ethylene group (dimethylene group) and a propylene group (ethylmethylene group, trimethylene group) is preferable, and an ethylene group (dimethylene group) and a trimethylene group are particularly preferable.
- Examples of the polyhydric alcohol residue having two or more residual hydroxyl groups in A above include ethylene glycol, propylene glycol, diethylene glycol, glycerol (glycerin), 1, 2,4-butanetriol, pentaerythritol, erythritol, arabinitol, and xylitol. , Ribitol, mannitol and the like, a residue obtained by removing one hydrogen atom from one hydroxyl group existing in a polyhydric alcohol having three or more hydroxyl groups in one molecule can be exemplified.
- residues of glycerol, pentaerythritol, 1,2,4-butanetriol and erythritol are preferable because they have three or more hydroxyl groups and are easily available for themselves and their derivatives, and particularly glycerol and pentaerythritol. Residues are preferred.
- n is a number having a viscosity of this organosilicon compound at 23 ° C. of 1 to 1,000 mPa ⁇ s, and therefore n is preferably a number of 1 to 200, more preferably 3 to 100. , More preferably 5 to 50, and particularly preferably 9 to 30.
- the viscosity of the organosilicon compound at 23 ° C. is 1 to 1,000 mPa ⁇ s, preferably 5 to 500 mPa ⁇ s, and more preferably 10 to 300 mPa ⁇ s.
- the viscosity is a numerical value measured by a rotational viscometer (for example, BL type, BH type, BS type, cone plate type, etc.) (hereinafter, the same applies).
- a rotational viscometer for example, BL type, BH type, BS type, cone plate type, etc.
- the number of repetitions (n) or the degree of polymerization of the diorganosiloxane unit in the organosilicon compound represented by the above formula (I) is the number average in terms of polystyrene in gel permeation chromatography (GPC) analysis using toluene or the like as a developing solvent. It can be determined as the degree of polymerization (or number average molecular weight) or the like.
- the organosilicon compound represented by the above formula (I) of the present invention can be produced by a conventionally known method.
- it has an alkenyl group of a polyvalent alcohol derivative having an alkenyl group in the molecule represented by the following formula (II) and a hydrogen atom bonded to a silicon atom at one end of the molecular chain represented by the following formula (III).
- a hydrosilyl group (Si—H group) of an organopolysiloxane a linear diorganopolysiloxane having one end of the molecular chain sealed with a triorganosyloxy group and the other end closed with a diorganohydrogensiloxy group).
- a hydrosilylation addition reaction is carried out in the presence of a platinum compound-containing catalyst, and a hydrosilylation group is added to the alkenyl group to form a carbon-silicon bond (that is, the alkenyl group Y in the following formula (II) and the following formula (III).
- the addition reaction between hydrogen atoms bonded (Si-H groups) to the silicon atom in) by forming a divalent hydrocarbon group R 2 in the above formula (I) is represented by the above formula (I) Manufacture organic silicon compounds.
- A represents the same meaning as above
- Y represents an alkenyl group having 2 to 10 carbon atoms.
- R 1, n represents the same meaning as above.
- Examples of the alkenyl group having 2 to 10 carbon atoms of Y include a linear alkenyl group such as a vinyl group, an allyl group, a propenyl group, and a butenyl group.
- a vinyl group and an allyl group are preferable, and an allyl group is particularly preferable, because of ease of synthesis and production.
- the hydroxyl group of the polyhydric alcohol derivative having the alkenyl ether structure represented by the above formula (II) may have a protecting group, which becomes a hydroxyl group through the deprotection step after the hydrosilylation reaction. ..
- the protection and deprotection of the hydroxyl group can be performed by a known method.
- the platinum compound-containing catalyst used in the hydrosilylation reaction is not particularly limited, and specific examples thereof include platinum chloride, an alcohol solution of platinum chloride, and platinum-1,3-divinyl-1,1,3. , 3-Tetramethyldisiloxane complex in toluene or xylene solution, tetraxtriphenylphosphine platinum, dichlorobistriphenylphosphine platinum, dichlorobis acetonitrile platinum, dichlorobisbenzonitrile platinum, dichlorocyclooctadiene platinum, platinum-carbon, platinum-alumina , Platinum-supporting catalysts such as silica, and the like.
- a toluene or xylene solution of platinum-1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex is preferable from the viewpoint of selectivity.
- the amount of the platinum compound-containing catalyst used is not particularly limited, but it is contained in 1 mol of the polyvalent alcohol derivative having an alkenyl group in the molecule represented by the formula (II) from the viewpoint of reactivity and productivity.
- the amount of the platinum atom to be formed is preferably 1 ⁇ 10 -7 to 1 ⁇ 10 ⁇ 2 mol, more preferably 1 ⁇ 10 -7 to 1 ⁇ 10 -3 mol.
- a co-catalyst may be used to improve the reactivity of the hydrosilylation reaction.
- a co-catalyst generally used for the hydrosilylation reaction can be used, but in the present invention, an ammonium salt of an inorganic acid, an acid amide compound, and a carboxylic acid are preferable.
- ammonium salts of inorganic acids include ammonium chloride, ammonium sulfate, ammonium ammonium sulfate, ammonium nitrate, monoammonium dihydrogen phosphate, diammonium hydrogen phosphate, triammonium phosphate, ammonium diaphosphate, ammonium carbonate, and hydrogen carbonate.
- Ammonium, ammonium sulfide, ammonium borate, ammonium borofluoride and the like can be mentioned. Of these, ammonium carbonate and ammonium hydrogen carbonate are preferable.
- the acid amide compound examples include formamide, acetamide, N-methylacetamide, N, N-dimethylacetamide, propionamide, acrylamide, malonamide, succinamide, maleamide, fumalamide, benzamide, phthalamide, palmitate amide, stearate amide and the like.
- formamide and stearic acid amide are preferable, and formamide is more preferable.
- carboxylic acids include formic acid, acetic acid, propionic acid, butyric acid, methoxyacetic acid, pentanic acid, caproic acid, heptanic acid, octanoic acid, lactic acid, glycolic acid, trifluoroacetic acid, maleic acid, fumaric acid, and succinic acid.
- carboxylic acids include formic acid, acetic acid, propionic acid, butyric acid, methoxyacetic acid, pentanic acid, caproic acid, heptanic acid, octanoic acid, lactic acid, glycolic acid, trifluoroacetic acid, maleic acid, fumaric acid, and succinic acid.
- tartrate acid and oxalic acid examples include tartrate acid and oxalic acid.
- formic acid, acetic acid, lactic acid, maleic acid, fumaric acid, succinic acid and trifluoroacetic acid are preferable, and acetic acid and trifluor
- the amount of the co-catalyst used is not particularly limited, but from the viewpoint of reactivity, selectivity, cost, etc., with respect to 1 mol of the polyhydric alcohol derivative having an alkenyl group in the molecule represented by the formula (II).
- 1 ⁇ 10 -5 to 1 ⁇ 10 -1 mol is preferable, and 1 ⁇ 10 -4 to 5 ⁇ 10 -1 mol is more preferable.
- a solvent can also be used.
- the solvent that can be used include hydrocarbon solvents such as pentane, hexane, cyclohexane, heptane, isooctane, benzene, toluene and xylene; ether solvents such as diethyl ether, tetrahydrofuran and dioxane; ethyl acetate, butyl acetate and the like.
- Ester-based solvents such as N, N-dimethylformamide; chlorinated hydrocarbon-based solvents such as dichloromethane and chloroform, and the like, even if one of these solvents is used alone, 2 A mixture of seeds or more may be used.
- the reaction temperature in the hydrosilylation reaction is not particularly limited and can be carried out from room temperature (23 ° C.) under heating, but room temperature (23 ° C.) to 200 ° C. is preferable. In order to obtain an appropriate reaction rate, it is preferable to carry out the reaction under heating, and from such a viewpoint, the reaction temperature is more preferably 40 to 110 ° C., and even more preferably 40 to 90 ° C. Further, the reaction time is not particularly limited, and is preferably 1 to 60 hours, more preferably 1 to 30 hours, still more preferably 1 to 20 hours.
- the reaction ratio between the alkenyl group of the polyhydric alcohol derivative having an alkenyl group in the molecule represented by the above formula (II) and the hydrosilyl group of the organopolysiloxane represented by the above formula (III) is the hydrosilylation reaction.
- the ratio of the alkenyl group to 1 mol of the hydrosilyl group is preferably 0.8 to 1.3 mol. A ratio of 0.9 to 1.2 mol is more preferable.
- Examples of the compound represented by the above formula (I) thus obtained include, but are not limited to, those represented by the following formula.
- n is a number having a viscosity of these organosilicon compounds at 23 ° C. of 1 to 1,000 mPa ⁇ s, and n is preferably a number of 1 to 200, more preferably. Is a number of 3 to 100, more preferably a number of 5 to 50, and particularly preferably a number of 9 to 30.
- the organosilicon compound of the present invention can be suitably used as a wetter (dispersant) for the filler in the silicone composition (organopolysiloxane composition) containing the filler.
- the silicone composition include an addition reaction curing type silicone composition, an organic peroxide curing type silicone composition, a condensation reaction curing type silicone composition, and a non-curing type silicone composition such as silicone grease.
- the filler to be filled in the silicone composition may be any of an inorganic filler, a metal filler, an organic resin filler and the like, and for example, fuming silica, precipitate silica, quartz powder and alumina (oxidation).
- Aluminum aluminum hydroxide, boron nitride, aluminum nitride, silicon nitride, iron oxide, magnesium oxide, titanium oxide, zinc oxide, zirconium oxide, calcium carbonate, carbon black, graphite, aluminum, gold, silver, copper, nickel, etc. Can be applied to the filler of.
- the tensile shear adhesive strength may be measured according to the provisions of JIS K 6850.
- the viscosity is a value measured by a rotational viscometer at 23 ° C.
- the molecular weight indicates a number average molecular weight in terms of polystyrene in GPC measurement using toluene as a developing solvent.
- Organosilicon compounds [Example 1] Synthesis of organosilicon compound 18.1 g of glycerin derivative having an alkenyl group represented by the following formula (IV), platinum-1, platinum-1, in a 500 mL separable flask equipped with a stirrer, a reflux condenser, a dropping funnel and a thermometer. 0.1 g of a toluene solution of 3-divinyl-1,1,3,3-tetramethyldisiloxane complex was placed and heated to 80 ° C. 100.0 g of an organopolysiloxane represented by the following formula (V) was added dropwise thereto, and the mixture was heated and stirred at 80 ° C. for 3 hours.
- organopolysiloxane represented by the following formula (V) was added dropwise thereto, and the mixture was heated and stirred at 80 ° C. for 3 hours.
- Example 2 Synthesis of organosilicon compound 2 Performed except that 24.1 g of a pentaerythritol derivative having an alkenyl group represented by the following formula (VI) was used instead of the glycerin derivative having an alkenyl group represented by the above formula (IV).
- Organosilicon compound 2 (viscosity: 275 mPa ⁇ s, number average molecular weight: 1140) was obtained in the same manner as in Example 1.
- Example 3 Synthesis of Organosilicon Compound 3 In the same manner as in Example 1 except that 281.5 g of the organopolysiloxane represented by the following formula (VII) was used instead of the organopolysiloxane represented by the above formula (V). Organosilicon compound 3 (viscosity: 32 mPa ⁇ s, number average molecular weight: 2720) was obtained.
- Example 4 Synthesis of Organosilicon Compound 2 In place of the glycerin derivative having an alkenyl group represented by the above formula (IV), 24.1 g of a pentaerythritol derivative having an alkenyl group represented by the above formula (VI), the above formula (V) In the same manner as in Example 1 except that 281.5 g of the organopolysiloxane represented by the above formula (VII) was used instead of the organopolysiloxane represented by the above formula (VII), the organosilicon compound 4 (viscosity: 138 mPa ⁇ s, Number average molecular weight: 2770) was obtained.
- the molecular chain has a viscosity of 400 mPa ⁇ s, both ends of the molecular chain are dimethylvinylsiloxy group-sealed dimethylpolysiloxane (vinyl group content; 0.44% by mass), 8 parts by mass, and the average particle size (BET method) is 20 ⁇ m. 67.5 parts by mass of spherical alumina powder, 22.5 parts by mass of amorphous alumina powder having an average particle size (BET method) of 2.2 ⁇ m, and an organosilicon compound synthesized in Example 1 as a dispersant (wetter).
- this rubber base has a viscosity of 25 mPa ⁇ s and has a hydrogen atom (SiH group) bonded to an average of 4 silicon atoms in one molecule.
- thermally conductive silicone rubber composition 1 was prepared by mixing parts by mass.
- thermoly conductive silicone rubber composition 2 was obtained in the same manner as in Reference Example 1 except that 1.5 parts by mass of organosilicon compound 2 was used instead of the organosilicon compound 1.
- thermoly conductive silicone rubber composition 3 was obtained in the same manner as in Reference Example 1 except that 1.5 parts by mass of the organosilicon compound 3 was used instead of the organosilicon compound 1.
- thermoly conductive silicone rubber composition 4 was obtained in the same manner as in Reference Example 1 except that 1.5 parts by mass of the organosilicon compound 4 was used instead of the organosilicon compound 1.
- the heat conductive silicone rubber composition 1, 2, 3, 4 or 5 is sandwiched between the adherends ⁇ aluminum plate manufactured by Partech Co., Ltd. (JIS H 4000, A1050P) ⁇ and then heated at 120 ° C. for 60 minutes. Then, it was cured to obtain a heat-conducting silicone rubber, which was used as an initial test piece.
- the adhesive area was 25 mm ⁇ 10 mm, and the thickness of the adhesive layer was 2 mm.
- the tensile shear adhesive strength of this thermally conductive silicone rubber was measured according to JIS K 6850. Further, the obtained heat-conducting silicone rubber was allowed to stand in a constant temperature and humidity chamber at 85 ° C.
- Reference Examples 1 to 4 have less change in adhesive strength between the initial stage and after the high temperature and high humidity test, and the organosilicon compound of the present invention has the adhesiveness of the heat conductive silicone rubber. It was shown that it can be suitably used as a wetter that reduces the change in the amount of silicon.
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Abstract
Provided are: an organosilicon compound that is suitable as a wetter that enables a silicone composition to be highly filled with a filler, that undergoes less change in adhesiveness even under a high temperature and humidity condition, and that enables obtaining a composition in which the amount of change particularly in tensile shear adhesion strength from an initial value is less than two-fold; and a method for producing the organosilicon compound. This organosilicon compound is represented by formula (I) (in the formula, each R1 independently represents an unsubstituted or substituted monovalent hydrocarbon group having 1-12 carbon atoms, R2 represents an unsubstituted or substituted divalent hydrocarbon group having 1-12 carbon atoms, A represents a polyhydric alcohol residue having two or more residual hydroxyl groups, and n is a number that sets the viscosity of the organosilicon compound to 1-1,000 mPa·s at 23°C).
Description
本発明は、新規な有機ケイ素化合物に関し、特にシリコーン組成物（オルガノポリシロキサン組成物）に熱伝導性充填剤等の充填剤を高充填することを可能とするウエッター（分散剤）として好適に用いることのできる有機ケイ素化合物及びその製造方法に関する。
The present invention relates to a novel organosilicon compound, and is particularly suitably used as a wetter (dispersant) capable of highly filling a silicone composition (organopolysiloxane composition) with a filler such as a heat conductive filler. The present invention relates to an organosilicon compound which can be used and a method for producing the same.
電子部品の多くは使用中に熱を発生させることから、その電子部品を適切に機能させるためには、熱を取り除くことが必要である。特にパーソナルコンピューターに使用されているＣＰＵ等の集積回路素子は、動作周波数の高速化により発熱量が増大し続け、熱に対する対策が重要な問題となっている。また、近年は自動車にも多くの電子部品が使われるようになり、高温高湿条件下などより過酷な条件で電子部品が使用されることがある。
Since many electronic components generate heat during use, it is necessary to remove the heat in order for the electronic components to function properly. In particular, integrated circuit elements such as CPUs used in personal computers continue to increase the amount of heat generated due to the increase in operating frequency, and countermeasures against heat have become an important problem. In recent years, many electronic components have been used in automobiles, and electronic components may be used under more severe conditions such as high temperature and high humidity conditions.
この熱を除去する手段として多くの方法が提案されている。特に発熱量の多い電子部品では、電子部品とヒートシンク等の部材との間に熱伝導性グリースや熱伝導性シートなどの熱伝導性材料を介在させて放熱する方法が提案されている（特許文献１、２）。特に熱伝導性グリースは不定形で、硬化後に基材に密着することで高い熱伝導性を示すことから好適に用いられている。また、このような熱伝導性材料としては、シリコーン（オルガノポリシロキサン）をベースとし、酸化亜鉛やアルミナ粉末を配合した放熱グリースや放熱接着剤が知られている（特許文献３、４）。
Many methods have been proposed as a means of removing this heat. Especially for electronic components that generate a large amount of heat, a method has been proposed in which a heat conductive material such as a heat conductive grease or a heat conductive sheet is interposed between the electronic parts and a member such as a heat sink to dissipate heat (Patent Documents). 1, 2). In particular, the heat conductive grease has an amorphous shape and is preferably used because it exhibits high heat conductivity by adhering to the base material after curing. Further, as such a heat conductive material, a heat radiating grease or a heat radiating adhesive which is based on silicone (organopolysiloxane) and contains zinc oxide or alumina powder is known (Patent Documents 3 and 4).
シリコーンをベースとし、高い熱伝導性を有する熱伝導性材料とするためには、熱伝導性充填剤を高充填することが必要である。しかし、ただ単に高充填しようとすると、熱伝導性材料の流動性が著しく低下し、塗布性（ディスペンス性、スクリーンプリント性）等の作業性が悪くなり、さらには電子部品やヒートシンク表面の微細な凹凸に追従できなくなるという問題が生じる。
そこで、この問題を解決するために、熱伝導性充填剤をウエッター（分散剤）で表面処理したものをベースポリマーであるシリコーン（オルガノポリシロキサン）に分散させ、熱伝導性材料の流動性を保つという方法が提案されている。現在、頻繁に用いられるウエッターとして、加水分解性基を有するメチルポリシロキサンや、加水分解性基を有するオリゴシロキサンがある（特許文献５、６）。これらのウエッターを使用することで、良好な流動性が得られるものの、高温高湿条件下では未反応の加水分解性基が電子部品と基板の接着性に大きな影響を及ぼし、接着強度が変化することで、電子部品に動きが加わった際に基材へも応力が生じ、電子部品や基板が割れたり、ズレたりする原因となっていた。 In order to make a heat conductive material based on silicone and having high heat conductivity, it is necessary to highly fill the heat conductive filler. However, if only a high filling is attempted, the fluidity of the heat conductive material is significantly reduced, workability such as coatability (dispensability, screen printability) is deteriorated, and the surface of electronic parts and heat sinks is fine. There is a problem that it cannot follow the unevenness.
Therefore, in order to solve this problem, the heat conductive filler surface-treated with a wetter (dispersant) is dispersed in the base polymer silicone (organopolysiloxane) to maintain the fluidity of the heat conductive material. The method is proposed. Currently, as wetters frequently used, there are methylpolysiloxane having a hydrolyzable group and oligosiloxane having a hydrolyzable group (Patent Documents 5 and 6). Although good fluidity can be obtained by using these wetters, unreacted hydrolyzable groups have a great influence on the adhesiveness between electronic components and substrates under high temperature and high humidity conditions, and the adhesive strength changes. As a result, when movement is applied to the electronic components, stress is also generated on the base material, which causes the electronic components and the substrate to crack or shift.
そこで、この問題を解決するために、熱伝導性充填剤をウエッター（分散剤）で表面処理したものをベースポリマーであるシリコーン（オルガノポリシロキサン）に分散させ、熱伝導性材料の流動性を保つという方法が提案されている。現在、頻繁に用いられるウエッターとして、加水分解性基を有するメチルポリシロキサンや、加水分解性基を有するオリゴシロキサンがある（特許文献５、６）。これらのウエッターを使用することで、良好な流動性が得られるものの、高温高湿条件下では未反応の加水分解性基が電子部品と基板の接着性に大きな影響を及ぼし、接着強度が変化することで、電子部品に動きが加わった際に基材へも応力が生じ、電子部品や基板が割れたり、ズレたりする原因となっていた。 In order to make a heat conductive material based on silicone and having high heat conductivity, it is necessary to highly fill the heat conductive filler. However, if only a high filling is attempted, the fluidity of the heat conductive material is significantly reduced, workability such as coatability (dispensability, screen printability) is deteriorated, and the surface of electronic parts and heat sinks is fine. There is a problem that it cannot follow the unevenness.
Therefore, in order to solve this problem, the heat conductive filler surface-treated with a wetter (dispersant) is dispersed in the base polymer silicone (organopolysiloxane) to maintain the fluidity of the heat conductive material. The method is proposed. Currently, as wetters frequently used, there are methylpolysiloxane having a hydrolyzable group and oligosiloxane having a hydrolyzable group (Patent Documents 5 and 6). Although good fluidity can be obtained by using these wetters, unreacted hydrolyzable groups have a great influence on the adhesiveness between electronic components and substrates under high temperature and high humidity conditions, and the adhesive strength changes. As a result, when movement is applied to the electronic components, stress is also generated on the base material, which causes the electronic components and the substrate to crack or shift.
したがって、本発明は、シリコーン組成物に充填剤を高充填することを可能とし、高温高湿条件下でも接着性に変化の少ない、特に引張りせん断接着強さの初期値からの変化量が２倍未満の組成物とすることが可能なウエッターとして好適な有機ケイ素化合物及びその製造方法を提供することを目的とする。
Therefore, the present invention makes it possible to highly fill a silicone composition with a filler, and there is little change in adhesiveness even under high temperature and high humidity conditions, and in particular, the amount of change in tensile shear adhesive strength from the initial value is doubled. It is an object of the present invention to provide an organosilicon compound suitable as a wetter having a composition of less than or less than that, and a method for producing the same.
本発明者らは、上記目的を達成するために鋭意研究した結果、特定の多価アルコール構造を有する有機ケイ素化合物が、上述した課題の解決に有用であることを見出し、本発明を完成した。
As a result of diligent research to achieve the above object, the present inventors have found that an organosilicon compound having a specific polyhydric alcohol structure is useful for solving the above-mentioned problems, and completed the present invention.
即ち、本発明は下記の有機ケイ素化合物およびその製造方法を提供するものである。
That is, the present invention provides the following organosilicon compound and a method for producing the same.
［１］
下記式（Ｉ）で表される有機ケイ素化合物。
（式中、Ｒ1は互いに独立に、非置換又は置換の炭素数１～１２の一価炭化水素基であり、Ｒ2は非置換又は置換の炭素数１～１２の二価炭化水素基であり、Ａは２個以上の残存水酸基を有する多価アルコール残基であり、ｎはこの有機ケイ素化合物の２３℃における粘度を１～１，０００ｍＰａ・ｓとする数である。）
［２］
Ａの多価アルコール残基が少なくとも３個の水酸基を有する多価アルコールから誘導される残基であり、該多価アルコール中の少なくとも１個の水酸基が隣接するＲ2とエーテル結合を形成しているものである［１］に記載の有機ケイ素化合物。
［３］
Ａの多価アルコール残基が、グリセロール又はペンタエリスリトールの残基である［２］に記載の有機ケイ素化合物。
［４］
硬化性シリコーン組成物に充填剤を高充填するためのウエッターである［１］～［３］のいずれか１つに記載の有機ケイ素化合物。
［５］
下記式（ＩＩ）
（式中、Ａは２個以上の残存水酸基を有する多価アルコール残基であり、Ｙは炭素数２～１０のアルケニル基である。）
で表される分子中にアルケニル基を有する多価アルコール誘導体と、下記式（ＩＩＩ）
（式中、Ｒ1は互いに独立に、異種または同種の非置換又は置換の炭素数１～１２の一価炭化水素基であり、ｎはこのオルガノポリシロキサンの２３℃における粘度を１～１，０００ｍＰａ・ｓとする数である。）
で表される分子鎖片末端にケイ素原子結合水素原子を有するオルガノポリシロキサンとを、白金化合物含有触媒存在下でヒドロシリル化反応させる工程を含む［１］～［４］のいずれか１つに記載の有機ケイ素化合物の製造方法。
[1]
An organosilicon compound represented by the following formula (I).
(In the formula, R 1 is an unsubstituted or substituted monovalent hydrocarbon group having 1 to 12 carbon atoms, and R 2 is an unsubstituted or substituted divalent hydrocarbon group having 1 to 12 carbon atoms. A is a polyhydric alcohol residue having two or more residual hydroxyl groups, and n is a number having a viscosity of this organic silicon compound at 23 ° C. of 1 to 1,000 mPa · s.)
[2]
The polyhydric alcohol residue of A is a residue derived from a polyhydric alcohol having at least 3 hydroxyl groups, and at least one hydroxyl group in the polyhydric alcohol forms an ether bond with an adjacent R 2. The organic silicon compound according to [1].
[3]
The organosilicon compound according to [2], wherein the polyhydric alcohol residue of A is a residue of glycerol or pentaerythritol.
[4]
The organosilicon compound according to any one of [1] to [3], which is a wetter for highly filling a curable silicone composition with a filler.
[5]
The following formula (II)
(In the formula, A is a polyhydric alcohol residue having two or more residual hydroxyl groups, and Y is an alkenyl group having 2 to 10 carbon atoms.)
A polyhydric alcohol derivative having an alkenyl group in the molecule represented by the following formula (III).
(In the formula, R 1 is a heterologous or homogeneous unsubstituted or substituted monovalent hydrocarbon group having 1 to 12 carbon atoms independently of each other, and n is the viscosity of this organopolysiloxane at 23 ° C. of 1 to 1, It is a number of 000 mPa · s.)
Described in any one of [1] to [4], which comprises a step of hydrosilylating a organopolysiloxane having a silicon atom-bonded hydrogen atom at one end of the molecular chain represented by (1) in the presence of a platinum compound-containing catalyst. Method for producing an organosilicon compound.
下記式（Ｉ）で表される有機ケイ素化合物。
［２］
Ａの多価アルコール残基が少なくとも３個の水酸基を有する多価アルコールから誘導される残基であり、該多価アルコール中の少なくとも１個の水酸基が隣接するＲ2とエーテル結合を形成しているものである［１］に記載の有機ケイ素化合物。
［３］
Ａの多価アルコール残基が、グリセロール又はペンタエリスリトールの残基である［２］に記載の有機ケイ素化合物。
［４］
硬化性シリコーン組成物に充填剤を高充填するためのウエッターである［１］～［３］のいずれか１つに記載の有機ケイ素化合物。
［５］
下記式（ＩＩ）
で表される分子中にアルケニル基を有する多価アルコール誘導体と、下記式（ＩＩＩ）
で表される分子鎖片末端にケイ素原子結合水素原子を有するオルガノポリシロキサンとを、白金化合物含有触媒存在下でヒドロシリル化反応させる工程を含む［１］～［４］のいずれか１つに記載の有機ケイ素化合物の製造方法。
[1]
An organosilicon compound represented by the following formula (I).
[2]
The polyhydric alcohol residue of A is a residue derived from a polyhydric alcohol having at least 3 hydroxyl groups, and at least one hydroxyl group in the polyhydric alcohol forms an ether bond with an adjacent R 2. The organic silicon compound according to [1].
[3]
The organosilicon compound according to [2], wherein the polyhydric alcohol residue of A is a residue of glycerol or pentaerythritol.
[4]
The organosilicon compound according to any one of [1] to [3], which is a wetter for highly filling a curable silicone composition with a filler.
[5]
The following formula (II)
A polyhydric alcohol derivative having an alkenyl group in the molecule represented by the following formula (III).
Described in any one of [1] to [4], which comprises a step of hydrosilylating a organopolysiloxane having a silicon atom-bonded hydrogen atom at one end of the molecular chain represented by (1) in the presence of a platinum compound-containing catalyst. Method for producing an organosilicon compound.
本発明の有機ケイ素化合物は、シリコーン組成物に熱伝導性充填剤等の充填剤（フィラー）を高充填することを可能とし、高温高湿条件下でも接着性に変化の少ない組成物を提供するためのウエッターとして有用である。
The organosilicon compound of the present invention makes it possible to highly fill a silicone composition with a filler such as a heat conductive filler, and provides a composition having little change in adhesiveness even under high temperature and high humidity conditions. It is useful as a wetter for.
以下、本発明につき更に詳しく説明する。
Hereinafter, the present invention will be described in more detail.
本発明に係る有機ケイ素化合物は、下記式（Ｉ）で表される。
The organosilicon compound according to the present invention is represented by the following formula (I).
式（Ｉ）中、Ｒ1は互いに独立に、非置換又は置換の炭素数１～１２の一価炭化水素基であり、Ｒ2は非置換又は置換の炭素数１～１２の二価炭化水素基であり、Ａは２個以上の残存水酸基を有する多価アルコール残基であり、ｎはこの有機ケイ素化合物の２３℃における粘度を１～１，０００ｍＰａ・ｓとする数である。
In formula (I), R 1 is an unsubstituted or substituted monovalent hydrocarbon group having 1 to 12 carbon atoms, and R 2 is an unsubstituted or substituted divalent hydrocarbon group having 1 to 12 carbon atoms. A is a group, A is a polyhydric alcohol residue having two or more residual hydroxyl groups, and n is a number having a viscosity of this organic silicon compound at 23 ° C. of 1 to 1,000 mPa · s.
上記Ｒ1の非置換又は置換の炭素数１～１２の一価炭化水素基としては、メチル基、エチル基、プロピル基、イソプロピル基、ブチル基、イソブチル基、ｔｅｒｔ－ブチル基、ペンチル基、ヘキシル基、ヘプチル基、オクチル基、ノニル基、デシル基、ドデシル基等のアルキル基；シクロペンチル基、シクロヘキシル基等のシクロアルキル基；ビニル基、アリル基、ブテニル基、ペンテニル基、ヘキセニル基等のアルケニル基；フェニル基、トリル基、キシリル基、α－，β－ナフチル基等のアリール基；ベンジル基、２－フェニルエチル基、３－フェニルプロピル基等のアラルキル基；また、これらの基の水素原子の一部又は全部が、Ｆ、Ｃｌ、Ｂｒ等のハロゲン原子やシアノ基等で置換された基、例えば、３－クロロプロピル基、３，３，３－トリフルオロプロピル基、２－シアノエチル基等を例示することができる。これらの中でも、メチル基、エチル基等のアルキル基が好ましく、メチル基が特に好ましい。
Examples of the unsubstituted or substituted monovalent hydrocarbon group having 1 to 12 carbon atoms of R 1 include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a tert-butyl group, a pentyl group and a hexyl. Alkyl group such as group, heptyl group, octyl group, nonyl group, decyl group, dodecyl group; cycloalkyl group such as cyclopentyl group and cyclohexyl group; alkenyl group such as vinyl group, allyl group, butenyl group, pentenyl group and hexenyl group. Aryl groups such as phenyl group, trill group, xsilyl group, α-, β-naphthyl group; aralkyl groups such as benzyl group, 2-phenylethyl group and 3-phenylpropyl group; and hydrogen atoms of these groups A group partially or wholly substituted with a halogen atom such as F, Cl, Br, or a cyano group, for example, a 3-chloropropyl group, a 3,3,3-trifluoropropyl group, a 2-cyanoethyl group, etc. It can be exemplified. Among these, an alkyl group such as a methyl group or an ethyl group is preferable, and a methyl group is particularly preferable.
上記Ｒ2の非置換又は置換の炭素数１～１２の二価炭化水素基としては、メチレン基、エチレン基（ジメチレン基）、プロピレン基（エチルメチレン基、トリメチレン基）、イソプロピレン基、ブチレン基、ペンチレン基、ヘキシレン基、ヘプチレン基、オクチレン基、ノニレン基、デシレン基、ドデシレン基等のアルキレン基；シクロペンチレン基、シクロヘキシレン基等のシクロアルキレン基；ビニレン基、アリレン基、ブテニレン基、ペンテニレン基、ヘキセニレン基等のアルケニレン基；また、これらの基の水素原子の一部又は全部が、Ｆ、Ｃｌ、Ｂｒ等のハロゲン原子やシアノ基等で置換された基等を例示することができる。これらの中でも、エチレン基（ジメチレン基）、プロピレン基（エチルメチレン基、トリメチレン基）等のアルキレン基が好ましく、特にエチレン基（ジメチレン基）、トリメチレン基が好ましい。
Examples of the unsubstituted or substituted divalent hydrocarbon group having 1 to 12 carbon atoms of R 2 include a methylene group, an ethylene group (dimethylene group), a propylene group (ethylmethylene group, trimethylene group), an isopropylene group and a butylene group. , Pentylene group, hexylene group, heptylene group, octylene group, nonylene group, decylene group, dodecylene group and other alkylene groups; cyclopentylene group, cyclohexylene group and other cycloalkylene groups; vinylene group, allylene group, butenylene group, pentenylene Alkenylene groups such as groups and hexenylene groups; and groups in which some or all of the hydrogen atoms of these groups are substituted with halogen atoms such as F, Cl and Br, cyano groups and the like can be exemplified. Among these, an alkylene group such as an ethylene group (dimethylene group) and a propylene group (ethylmethylene group, trimethylene group) is preferable, and an ethylene group (dimethylene group) and a trimethylene group are particularly preferable.
上記Ａの、２個以上の残存水酸基を有する多価アルコール残基としては、エチレングリコール、プロピレングリコール、ジエチレングリコール、グリセロール（グリセリン）、１、２、４－ブタントリオール、ペンタエリスリトール、エリスリトール、アラビニトール、キシリトール、リビトール、マンニトール等の１分子中に３個以上の水酸基を有する多価アルコール中に存在する１個の水酸基から水素原子を１個除いた残基等を例示することができる。これらの中でも、３個以上の水酸基を有し、かつそれ自体及び誘導体の入手容易さからグリセロール、ペンタエリスリトール、１、２、４－ブタントリオール、エリスリトールの残基が好ましく、特にグリセロール、ペンタエリスリトールの残基が好ましい。
Examples of the polyhydric alcohol residue having two or more residual hydroxyl groups in A above include ethylene glycol, propylene glycol, diethylene glycol, glycerol (glycerin), 1, 2,4-butanetriol, pentaerythritol, erythritol, arabinitol, and xylitol. , Ribitol, mannitol and the like, a residue obtained by removing one hydrogen atom from one hydroxyl group existing in a polyhydric alcohol having three or more hydroxyl groups in one molecule can be exemplified. Among these, residues of glycerol, pentaerythritol, 1,2,4-butanetriol and erythritol are preferable because they have three or more hydroxyl groups and are easily available for themselves and their derivatives, and particularly glycerol and pentaerythritol. Residues are preferred.
式（Ｉ）中、ｎはこの有機ケイ素化合物の２３℃における粘度を１～１，０００ｍＰａ・ｓとする数であり、このため、ｎは好ましくは１～２００の数、より好ましくは３～１００の数、さらに好ましくは５～５０の数、特に好ましくは９～３０の数である。ここで、該有機ケイ素化合物の２３℃における粘度は、１～１，０００ｍＰａ・ｓであり、好ましくは５～５００ｍＰａ・ｓ、より好ましくは１０～３００ｍＰａ・ｓである。なお、粘度は回転粘度計（例えば、ＢＬ型、ＢＨ型、ＢＳ型、コーンプレート型等）による数値である（以下、同じ。）。また、上記式（Ｉ）で示される有機ケイ素化合物中におけるジオルガノシロキサン単位の繰り返し数（ｎ）又は重合度は、トルエン等を展開溶媒としてゲルパーミエーションクロマトグラフィ（ＧＰＣ）分析におけるポリスチレン換算の数平均重合度（又は数平均分子量）等として求めることができる。
In the formula (I), n is a number having a viscosity of this organosilicon compound at 23 ° C. of 1 to 1,000 mPa · s, and therefore n is preferably a number of 1 to 200, more preferably 3 to 100. , More preferably 5 to 50, and particularly preferably 9 to 30. Here, the viscosity of the organosilicon compound at 23 ° C. is 1 to 1,000 mPa · s, preferably 5 to 500 mPa · s, and more preferably 10 to 300 mPa · s. The viscosity is a numerical value measured by a rotational viscometer (for example, BL type, BH type, BS type, cone plate type, etc.) (hereinafter, the same applies). Further, the number of repetitions (n) or the degree of polymerization of the diorganosiloxane unit in the organosilicon compound represented by the above formula (I) is the number average in terms of polystyrene in gel permeation chromatography (GPC) analysis using toluene or the like as a developing solvent. It can be determined as the degree of polymerization (or number average molecular weight) or the like.
製造方法
本発明の上記式（Ｉ）で表される有機ケイ素化合物は、従来公知の方法によって製造することができる。例えば、下記式（ＩＩ）で表される分子中にアルケニル基を有する多価アルコール誘導体のアルケニル基と、下記式（ＩＩＩ）で表される分子鎖片末端にケイ素原子に結合した水素原子を有するオルガノポリシロキサン（分子鎖片末端がトリオルガノシロキシ基で封鎖され他方の末端がジオルガノハイドロジェンシロキシ基で封鎖された直鎖状ジオルガノポリシロキサン）のヒドロシリル基（Ｓｉ－Ｈ基）とを、白金化合物含有触媒存在下でヒドロシリル化付加反応を行い、アルケニル基にヒドロシリル基を付加させて炭素－ケイ素結合を形成することによって（即ち、下記式（ＩＩ）中のアルケニル基Ｙと下記式（ＩＩＩ）中のケイ素原子に結合した水素原子（Ｓｉ－Ｈ基）との付加反応により上記式（Ｉ）中の二価炭化水素基Ｒ2を形成することによって）、上記式（Ｉ）で表される有機ケイ素化合物を製造する。
（式中、Ａは、上記と同じ意味を表し、Ｙは炭素数２～１０のアルケニル基を表す。）
（式中、Ｒ1、ｎは、上記と同じ意味を表す。）
Production Method The organosilicon compound represented by the above formula (I) of the present invention can be produced by a conventionally known method. For example, it has an alkenyl group of a polyvalent alcohol derivative having an alkenyl group in the molecule represented by the following formula (II) and a hydrogen atom bonded to a silicon atom at one end of the molecular chain represented by the following formula (III). A hydrosilyl group (Si—H group) of an organopolysiloxane (a linear diorganopolysiloxane having one end of the molecular chain sealed with a triorganosyloxy group and the other end closed with a diorganohydrogensiloxy group). A hydrosilylation addition reaction is carried out in the presence of a platinum compound-containing catalyst, and a hydrosilylation group is added to the alkenyl group to form a carbon-silicon bond (that is, the alkenyl group Y in the following formula (II) and the following formula (III). the addition reaction between hydrogen atoms bonded (Si-H groups) to the silicon atom in) by forming a divalent hydrocarbon group R 2 in the above formula (I)), is represented by the above formula (I) Manufacture organic silicon compounds.
(In the formula, A represents the same meaning as above, and Y represents an alkenyl group having 2 to 10 carbon atoms.)
(Wherein, R 1, n represents the same meaning as above.)
本発明の上記式（Ｉ）で表される有機ケイ素化合物は、従来公知の方法によって製造することができる。例えば、下記式（ＩＩ）で表される分子中にアルケニル基を有する多価アルコール誘導体のアルケニル基と、下記式（ＩＩＩ）で表される分子鎖片末端にケイ素原子に結合した水素原子を有するオルガノポリシロキサン（分子鎖片末端がトリオルガノシロキシ基で封鎖され他方の末端がジオルガノハイドロジェンシロキシ基で封鎖された直鎖状ジオルガノポリシロキサン）のヒドロシリル基（Ｓｉ－Ｈ基）とを、白金化合物含有触媒存在下でヒドロシリル化付加反応を行い、アルケニル基にヒドロシリル基を付加させて炭素－ケイ素結合を形成することによって（即ち、下記式（ＩＩ）中のアルケニル基Ｙと下記式（ＩＩＩ）中のケイ素原子に結合した水素原子（Ｓｉ－Ｈ基）との付加反応により上記式（Ｉ）中の二価炭化水素基Ｒ2を形成することによって）、上記式（Ｉ）で表される有機ケイ素化合物を製造する。
Ｙの炭素数２～１０のアルケニル基は、ビニル基、アリル基、プロぺニル基、ブテニル基等の直鎖状アルケニル基等を例示することができる。この中でも、合成、製造の容易さからビニル基、アリル基が好ましく、特にアリル基が好ましい。
Examples of the alkenyl group having 2 to 10 carbon atoms of Y include a linear alkenyl group such as a vinyl group, an allyl group, a propenyl group, and a butenyl group. Among these, a vinyl group and an allyl group are preferable, and an allyl group is particularly preferable, because of ease of synthesis and production.
上記式（ＩＩ）で表されるアルケニルエーテル構造を有する多価アルコール誘導体の水酸基は、保護基を有しているものでもよく、これは、上記ヒドロシリル化反応後に脱保護の工程を経て水酸基となる。水酸基の保護、脱保護については、公知の方法によって行うことができる。
The hydroxyl group of the polyhydric alcohol derivative having the alkenyl ether structure represented by the above formula (II) may have a protecting group, which becomes a hydroxyl group through the deprotection step after the hydrosilylation reaction. .. The protection and deprotection of the hydroxyl group can be performed by a known method.
上記ヒドロシリル化反応で用いられる白金化合物含有触媒は特に限定されるものではなく、その具体例としては、塩化白金酸、塩化白金酸のアルコール溶液、白金－１，３－ジビニル－１，１，３，３－テトラメチルジシロキサン錯体のトルエンまたはキシレン溶液、テトラキストリフェニルホスフィン白金、ジクロロビストリフェニルホスフィン白金、ジクロロビスアセトニトリル白金、ジクロロビスベンゾニトリル白金、ジクロロシクロオクタジエン白金、白金－炭素、白金－アルミナ、白金－シリカ等の担持触媒などが挙げられる。これらの中でも、選択性の面から、白金－１，３－ジビニル－１，１，３，３－テトラメチルジシロキサン錯体のトルエンまたはキシレン溶液が好ましい。
The platinum compound-containing catalyst used in the hydrosilylation reaction is not particularly limited, and specific examples thereof include platinum chloride, an alcohol solution of platinum chloride, and platinum-1,3-divinyl-1,1,3. , 3-Tetramethyldisiloxane complex in toluene or xylene solution, tetraxtriphenylphosphine platinum, dichlorobistriphenylphosphine platinum, dichlorobis acetonitrile platinum, dichlorobisbenzonitrile platinum, dichlorocyclooctadiene platinum, platinum-carbon, platinum-alumina , Platinum-supporting catalysts such as silica, and the like. Among these, a toluene or xylene solution of platinum-1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex is preferable from the viewpoint of selectivity.
白金化合物含有触媒の使用量は特に限定されるものではないが、反応性、生産性の点から、式（ＩＩ）で表される分子中にアルケニル基を有する多価アルコール誘導体１ｍｏｌに対し、含有される白金原子が１×１０-7～１×１０-2ｍｏｌとなる量が好ましく、１×１０-7～１×１０-3ｍｏｌとなる量がより好ましい。
The amount of the platinum compound-containing catalyst used is not particularly limited, but it is contained in 1 mol of the polyvalent alcohol derivative having an alkenyl group in the molecule represented by the formula (II) from the viewpoint of reactivity and productivity. The amount of the platinum atom to be formed is preferably 1 × 10 -7 to 1 × 10 −2 mol, more preferably 1 × 10 -7 to 1 × 10 -3 mol.
また、ヒドロシリル化反応の反応性向上のために助触媒を使用してもよい。この助触媒としては、一般的にヒドロシリル化反応に用いられている助触媒を使用できるが、本発明では、無機酸のアンモニウム塩、酸アミド化合物、カルボン酸が好ましい。
Further, a co-catalyst may be used to improve the reactivity of the hydrosilylation reaction. As the co-catalyst, a co-catalyst generally used for the hydrosilylation reaction can be used, but in the present invention, an ammonium salt of an inorganic acid, an acid amide compound, and a carboxylic acid are preferable.
無機酸のアンモニウム塩の具体例としては、塩化アンモニウム、硫酸アンモニウム、アミド硫酸アンモニウム、硝酸アンモニウム、リン酸二水素一アンモニウム、リン酸水素二アンモニウム、リン酸三アンモニウム、ジ亜リン酸アンモニウム、炭酸アンモニウム、炭酸水素アンモニウム、硫化アンモニウム、ホウ酸アンモニウム、ホウフッ化アンモニウム等が挙げられる。中でも、炭酸アンモニウム、炭酸水素アンモニウムが好ましい。
Specific examples of ammonium salts of inorganic acids include ammonium chloride, ammonium sulfate, ammonium ammonium sulfate, ammonium nitrate, monoammonium dihydrogen phosphate, diammonium hydrogen phosphate, triammonium phosphate, ammonium diaphosphate, ammonium carbonate, and hydrogen carbonate. Ammonium, ammonium sulfide, ammonium borate, ammonium borofluoride and the like can be mentioned. Of these, ammonium carbonate and ammonium hydrogen carbonate are preferable.
酸アミド化合物の具体例としては、ホルムアミド、アセトアミド、Ｎ－メチルアセトアミド、Ｎ，Ｎ－ジメチルアセトアミド、プロピオンアミド、アクリルアミド、マロンアミド、スクシンアミド、マレアミド、フマルアミド、ベンズアミド、フタルアミド、パルミチン酸アミド、ステアリン酸アミド等が挙げられ、これらの中でも、ホルムアミド、ステアリン酸アミドが好ましく、ホルムアミドがより好ましい。
Specific examples of the acid amide compound include formamide, acetamide, N-methylacetamide, N, N-dimethylacetamide, propionamide, acrylamide, malonamide, succinamide, maleamide, fumalamide, benzamide, phthalamide, palmitate amide, stearate amide and the like. Among these, formamide and stearic acid amide are preferable, and formamide is more preferable.
カルボン酸の具体例としては、ギ酸、酢酸、プロピオン酸、酪酸、メトキシ酢酸、ペンタン酸、カプロン酸、ヘプタン酸、オクタン酸、乳酸、グリコール酸、トリフルオロ酢酸、マレイン酸、フマル酸、コハク酸、酒石酸、シュウ酸等が挙げられ、これらの中でも、ギ酸、酢酸、乳酸、マレイン酸、フマル酸、コハク酸、トリフルオロ酢酸が好ましく、酢酸、トリフルオロ酢酸がより好ましい。
Specific examples of carboxylic acids include formic acid, acetic acid, propionic acid, butyric acid, methoxyacetic acid, pentanic acid, caproic acid, heptanic acid, octanoic acid, lactic acid, glycolic acid, trifluoroacetic acid, maleic acid, fumaric acid, and succinic acid. Examples thereof include tartrate acid and oxalic acid. Among these, formic acid, acetic acid, lactic acid, maleic acid, fumaric acid, succinic acid and trifluoroacetic acid are preferable, and acetic acid and trifluoroacetic acid are more preferable.
助触媒の使用量は特に限定されるものではないが、反応性、選択性、コスト等の観点から、式（ＩＩ）で表される分子中にアルケニル基を有する多価アルコール誘導体１ｍｏｌに対して１×１０-5～１×１０-1ｍｏｌが好ましく、１×１０-4～５×１０-1ｍｏｌがより好ましい。
The amount of the co-catalyst used is not particularly limited, but from the viewpoint of reactivity, selectivity, cost, etc., with respect to 1 mol of the polyhydric alcohol derivative having an alkenyl group in the molecule represented by the formula (II). 1 × 10 -5 to 1 × 10 -1 mol is preferable, and 1 × 10 -4 to 5 × 10 -1 mol is more preferable.
なお、上記ヒドロシリル化反応は無溶媒でも進行するが、溶媒を用いることもできる。使用可能な溶媒の具体例としては、ペンタン、ヘキサン、シクロヘキサン、ヘプタン、イソオクタン、ベンゼン、トルエン、キシレン等の炭化水素系溶媒；ジエチルエーテル、テトラヒドロフラン、ジオキサン等のエーテル系溶媒；酢酸エチル、酢酸ブチル等のエステル系溶媒；Ｎ，Ｎ－ジメチルホルムアミド等の非プロトン性極性溶媒；ジクロロメタン、クロロホルム等の塩素化炭化水素系溶媒などが挙げられ、これらの溶媒は、１種を単独で用いても、２種以上を混合して用いてもよい。
Although the hydrosilylation reaction proceeds without a solvent, a solvent can also be used. Specific examples of the solvent that can be used include hydrocarbon solvents such as pentane, hexane, cyclohexane, heptane, isooctane, benzene, toluene and xylene; ether solvents such as diethyl ether, tetrahydrofuran and dioxane; ethyl acetate, butyl acetate and the like. Ester-based solvents; aprotonic polar solvents such as N, N-dimethylformamide; chlorinated hydrocarbon-based solvents such as dichloromethane and chloroform, and the like, even if one of these solvents is used alone, 2 A mixture of seeds or more may be used.
上記ヒドロシリル化反応における反応温度は特に限定されるものではなく、室温（２３℃）から加熱下で行うことができるが、室温（２３℃）～２００℃が好ましい。適度な反応速度を得るためには加熱下で反応させることが好ましく、このような観点から、反応温度は４０～１１０℃がより好ましく、４０～９０℃がより一層好ましい。また、反応時間も特に限定されるものではなく、１～６０時間が好ましく、１～３０時間がより好ましく、１～２０時間がさらに好ましい。
The reaction temperature in the hydrosilylation reaction is not particularly limited and can be carried out from room temperature (23 ° C.) under heating, but room temperature (23 ° C.) to 200 ° C. is preferable. In order to obtain an appropriate reaction rate, it is preferable to carry out the reaction under heating, and from such a viewpoint, the reaction temperature is more preferably 40 to 110 ° C., and even more preferably 40 to 90 ° C. Further, the reaction time is not particularly limited, and is preferably 1 to 60 hours, more preferably 1 to 30 hours, still more preferably 1 to 20 hours.
上記式（ＩＩ）で表される分子中にアルケニル基を有する多価アルコール誘導体のアルケニル基と、上記式（ＩＩＩ）で表されるオルガノポリシロキサンのヒドロシリル基との反応割合は、ヒドロシリル化反応時の副生物を抑制するとともに、得られる有機ケイ素化合物の保存安定性や特性を高めることを考慮すると、上記ヒドロシリル基１ｍｏｌに対し、上記アルケニル基が０．８～１．３ｍｏｌとなる割合が好ましく、０．９～１．２ｍｏｌとなる割合がより好ましい。
The reaction ratio between the alkenyl group of the polyhydric alcohol derivative having an alkenyl group in the molecule represented by the above formula (II) and the hydrosilyl group of the organopolysiloxane represented by the above formula (III) is the hydrosilylation reaction. Considering that the by-products of the above are suppressed and the storage stability and properties of the obtained organosilicon compound are enhanced, the ratio of the alkenyl group to 1 mol of the hydrosilyl group is preferably 0.8 to 1.3 mol. A ratio of 0.9 to 1.2 mol is more preferable.
このようにして得られる上記式（Ｉ）で表される化合物としては、以下の式で表されるもの等が挙げられるが、これらに限定されるものではない。
Examples of the compound represented by the above formula (I) thus obtained include, but are not limited to, those represented by the following formula.
式（１’）～（４’）中、ｎはこれらの有機ケイ素化合物の２３℃における粘度を１～１，０００ｍＰａ・ｓとする数であり、ｎは好ましくは１～２００の数、より好ましくは３～１００の数、さらに好ましくは５～５０の数、特に好ましくは９～３０の数である。
In the formulas (1') to (4'), n is a number having a viscosity of these organosilicon compounds at 23 ° C. of 1 to 1,000 mPa · s, and n is preferably a number of 1 to 200, more preferably. Is a number of 3 to 100, more preferably a number of 5 to 50, and particularly preferably a number of 9 to 30.
上記式（１’）～（４’）で表されるものの具体例としては、以下の式（１）～（８）で表されるものが挙げられるが、これらに限定されるものではない。
Specific examples of those represented by the above formulas (1') to (4') include, but are not limited to, those represented by the following formulas (1) to (8).
本発明の有機ケイ素化合物は、充填剤を含むシリコーン組成物（オルガノポリシロキサン組成物）において、該充填剤のウエッター（分散剤）として好適に使用することができる。シリコーン組成物としては、付加反応硬化型シリコーン組成物、有機過酸化物硬化型シリコーン組成物、縮合反応硬化型シリコーン組成物、シリコーングリース等の非硬化タイプのシリコーン組成物等が挙げられる。シリコーン組成物に充填される充填剤としては、無機質充填剤、金属充填剤、有機樹脂製充填剤等のいずれであってもよく、例えば、煙霧質シリカ、沈降性シリカ、石英粉、アルミナ（酸化アルミニウム）、水酸化アルミニウム、窒化ホウ素、窒化アルミニウム、窒化ケイ素、酸化鉄、酸化マグネシウム、酸化チタン、酸化亜鉛、酸化ジルコニウム、炭酸カルシウム、カーボンブラック、グラファイト、アルミニウム、金、銀、銅、ニッケル等公知の充填剤に適用することができる。
The organosilicon compound of the present invention can be suitably used as a wetter (dispersant) for the filler in the silicone composition (organopolysiloxane composition) containing the filler. Examples of the silicone composition include an addition reaction curing type silicone composition, an organic peroxide curing type silicone composition, a condensation reaction curing type silicone composition, and a non-curing type silicone composition such as silicone grease. The filler to be filled in the silicone composition may be any of an inorganic filler, a metal filler, an organic resin filler and the like, and for example, fuming silica, precipitate silica, quartz powder and alumina (oxidation). Aluminum), aluminum hydroxide, boron nitride, aluminum nitride, silicon nitride, iron oxide, magnesium oxide, titanium oxide, zinc oxide, zirconium oxide, calcium carbonate, carbon black, graphite, aluminum, gold, silver, copper, nickel, etc. Can be applied to the filler of.
上記シリコーン組成物の接着強度は例えばＪＩＳ Ｋ ６８５０の規定に従って引張りせん断接着強さを測定すればよい。
For the adhesive strength of the above silicone composition, for example, the tensile shear adhesive strength may be measured according to the provisions of JIS K 6850.
以下、実施例および参考例を挙げて本発明をより具体的に説明するが、本発明はこれらの実施例に限定されるものではない。なお、粘度は２３℃における回転粘度計による測定値であり、分子量はトルエンを展開溶媒としたＧＰＣ測定におけるポリスチレン換算の数平均分子量を示す。
Hereinafter, the present invention will be described in more detail with reference to Examples and Reference Examples, but the present invention is not limited to these Examples. The viscosity is a value measured by a rotational viscometer at 23 ° C., and the molecular weight indicates a number average molecular weight in terms of polystyrene in GPC measurement using toluene as a developing solvent.
有機ケイ素化合物の合成
［実施例１］
有機ケイ素化合物１の合成
撹拌機、還流冷却器、滴下ロートおよび温度計を備えた５００ｍＬセパラブルフラスコに、下記式（ＩＶ）で表されるアルケニル基を有するグリセリン誘導体１８．１ｇ、白金－１，３－ジビニル－１，１，３，３－テトラメチルジシロキサン錯体のトルエン溶液０．１ｇを納め、８０℃に加熱した。その中に、下記式（Ｖ）で表されるオルガノポリシロキサン１００．０ｇを滴下投入し、８０℃にて３時間加熱撹拌した。1Ｈ－ＮＭＲ測定により原料のアルケニル基およびヒドロシリル基由来のピークが完全に消失したことを確認し、反応終了とした。反応終了後の混合物について減圧留去（８０℃、５ｍｍＨｇ）を２時間実施し、濾過することで、有機ケイ素化合物１（粘度：１３ｍＰａ・ｓ、数平均分子量：１０９０）を１１４ｇ得た。
Synthesis of organosilicon compounds [Example 1]
Synthesis of organosilicon compound 18.1 g of glycerin derivative having an alkenyl group represented by the following formula (IV), platinum-1, platinum-1, in a 500 mL separable flask equipped with a stirrer, a reflux condenser, a dropping funnel and a thermometer. 0.1 g of a toluene solution of 3-divinyl-1,1,3,3-tetramethyldisiloxane complex was placed and heated to 80 ° C. 100.0 g of an organopolysiloxane represented by the following formula (V) was added dropwise thereto, and the mixture was heated and stirred at 80 ° C. for 3 hours. 1 It was confirmed by 1 H-NMR measurement that the peaks derived from the alkenyl group and the hydrosilyl group of the raw materials had completely disappeared, and the reaction was terminated. After completion of the reaction, the mixture was distilled off under reduced pressure (80 ° C., 5 mmHg) for 2 hours and filtered to obtain 114 g of organosilicon compound 1 (viscosity: 13 mPa · s, number average molecular weight: 1090).
［実施例１］
有機ケイ素化合物１の合成
撹拌機、還流冷却器、滴下ロートおよび温度計を備えた５００ｍＬセパラブルフラスコに、下記式（ＩＶ）で表されるアルケニル基を有するグリセリン誘導体１８．１ｇ、白金－１，３－ジビニル－１，１，３，３－テトラメチルジシロキサン錯体のトルエン溶液０．１ｇを納め、８０℃に加熱した。その中に、下記式（Ｖ）で表されるオルガノポリシロキサン１００．０ｇを滴下投入し、８０℃にて３時間加熱撹拌した。1Ｈ－ＮＭＲ測定により原料のアルケニル基およびヒドロシリル基由来のピークが完全に消失したことを確認し、反応終了とした。反応終了後の混合物について減圧留去（８０℃、５ｍｍＨｇ）を２時間実施し、濾過することで、有機ケイ素化合物１（粘度：１３ｍＰａ・ｓ、数平均分子量：１０９０）を１１４ｇ得た。
Synthesis of organosilicon compound 18.1 g of glycerin derivative having an alkenyl group represented by the following formula (IV), platinum-1, platinum-1, in a 500 mL separable flask equipped with a stirrer, a reflux condenser, a dropping funnel and a thermometer. 0.1 g of a toluene solution of 3-divinyl-1,1,3,3-tetramethyldisiloxane complex was placed and heated to 80 ° C. 100.0 g of an organopolysiloxane represented by the following formula (V) was added dropwise thereto, and the mixture was heated and stirred at 80 ° C. for 3 hours. 1 It was confirmed by 1 H-NMR measurement that the peaks derived from the alkenyl group and the hydrosilyl group of the raw materials had completely disappeared, and the reaction was terminated. After completion of the reaction, the mixture was distilled off under reduced pressure (80 ° C., 5 mmHg) for 2 hours and filtered to obtain 114 g of organosilicon compound 1 (viscosity: 13 mPa · s, number average molecular weight: 1090).
［実施例２］
有機ケイ素化合物２の合成
上記式（ＩＶ）で表されるアルケニル基を有するグリセリン誘導体の代わりに、下記式（ＶＩ）で表されるアルケニル基を有するペンタエリスリトール誘導体２４．１ｇを使用した以外は実施例１と同様にして、有機ケイ素化合物２（粘度：２７５ｍＰａ・ｓ、数平均分子量：１１４０）を得た。
[Example 2]
Synthesis of organosilicon compound 2 Performed except that 24.1 g of a pentaerythritol derivative having an alkenyl group represented by the following formula (VI) was used instead of the glycerin derivative having an alkenyl group represented by the above formula (IV). Organosilicon compound 2 (viscosity: 275 mPa · s, number average molecular weight: 1140) was obtained in the same manner as in Example 1.
有機ケイ素化合物２の合成
上記式（ＩＶ）で表されるアルケニル基を有するグリセリン誘導体の代わりに、下記式（ＶＩ）で表されるアルケニル基を有するペンタエリスリトール誘導体２４．１ｇを使用した以外は実施例１と同様にして、有機ケイ素化合物２（粘度：２７５ｍＰａ・ｓ、数平均分子量：１１４０）を得た。
Synthesis of organosilicon compound 2 Performed except that 24.1 g of a pentaerythritol derivative having an alkenyl group represented by the following formula (VI) was used instead of the glycerin derivative having an alkenyl group represented by the above formula (IV). Organosilicon compound 2 (viscosity: 275 mPa · s, number average molecular weight: 1140) was obtained in the same manner as in Example 1.
［実施例３］
有機ケイ素化合物３の合成
上記式（Ｖ）で表されるオルガノポリシロキサンの代わりに、下記式（ＶＩＩ）で表されるオルガノポリシロキサン２８１．５ｇを使用した以外は実施例１と同様にして、有機ケイ素化合物３（粘度：３２ｍＰａ・ｓ、数平均分子量：２７２０）を得た。
[Example 3]
Synthesis of Organosilicon Compound 3 In the same manner as in Example 1 except that 281.5 g of the organopolysiloxane represented by the following formula (VII) was used instead of the organopolysiloxane represented by the above formula (V). Organosilicon compound 3 (viscosity: 32 mPa · s, number average molecular weight: 2720) was obtained.
有機ケイ素化合物３の合成
上記式（Ｖ）で表されるオルガノポリシロキサンの代わりに、下記式（ＶＩＩ）で表されるオルガノポリシロキサン２８１．５ｇを使用した以外は実施例１と同様にして、有機ケイ素化合物３（粘度：３２ｍＰａ・ｓ、数平均分子量：２７２０）を得た。
Synthesis of Organosilicon Compound 3 In the same manner as in Example 1 except that 281.5 g of the organopolysiloxane represented by the following formula (VII) was used instead of the organopolysiloxane represented by the above formula (V). Organosilicon compound 3 (viscosity: 32 mPa · s, number average molecular weight: 2720) was obtained.
［実施例４］
有機ケイ素化合物４の合成
上記式（ＩＶ）で表されるアルケニル基を有するグリセリン誘導体の代わりに、上記式（ＶＩ）で表されるアルケニル基を有するペンタエリスリトール誘導体２４．１ｇ、上記式（Ｖ）で表されるオルガノポリシロキサンの代わりに、上記式（ＶＩＩ）で表されるオルガノポリシロキサン２８１．５ｇを使用した以外は実施例１と同様にして、有機ケイ素化合物４（粘度：１３８ｍＰａ・ｓ、数平均分子量：２７７０）を得た。
[Example 4]
Synthesis of Organosilicon Compound 2 In place of the glycerin derivative having an alkenyl group represented by the above formula (IV), 24.1 g of a pentaerythritol derivative having an alkenyl group represented by the above formula (VI), the above formula (V) In the same manner as in Example 1 except that 281.5 g of the organopolysiloxane represented by the above formula (VII) was used instead of the organopolysiloxane represented by the above formula (VII), the organosilicon compound 4 (viscosity: 138 mPa · s, Number average molecular weight: 2770) was obtained.
有機ケイ素化合物４の合成
上記式（ＩＶ）で表されるアルケニル基を有するグリセリン誘導体の代わりに、上記式（ＶＩ）で表されるアルケニル基を有するペンタエリスリトール誘導体２４．１ｇ、上記式（Ｖ）で表されるオルガノポリシロキサンの代わりに、上記式（ＶＩＩ）で表されるオルガノポリシロキサン２８１．５ｇを使用した以外は実施例１と同様にして、有機ケイ素化合物４（粘度：１３８ｍＰａ・ｓ、数平均分子量：２７７０）を得た。
Synthesis of Organosilicon Compound 2 In place of the glycerin derivative having an alkenyl group represented by the above formula (IV), 24.1 g of a pentaerythritol derivative having an alkenyl group represented by the above formula (VI), the above formula (V) In the same manner as in Example 1 except that 281.5 g of the organopolysiloxane represented by the above formula (VII) was used instead of the organopolysiloxane represented by the above formula (VII), the organosilicon compound 4 (viscosity: 138 mPa · s, Number average molecular weight: 2770) was obtained.
［参考例］
本発明の有機ケイ素化合物の効果を参考例により詳細に説明する。なお、参考例中の特性は２３℃における値である。 [Reference example]
The effect of the organosilicon compound of the present invention will be described in detail with reference to reference examples. The characteristics in the reference example are values at 23 ° C.
本発明の有機ケイ素化合物の効果を参考例により詳細に説明する。なお、参考例中の特性は２３℃における値である。 [Reference example]
The effect of the organosilicon compound of the present invention will be described in detail with reference to reference examples. The characteristics in the reference example are values at 23 ° C.
［参考例１］
ミキサーにより、粘度が４００ｍＰａ・ｓである分子鎖両末端ジメチルビニルシロキシ基封鎖ジメチルポリシロキサン（ビニル基の含有量；０．４４質量％）８質量部、平均粒径（ＢＥＴ法）が２０μｍである真球状のアルミナ粉末６７．５質量部、平均粒径（ＢＥＴ法）が２．２μｍである不定形状のアルミナ粉末２２．５質量部、分散剤（ウェッター）として実施例１で合成した有機ケイ素化合物１を１．５質量部混合して熱伝導性シリコーンゴムベースを調製した。次に、このゴムベースに、粘度が２５ｍＰａ・ｓであり、１分子中に平均４個のケイ素原子に結合した水素原子（ＳｉＨ基）を有する分子鎖両末端トリメチルシロキシ基封鎖ジメチルシロキサン・メチルハイドロジェンシロキサンコポリマー１．０質量部、接着付与成分としてトリアリイソシアヌレート０．０３質量部、３－グリシドキシプロピルトリメトキシシラン０．２質量部、および硬化反応抑制剤として、１－エチニル－１－シクロヘキサノール０．０２質量部を混合し、最後に、白金含有量が０．５質量％である白金の１，３－ジビニル－１，１，３，３－テトラメチルジシロキサン錯体０．０２質量部を混合して熱伝導性シリコーンゴム組成物１を調製した。 [Reference Example 1]
By a mixer, the molecular chain has a viscosity of 400 mPa · s, both ends of the molecular chain are dimethylvinylsiloxy group-sealed dimethylpolysiloxane (vinyl group content; 0.44% by mass), 8 parts by mass, and the average particle size (BET method) is 20 μm. 67.5 parts by mass of spherical alumina powder, 22.5 parts by mass of amorphous alumina powder having an average particle size (BET method) of 2.2 μm, and an organosilicon compound synthesized in Example 1 as a dispersant (wetter). 1 was mixed in an amount of 1.5 parts by mass to prepare a thermally conductive silicone rubber base. Next, this rubber base has a viscosity of 25 mPa · s and has a hydrogen atom (SiH group) bonded to an average of 4 silicon atoms in one molecule. 1.0 part by mass of gensiloxane copolymer, 0.03 part by mass of trialiisocyanurate as an adhesion-imparting component, 0.2 part by mass of 3-glycidoxypropyltrimethoxysilane, and 1-ethynyl-1 as a curing reaction inhibitor. -Mix 0.02 parts by mass of cyclohexanol, and finally, 1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex 0.02 of platinum having a platinum content of 0.5% by mass. The thermally conductive silicone rubber composition 1 was prepared by mixing parts by mass.
ミキサーにより、粘度が４００ｍＰａ・ｓである分子鎖両末端ジメチルビニルシロキシ基封鎖ジメチルポリシロキサン（ビニル基の含有量；０．４４質量％）８質量部、平均粒径（ＢＥＴ法）が２０μｍである真球状のアルミナ粉末６７．５質量部、平均粒径（ＢＥＴ法）が２．２μｍである不定形状のアルミナ粉末２２．５質量部、分散剤（ウェッター）として実施例１で合成した有機ケイ素化合物１を１．５質量部混合して熱伝導性シリコーンゴムベースを調製した。次に、このゴムベースに、粘度が２５ｍＰａ・ｓであり、１分子中に平均４個のケイ素原子に結合した水素原子（ＳｉＨ基）を有する分子鎖両末端トリメチルシロキシ基封鎖ジメチルシロキサン・メチルハイドロジェンシロキサンコポリマー１．０質量部、接着付与成分としてトリアリイソシアヌレート０．０３質量部、３－グリシドキシプロピルトリメトキシシラン０．２質量部、および硬化反応抑制剤として、１－エチニル－１－シクロヘキサノール０．０２質量部を混合し、最後に、白金含有量が０．５質量％である白金の１，３－ジビニル－１，１，３，３－テトラメチルジシロキサン錯体０．０２質量部を混合して熱伝導性シリコーンゴム組成物１を調製した。 [Reference Example 1]
By a mixer, the molecular chain has a viscosity of 400 mPa · s, both ends of the molecular chain are dimethylvinylsiloxy group-sealed dimethylpolysiloxane (vinyl group content; 0.44% by mass), 8 parts by mass, and the average particle size (BET method) is 20 μm. 67.5 parts by mass of spherical alumina powder, 22.5 parts by mass of amorphous alumina powder having an average particle size (BET method) of 2.2 μm, and an organosilicon compound synthesized in Example 1 as a dispersant (wetter). 1 was mixed in an amount of 1.5 parts by mass to prepare a thermally conductive silicone rubber base. Next, this rubber base has a viscosity of 25 mPa · s and has a hydrogen atom (SiH group) bonded to an average of 4 silicon atoms in one molecule. 1.0 part by mass of gensiloxane copolymer, 0.03 part by mass of trialiisocyanurate as an adhesion-imparting component, 0.2 part by mass of 3-glycidoxypropyltrimethoxysilane, and 1-ethynyl-1 as a curing reaction inhibitor. -Mix 0.02 parts by mass of cyclohexanol, and finally, 1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex 0.02 of platinum having a platinum content of 0.5% by mass. The thermally conductive silicone rubber composition 1 was prepared by mixing parts by mass.
［参考例２］
有機ケイ素化合物１の代わりに、有機ケイ素化合物２を１．５質量部使用した以外は参考例１と同様にして熱伝導性シリコーンゴム組成物２を得た。 [Reference Example 2]
A thermally conductive silicone rubber composition 2 was obtained in the same manner as in Reference Example 1 except that 1.5 parts by mass of organosilicon compound 2 was used instead of the organosilicon compound 1.
有機ケイ素化合物１の代わりに、有機ケイ素化合物２を１．５質量部使用した以外は参考例１と同様にして熱伝導性シリコーンゴム組成物２を得た。 [Reference Example 2]
A thermally conductive silicone rubber composition 2 was obtained in the same manner as in Reference Example 1 except that 1.5 parts by mass of organosilicon compound 2 was used instead of the organosilicon compound 1.
［参考例３］
有機ケイ素化合物１の代わりに、有機ケイ素化合物３を１．５質量部使用した以外は参考例１と同様にして熱伝導性シリコーンゴム組成物３を得た。 [Reference Example 3]
A thermally conductive silicone rubber composition 3 was obtained in the same manner as in Reference Example 1 except that 1.5 parts by mass of the organosilicon compound 3 was used instead of the organosilicon compound 1.
有機ケイ素化合物１の代わりに、有機ケイ素化合物３を１．５質量部使用した以外は参考例１と同様にして熱伝導性シリコーンゴム組成物３を得た。 [Reference Example 3]
A thermally conductive silicone rubber composition 3 was obtained in the same manner as in Reference Example 1 except that 1.5 parts by mass of the organosilicon compound 3 was used instead of the organosilicon compound 1.
［参考例４］
有機ケイ素化合物１の代わりに、有機ケイ素化合物４を１．５質量部使用した以外は参考例１と同様にして熱伝導性シリコーンゴム組成物４を得た。 [Reference example 4]
A thermally conductive silicone rubber composition 4 was obtained in the same manner as in Reference Example 1 except that 1.5 parts by mass of the organosilicon compound 4 was used instead of the organosilicon compound 1.
有機ケイ素化合物１の代わりに、有機ケイ素化合物４を１．５質量部使用した以外は参考例１と同様にして熱伝導性シリコーンゴム組成物４を得た。 [Reference example 4]
A thermally conductive silicone rubber composition 4 was obtained in the same manner as in Reference Example 1 except that 1.5 parts by mass of the organosilicon compound 4 was used instead of the organosilicon compound 1.
［参考例５］
有機ケイ素化合物１の代わりに、下記式：
で表される有機ケイ素化合物（分子鎖片末端がトリメチルシロキシ基で封鎖され他方の末端が（トリメトキシシリルエチル）ジメチルシロキシ基で封鎖された重合度約３０の直鎖状ジメチルポリシロキサン、粘度：３０ｍＰａ・ｓ）を１．５質量部使用した以外は参考例１と同様にして熱伝導性シリコーンゴム組成物５を得た。
[Reference Example 5]
Instead of organosilicon compound 1, the following formula:
Organosilicon compound represented by (a linear dimethylpolysiloxane having a degree of polymerization of about 30 in which one end of the molecular chain is sealed with a trimethylsiloxy group and the other end is closed with a (trimethoxysilylethyl) dimethylsiloxy group, viscosity: A thermally conductive silicone rubber composition 5 was obtained in the same manner as in Reference Example 1 except that 1.5 parts by mass of 30 mPa · s) was used.
有機ケイ素化合物１の代わりに、下記式：
Instead of organosilicon compound 1, the following formula:
［熱伝導性シリコーンゴムの接着強さ］
熱伝導性シリコーンゴム組成物１、２、３、４又は５を、被着体｛株式会社パルテック製のアルミニウム板（ＪＩＳ Ｈ ４０００、Ａ１０５０Ｐ）｝の間に挟み込んだ後、１２０℃で６０分間加熱することにより硬化させ、熱伝導性シリコーンゴムを得て、これを初期試験体とした。なお、接着面積は２５ｍｍ×１０ｍｍとし、接着層の厚さは２ｍｍとした。この熱伝導性シリコーンゴムの引張りせん断接着強さをＪＩＳ Ｋ ６８５０の規定に従って測定した。また、得られた熱伝導性シリコーンゴムを８５℃ ８５％ＲＨの恒温恒湿機に１週間静置したものを高温高湿試験体とした。室温（２３℃）に戻した試験体の引張りせん断接着強さを測定し、初期と高温高湿試験後の接着強さを比較、判定した。初期と高温高湿試験後の接着強さの差が２倍未満であれば〇、２倍以上であれば×とした。 [Adhesive strength of thermally conductive silicone rubber]
The heat conductive silicone rubber composition 1, 2, 3, 4 or 5 is sandwiched between the adherends {aluminum plate manufactured by Partech Co., Ltd. (JIS H 4000, A1050P)} and then heated at 120 ° C. for 60 minutes. Then, it was cured to obtain a heat-conducting silicone rubber, which was used as an initial test piece. The adhesive area was 25 mm × 10 mm, and the thickness of the adhesive layer was 2 mm. The tensile shear adhesive strength of this thermally conductive silicone rubber was measured according to JIS K 6850. Further, the obtained heat-conducting silicone rubber was allowed to stand in a constant temperature and humidity chamber at 85 ° C. and 85% RH for one week, and used as a high-temperature and high-humidity test piece. The tensile shear adhesive strength of the test piece returned to room temperature (23 ° C.) was measured, and the adhesive strength at the initial stage and after the high temperature and high humidity test were compared and judged. If the difference in adhesive strength between the initial stage and the high temperature and high humidity test was less than 2 times, it was evaluated as 〇, and if it was 2 times or more, it was evaluated as x.
熱伝導性シリコーンゴム組成物１、２、３、４又は５を、被着体｛株式会社パルテック製のアルミニウム板（ＪＩＳ Ｈ ４０００、Ａ１０５０Ｐ）｝の間に挟み込んだ後、１２０℃で６０分間加熱することにより硬化させ、熱伝導性シリコーンゴムを得て、これを初期試験体とした。なお、接着面積は２５ｍｍ×１０ｍｍとし、接着層の厚さは２ｍｍとした。この熱伝導性シリコーンゴムの引張りせん断接着強さをＪＩＳ Ｋ ６８５０の規定に従って測定した。また、得られた熱伝導性シリコーンゴムを８５℃ ８５％ＲＨの恒温恒湿機に１週間静置したものを高温高湿試験体とした。室温（２３℃）に戻した試験体の引張りせん断接着強さを測定し、初期と高温高湿試験後の接着強さを比較、判定した。初期と高温高湿試験後の接着強さの差が２倍未満であれば〇、２倍以上であれば×とした。 [Adhesive strength of thermally conductive silicone rubber]
The heat conductive silicone rubber composition 1, 2, 3, 4 or 5 is sandwiched between the adherends {aluminum plate manufactured by Partech Co., Ltd. (JIS H 4000, A1050P)} and then heated at 120 ° C. for 60 minutes. Then, it was cured to obtain a heat-conducting silicone rubber, which was used as an initial test piece. The adhesive area was 25 mm × 10 mm, and the thickness of the adhesive layer was 2 mm. The tensile shear adhesive strength of this thermally conductive silicone rubber was measured according to JIS K 6850. Further, the obtained heat-conducting silicone rubber was allowed to stand in a constant temperature and humidity chamber at 85 ° C. and 85% RH for one week, and used as a high-temperature and high-humidity test piece. The tensile shear adhesive strength of the test piece returned to room temperature (23 ° C.) was measured, and the adhesive strength at the initial stage and after the high temperature and high humidity test were compared and judged. If the difference in adhesive strength between the initial stage and the high temperature and high humidity test was less than 2 times, it was evaluated as 〇, and if it was 2 times or more, it was evaluated as x.
表１の結果より、参考例１～４は参考例と５比べて、初期と高温高湿試験後の接着強さの変化が少なく、本発明の有機ケイ素化合物が熱伝導性シリコーンゴムの接着性の変化を少なくするウエッターとして好適に用いることができることが示された。
From the results in Table 1, Reference Examples 1 to 4 have less change in adhesive strength between the initial stage and after the high temperature and high humidity test, and the organosilicon compound of the present invention has the adhesiveness of the heat conductive silicone rubber. It was shown that it can be suitably used as a wetter that reduces the change in the amount of silicon.
Claims (5)
- 下記式（Ｉ）で表される有機ケイ素化合物。
- Ａの多価アルコール残基が少なくとも３個の水酸基を有する多価アルコールから誘導される残基であり、該多価アルコール中の少なくとも１個の水酸基が隣接するＲ2とエーテル結合を形成しているものである請求項１に記載の有機ケイ素化合物。 The polyhydric alcohol residue of A is a residue derived from a polyhydric alcohol having at least 3 hydroxyl groups, and at least one hydroxyl group in the polyhydric alcohol forms an ether bond with an adjacent R 2. The organic silicon compound according to claim 1.
- Ａの多価アルコール残基が、グリセロール又はペンタエリスリトールの残基である請求項２に記載の有機ケイ素化合物。 The organosilicon compound according to claim 2, wherein the polyhydric alcohol residue of A is a residue of glycerol or pentaerythritol.
- 硬化性シリコーン組成物に充填剤を高充填するためのウエッターである請求項１～３のいずれか１項に記載の有機ケイ素化合物。 The organosilicon compound according to any one of claims 1 to 3, which is a wetter for highly filling a curable silicone composition with a filler.
- 下記式（ＩＩ）
で表される分子中にアルケニル基を有する多価アルコール誘導体と、下記式（ＩＩＩ）
で表される分子鎖片末端にケイ素原子結合水素原子を有するオルガノポリシロキサンとを、白金化合物含有触媒存在下でヒドロシリル化反応させる工程を含む請求項１～４のいずれか１項に記載の有機ケイ素化合物の製造方法。 The following formula (II)
A polyhydric alcohol derivative having an alkenyl group in the molecule represented by the following formula (III).
The organic according to any one of claims 1 to 4, which comprises a step of hydrosilylating a organopolysiloxane having a silicon atom-bonded hydrogen atom at one end of the molecular chain represented by the above in the presence of a platinum compound-containing catalyst. A method for producing a silicon compound.
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